2D Nanomaterials Chemistry and Properties Ram K. Gupta

2D Nanomaterials
2D Nanomaterials
Chemistry and Properties
Edited by
Ram K. Gupta
First edition published 2022
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Library of Congress Cataloging-in-Publication Data

Names: Gupta, Ram K., editor.
Title: 2D nanomaterials : chemistry and properties / edited by Ram K. Gupta.
Description: First edition. | Boca Raton : CRC Press, 2022. |
Includes bibliographical references and index.
Identifers: LCCN 2021058577 (print) | LCCN 2021058578 (ebook) |
ISBN 9781032013947 (hardback) | ISBN 9781032013992 (paperback) |
ISBN 9781003178453 (ebook)
Subjects: LCSH: Two-dimensional materials.
Classifcation: LCC TA418.9.T96 A123 2022 (print) | LCC TA418.9.T96
(ebook) | DDC 620.1/12—dc23/eng/20220120
LC record available at https://lccn.loc.gov/2021058577
LC ebook record available at https://lccn.loc.gov/2021058578
ISBN: 978-1-032-01394-7 (hbk)

ISBN: 978-1-032-01399-2 (pbk)
ISBN: 978-1-003-17845-3 (ebk)
DOI: 10.1201/9781003178453
Typeset in Times
by codeMantra
I would like to dedicate this book to my parents who
taught me the importance of electricity (energy).
Contents
Preface.......................................................................................................................xi
Author .................................................................................................................... xiii
Contributors ............................................................................................................. xv
Chapter 1 Chemistry of 2D Materials for Energy Applications ...........................1

Charu Goyal, Anuj Kumar, and Ram K. Gupta
Chapter 2 Advanced 2D Materials for Energy Applications .............................. 21

Immanuel Paulraj and Chia-Jyi Liu
Chapter 3 Top-Down Synthesis of 2D Nanomaterials........................................ 37

Arpana Agrawal
Chapter 4 Bottom-Up Synthesis of 2D Nanomaterials for

Energy Applications ........................................................................... 53
Felipe de Souza and Ram K. Gupta
Chapter 5 Types of Energy Devices and Working Principles............................. 71

Yuyan Wang, Yang Liu, Linrui Hou, and Changzhou Yuan
Chapter 6 Theoretical Considerations of 2D Materials in

Energy Applications ........................................................................... 89
Harsha Rajagopalan, Pawan Kumar Dubey,
Jyotsna Chaturvedi, and Laxmi Narayan Tripathi
Chapter 7 2D Nanomaterials Using Thin Film Deposition Technologies ........ 109

Kwadwo Mensash-Darkwa, Daniel Nframah Ampong,
Daniel Yeboah, Emmanuel Acheampong Tsiwah,
and Ram K. Gupta
Chapter 8 Wafer-Scale Growth and High-Throughput Characterization

of Ultrathin 2D Transition Metal Dichalcogenides (TMDCs) for
Energy Applications ......................................................................... 139
Shraddha Ganorkar and Mangesh Diware
vii
viii Contents
Chapter 9 Morphological Aspects of 2D Nanomaterials for

Jing Ning, Maoyang Xia, Dong Wang, Jincheng Zhang,
and Yue Hao
Chapter 10 Effect of Exfoliation on Structural and Electrochemical

Properties ......................................................................................... 175
Gibin George, Deepthi Panoth, Brijesh K, Anjali Paravannoor,
Nagaraja Hosakoppa, Yu-Hsu Chang, and
Sreejesh Moolayadukkam
Chapter 11 Tuning of Bandgap and Electronic Properties for

Maoyang Xia, Jing Ning, Dong Wang, Jincheng Zhang,
and Yue Hao
Chapter 12 Electrolyte Membrane for 2D Nanomaterials ..................................205

S. Mohanapriya, S. Vinod Selvaganesh, and P. Dhanasekaran
Chapter 13 Nanocomposites of 2D Materials for Enhanced

Electrochemical Properties .............................................................. 223
Nitika Devi, Alok Kumar Rai, and Rajesh Kumar Singh
Chapter 14 Recent Developments in Group II-VI Based Chalcogenides

and Their Potential Application in Solar Cells ................................ 245
Saif Ali, Faheem K. Butt, Junaid Ahmad, Zia Ur Rehman,
Sami Ullah, Mashal Firdous, Sajid Ur Rehman,
and Zeeshan Tariq
Chapter 15 Photovoltaic Application of Graphene Oxide and Reduced

Graphene Oxide: Perspectives on Material Characteristics
and Device Performance .................................................................. 263
Tabitha A. Amollo and Vincent O. Nyamori
Chapter 16 Revolutionizing the Field of Solar Cells by Utilization of

Nanoscale Metal Oxide/Hydroxide Based 2D Materials................. 279
Shaan Bibi Jaffri and Khuram Shahzad Ahmad
Contents ix
Chapter 17 2D Materials for Flexible Photo Detector Applications................... 291

Aruna Pattipati and Joseph Chennemkeril Mathew
Chapter 18 2D Nanomaterials for Electrocatalytic Hydrogen Production ......... 303

Arun Prasad Murthy and Nihila Rahamathulla
Chapter 19 Application of Graphene Family Materials for

High-Performance Batteries and Fuel Cells..................................... 321
Chen Shen and S. Olutunde Oyadiji
Chapter 20 2D Transition Metal Dichalcogenides (TMD)-Based

Nanomaterials for Lithium/Sodium-ion Batteries............................ 341
Tian Wang, Ashok Kumar Kakarla, and Jae Su Yu
Index...................................................................................................................... 361
Preface
Energy serves as a focal point for every activity that is carried out in our daily lives.
The human brain, for instance, is considered the most effcient processing system,
faster than that of any supercomputer ever developed to date and, consumes energy
as low as 20 W. “Aurora” the supercomputer being developed by Intel is claimed to
hit a computing speed of 1 exafop – equivalent to one quintillion foating-point com-
putations per second. The United States Department of Energy estimates electricity
target to power “Aurora” will be 40 mW. Although we are trying to hit the extrava-
gant effciencies closer to the brain, the devices that are as effcient to the low energy
consumption of the brain remain a challenge. The answer to all these problems is
hidden in the material science of electronic devices that are being fabricated. The
development of materials has allowed us to ft billions of transistors in small-sized
chips and allow progress per Moore’s law. The major contribution to these materials
includes two-dimensional (2D) nanomaterials, which are widely used materials in
energy applications due to their unique structure at low cost.
2D nanomaterials have emerged as promising candidates for energy devices
owing to their superior electrochemical properties, surface area, nano-device inte-
gration, multifunctionality, printability, and mechanical fexibility. In this book, we
summarize research aspects for different materials in the 2D category such as gra-
phene and its derivatives, transition metal chalcogenides, and transition metal oxides/
hydroxides for energy applications such as in batteries, supercapacitors, solar cells,
and fuel cells. Apart from conventional techniques, this book explores new aspects
of synthesizing 2D nanomaterials beyond traditionally layered structures such as 2D
metal oxides and polymers, broadening the vision for readers to explore novel mate-
rial systems for enhanced energy applications.
The book is divided into two volumes to cover synthesis, properties, and applica-
tions of 2D nanomaterials for energy. The frst volume (this volume) covers basic
concepts, chemistries, the importance of 2D nanomaterials for energy along theoreti-
cal consideration in designing new 2D nanomaterials. The effect of doping, struc-
tural variation, phase, and exfoliation on structural and electrochemical properties
of 2D nanomaterials are discussed for their applications in the energy sector. Types
of energy devices and their working principles are covered in detail. Some of the
advanced applications such as fexible photodetectors, batteries, fuel cells, and pho-
tovoltaics are discussed. The second volume covers a wide range of applications of
2D nanomaterials for energy.
Ram K. Gupta, Associate Professor

Department of Chemistry
Kansas Polymer Research Center
Pittsburg State University
Pittsburg, Kansas, United States
xi
Author
Dr. Ram K. Gupta is an Associate Professor at Pittsburg
State University. Dr. Gupta’s research focuses on conduct-
ing polymers and composites, green energy production and
storage using biowastes and nanomaterials, optoelectronics
and photovoltaics devices, organic-inorganic hetero-
junctions for sensors, bio-based polymers, fame-retardant
polymers, bio-compatible nanofbers for tissue regenera-
tion, scaffold and antibacterial applications, corrosion
inhibiting coatings, and bio-degradable metallic implants.
Dr. Gupta has published over 235 peer-reviewed articles,
made over 300 national, international, and regional presen-
tations, chaired many sessions at national/international meetings, edited many books,
and written several book chapters. He has received over two and a half million dol-
lars for research and educational activities from many funding agencies. He is serv-
ing as Editor-in-Chief, Associate Editor, and editorial board member for numerous
journals.
xiii
Contributors
Arpana Agrawal K. Brijesh
Department of Physics Department of Physics
Shri Neelkantheshwar Government National Institute of Technology
Post-Graduate College Karnataka (NITK)
Khandwa, India Surathkal, India
Junaid Ahmad Faheem K. Butt

Department of Physics Department of Physics
Division of Science and Technology Division of Science and Technology
University of Education University of Education
Lahore, Pakistan Lahore, Pakistan
Yu-Hsu Chang
Khuram Shahzad Ahmad Department of Materials and Mineral
Department of Environmental Sciences Resources Engineering
Fatima Jinnah Women University Institute of Mineral Resources
Rawalpindi, Pakistan Engineering
National Taipei University of
Saif Ali Technology
Department of Physics Taipei, Taiwan
Division of Science and Technology
University of Education Jyotsna Chaturvedi
Lahore, Pakistan Department of Inorganic and Physical
Chemistry
Indian Institute of Science
Tabitha A. Amollo Bangalore, India
Department of Physics
Njoro Campus Felipe de Souza
Egerton University Kansas Polymer Research Center
Egerton Nakuru, Kenya Pittsburg State University
Pittsburg, Kansas
Daniel Nframah Ampong
Department of Materials Engineering Nitika Devi
College of Engineering, Kwame School of Physics & Material Science
Nkrumah Shoolini University
University of Science and Technology Solan, India
Kumasi, Ghana
P. Dhanasekaran
Sourabh Barua Fuel Cells Division
Department of Physics CSIR-Central Electrochemical Research
Birla Institute of Technology Mesra Institute-Madras Unit
Ranchi, India Chennai, India
xv
xvi Contributors
Mangesh Diware Yue Hao

Center for Novel State of Complex The State Key Discipline Laboratory
Materials Research of Wide Band Gap Semiconductor
Department of Physics and Astronomy Technology
Seoul National University Xidian University
Seoul, Republic of Korea Xi’an, China
and
Pawan Kumar Dubey Shaanxi Joint Key Laboratory of
Electroptics Laboratory Graphene
Department of Electrical and Xidian University
Electronics Engineering Xi’an, China
Ariel University
Ariel, Israel Nagaraja Hosakoppa
Sumit Dutta National Institute of Technology
Department of Physics Karnataka (NITK)
Birla Institute of Technology Surathkal, India
Mesra
Ranchi, India Linrui Hou
School of Materials Science &
Mashal Firdous Engineering
Department of Physics University of Jinan
Division of Science and Technology Jinan, PR China
University of Education
Lahore, Pakistan Shaan Bibi Jaffri
Department of Environmental
Shraddha Ganorkar Sciences
Advanced Mechanics and Material Fatima Jinnah Women University
Design Lab Rawalpindi, Pakistan
Department of Mechanical Engineering
Sungkyunkwan University Ashok Kumar Kakarla
Suwon, Republic of Korea Department of Electronics and
Information Convergence
Gibin George Engineering
Department of Mechanical Institute for Wearable Convergence
Engineering Electronics
SCMS School of Engineering and Kyung Hee University
Technology Yongin-si, Republic of Korea
Ernakulam, India
Anuj Kumar
Charu Goyal Department of Chemistry
Department of Chemistry GLA University
GLA University Mathura, India
Mathura, India
Contributors xvii
Chia-Jyi Liu Jing Ning

Department of Physics The State Key Discipline Laboratory
National Changhua University of of Wide Band Gap Semiconductor
Education Technology
Changhua, Taiwan Xidian University
Xi’ an, China
Yang Liu and
School of Materials Science & Shaanxi Joint Key Laboratory of
Engineering Graphene
University of Jinan Xidian University
Jinan, PR China Xi’ an, China
Joseph Chennemkeril Mathew Vincent O. Nyamori

Department of Physics School of Chemistry and Physics
Dayananda Sagar College of Engineering Westville Campus
Bangalore, India University of KwaZulu-Natal
Durban, South Africa
Kwadwo Mensah-Darkwa
Department of Materials Engineering S. Olutunde Oyadiji
College of Engineering, Kwame Department of Mechanical, Aerospace
Nkrumah and Civil Engineering
University of Science and Technology School of Engineering, Faculty of
Kumasi, Ghana Science and Engineering
The University of Manchester
S. Mohanapriya Manchester, United Kingdom
Bionanomaterials Lab
Department of Chemistry Deepthi Panoth
Periyar University School of Chemical Sciences
Salem, India Kannur University
Payyanur, India
Centre for Nano and Soft Matter Anjali Paravannoor
Sciences (CeNS) School of Chemical Sciences
Bangalore, India Kannur University
Payyanur, India
Arun Prasad Murthy
Department of Chemistry Aruna Pattipati
School of Advanced Sciences Department of Physics
Vellore Institute of Technology Dayananda Sagar College of
Vellore, India Engineering
Bangalore, India
xviii Contributors
Immanuel Paulraj Rajesh Kumar Singh

Department of Physics School of Physical and material Sciences
National Changhua University of Central University of Himachal Pradesh
Education Dharamshala, India
Changhua, Taiwan
Zeeshan Tariq
Nihila Rahamathulla School of Science
Department of Chemistry Optoelectronic Research Center
School of Advanced Sciences Minzu University of China
Vellore Institute of Technology Beijing, China
Vellore, India
Laxmi Narayan Tripathi
Alok Kumar Rai School of Advanced Science
Department of Chemistry Vellore Institute of Technology
University of Delhi (North Campus) Vellore, India
New Delhi, India
Emmanuel Acheampong Tsiwah
Harsha Rajagopalan Department of Materials Science and
Department of Physics Engineering
School of Advanced Science School of Chemistry and Materials
Vellore Institute of Technology Science
Vellore, India University of Science and Technology
of China
Hefei, China
Sajid Ur Rehman
School of Science, Optoelectronic Sami Ullah
Research Center Department of Physics
Minzu University of China Division of Science and Technology
Beijing, China University of Education
Lahore, Pakistan
Zia Ur Rehman
School of Physics S. Vinod Selvaganesh
College of physical Science and Indian Institute of Technology-Madras
Technology and School of Chennai, India
Environmental Science and
Engineering Dong Wang
Yangzhou University The State Key Discipline Laboratory
Yangzhou, PR China of Wide Band Gap Semiconductor
Technology
Chen Shen Xidian University
Department of Mechanical Xi’an, China
Aerospace and Civil Engineering, and
School of Engineering, Faculty of Shaanxi Joint Key Laboratory of
Science and Engineering Graphene
The University of Manchester Xidian University
Manchester, United Kingdom Xi’an, China
Contributors xix
Tian Wang Jae Su Yu

Department of Electronics and Department of Electronics and
Information Convergence Information Convergence
Engineering Engineering
Institute for Wearable Convergence Institute for Wearable Convergence
Electronics Electronics
Kyung Hee University Kyung Hee University
Yongin-si, Republic of Korea Yongin-si, Republic of Korea
Yuyan Wang Changzhou Yuan

School of Materials Science & School of Materials Science &
Engineering Engineering
University of Jinan University of Jinan
Jinan, PR China Jinan, PR China
Maoyang Xia Jincheng Zhang

The State Key Discipline Laboratory The State Key Discipline Laboratory
of Wide Band Gap Semiconductor of Wide Band Gap Semiconductor
Technology Technology
Xidian University Xidian University
Xi’ an, China Xi’an, China
and and
Shaanxi Joint Key Laboratory of Shaanxi Joint Key Laboratory of
Graphene Graphene
Xidian University Xidian University
Xi’ an, China Xi’an, China
Daniel Yeboah
Department of Materials and
Manufacturing
Institute of Industrial Research - Council
for Scientifc and Industrial Research
Accra, Ghana
1 Chemistry of 2D
Materials for Energy
Applications
Charu Goyal and Anuj Kumar
GLA University
Ram K. Gupta
CONTENTS
1.1 Introduction ......................................................................................................1
1.2 Chemistry, Structures, and Properties of 2D Materials ...................................3
1.2.1 Transition Metal Di-Chalcogenides-based 2D Materials .....................3
1.2.2 MXenes-Based 2D Materials ...............................................................4
1.2.3 Graphene-Based 2D Materials .............................................................6
1.3 Energy Application of 2D Materials ................................................................7
1.3.1 Electrochemical Hydrogen Evolution Reaction.................................... 8
1.3.2 Electrochemical Oxygen Evolution Reaction ....................................... 8
1.3.3 Electrochemical Oxygen Reduction Reaction ......................................9
1.3.4 Electrochemical Carbon Dioxide Reduction Reaction.........................9
1.3.5 2D Materials for Advanced Batteries ................................................. 10
1.3.6 2D Materials for Supercapacitor Devices........................................... 12
1.4 Conclusion ...................................................................................................... 13
References................................................................................................................ 14
1.1 INTRODUCTION
In modern society, signifcant energy needs and environmental crises have acceler-
ated the development of energy storage technology. Due to their high effciency and
environmental acceptability, different electrochemical energy storage technologies
have attracted recent interest. Supercapacitors, especially, can collect and generate
electricity at excessive power densities, joining the power and energy gap between
batteries and capacitors. Alkali metal (Li, Na, K) -ion batteries have high energy den-
sities and wider operating voltages, making them suitable for use in mobiles, laptops,
and e-mobility. Metal-air batteries, which have a potential energy density equivalent
to gasoline, can power long-distance electric motors [1]. Without a question, these
gadgets offer a lot of promise; nevertheless, meeting the growing demand for practical
DOI: 10.1201/9781003178453-1 1
2 2D Nanomaterials
applications is still a challenge. One of the most signifcant barriers is the electrode
materials, which are either too costly or inactive. As a result, innovative materials for
electrodes having excessive effciency and being cheap are urgently required.
Two-dimensional (2D) materials, which are a type of independent planar material,
have a large size to thickness ratio. They show many unique physicochemical char-
acteristics such as (a) high specifc surfaces to enhance ion adsorption and improve
capacitance, (b) high conductivity to speed up electron transfer, (c) high ion intercala-
tion to provide high energy density, and (d) tunable active sites to provide rich elec-
trocatalytic properties for enhanced energy storage. Graphene is a characteristic 2D
substance that is a carbon allotrope in which the atoms are arranged in a honeycomb
lattice. It got wide attention in 2004 when micromechanical cleavage using Scotch
tape was used to prepare graphene from graphite [2]. Since then, graphene has been
widely investigated, and numerous intriguing characteristics, such as good mechani-
cal qualities, large thermal and electrical conductivity, amazing surface area, and
exceptional optical characteristics have been discovered. Graphene has been used
in a variety of disciplines, including energy, catalysis, optoelectronic devices, and
healthcare, due to its unique characteristics.
Several types of 2D materials have been noted in the wake of graphene's discovery,
containing mono-elemental analogues (MEAs) of graphene, transition metal dichal-
cogenides (TMDs), carbides, nitrides, and carbonitrides (MXene) of transition met-
als. The typical architecture of popular 2D materials is shown in Figure 1.1. MEAs
are 2D materials that are made up of only one kind of element with 2D structures
similar to graphene. MX2, in which M is a transition metal atom (including Mo,
Nb, V, or W) and X is represented as a chalcogen atom, is the chemical formula
for TMDs (including S, Se, or Te). 2D transition metal dichalcogenides have a wide
range of applications in high-end electronics, spin-manipulated electronics technol-
ogy, optoelectronic devices, and energy storage and conversion due to their sturdy
spin–orbit coupling and favorable electrical as well as mechanical characteristics [3].
MXenes are typically made by carefully removing the ‘A’ components from MAX
phases, which have the chemical stoichiometry of Mn+1AXn (where M is an earlier
transition metal, A is a group 12–16 element, and X is carbon or nitrogen). Large
electrical conductivity, appropriate hydrophilic behavior, good thermal stability,
FIGURE 1.1 Structural representation of some common 2D materials. Adapted with per-
mission from [5]. Copyright (2021), Wiley-VCH.
Chemistry of 2D Materials 3
broad interlayer spacing, with readily adjustable structure have all been discovered in
MXenes [4], which makes it a potential material for electrochemical energy storage.
The newest advancements in 2D materials for electrochemical power storage are
the subject of this study. We want to improve our intellect of the link between 2D
materials' arrangements, characteristics, and applications, as well as encourage the use
of high-effciency 2D materials. The applications of energy to supercapacitors, alkali
metal-ion/metal-air batteries are then discussed. Lastly, some broad ideas for future
research into new 2D materials for electrochemical power storage are suggested.
1.2 CHEMISTRY, STRUCTURES, AND

PROPERTIES OF 2D MATERIALS
1.2.1 TRANSITION METAL DI-CHALCOGENIDES-BASED 2D MATERIALS
Since molybdenum disulfde (MoS2) has a direct bandgap, high mobility, and quantum
confnement, it is a major fgure among 2D stacked materials in the feld of nano-elec-
tronics and optoelectronics. This will be very useful for low-power devices in post-Si
technologies. For example, MoS2 is useful in photocatalysts and solar cells [6]. MoS2 and
other TMDC isomorphs have been intensively investigated in this context for accessible
applications in water and air purifcation, hydrogen evolution reaction (HER), as well as
power storage [7]. Usually, MoS2 has a non-centrosymmetric crystal structure having
long-range periodic order and is a direct bandgap material. It is an sp3 linked solid made
up of two covalent bonds of Mo-S in a layered form with each layer joined by van der
Waals interaction in between the layers [8]. The fundamental building block of MoS2 is
a hexagonal (honeycomb-like) system of Mo and S atoms that looks like graphene. Bi-/
trilayer MoS2 is formed when two or three single layers of S-Mo-S are stacked on top of
each other and held together by weak van der Waals forces. It's possible to create three-
dimensional (3D) bulk MoS2 by layering over 100 single layers of MoS2.
A revised MoS2 structure was computed using density-based theory and local
density approximations. The MoS2 cell has been found to consist of a honeycomb-
like lattice structure having a lattice factor of 3.12 Å and vertical spacing between
layers of sulfur of 3.11 Å [9]. MoS2 is classed as per a d-orbital material since Mo
d-orbits both constitute the highest bands of valence and the lowest bands of conduc-
tion [10,11]. In addition, the external d-electron interactions lead to a gap in the band
(approx. 1 eV) between the occupied and unoccupied d-states of 2D MoS2, making
it distinguishable with other nanostructures that are sp-hybridized semiconductors.
Remarkably, when the 3D bulk structures transform into 2D constructions, it con-
verts from indirect to direct bandgap [12]. The indirect bandgap in 3D MoS2 sits
underneath the direct bandgap. Nevertheless, when the number of layers is reduced,
the direct bandgap changes higher, leading to a transversal to a direct gap mate in
the individual MoS2 layer [12]. This shift to the bandgap happens to the 3D structure
because of the substantial quantum containment of the 2D structure. This is due to
transitions of direct gap between the split-valence band maxima and the conduction
band minima around the K point of the Brillouin zone that contributes to the photo-
luminescence characteristics [12]. This is the principal cause why MoS2 shows pho-
toluminescence among its 2D forms but lacks photoluminescence in its 3D crystal
4 2D Nanomaterials
structures [8,13]. Similarly, atomic layer thickness TMDC materials are distinguish-
able from other sp3 bonded semiconductor materials by the quantum captivity they
display [8]. Dimension reliant on bandgap changes besides the visible to near-IR light
system, on the other hand, are expressions of carrier production, implying that these
materials might be used in sustainable solar-energy conversion systems [14].
1.2.2 MXENES-BASED 2D MATERIALS

MXene's crystal shape resembles that of its MAX-phase predecessor, with a hex-
agonal close-packed arrangement. Here, M atoms are organized in a close-packed
arrangement, while X atoms occupy octahedral positions. Similar to other 2D mate-
rials, neighboring stacked units are linked by van der Waals forces. MXenes, particu-
larly acidic fuorides, are generally made in aqueous solutions. As a result, MXenes
have a combination of OH, F, and O terminations on their surfaces. These molecules
are abbreviated as Mn+1XnTx, where T denotes the surface termination. There are
MXenes with the structures M2XTx, M3X2Tx, and M4X3Tx (Figure 1.2) [15]. The lat-
est computer simulations show that the surface termination of MXenes has a big
infuence on their characteristics. Hu et al. [16], for instance, have systematically
investigated Bader charging analysis and thermodynamic calculations on the chemi-
cal origin of termination-specifc MXenes; the material has demonstrated stability
order such as Ti3C2O2 > Ti3C2F2 > Ti3C2(OH)2 > Ti3C2H2 > Ti3C2, attributable to the
scatter of the 3d strongly degenerated surface orbits of Ti. In a separate study, Fu
et al. [17] methodically examined the impact of many functional groups (such as Cl,
F, H, O, and OH) on the stabilization, electronic structures, and mechanical proper-
ties of an MXene (Ti3C2); the researchers noted that oxygen-functionalized Ti3C2
has stronger thermodynamic stabilization and toughness than its other counterparts
FIGURE 1.2 Three different formulas (M2XTx, M3X2Tx, and M4X3Tx) and compositions
(mono-MMXenes and double-M MXenes) of MXenes. Reproduced with permission from
[15]. Copyright (2021), Wiley-VCH.
because of cation exchange between the inner bond and outer surface. Surface ter-
mination of MXenes such as Ti3C2Tx and V2CTx has also been studied utilizing
experimental approaches in addition to theoretical investigations. Wang et al. [18],
for example, used aberration-corrected scanning transmission electron microscopy
(STEM) to reveal the surface atomic scale of Ti3C2Tx; the group discovered that
surface functional groups (e.g., OH, F, and O) are randomly distributed on MXene
surfaces and prefer to occupy the top sites of the central Ti atom. Karlsson’s group
[19] used aberration-corrected STEM coupled with electron energy loss spectros-
copy (EELS) to study individual and double sheets of Ti3C2, revealing sheet cover-
age, inherent defects, and TiOx adatom complexes. Surface termination of MXenes
such as Ti3C2Tx and V2CTx is also being studied utilizing experimental approaches in
addition to theoretical investigations. Wang and co-workers [17], for example, used
aberration-corrected STEM to reveal the surface atomic scale of Ti3C2Tx; the group
discovered that surface functional groups (e.g., OH, F, and O) are randomly spread
on MXene surfaces and favor to enter the top sites of the center atom of Ti. Karlsson's
group [19] used aberration-corrected STEM-EELS to study individual and double
sheets of Ti3C2, revealing sheet coverage, inherent imperfections, as well as TiOx
adsorption complexes. Sang and colleagues used STEM to discover various point
defects in monolayer Ti3C2 nanosheets using the minimum intense layer delamina-
tion technique [20]. Hope and colleagues [21] used 1H and 19F nuclear magnetic
resonance (NMR) studies to quantify the surface functional groups of Ti3C2Tx and
discovered that the proportions of distinct surface terminations are signifcantly
dependent on the material's production process. Harris and co-workers used stable
NMR to directly quantify the surface termination groups of V2CTx MXenes [22].
The inherent good electrical characteristics of MXene materials are primar-
ily responsible for their use in energy storage and electrocatalysis. The infuence of
various M, X, and surface functional groups on the electrical characteristics of most
MXenes has been investigated in recent theoretical computational research. Because
MXenes contain a variety of transition metals, their electrical characteristics might
range from metallic to semiconducting [23]. Since they may also contain heavy transi-
tion metals like Mo, W, and Cr, some MXenes could be topological insulators [15,24].
Surface termination may also affect the electrical characteristics of uncoated MXenes.
For instance, Fredrickson and co-workers used density-functional theory (DFT) cal-
culations to study the structural and electrical characteristics of layered bulk Ti2C and
Mo2C with various functional groups in aqueous environments [25]. Surface functional
groups and water intercalation have a signifcant impact on the out-of-plane lattice
parameter of bulk MXenes. Bulk MXenes (Ti2C and Mo2C) were functionalized by
one monolayer of O at no applied voltage. However, regardless of the applied potential,
bare MXenes were unstable. Furthermore, with an applied potential, changes in the
surface functional groups of Ti2C from O-covered to H-covered might induce metal-
insulator transition. Tang and co-workers found that uncoated MXenes (such as Ti3C2)
have metallic characteristics, but functionalizing Ti3C2 with various groups (such as
–OH, –F, and –I) results in semiconductor qualities with small bandgaps [26]. It was
also shown that the M layer has a signifcant impact on the electrical characteristics of
the fnal material. Remarkably, MXenes containing Mo have semiconductor charac-
teristics, while Ti3C2Tx is metallic. DFT calculations revealed that Ni2N MXenes had
6 2D Nanomaterials
inherent half-metallicity [27]. The nanostructures of MXene have been linked to their
electrical characteristics. For example, Enyashin and Ivanovskii [28] anticipated that
hydroxylated Ti3C2 nanotubes will have metallic-like properties. Ti3C2 nanoribbons,
according to Zhao et al. [29], show unique electrical characteristics from nanosheets of
MXenes. The electronic characteristics of MXenes have been studied in many experi-
ments. Just the electrical characteristics of a few MXenes, such as Ti2CTx, Ti3C2Tx,
and Mo2CTx, have been examined experimentally thus far [30]. Halim and colleagues
[31], for instance, studied the electrical conductivity of Ti3C2Tx and Mo2CTx flms.
The electrical characteristics of monolayer Ti3C2Tx fakes were measured by Lipatov
and colleagues [32]. The outstanding electrical characteristics of 2D Ti2CTx were
discovered by Lai et al. [33]. MXenes offer outstanding electronic characteristics, as
demonstrated by computational and experimental studies, and are attractive candidate
materials for electrochemistry, energy storage, and electrocatalysis.
1.2.3 GRAPHENE-BASED 2D MATERIALS

Graphene is a carbon allotrope with 2D characteristics that is crystalline. Carbon
atoms are tightly packed in graphene in an atomic-scale sp2-bonded hexagonal
arrangement. A one-atom-thick sheet of graphite is referred to as graphene. Other
allotropes, such as graphite, charcoal, carbon nanotubes, and fullerenes, have it
as a structural constituent. Graphene is a promising active material in electroca-
talysis due to its unique features of high electrical conductivity and huge surface
area. Because of the original graphene’s low catalytic activity, [34] graphene with
a large planer conjugated structure is generally coupled with components capable
of electrocatalytic activity through intermolecular interactions at the start. Many
attempts have lately been made to improve graphene’s intrinsic performance by
developing active sites and electronic control, therefore increasing the catalytic
process of graphene hybrids via strong electronic coupling between graphene and
other materials [35–37]. Regulation methods for graphene-based electrocatalysts
may be categorized into four groups (Figure 1.3): (a) graphene’s inherent defect
control, (b) non-metallic element doping, (c) graphene coupling with active compo-
nents (graphene-based composites), and (d) graphene-based single-atom catalyst.
The use of various techniques in electrocatalytic areas is thoroughly summarized
in this section.
The variety of heteroatoms and matrix materials provides an ever-increasing
number of design possibilities for active materials. Graphene, with its 2D mono-
layer structure, has a huge specifc surface area (SSA), many defect sites, and oxy-
gen-containing functional groups on both plane and edge, making it an excellent
matrix material for heteroatom doping. Heteroatom doping can signifcantly enhance
the electronic structure of graphene, resulting in improved catalytic performance.
Doping heteroatoms, such as N, P, S, B, and others, can offer numerous active sites
and modify the local electronic structure, therefore increasing the system's reaction
activity [38]. Non-metal heteroatoms doping is extensively utilized in a variety of
energy-related sectors, including lithium-ion batteries, sodium-ion batteries, lithium-
sulfur batteries [39], supercapacitors [40], electrocatalysis [38,41,42], photocatalysis
[43], and many more.
FIGURE 1.3 Graphene-based catalysts are regulated by introducing defects, nonmetal-

lic elements, single atoms, and other active components into the graphene system. Adapted
from Ref. [44]. Copyright (2021) Nature. Adapted from Ref. [45]. Copyright 2021 American
Chemical Society. Adapted from Ref. [46]. Copyright (2021) Wiley-VCH. Adapted from Ref.
[47]. Copyright (2021) Tsinghua University Press and Springer-Verlag GmbH Germany.
1.3 ENERGY APPLICATION OF 2D MATERIALS

In addition to the larger SSA, functionalization of surface, reversible ion and trans-
port of mass, and dependable mechanical resilience, controlled construction of 2D
materials at the nanoscale into desired designs have released valuable approaches. A
thorough grasp of current structural engineering methodologies is also useful for the
best design of suitable structures, which may be employed for practical energy pur-
poses [48–50]. Particles or molecules can be intercalated in 2D materials by manipu-
lating their layer spacing. When it comes to secondary batteries and supercapacitors,
the capacity of the 2D host to trap charged particles/molecules in a regulated revers-
ible manner is crucial for successful power storage. For example, chemical composi-
tion, surface wetness, effective surface area, and the charge transfer characteristics
of an electrode structure may all infuence the amount of energy that can be stored
by 2D materials (i.e. the extreme energy density). The surface chemistry/geometry
and charge and/or mass transport characteristics of a catalytic structure, on the other
hand, will infuence the primary performance in energy conversion systems after
being paired with diverse energy sources, such as current density and onset volt-
age [51–54]. The major challenge of energy conversion technologies nowadays is
to discover new electrocatalysts. 2D framework materials are very capable electro-
catalysts with high conversion effciency at low energy input due to their precise
8 2D Nanomaterials
composition and/or structure tunability, large surface area, dense exposed catalytic
sites, also enhanced conductivity compared to bulk counterparts. HER, oxygen evo-
lution reaction (OER), oxygen reduction reaction (ORR), and CO2 reduction reaction
(CO2RR) are only a few of the key energy conversion processes that use 2D frame-
work electrocatalysts.
1.3.1 ELECTROCHEMICAL HYDROGEN EVOLUTION REACTION

It has been universally accepted that electrocatalytic hydrogen generation via water
splitting produces high-grade H2 in a clean and sustainable method. Integration of
transition metal (Fe, Co, Ni, etc.) into 2D framework catalysts has been studied
in the past to increase the HER catalytic activity [55–60]. Using a liquid–liquid
interfacial method, the Marinescu group successfully synthesized a cobalt dithi-
olene-fused 2D metal-organic frameworks (MOF) [57]. With a HER overpotential
of 0.3 V at 10 mA cm−2 in an acidic medium, the target MOS electrocatalyst showed
outstanding performance due to its high catalytic site loading and remarkable sta-
bility. For electrocatalytic HER, different metal dithiolene-based 2D framework
electrocatalysts were created. Dong et al. rationally integrated metal dithiolene–
diamine (MS2N2, M = Co/Ni) into carbon-rich 2D MOFs as a model carbon elec-
trocatalyst for HER in addition to metal dithiolene sites [56]. In the sequence,
MS2N2 > MN4 > MS4, the electrocatalytic HER activity of these 2D MOFs changed
for the various metal coordination modes. Nanosheet protonation favors M–N sites
situated in the MS2N2 coordination spheres. They helped us get a better knowledge
of various metal complexes (MNX and MSX) as well as shed insight on the develop-
ment of high-performance catalysts. For electrocatalytic HER, 2D covalent-organic
frameworks (COFs) without metal having numerous functional groups were also
produced. The Pradhan group was the frst to publish a metal-free HER electro-
catalyst based on imine-based conjugated pyrene and porphyrin-based 2D COF
(such as SB-PORPy COF) [61]. As a catalytic center, the imine nitrogen sites in the
SBPORPy COF showed exceptional activity of catalysts with a low onset poten-
tial of 50 mV and good stability in acid electrolyte. Due to their poorer stability
and overall conductivity, contemporary 2D framework-based electrocatalysts have
lower catalytic activity than the industry-recognized inorganic catalysts, despite
substantial advances.
1.3.2 ELECTROCHEMICAL OXYGEN EVOLUTION REACTION

2D frameworks for oxygen evolution have demonstrated amazing performance
equivalent to the best OER electrocatalysts available today. According to Du's team,
a 2D nickel phthalocyanine MOF (NiPc-MOF) with a low onset potential of 1.48
V with the high mass activity of 883 A g−1 in alkaline medium has been produced
from the bottom up [61]. The 2D structure and high conductivity of 2D MOFs had
a major role in the excellent OER activity. As compared to the benchmark noble
metal-based catalyst, the ultrathin NiCo bimetallic framework nanosheets produced
by Tang and colleagues needed an exceptionally low overpotential of 250 mV at 10
mA cm−2 in OER under alkaline circumstances (IrO2 and RuO2). Because of their
high electrocatalytic activity, the unsaturated metal atoms and the coupling effect
between Ni and Co metals are essential. MOFs have also been proposed to increase
OER catalytic activity by fabricating ultrathin or lattice-strained nanosheet arrays of
2D MOFs on current collectors, as well as hybrid 2D MOFs.
1.3.3 ELECTROCHEMICAL OXYGEN REDUCTION REACTION

Electrocatalytic ORR in 2D frameworks has shown promising development, even if
most relevant instances only address their non-exfoliated variants [62–66]. Thin flms
of the conductive MOF Ni3(HITP)2 (thickness of around 120 nm, coated on glassy
carbon electrodes) with well-defned NiN units as an ORR electrocatalyst in alkaline
electrolyte were reported in 2016 by the Dinc group [63]. The electrocatalyst showed
an onset potential of 0.82 V with good stability over protracted polarization. This
highlights the importance of layer-conductive MOFs in the development of tuneable
and rational electrocatalysts. When Ni/Co metal sources with 2,3,6,7,10,11-hexaimi-
notriphenylene (HITP) are used in various ratios, 2D MOFs are produced [65].
To compensate for the unpaired 3dZ2 electron in Co, the Co3HITP2’s quadrilateral
structure deformed and its conductivity dropped. In alkaline electrolyte, however, it
showed remarkable ORR performance (onset potential of 0.9 V and electron transfer
number of 3.97) because the unpaired electron on Co 3dZ2 in the catalytically active
CoN4 center is benefcial for promoting the binding of oxygen intermediates and thus
accelerates the ORR energetics despite the reduced electric conductivity. As opposed
to weakly bound Ni3HITP2, which travels through a two-electron ORR route with
reduced catalytic activity. A highly active electrocatalyst for ORR may be developed
by optimizing the architectural and electrical structure of layered MOF materials.
1.3.4 ELECTROCHEMICAL CARBON DIOXIDE REDUCTION REACTION

To regulate the activity of the catalyst, effciency, and selectivity in one system with
excellent performance toward the target products, tailored 2D frameworks electro-
catalysts would be an ideal choice in CO2RR electrocatalysis. As active centers,
cobalt porphyrins were used to fabricate ultrathin 2D MOF nanosheets (TCPP(Co)/
Zr-BTB), which had a turn of frequency (TOF) of 4768/h at −0.919 V vs. RHE.
In addition, a post-modifcation technique was used to enhance the catalytic per-
formance of the catalyst. Modifed samples of p-sulfamidobenzoic acid showed an
enhanced TOF of 5315/h at −0.769 V with a faradaic effciency of 85.7% for CO and
long-term durability, compared to unmodifed samples [67]. As a result, increased
use of active sites and optimal post-modifcation are viable ways to improve CO2RR
performance. An electrocatalyst that is extremely active and selective for CO2RR
was created by the Feng group, for example, using a bimetallic conjugated MOF
(2D c-MOFs). It had a CO selectivity of 88% and a TOF of 0.39/s in the 2D c-MOF
(PcCu-O-Zn). This has been demonstrated by in situ X-ray absorption spectroscopy,
surface-enhanced infrared absorption petro-electrochemistry, and theoretical calcu-
lation investigations. This innovative method for creating MOF-based electrocata-
lyst uses ZnO4 complexes as CO2RR catalytic sites, while CuN4 centers enhance
the protonation of adsorbed CO2 during CO2RR [68]. In addition, the Lan group
10 2D Nanomaterials
proposed directed effcient electron transmission by metalloporphyrins, to accom-

plish extremely active electrocatalytic CO2 to CO conversion by the application of
tetrathiafulvalene as an electron donator [69]. When Co-TTCOF was exfoliated, it
showed an impressive faradic effciency for CO (above 90% across a larger potential
range), with the highest value reaching up to 99.7%, which is better than the existing
state-of-the-art catalysts.
1.3.5 2D MATERIALS FOR ADVANCED BATTERIES

The majority of secondary battery research has focused on improving power density
and charging and/or discharging kinetics because of their critical share as a power
source for electronic devices/vehicles. This has been driven by the current appear-
ance of novel 2D materials with large surface area and easy charge transportation.
These advantages can be attributed in part to the electrode structure's optimum design.
Although there have been some recent advances, there are still signifcant obstacles
to the rapid use of 2D materials without structural modifcation. Limited stability of
electrochemical window (connected to redox potential) and small initial coulombic
effciency are some of the problems (correlated to Faraday effect) [70,71]. Designing
3D buildings using fexible networks made of 2D materials is a viable method for
addressing the problems outlined above. However, these structures also handle the vol-
ume shift that occurs after repeated charging/discharging cycles, eliminating capacity
fading. Li+ or Na+ ions may be able to travel short distances through these materials'
porous frameworks, which might affect the voltage window and columbic effciency.
Using 2D graphene as an encapsulant for active materials for the electrode
(such as Si nanoparticles), Lee et al. published a groundbreaking study in this feld
(Figure 1.4a) [72]. Accordingly, Zhang and co-workers examined the potential of gra-
phene interweaved as anode material in the same way [73]. Such nanoarchitectures, as
can be shown in Figure 1.4b, might effectively limit the accumulation of active mate-
rials and buffer the mechanical strain which comes from signifcant volume shifts.
Furthermore, nanoparticles enclosed in 2D materials can contribute to structural
integrity. As a result of the capacity to enclose 0D materials, new cathode architec-
tures have been developed as well. Of the use of silica spheres as templates, Zhu and
co-workers produced 3D macro-porous composites with Li2FeSiO4 and 2D materials.
The constant cycle windows for Na+ ions in some TMDCs, such as TiS2 and NbS2,
have been observed [74,75]. Another promising Li–S battery material is MXene,
a group of transition metals, nitrides, carbides, and carbonitrides. Among these
improvements is the use of dipole-type polaritonic excitation for effective trapping
of polysulfde with rich surface chemistry. Ti3C2Tx nanosheets with a negative charge
tend to be superior at forming certain microstructures when combined with posi-
tively charged melamine, as illustrated in Figure 1.4c [76]. Nitrogen insertion into the
MXene framework allows polysulfde to easily adsorb on the MXene surface, which
is extremely desired for Li–S battery applications, as well. Few studies have been
carried out in 1D nanoscale assembly for secondary batteries because surface contact
in 1D geometry is challenging [77]. It’s clear from recent developments, however,
that new battery topologies, such as those based on wires and fabrics, as well as new
approaches for manipulating 2D materials structurally, are not far [78].
Chemistry of 2D Materials
FIGURE 1.4 Secondary batteries made from 2D materials. (a) Graphite's self-encapsulation (i) scheme of graphite’s self-encapsulation is shown,
where the pH was adjusted for electrostatic interaction between SiO2 surface and N-doped sites at graphitic carbons. (ii) HR-SEM. (iii) HR-TEM
pictures of Si particles with captured N-doped CNTs and graphene. (iv) Coulombic effecienecy vs cycle number, and (v) Discharge current vs cycle
number for samples. Adapted with permission 2021, [72] Royal Society of Chemistry copyright (2021). (b) Production of MgH2 nanoparticles (NPs) that
are evenly attached to graphene as anode materials for Li-ion batteries via bottom-up self-assembly (LIBs). (c) Preparation of N-Ti3C2Tx /S composites.
Adapted with permission [76], (Copyright) 2021, Wiley-VCH.
11
12 2D Nanomaterials
1.3.6 2D MATERIALS FOR SUPERCAPACITOR DEVICES

As opposed to secondary batteries, supercapacitors are the usual energy systems that
have excellent power performance. Due to their very basic charge storage process of
keeping a charged particle under an electrical feld, they exhibit high power density.
Most recently, a new device mechanism based on the nanoscale assemblage of 2D
materials has been developed, which uses a 3D network structure to store charge in
a faradic (such as pseudocapacitors) or nonfaradic method (such as electric double
layer capacitor, EDLC). Studies in the literature provide more details on how e− and
ions can be kept effectively on the surface of 2D materials [79,80]. High-power super-
capacitors require interpenetrating electron and ion transport routes, which provide
effective interfacial ion storage or intercalated pseudocapacitance, to function prop-
erly. Due to strong interactions, 2D layers tend to recollect when manufactured into
a structure of electrode without consistent shape engineering, reducing the available
surface area and limiting the transfer of charged species [81]. Idealized supercapaci-
tor electrode architectures may be fabricated using nanoscale-constructed 2D mate-
rials that exhibit desirable properties like out-of-plane fexibility and dipole-type
polaritonic activity. The excellent gravimetric capabilities of these supercapacitor
electrode topologies have already beneftted several early research initiatives concen-
trating on the creation of hierarchically porous structures. Supercapacitors are ham-
pered by their low packing density, which results in limited volumetric capacity and
weak networks in practice. It follows from this that, in order to optimize the design
of supercapacitors based on 2D materials, the permeability and volume density of
electrode structure must be carefully balanced.
Core architectures are extremely advantageous in the case of fber-type super-
capacitors, where two distinct constituents at the core and shell may play different
essential roles. For example, conductive polymer core and 2D material shells in a
fber shape provide interfacial charge storage and intercalated pseudocapacitance,
as well as mechanical robustness. It was possible to produce the same synergistic
effect in a hydrogel structure by adding metal cations to 2D material dispersants
(Figure 1.5) [82]. Cooperation-based crosslinking of multivalent metal cations in
2D materials can lead to stable hydrogel formation with strong EDLC performance,
as well as increased pseudocapacitance with existing cations. Because graphene is
chemically inert, the EDLC mechanism dominates in TMDC, MXene, and black
phosphorous electrochemical energy storage. MXene-like V2CTx, produced using the
Cation Exchange Method, has good rate capability and great gravimetric capacity
(Figure 1.6a) [83]. Cation exchange enhances electrical conductivity and structural
integration in the various MXene families. By inserting new low-dimensional mate-
rials, the dominating organization of 2D materials may be changed. Unfortunately,
block phosphorous' weak electron conduction and restacking tendencies preclude it
from being utilized in superconducting capacitors, which have a wider interlayer
spacing. Structured BP/CNT (CNT in the form of buckypaper) has shown a great
potential for high energy density performance (96.5 mWh cm−3) in comparison to
previously reported 2D material-based structures (MoS2-based structures, 1.6 mWh
cm−3 graphene-based structures, 6.3 mWh cm−3 MnO2-based structures, 11.1 mWh
cm−3 and MXene-based, 32.6 mWh cm−3) (Figure 1.6b) [84].
FIGURE 1.5 Supercapacitors fabricated using 2D materials. (a) Graphene@polymer core–

shell fbers (G@PFs) manufacturing process. Photograph of three G@PEDOT fber superca-
pacitors that light up a green LED when serially connected. Adapted with permission from
[85] Copyright (2021), American Chemical Society. (b) (i) Optical picture of local graphene
gelation on a prepatterned Zn substrate. (ii) Image of graphene gel tube produced with Z wire
in SEM, (iii) Monolithic graphene gel fber net optical picture, (iv, v) 3D graphene gel opti-
cal pictures, (vi) SEM image, (vii) Image of vertical gel tube taken with a SEM microscope
graphene gel and capacity retention curves after 4,000 cycles. Adapted with permission from
[82], Copyright (2021), American Chemical Society.
1.4 CONCLUSION
With fast advancements in novel exfoliation processes, the development of 2D frame-
work materials is seeing a highly dynamic expansion, opening the door for diverse
technical applications in the energy industry. Many studies that examine the effects
on materials characteristics of nano-sizing along one axis describe just one ultra-
thin material, which is frequently not fully described using acceptable methodolo-
gies (i.e. microscopy). So that researchers may better grasp the underlying impacts,
they should compare a wider range of materials, rather than just a single undefned
exfoliated material. In addition, most of the study is focused on the behavior of a
small number of well-understood materials systems, which opens up an exciting
opportunity to examine the applicability of principles established thus far to more
14 2D Nanomaterials
FIGURE 1.6 (a) Assembling pseudocapacitive electrodes with improved electrochemical

characteristics from normally unstable 2D V2CTx MXene fakes via a cation-driven assembly
method. (i–v) microstructure and optical images of the sample. Adapted with permission from
[83] Copyright (2021) Wiley-VCH. (b) Microfuidic-spinning-technique (MST) production of
BP/CNT macrofbers. Published under the Creative Commons Attribution 4.0 International
License (CC-BY). Adapted with permission from [84], Copyright (2021), Nature.
complicated systems customized for specifc applications. The compatibility of fat

2D sheets with a wide range of device confgurations opens up a wide range of inter-
esting applications. Material-specifc compounds with low packing density should
not be overvalued. There is already a lot of promising research being conducted in
this area, and we expect that with a better understanding of and control over the for-
mation of few-layer structures, even better results will be possible.
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2 Advanced 2D Materials
for Energy Applications
Immanuel Paulraj and Chia-Jyi Liu
National Changhua University of Education
CONTENTS
2.1 Introduction .................................................................................................... 21
2.2 Preparation Methods of MXenes.................................................................... 23
2.2.1 Chemical Vapor Deposition (CVD).................................................... 23
2.2.2 Hydrofuoric Acid ............................................................................... 23
2.2.3 Molten Salts ........................................................................................24
2.2.4 Electrochemical Etching.....................................................................24
2.3 Conjugated Microporous Polymer/MXene Composites.................................24
2.4 Supercapacitors...............................................................................................25
2.5 Thermoelectric Materials ............................................................................... 27
2.5.1 Graphene.............................................................................................28
2.5.2 Black Phosphorus ............................................................................... 30
2.5.3 TMDs.................................................................................................. 31
2.6 Summary ........................................................................................................ 32
Acknowledgment ..................................................................................................... 32
References................................................................................................................ 32
2.1 INTRODUCTION
Over the past decade, two-dimensional (2D) materials have been the hot spot for exten-
sive research efforts, particularly MXenes, transition metal dichalcogenides (TMDs),
and graphene due to their unique chemical, structural, morphological, optical, elec-
tronic, thermal, and mechanical properties. Compared to 0D and 1D materials, 2D
materials have fascinating properties such as low electrical resistivity, large surface
area, and robustness in mechanical strength. These properties make 2D materials to be
developed as multifunctional nanomaterials in applications of electronic devices, energy
storage, tissue engineering, and biomedicine. As fossil reserves are rapidly declining, it
is imperative to develop and integrate materials and devices for energy harvesting and
energy storage. Due to the rapid growth of research interest in energy applications of 2D
materials, it would be advantageous to outline the research progress of layered materials.
Thermal energy can be stored using a class of materials called phase transition mate-
rials or phase change materials (PCMs). PCMs could absorb or release a signifcant
amount of latent heat during phase transition. PCMs exhibit large storage densities with
5–10 times more than sensible heat storage capacity. Delcase and Raymond studied
DOI: 10.1201/9781003178453-2 21
22 2D Nanomaterials
the PCMs in 1940 and pioneered the research on PCMs as energy storage materials
for heat management during the 1973–1974 energy crisis. The selection of the proper
phase-changing materials is very important in the design of latent heat thermal energy
storage system. PCMs can be categorized into three types: (a) inorganic salt hydrates
(AxBy·nH2O), (b) organic paraffns (CnH2n+2), lipids, and sugar alcohols, and (c) eutectic
system (inorganic–inorganic, organic–organic, and inorganic–organic). Rashid et al. [1]
used the PCMs of polyvinylpyrrolidone, polyethylene glycol, and carboxymethyl cel-
lulose sodium salt to study the effciency of thermal energy storage. Their results reveal
that PCMs can store thermal energy 25%–40% more effciently than those without
using PCMs. Zendehboudi et al. [2] studied the thermal conductivity of nano-PCM-
based graphene by response surface methodology. By adding graphene fakes as a fller
in a PCM of Paraffn Wax, the thermal conductivity of the nanocomposite increases.
Hence the energy storage capacity is signifcantly enhanced. To improve the overall
performance of PCMs, however, there are still a few issues to address concerning ther-
mal stability, energy storage capacity, and preparation methods.
Since the isolation of one atom thick, 2D crystal graphene from graphite in 2004,
numerous 2D materials have been discovered including TMD monolayers, 2D hex-
agonal boron nitrides (2D-hBN), and MXenes. The 2D materials MXenes consist of
few-atoms-thick layers of metal carbides (MCs), nitrides, or carbonitrides. MXenes
are composed of Mn+1Xn stacked sheets, which are held together by van der Waals
interactions and/or hydrogen bonds. MXenes are used in a wide range of applications
because of their unique and rich properties such as metallic conductivity, tunable sur-
faces, excellent mechanical strength, transparency, high transmittance, and acting as a
host for intercalation. MXenes have three structures and are inherited from the parent
MAX phases: M2X, M3X2, and M4X3. In 2011, Naguib et al. [3] developed a method to
produce 2D nanosheets composed of a few Ti3C2 layers and conical scrolls by selec-
tively etching out “A” elements (Al) from a MAX phase (Ti3AlC2) at room temperature
in hydrofluoric acid. The MAX phases have a hexagonal layered structure with the
general formula of Mn+1AXn, (MAX) where A is an element from group 13 or 14 of the
periodic table. Since the surfaces of MXene sheets are often terminated by a functional
group such as O, F, OH, or Cl, they are represented by a general formula Mn+1XnTx,
where n = 1 to 4, M is an early transition metal, X either carbon and/or nitrogen and T
a functional group. MXene-based PCMs have recently attracted attention due to their
good thermal performance. MXene-based PCM composite flms are easy to make and
have high electrical conductivity; they are also stable in water, strong and stiff.
Different strategies are adopted to enhance the properties and applications of
MCs. Besides, the chemical functionalization of F, OH, and O groups on the sur-
face of MXenes could be used to create new electronic and magnetic properties of
2D transition metal carbides (TMCs) and nitrides (TMNs). Dinh et al. [4] gave a
comprehensive evaluation on the preparation of nanostructured TMCs, transition
metal borides, transition metal phosphides, TMNs. Li et al. [5] summarized the lat-
est development of 2D materials of TMCs and their nanocomposites for tuning the
mechanical, structural, electrical, and chemical properties of TMCs. Shahzad et al.
[6] summarized recent developments of using 2D TMCs for electrochemical sensing
of diverse types of valuable analytes such as small molecules, heavy metals, dyes,
and biomolecules. Regarding 2D materials for energy applications, we specifcally
cover the topics on the preparation methods of advanced 2D materials MXene and
Advanced 2D Materials 23
briefy discuss conjugated microporous polymer (CMP)/MXene composites, super-

capacitor (SC), and thermoelectric (TE) materials [7]. The synthesis of 2D MXenes
includes chemical vapor deposition (CVD), hydrofuoric acid (HFA) etching process,
molten salt methods, and electrochemical etching methods.
2.2 PREPARATION METHODS OF MXenes

In general, there are two approaches to preparing MXenes.
1. Bottom-up approach
2. Top-down approach
CVD is one of the bottom-up methods of preparing uniform and high-
quality thin 2D materials. The ball milling method is the top-down approach
alternative to preparing MXenes. However, some accounts are given to the
following methods of preparing MXenes.
• CVD
• HFA
• Molten salts
• Electrochemical etching
2.2.1 CHEMICAL VAPOR DEPOSITION (CVD)

CVD is a chemical deposition technique used to produce solid materials with high
purity and good performance. The semiconductor industry uses this technology to
grow thin flms. This process uses a gaseous form of reagents to carry out thermally
induced chemical reactions at the surface of a heated substrate. The well-developed
CVD technique is adopted to fabricate a huge variety of 2D ultrathin crystals such
as tungsten carbide (WC) and tantalum carbide (TaC). Ultrathin tantalum carbide
(TaC), nitride (TaN), and boride (TaB) were grown on Cu surface by CVD using
acetylene, boron, and ammonia reacting with a heated Ta-Cu bilayer, respectively
[8]. Compared to other methods, however, the CVD process is not a cost-effective
and facile method to synthesize MXenes.
2.2.2 HYDROFLUORIC ACID

MCs have recently been produced using the HFA etching process. Due to relatively
weakly bonded “A” layers as compared to the M-X bonding, MCs are synthesized by
selectively etching the “A” layers from the parent-layered MAX phase with the con-
trol of the reaction time and acid concentration at low temperatures. Naguib et al. [9]
immersed MAX powders (Mn+1AlXn) in concentrated HFA for 2 hours at room temper-
ature to form MXenes (Mn+1Xn). As a result, the immersed powders exfoliate to form
2D TMCs and transition metal carbonitrides. Since then the acid etching approach has
been routinely followed. However, HFA is highly corrosive and can penetrate our body
such as bones, skin, and muscle tissue, causing handling and disposal hazards. Recent
research tends to avoid using concentrated HFA in the synthesis of MCs. For instance,
Ghidiu et al. [10] developed a safer and faster route to synthesize MXenes with high
yield using a combination of inexpensive hydrochloric acid and fuoride salts such as
24 2D Nanomaterials
lithium fuoride LiF. In this process, Ti3AlC2 powders are slowly added to HCl contain-
ing LiF. The resulting solution is then heated up to 40°C for 45 hours. Consequently, a
greater lateral size enlargement is observed except nanosized defects that are regularly
observed samples corroded by HFA. With this method, a huge number of single-layer
and large-sized MC can be easily attained. Guan et al. [11] obtained high-quality and
uniform multilayer 2D V2C MXene using LiF/HCl as etchants to etch V2AlC powders
at 90°C for different lengths of duration. The above two synthetic processes are the
most mature etching routes in making multilayer MXene with different shapes and
surface chemistry. Unfortunately, both methods cause environmental pollution because
of the presence of fuorine. Green strategies for synthesizing MXenes are currently
explored to prevent polluting our environments.
2.2.3 MOLTEN SALTS

Both Ti3SiC2 and Cr2AlC had been synthesized by using molten salt methods; how-
ever, their micron-sized grain size is too big to become 2D materials for applications.
Nanosized Ti3AlC2 powders can now be synthesized using molten salt methods. Li
et al. [12] synthesized a series of novel nanolaminated MAX phases (Ti3ZnC2, Ti2ZnC,
Ti2ZnN, and V2ZnC) and Cl-terminated MXenes (Ti3C2Cl2 and Ti2CCl2) based on
element exchange reaction between traditional MAX phase such as Ti3AlC2, Ti2AlC,
Ti2AlN, V2AlC, and molten ZnCl2 and subsequent exfoliation. Both the A-site ele-
ment exchange reaction and A-site element etching process are top-down routes
to synthesize novel MAX phase and Cl-terminated MXenes, respectively. The
Cl-functionalized MXenes have shown enhanced electrochemical performance and
could have potential applications in energy storage.
2.2.4 ELECTROCHEMICAL ETCHING

Electrochemical etching is a very convenient and effective method to synthesize
MXenes because it is fuorine-free and environmentally friendly. Molten fuoride
salt methods have diffculty to completely remove the fuoride or other residues in
etching the MAX phase, which can be easily dealt with using electrochemical etch-
ing methods. Fluorine-free Ti2CTx (MXene), T = Cl, O, and OH were synthesized
using electrochemical etching in diluted HCl aqueous electrolyte [13]. However,
over-etching of the parent MAX phases to carbide-derived carbon on the surface
should be avoided by careful balances in etching parameters. In another report, it was
advised that the choice of electrolytes determines whether one can selectively remove
the Al layers while preserving the 2D structure of Ti3C2 [14].
2.3 CONJUGATED MICROPOROUS POLYMER/

MXene COMPOSITES
Even though 2D MXenes have received great attention due to their remarkable physi-
cal and chemical properties, however, they are readily deteriorated by restacking
of MXene fakes and by the oxidation between MXenes and oxygen in the ambient
environment, thereby losing their functional features and limiting their applications.
Therefore, it would be benefcial to develop strategies of preventing restacking and

agglomeration of nanosheets and keeping away from oxidation. CMPs are a subclass
of porous materials and are composed of infexible conjugated molecules via covalent
bonds. Compared to organic polymers, CMPs possess a large surface area and porous
structure. The size of both the surface area and porosity of CMPs can be tailored for
various applications. The properties of CMPs can be optimized by tuning the diversi-
fed π units in their building blocks. Besides, the synthesis of CMPs is cost-effective.
Therefore, CMPs have extensive attention in energy storage. Recent studies have
mainly focused on fabricating CMP composites. Yang et al. [15] reported an effec-
tive strategy to synthesize MXene-based CMPs by covalently sandwiching MXene
between CMPs using p-iodophenyl functionalized MXene as templates. The MXene-
based CMPs exhibit 2D architecture and high electrical conductivity inherited from
MXene and hierarchical porous structure and large specifc surface area inherited
from CMPs. Both the hierarchical porous structure and large specifc surface area play
a key role in electrochemical energy storage. In general, polymers exhibit amorphous
structure with agglomerated microstructure. Nevertheless, after MXene compositing
with CMPs, the MXene-based CMPs composite exhibits a sheet-like structure based
on morphology observation using scanning electron microscope. Furthermore, no
pristine CMP or MXene nanosheets are observed, which indicates most of the poly-
mer units are grafted on the surface of MXene. Furthermore, sandwiching MXene
between CMPs brings about the effects of effectively increasing the interlayer distance
of MXene, increasing available active sites of CMPs, and shortening the ion diffu-
sion path. Accordingly, the electrochemical performance is enhanced. Since the draw-
backs of restacking and poor oxidation stability of MXene nanosheets are overcome
by sandwiching MXene between CMPs, the MXene-based CMPs composite exhibits
potential as SC electrode for applications in energy storage and conversion.
2.4 SUPERCAPACITORS
Supercapacitors (SCs), also known as electrochemical capacitors, have high specifc
capacitance, high power density, fast charging and discharging characteristics, com-
pact design, and low maintenance cost [16,17]. They can charge and discharge faster
than batteries, store much more energy per unit mass than electrolytic capacitors, and
tolerate much more life cycles than rechargeable batteries. SCs are used in diversi-
fed applications requiring many rapid charge/discharge cycles rather than long-term
compact energy storage. SCs could be used to store the electricity for portable elec-
tronic devices, to store energy temporarily in energy-harvesting systems, to stabilize
the power supply, to power uninterruptible power supplies, to deliver 500 J in def-
brillators, to supply short-term high currents for motor startup and buffer batteries,
to deliver power for photographic fashes, to provide bursts of power in vehicles, to
recover breaking energy, and to deliver starting energy in transportation.
Figure 2.1 shows different categories of the SCs. There are three main mechanisms
for energy storage in SCs, depending on the accumulation of charge or reversible
redox reactions: (a) electric double layer capacitors (EDLCs); (b) pseudocapacitor;
(c) hybrid supercapacitor (HSC) – the combination of EDLC and pseudocapacitor.
EDLCs refer to their charges being adsorbed electrostatically on the interface of
26 2D Nanomaterials
FIGURE 2.1 Classifcation of supercapacitors.
electrode/electrolyte; pseudocapacitors refer to their energy being stored through

redox reaction; HSCs refer to the charge storage via a combination of the above
two mechanisms. The active materials of EDLC include activated carbon, graphene,
multi-walled carbon nanotubes (MWCNTs), TMDs, etc. There are two types of redox
reactions for pseudocapacitors: (a) surface redox reactions and (b) ion intercalation.
For the energy storage applications, the 2D TMDs such as VS2, MoS2, ReS, WS2,
and VSe2 are the candidates to be used as active electrode materials in SCs due to their
large surface area and variable oxidation states. Since the electrical conductivity of
2D TMDs is low and hence low power density. To enhance the electrical conductivity
of TMDs, which is one of the major factors infuencing the electrochemical perfor-
mance of SCs, the following strategies are approached: (a) hybridizing with highly
conducting materials, e.g., carbon nanotube (CNT), graphene, and organic conduc-
tive polymers (OCPs); (b) tuning the electronic structure; and (c) defect engineering.
MoS2 is one of the attractive SC electrode materials in 2D TMDs due to its gra-
phene-like morphology and large surface area. The charge storage mechanisms of
MoS2 include interlayer EDLC, intralayer EDLC between individual MoS2 atoms,
and faradaic charge transfer on the Mo centers arising from the various oxidation
states of Mo. It has been proven effective to overcome the drawbacks of intrinsic low
conductivity of MoS2 by adding conductive carbon material and hence enhance its
capacitance and energy density. To enhance the electrochemical performance, MoS2
are wrapped onto conductive network such as CNT, reduced graphene oxide (RGO)
and conductive polymers (CP) to construct a hierarchical porous network composite,
to increase electrode conductivity, and to constrain the volume charge. Kumuthini
et al. [18] synthesized MoS2@C composite nanofbers via electrospinning technique
followed by stabilization using iodine as a stabilizer and carbonization at 900°C for
2 hours. The resulting MoS2@C nanofbers exhibited a high specifc capacitance of
355.6 F g−1 at a scan rate of 5 mV s−1 in 6 M KOH electrolyte as compared to 36.1 F

g−1 for the bulk MoS2, and long cycling stability with specifc capacitance retention
of 93% up to 2,000 cycles. Sari et al. [19] adopted a microwave-assisted hydrother-
mal method under an acidic condition to fabricate a composite electrode by directly
growing MoS2 nanowalls onto highly conductive vapor grown carbon nanofbers and
obtained high electrical conductivity and good specifc capacitance of 284 F g−1 at 5
mVs−1. The resulting composite electrode exhibited excellent electrochemical stability
with a retention of 96% after 1,000 cycles at a high charge rate of 200 mV s−1. Sun et
al. [20] synthesized a hierarchical graphene-wrapped CNT@MoS2 composite electrode
in two stages. At the frst stage, CNT@MoS2 composites were frst synthesized via
solvothermal reaction, followed by surface modifcation via dispersing CNT@MoS2
into 1 wt% poly(diallyldimethylammoniuurm chloride) (PDDA) solution. At the second
stage, the graphene-wrapped CNT@MoS2 composite was synthesized via electrostatic
interaction between the PDDA-modifed CNT@MoS2 dispersion and graphene oxide
(GO) suspension, followed by chemical reduction using NaBH4 maintained at 40°C for
10 hours. The composite electrode exhibited a high specifc capacitance of 498 F g−1
and demonstrated long-term cycle-life stability with only 5.7% loss of its initial capaci-
tance after 10,000 cycles at a high current density of 5 A g−1. Tiwari et al. [21] used
magnetron sputtering to directly grow atomically thin hierarchal MoS2 nanofakes
on CVD grown CNT as electrodes for all solid-state symmetric SCs. The resulting
MoS2@CNT electrodes possessed high areal capacitance of 131 mF cm−2, volumet-
ric capacitance of 2.9 F cm−3, and high cyclic stability of 97.6% after 2,500 cycles.
Sun et al. [22] fabricated MoS2-rGO/MWCNT fbers as the anode and rGO/MWCNT
fbers as the cathode for solid-state fexible asymmetric supercapacitors (ASCs), which
can operate in a wide potential window of 1.4 V with high coulombic effciency, high
energy density, good rate, and cycling stability. ASCs refer to hybrid capacitors com-
posed of two dissimilar electrodes of a capacitor kind and a battery kind electrode. Sun
et al. [23] adopted pulsed laser deposition to fabricate defect-rich MoS2@CNTs/Ni core/
shell-structured electrode. The MoS2–x nanolayer was deposited on CNTs surface as the
substrate, which was in situ grown on Ni mesh. The resulting electrode has a specifc
capacitance of 512 F g−1 at 1 A g−1 and long cycle life without any decay after 2,000
cycles in 1 M Na2SO4 electrolyte. An ASC with MoS2−x@CNTs/Ni as the positive elec-
trode and CNT networks as the negative electrode exhibited a large energy density of
63 Wh kg−1 at 850 W kg−1 and a power density of 25.5 kW kg−1 at 44.2 Wh kg−1.
2.5 THERMOELECTRIC MATERIALS

TE materials can directly convert waste heat energy into electric voltage and
therefore can harvest waste heat or exhausted heat, which are often dissipated
to the environment. The effciency of a TE material depends on the TE dimen-
S2 ˜
sionless fgure of merit zT = T , where S is the thermopower or Seebeck
ke + kl
coeffcient, σ the electrical conductivity, k = ke + kl the total thermal conductivity,
ke the electronic thermal conductivity contributed from charge carriers, kl lattice
thermal conductivity contributed from atomic vibration, and T the absolute tempera-
ture [24,25]. To enhance the effciency of a given TE material requires high electri-
cal conductivity, large thermopower, and low total thermal conductivity. However,
28 2D Nanomaterials
the three transport parameters of electrical conductivity, thermopower, and thermal

conductivity depend mutually based on the Boltzmann transport equation, the high
electrical conductivity would be accompanied by a small thermopower for materials
with one type of charge carrier. Moreover, the Wiedemann–Franz law governs the
relationship between electrical conductivity and electronic thermal conductivity at a
given temperature, provided that a common relaxation time exists for electrical and
thermal processes. It is thereby intrinsically challenging to develop TE materials
with high zT values.
Due to the unique density of states of confned electrons and holes, low dimension-
ality (1D and 2D) provides novel ways to high TE power factors. Low dimensional
d ln N ( E )
materials have larger near Fermi level than the bulk, their thermopower
dE
˝ d ln N ( E ) ˇ
(S) could be signifcantly enhanced according to S˛ ˆ ˘ . Besides, ther-
˙ dE E = EF
mal transport of 2D materials behaves differently from bulk materials due to inter-
faces, sample size, strain, and defects. Thermal transport of 2D materials can be
tuned by their thickness and the feature size in the basal planes. Chemical doping via
surface functionalization or intercalation can be also used to tune thermal transport
of 2D materials. Calculations were carried out to study the zT of Bi2Te3 layers in a
quantum-well superlattice structure under the assumptions of one-band material with
parabolic shape and a constant relaxation time [26]. It was theoretically found that a
10 Å thick Bi2Te3 flm prepared with layers in the a-c planes has zT enhancement by
a factor of 13 over the bulk value; if the multilayers are prepared in the a-b direction,
the zT is enhanced by a factor of 3.
The wearable devices in the recent rapid development only require low power
energy consumption. Large-area fexible TE devices can be fabricated to serve for
sensing and Internet of Things (IoT) applications by using the temperature dif-
ference between body heat and the ambient environment. Therefore, TE energy
conversion based on large area fexible materials has attracted much attention.
Atomically thin (<1 nm) graphene and akin 2D materials are rigid against the
bending and intrinsically fexible, they are potential candidates for practical fex-
ible TE devices as long as their TE properties are optimized. Therefore, 2D mate-
rials graphene, black phosphorus, and TMDs have attracted great attention due to
their unique geometric structure and TE properties [27]. The recent progress on
the TE performance of 2D TE materials of graphene, black phosphorus, and TMDs
are presented as follows. Figure 2.2 shows the classifcation of 2D TE materials.
2.5.1 GRAPHENE
As shown in Figure 2.3, graphene is a single layer of carbon atoms bonded together
in a 2D hexagonal honeycomb lattice with features of zero bandgap semiconductor
and massless Dirac fermion characteristics. Charge transport of graphene is essen-
tially governed by Dirac's (relativistic) equation and exhibits ambipolar characteris-
tics with exceptional carrier mobility [28,29]. External electric and magnetic felds
can be used to control the Dirac electrons.
FIGURE 2.2 Classifcation of 2D thermoelectric materials.
FIGURE 2.3 Crystal structure of graphene.
Graphene attracts much attention for TE applications due to its remarkable trans-
port properties and large TE power factor. Since the CVD process has been devel-
oped to grow large-area single-crystalline and poly-crystalline graphene flms with
ultra-high uniformity, graphene is one of the candidates for TE generators. The
maximum power factor of ∼45 μW cm−1 K−2 is attained at 575 K for few layers gra-
phene (FLG) flms after the CVD-grown graphene is treated with oxygen plasma
for a few seconds [30]. It is about a 15-fold enhanced power factor of the pristine
FLG. This enhancement is attributed to generation of local disordered carbon that
is opening the bandgap. However, the oxygen plasma treatment is not suitable for
single-layer graphene flms and reduced graphene oxide (rGO) flms since it results
in no enhancement of the power factor. Moreover, the pristine FLG flms grown by
the CVD process have a thermopower of ∼40 μV K−1. The thermopower is increased
to ∼180 μV K−1 after the FLG flms treated with 1,10-azobis(cyanocyclohexane)
30 2D Nanomaterials
(ACN) or 1,3,6,8-pyrenetetrasulfonic acid (TPA). Even though the attachment of

ACN or TPA onto the FLG flms led to an increase of electrical resistivity, the result-
ing power factor is about 4.5-fold, while the electrical resistivity increase is depend-
ing on the treating concentration. As a result, the power factor is enhanced by 4.5-fold
by molecular attachment onto FLG flms [31]. Another promising report is that the
peak power factor of 69.3 and 32.9 μW cm−1 K−2 are attained for p- and n-type car-
rier doping of large-area CVD-grown graphene flms, respectively. The enhancement
of power factor is achieved by continuous doping of hole or electron carriers and
modulation of the Fermi energy via the electric double layer (EDL) gating technique.
Therefore, the CVD-grown large-area graphene flm is one of the candidates to be
applied for the power generator of IoT devices [32].
2.5.2 BLACK PHOSPHORUS

Although having superior power factors, graphene possesses high thermal conductiv-
ity and hence its zT value is not good enough. Another interesting 2D material is the
black phosphorus. Like graphene, the black phosphorus atoms are strongly bonded
within a single layer while adjacent layers are weakly stacked together via van der
Waals forces in the black phosphorus lattice. Figure 2.4 shows the crystal structure of
black phosphorous. Unlike in graphite, black phosphorus forms a puckered honeycomb
lattice due to the phosphorus atom bonding together via sp3 hybridized orbitals [33].
The black phosphorus exhibits zigzag and armchair structural anisotropy and hence
anisotropic electrical and thermal properties in the zigzag and armchair directions.
Moreover, graphene is a zero-gap semiconductor, while the black phosphorus is a semi-
conductor with a sizeable gap depending on its thickness of the layers. Monolayer black
phosphorus (phosphorene) has a predicted direct bandgap of ca. 2 eV at the Γ point of
the frst Brillouin zone. The size of the bandgap decreases with the number of layers
due to interlayer interaction for few-layer phosphorene and would be 0.3 eV for bulk
black phosphorus [34]. Bulk black phosphorous is experimentally determined to have
thermopower of S = 335 ± 10 μV K−1 at room temperature and increases with increasing
FIGURE 2.4 Crystal structure of black phosphorous.

temperature reaching the maximum value of Smax = 415 μV K−1 at 380 K [35]. The
energy gap of bulk black phosphorous is estimated to be 0.32 eV using Smax = Eg/2eT,
where e is the electron charge. Besides, the electrical resistance drops 40% as the tem-
perature increases from room temperature to 385 K. The thermopower of 10−30 nm
thick black phosphorous is ca. 400 μV K−1 near room temperature [36]. It is also found
that 2D Mott’s variable range hopping dominates the transport at low temperatures.
Since the lone pair electrons of phosphorous react easily with oxygen in the air,
black phosphorus is not stable in ambient conditions. This instability causes changes in
composition and physical properties and consequently prevents black phosphorus from
TE applications. Mechanically exfoliated black phosphorus is very tiny. Considering
the TE applications, liquid-exfoliated polycrystalline black phosphorus materials seem
to be more suitable due to their availability of surface modifcation and chemical dop-
ing. Au nanoparticles are used to functionalize the surface of exfoliated black phospho-
rus via a redox reaction of Au precursors. As a result, a signifcant enhancement of TE
performance and long-term stability in the air is achieved. The electrical conductivity
of the Au-decorated black phosphorus increases from 0.001 to 63.3 S cm−1 by enhanc-
ing the carrier concentration [37]. Consequently, its power factor increases signifcantly
to 0.685 μV cm−1 K−2, which is quite small and smaller than graphene; however, is much
greater than that of the pristine black phosphorus. A power output of 79.3 nW with
ΔT = 2°C is attained using Au-decorated BP as p-legs in a vertical TE generator.
2.5.3 TMDS
Another alternative for potential TE applications is the 2D TMDs with gapped and tun-
able band structure. The TMDs with the general formula of MX2 such as M = Mo, W, Ti
and X = S, Se, Te have recently attracted extensive interest due to their rich and interest-
ing characteristics in chemistry and physics such as large effective mass, a wide-range
bandgap, valley degeneracy, high mobility, chemical stability, excellent mechanical
properties, and confnement effects. TMDs are hexagonally packed structure composed
of three atomic planes with metals sandwiched between two layers of chalcogens. The
metal coordination environment is either octahedral or trigonal prismatic. The nature
of interaction between layers is weak van der Waals force, while it has more covalent
bonding character between metals and chalcogenides. Among TMDs, TE properties
have been investigated for MoS2, SnS2, TiS2, WSe2, PtSe2, and 1T′-MoTe2.
MoS2 has a large intrinsic bandgap of 1.8 eV and a large in-plane mobility of
200−500 cm2 V−1s−1. TE properties of mechanical-exfoliated and CVD-grown single
crystalline MoS2 monolayers have been investigated. Due to the quantum-well struc-
ture, a large thermopower of −5160 μVK−1 at a resistivity of 490 Ω m is observed
in single-layer MoS2 by electric feld modulation, [38] which is consistent with the
˝ dlnN ( E ) ˇ
Mott’s formula for thermopower, i.e., S ˛ ˆ [39,40]. High power fac-
˙ dE ˘ E = EF
tor of 8,500 μW m−1 K−2 of bilayer MoS2 fakes is attained at 300 K in the metallic
regime with high carrier concentration. The enhanced power factor comes from the
high electrical conductivity and a large thermopower due to its high valley degen-
eracy of gv = 6 and large effective mass of 0.68 m0 at conduction band minimum [41].
32 2D Nanomaterials
However, low thermal conductivity is still required to obtain high zT for practical
TE applications. The measured thermal conductivity values for the single-layer and
multilayer MoS2 are usually larger than 30 W mK−1 [42]. Nevertheless, high power
factor itself might fnd its application in in-plane Peltier cooling [43].
Tin diselenide SnSe2 has a CdI2-type structure and a bandgap of ~1.6 eV at room
temperature. The SnSe2 nanosheets pellets are fabricated by spark plasma sintering
and obtain preferential orientation of (00l) facets. Its in-plane power factor at room
temperature is enhanced to 8 μW cm−1 K−2 through simultaneously introducing Se
defciency and chlorine doping. zT = 0.63 is attained at 673 K [44]. Intercalation of
TiS2 can be readily achieved to modify the transport properties of the pristine TiS2.
For Cu-intercalated Cu0.02TiS2, zT ≈ 0.45 at 800 K [45]. A random stacking of WSe2
flm is synthesized by modulated elemental reactants method [46]. An ultra-low
cross-plane thermal conductivity of 0.05 W m−1 K−1 is attained at 300 K. This mag-
nitude is 30-fold smaller than the c-axis thermal conductivity of single-crystal WSe2
and 6-fold smaller than the calculated minimum thermal conductivity for WSe2. The
ultra-low thermal conductivity is attributed to the localization of lattice vibrations
induced by the random stacking of 2D crystalline WSe2 sheets.
Moreover, the feld-effect-modulated TE properties of CVD-grown large-area
WSe2 monolayers are investigated by using EDL gating [47]. The charge carrier type
of WSe2 is tuned via electrostatic doping to control the energy band flling. Due to
the atomically thin structure, the maximum absolute thermopowers of 380 μVK−1
and 250 μVK−1 are attained for the p-type the n-type WSe2, respectively. The maxi-
mum power factor is 3 μWcm−1 K−2 for the p type and 1 μWcm−1 K−2 for the n type.
As compared to the bulk sample, the enhancement of TE properties is attributed to
the low-dimensional effects.
2.6 SUMMARY
We briefy describe the recent research progress on 2D materials of MXenes, gra-
phene, black phosphorus, TMDs, and their applications in supercapacitors and TEs.
With progressive efforts, the reported data have shown excellent properties with the
advanced fabrication methods. These 2D materials are promising for the next genera-
tion energy applications.
ACKNOWLEDGMENT
This work was supported by the ministry of science and technology of Taiwan
(MOST) under grant 107–2112-M-018-006-MY3.
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3 Top-Down Synthesis
of 2D Nanomaterials
Arpana Agrawal
Shri Neelkantheshwar Government Post-Graduate College
CONTENTS
3.1 Introduction .................................................................................................... 37
3.2 Top-Down Synthesis of 2D Nanomaterials .................................................... 38
3.2.1 Scotch-Tape-Based Micromechanical Cleavage................................. 38
3.2.2 Ball Milling Exfoliation ..................................................................... 39
3.2.3 Sonication-Driven Liquid Phase Exfoliation ...................................... 41
3.2.4 Electrochemical Exfoliation Approach .............................................. 45
3.2.5 Unzipping of the NTs.......................................................................... 47
3.3 Conclusions..................................................................................................... 49
References................................................................................................................ 50
3.1 INTRODUCTION
Two-dimensional (2D) nanomaterials including graphene, hexagonal boron nitride
(h-BN), transition metal dichalcogenides (TMDs) such as MoS2, MoSe2, WS2, WSe2,
TaS2, and TaSe2 are one of the emerging classes of nanomaterials which exhibits ultra-
thin sheet-like characteristics whose size may vary from 1 nanometer (nm) to few
micrometers. In bulk form, these materials demonstrate insulating behavior and if it is
possible to reduce the dimensionality somehow either by fuorination, hydrogenation,
oxygen functionalization, and switch those from bulk form to 2D nanosheets (NSs),
nanotubes (NTs), or nanoribbons (NRs), then the functionalities of these materials get
signifcantly enhanced. They generally show intriguing edge magnetism, encourag-
ing electrically conductive behavior, excellent optical properties, and many more.
Remarkable progress in the feld of 2D nanomaterials was marked after 2004
when 2D counterpart of carbon, i.e., graphene was mechanically exfoliated from
graphite using a scotch tape, for which the 2009 Nobel prize in Physics has also been
awarded [1]. Graphene is a 2D allotrope of carbon which is one atomic thick layer
having a thickness of 0.34 nm with sp2 hybridized carbon atoms that are held together
in a hexagonal closed pack. One atomic thick layer of graphene (zero bandgap mate-
rial) can transmit 97.7% of light and hence possess outstanding transparency. Hence,
knowing the transmittance of the graphene layer, one can estimate the number of
graphene layers. However, a more accurate determination of the number of layers
can be inferred from the Raman spectra of graphene. Apart from graphene, other
graphene-like 2D nanomaterials including h-BN, TMDs, etc. are also engendered
DOI: 10.1201/9781003178453-3 37
38 2D Nanomaterials
great scientifc research interest from a fundamental to a technological viewpoint.

BN is isostructural and isoelectronic to carbon having an equivalent composition of
nitrogen and boron atoms which are bonded together with a covalent bond within
each layer and a single h-BN layer is analogous to graphene and known as white gra-
phene [2]. Also, TMDs are chemical compounds with formula MX2 (M = transition
metal ion; X = Chalcogen), where each TMD monolayer is made up of one transition
metal layer sandwiched between two chalcogen layers (X-M-X) [3]. However, the
stacked layers of all these 2D nanomaterials are held together with weak van der
Waal force. Such materials are potentially important candidates for several attractive
device applications, e.g., fexible electronics, carrier (hole/electron) transport layer in
photovoltaics/solar cells, transparent conducting electrodes, sensor applications, and
optoelectronic applications [4–10].
It is worth mentioning here that the synthesis methods of these nanomaterials
are one of the decisive factors for their utility in various specifc device applica-
tions. The technological importance of these nanomaterials signifcantly encour-
ages researchers to work for the development of effcient synthesis approaches for
the mass production of high-quality ultrathin sheets of 2D nanomaterials. Several
well-established synthesis approaches for the growth of these nanomaterials
include mechanical exfoliation/cleavage, ball milling, electrochemical exfoliation
(ECE), sonication-assisted liquid-phase exfoliation (LPE), and unzipping of the
corresponding NTs. However, each of these techniques has its synthesis condi-
tions and requirement and hence the benefts and limitations. Accordingly, the
present chapter presents an inclusive overview of various synthesis approaches
particularly top-down methods for the growth of high-quality 2D nanomaterials
along with the recent studies being carried out on 2D nanomaterials.
3.2 TOP-DOWN SYNTHESIS OF 2D NANOMATERIALS

It is worth stressing that the properties of a material can be effectively altered by
reducing the dimensions of material. Among the reduced dimensional materials, 2D
nanomaterials have attracted enormous research interest in today’s technological era.
Additionally, the properties of such 2D nanomaterials can be further manipulated
physically and/or chemically. The basic idea behind the top-down approach for the
synthesis of 2D nanomaterials is the breakup of bulk graphite materials to produce
nanosized graphene layers. The layered nature of the 2D nanomaterials facilitates them
to be easily exfoliated into thin 2D NSs via several top-down-based exfoliation meth-
ods including scotch tape-based mechanical exfoliation/cleavage [1,3,11], ball milling
[12–14], sonication-assisted LPE [15,16], ECE [17–19], unzipping of corresponding
NTs via various routes such as chemical etching or ion intercalation [2,20], etc.
3.2.1 SCOTCH-TAPE-BASED MICROMECHANICAL CLEAVAGE

Scotch tape-based mechanical exfoliation/cleavage is the very frst approach that
was developed by Geim and Novoselov in 2004 to isolate the 2D graphene layer
from bulk graphite [1]. They applied an adhesive tape onto the graphite and then
peeled it off from its surface so that an atomically thin 2D graphene layer has been
Synthesis of 2D Nanomaterials 39
FIGURE 3.1 (a) Scotch tape-based mechanical exfoliation of graphene layer from bulk
graphite. (b) Normal-force and shear-force-based mechanical exfoliation for 2D nanomateri-
als. Adapted with permission from [21]. Copyright (2020) Elsevier.
obtained. Figure 3.1a schematically illustrates the exfoliation of ultrathin atomic-

layered graphene having a thickness of 0.34 nm from graphite employing an adhe-
sive tape. Since then, it has become the most commonly used and simplest approach
that has been adopted for other 2D materials as well. Li et al. [3] have reported the
growth and characterization of various TMDs including WSe2, TaS2, and TaSe2 on
Si/SiO2 substrate using scotch tape-based mechanical exfoliation/cleavage approach.
They have isolated the TMD NSs from the respective bulk single crystals and depos-
ited them onto 90 nm/300 nm Si substrate coated with SiO2 oxide layer. The same
mechanical cleavage method has also been extended to synthesize atomically thin
h-BN NSs by Alem et al. [11]. However, the isolation of monolayer h-BN is quite
diffcult due to the strong interplanar bonding in h-BN. Accordingly, Alem et al. [11]
have adopted a mechanical exfoliation followed by a reactive ion etching process for
the growth of any desired number of h-BN NSs. Depending upon the direction of the
force applied on the bulk material for their exfoliation to synthesize 2D nanomateri-
als, the mechanical exfoliation/cleavage process can be either normal-force- or shear-
force-based exfoliation and is schematically shown in Figure 3.1b.
3.2.2 BALL MILLING EXFOLIATION

The ball milling exfoliation method is based on the shear force that was applied by
the metallic balls on the bulk crystal/material, loaded together in a rotating steel
chamber, and milled under suitable conditions. As a consequence of the impact of
the metallic balls, the particle size reduces continuously leading to the formation of
exfoliated 2D-layered materials. For the synthesis of graphene, h-BN and TMDs,
bulk graphite, bulk h-BN crystals, and bulk TMDs, respectively, are employed
as precursors. This shear force deteriorates the interlayer van der Waal’s attrac-
tion leading to rupturing of bulk materials and hence results in 2D nanomaterials.
Several milling agents and solvents/surfactants are reported to be utilized as the
milling agent including salts (NaCl) [22] or melamine (Na2SO4) [23], kerosene [24],
40 2D Nanomaterials
N-methyl-2-pyrrolidone (NMP) [14], and di-methyl-formamide (DMF) [25] for the

synthesis of 2D nanomaterials. Apart from this, one has to take care of the several
milling parameters for effective ball milling exfoliation which includes the milling
revolution per minute, grinding material such as size, static flling rate, etc., graphite
powder to ball ratio, milling time, ball diameter, etc.
Ball milling exfoliation of graphite to prepared exfoliated graphene has been
reported by several groups [22–25]. A correlation between the defect density in ball-
milled graphite and the total oxygen content of graphene oxide produced by oxi-
dizing ball-milled graphite has been reported by Mohanta et al. [12]. Xing et al.
[26] have demonstrated the growth of 2D nanomaterial mainly, graphene, h-BN, and
MoS2 via ball milling exfoliation of their bulk crystals in the presence of two dif-
ferent gases (argon and ammonia) individually for various milling times. The bulk
crystals were milled together with four steel balls having a diameter of 2.5 cm in the
presence of argon (Ar) and ammonia (NH3) gases in a milling jar rotating at a speed
of 150 rpm for different milling times. Figures 3.2a–f represent the x-ray diffraction
(XRD) profles of graphite, h-BN, and MoS2 ball milled for different times in Ar
and NH3 gases, respectively. The XRD peaks in Figures 3.2a and b corresponding to
(+), (O), and (*) signs show the peaks of graphite, stainless steel, and hardened steel,
respectively, and evidence shows the different crystal structures of the grown 2D
nanomaterials. As compared to the ball milling results in NH3 gas, (002) diffraction
peak shows broadening in the case of Ar gas.
FIGURE 3.2 XRD profles graphite (a, b), h-BN (c, d), and MoS2 (e, f) in the presence of Ar
and NH3 gases for various milling times, respectively. Adapted with permission from [26].
Copyright (2016) The Authors, some rights reserved; exclusive licensee [Springer Nature].
Distributed under a Creative Commons Attribution License 4.0 (CC BY) https://creativecom-
mons.org/licenses/by/4.0/.
Recently, xylitol-assisted planetary ball milling exfoliation of h-BN NSs was

reported by Wang et al. [27], where BN powder and xylitol crystals were loaded in a
500 ml agate tank rotating at a speed of 500 rpm for 12 hours. The obtained product
contains residual xylitol, which can be washed away using simple washing by dis-
tilled water followed by sonication of collect BN paste dispersed in 280 mL DI water
for 30 minutes. Finally, the residual h-BN was collected by centrifugation method
carried out at 200 rpm for 30 minutes giving a high production yield (80.4 wt.%)
of h-BN. Large-scale mechanical peeling via low energy ball milling process for
the production of BN NSs has been reported by Li et al. [28]. They have manipu-
lated the ball milling conditions to obtain the high yield of quality NSs of BN with
enhanced effciency. Herein, a planetary mill containing 0.5 g h-BN, 6 mL benzyl
benzoate (effective lubricant), and 50 Steel balls (12.7 mm diameter) were milled
together in a steel chamber, which was rotated at speed of 150 rpm due to which a
shear force induces, resulting in exfoliated h-BN NSs. Finally, the milled sample
was sonicated for 0.5 hours and centrifuge to remove unexfoliated BN particles. The
same group has also studied the photoluminescence of BN NSs produced using the
same approach except the milling time was increased to 15 hours with 50 steel balls
of the same diameter. A vortex fuidic device was also discussed by Chen et al. [29],
for the exfoliation of h-BN suspension in NMP solvent within an inclined glass tube
rotating at a speed of 7,000 rpm for 30 minutes. A thin layer of NMP forms at the
inner wall of the tube and rotating shaft to provide suffcient shear force to weaken
the interlayer van der Waal force leading to the formation of h-BN NSs. Small lateral-
sized, few-layered BN NSs have also been reported to be prepared using the wet ball
milling process [13].
The ball milling process has been further extended to synthesize 2D TMDs. Dai
et al. [30] have reported the synthesis of exfoliated WS2 by ball milling of WS2 pow-
der with agate balls (90 g) using sodium dodecyl sulfate solution as a surfactant. The
mixture was milled for a constant time of 12 hours with varying rotation speeds of
100, 200, and 250 rpm. All the obtained suspensions were then sonicated and cen-
trifuged at 8,000 rpm. The residual surfactant was then washed away by using ethyl
alcohol and deionized water followed by drying at 60°C. Coupled ultrasonication
milling process was proposed by Dong et al. [14] to produce high yield MoS2 NSs via
direct exfoliation of naturally occurring molybdenite powders in NMP with polyvi-
nylpyrrolidone molecules.
3.2.3 SONICATION-DRIVEN LIQUID PHASE EXFOLIATION

The LPE method involves the ultrasonication of bulk material (either in the form of
fakes or powders) in a suitable solvent under suitable conditions. Surface tension
(ST) matching between the electrolyte and the 2D nanomaterial that is to be obtained
is the foremost requirement of the solvent utilized for such exfoliations. In general,
the ST of 2D materials including graphene, h-BN, and TMDs lies in between 40
and 65 mJ m−2 and hence the solvents that are commonly used for exfoliation of
such nanomaterials include NMP (boiling point (BP) = 203°C; ST = 40 mJ m−2),
N, N dimethylacetamide (BP = 165°C; ST = 36.7 mJ m−2), ortho-dichlorobenzene
(ODCB) (BP = 181°C; ST = 37 mJ m−2), N, N dimethylformamide (BP = 154°C;
42 2D Nanomaterials
ST = 37.1 mJ m−2), Y-butyroloctane (BP = 204°C; ST = 46.5 mJ m−2), dimethylsulf-

oxide (BP = 189°C; ST = 42.9 mJ m−2), and acetonitrile. Such ST matched solvents
relax the exfoliation process because of the minimum mixing enthalpy. However,
the high BP of such solvents needs an additional purifcation process to remove the
solvent after 2D nanomaterial’s production as low BP solvents facilitate the easy
purifcation process. Apart from the proper choice of solvent, several sonication
parameters such as temperature, sonication time, and intensity are also very crucial
for effective exfoliation because they offer suitable cavitational effects for producing
defect-free 2D nanomaterials.
Sonication-assisted LPE was frst employed by Coleman et al. [31] for the produc-
tion of 2D graphene layers via the exfoliation of graphite where they have dispersed
graphite powder/fakes in NMP solvent, which undergoes sonication and is fnally
purifed using the centrifugation process. Effcient exfoliation of graphite in a mix-
ture of n-octylbenzene (NOTBZ) and organic solvents, e.g., NMP or ODCB has also
been demonstrated by Haar et al. [15], where NOTBZ acts as a graphene-dispersion
stabilizing agent. The graphite fakes were separately sonicated in the solvent mix-
tures (NMP and NOTBZ; ODCB and NOTBZ). Initially, the dispersion of graphite
fakes in NMP and ODCB was prepared via sonication at 600 W and 40oC in an
ultrasonic bath for 6 hours. After this, various amounts of NOTBZ were added in
the prepared dispersions and again sonicated to form a homogenous gray liquid,
followed by centrifugation at 10,000 rpm for 30 minutes to eliminate unexfoliated
graphite fakes. Figures 3.3a and b show the photographs of graphene dispersion
obtained by graphite exfoliation in NMP and ODCB with different volume percent-
age of NOTBZ, respectively. The variation of percentage of graphene concentra-
tion dispersed in NMP and ODCB corresponding to various volume percentages of
NOTBZ has been shown in Figures 3.3c and d. Figure 3.3e illustrates the Raman
spectra of prepared dispersion after adding NOTBZ along with reference graphite,
which shows the growth of single- and few-layer graphene formation. Figure 3.3f sta-
tistically represents the thickness distribution of graphite fakes in NMP and ODCB
solvents before and after adding NOTBZ. High-resolution transmission electron
microscope (HR-TEM) and TEM images for the monolayer graphene have also been
shown in Figures 3.3g and h, respectively.
Growth of poly (3-hexalthiophene) (P3HT)/graphene composite in toluene has also
been reported [32]. Graphene is dispersed in P3HT via ultrasonication process in tolu-
ene solvent at a temperature of 80°C for 30 minutes. To remove the unexfoliated or
thick graphite fakes, the prepared dispersion then undergoes centrifugation process
and is fnally collected as graphene dispersion. This dispersion was then fltered using
a flter paper (pore size ~ 4 μm) followed by drying at 100°C for 5 minutes to prepare
the P3HT/graphene composite flm paper. Effcient sonication-assisted LPE of h-BN
in surface energy matched n poly(vinyl alcohol) and epoxy matrices are reported by
Song et al. [33]. A mixed solvent approach has also been demonstrated for the LPE of
h-BN by Cao et al. [16] who have illustrated a sonication-assisted LPE for the growth
of 2D h-BN NSs in a solution of isopropylalcohol (IPA) (44–65 mJ m−2) and NH3
(NH3:IPA = 4:1; 2:3; 3:2; 1:4; 1:1). Commercial bulk h-BN undergoes sonication for
different sonication times (1, 5, 10, 30, 35, 40, 50, 65 hours) where the high yield was
obtained for the optimized time of 35 hours and then the dispersion was confgured.
FIGURE 3.3 Photographs of graphene dispersions obtained from graphite exfoliation in

NMP (a) and ODCB (b) with various volume percentages of NOTBZ. Average concentration
of graphene dispersed in NMP (c) and ODCB (d) with various volume percentage of NOTBZ.
(e) Raman spectra of prepared dispersion after adding NOTBZ. (f) Statistical variation of
thickness distribution of prepared dispersion before and after adding NOTBZ. (g) and (h)
HRTEM and TEM images of the prepared monolayer, respectively. Adapted with permission
from [15]. Copyright (2015) The Authors, some rights reserved; exclusive licensee [Springer
Nature]. Distributed under a Creative Commons Attribution License 4.0 (CC BY) https://
creativecommons.org/licenses/by/4.0/.
Effcient exfoliation of bulk h-BN powder in thionyl chloride (SoCl2) to synthesize

ultrathin h-BN NSs with a very high production yield (20 wt.%) has also been reported
by Sun et al. [34], without utilizing any dispersion agent. A mixture of h-BN pow-
der and SoCl2 was sonicated for an optimized sonication time of 20 hours and then
the collected product undergoes centrifugation process for 5 minutes at a speed of
2,000–25,000 rpm. The obtained product was then vacuum dried at 70°C for 24 hours.
LPE synthesis of WS2 NSs has also been reported by Han et al. [35], via direct
dispersion of WS2 powder in DMF (exfoliation solvent) followed by ultrasonication
process. In this technique, bulk WS2 powder was dispersed in a 50 mL beaker con-
taining 30 mL DMF solution, which was then undergoing sonication for 5 hours. The
resultant dispersion was left undisturbed for 72 hours. To remove the unexfoliated
WS2 (if any), the obtained product was then fnally centrifuged for 45 minutes at a
speed of 1,500 rpm. Adilbekova et al. [5] have demonstrated the LPE of bulk MoS2
and WS2 powder in aqueous NH3 (NH3(aq.)), which can produce a high concentration
(0.5–1.0 mg mL−1) of MoS2 and WS2 NSs. It should be noted that the ST of NH3(aq.)
44 2D Nanomaterials
matches well with that of TMDs and hence allows effcient exfoliation of TMDs in
this solvent; however, it is less environmentally friendly. The powder was sonicated
in 10 mL NH3(aq.) solution for 3 hours in a water bath cooling system to maintain a
constant temperature of 5°C. The resultant dispersions were then centrifuged at dif-
ferent rotation speeds varying from 3,000 to 8,000 rpm.
Epigallocatechin-assisted LPE of MoS2 and WS2 to produce 2D MoS2 and WS2
NSs has been illustrated by Zhao et al. [8]. Sonication (950 W) was done for 10–720
minutes in a water-cooled bath followed by high-speed centrifugation at 10,000 rpm
for 30 minutes. NSs of MoS2 (E-MoS2) and WS2 (E-WS2) were prepared in 2 mg
mL−1 EGCG solution for a constant sonication time of 12 hours. SEM images for
bulk MoS2, E-MoS2 NSs, and E-WS2 NS under different magnifcations are shown
in Figures 3.4(a, a’), (b, b’), (c, c’), respectively. Figures 3.4(d, d’) and (e, e’) repre-
sent the TEM micrographs (different magnifcation) for MoS2 NSs and E-WS2 NS,
respectively, while the atomic force microscope (AFM) images of MoS2 NSs and
E-WS2 NS are illustrated in Figures 3.4f and g, respectively.
FIGURE 3.4 (a, a’), (b, b’), (c, c’) SEM images with different magnifcation for bulk MoS2,
E-MoS2 NSs, and E-WS2 NSs, respectively. (d, d’) and (e, e’) TEM images different magnif-
cation for MoS2 NSs and E-WS2 NSs, respectively. (f) and (g) AFM images of MoS2 NSs and
E-WS2 NSs, respectively. E-MoS2 and E-WS2 NSs are prepared in 2 mg mL−1 EGCG solu-
tion for a constant sonication time of 12 hours. Adapted with permission from [8]. Copyright
(2019) Elsevier.
An atomically thin layer of MoSe2 was also reported to be synthesized by LPE

carried out in deionized water [36]. Sonication of bulk MoSe2 dispersed in deionized
water was performed at 50°C for 24 hours. The collected dark green suspension was
centrifuged at a speed of 8,000 rpm for 20 minutes. Pan et al. [37] have also utilized
water as an exfoliation solvent for the synthesis of exfoliated 2D WS2 NSs. Grayfer
et al. [38] have presented a compilation of several reports for the exfoliation of MoS2,
MoSe2, and WS2 powders in colloidal solution to produce the colloidal dispersion
solutions containing their respective 2D NSs. Growth of 2D WSe2 NSs was also
reported via LPE of bulk WSe2 in a mixture of water and n-propanol (1:1 v/v) [39].
3.2.4 ELECTROCHEMICAL EXFOLIATION APPROACH

ECE is an important technique that ensures the high-quality production of 2D nano-
materials with a high yield. Generally, in this technique, the 2D material that is to
be obtained is in the form of an electrode named a working electrode and immersed
in an electrolyte containing a counter electrode, which is made up of platinum (Pt)
wire/plate. A suitable potential is applied to the working electrode, which facilitates
its exfoliation leading to the formation of exfoliated 2D material. The basic idea
behind this exfoliation is the intercalation of ionic species present in the electrolyte
in between the layers of bulk material (working electrode), which weakens the van
der Waals force between the layers resulting in its expansion and hence gets exfoli-
ated. So far, several electrolytes are being utilized for this purpose. Parvez et al. [40]
have presented a compilation of several electrolytes such as (NH4)2SO4, K2SO4, and
Na2SO4 for the exfoliation of graphite to produce 2D graphene layers. Synthesis of
graphene layers has also been reported by Rao et al. [17]. They have employed an
anodic ECE approach to synthesize graphene layers where graphite and Pt electrodes
were dipped in sodium hydroxide/hydrogen peroxide/water (NaOH/H2O2/H2O) elec-
trolyte. The same group has also utilized organic compounds in electrolyte namely
glycine (Gly). HSO4 ionic complex signifcantly improves the exfoliation effciency
by facilitating the intercalation of SO4 and HSO ions into the graphite electrode [41].
The ECE method of compressed graphite has also been employed for the production
of high-quality graphene NSs by Achee et al. [42].
You et al. [43] have discussed a facile ECE route for large-scale production of
high-quality MoS2 NSs. They have employed a Pt wire and MoS2 bulk crystal act-
ing as counter and working electrodes, respectively, dipped in an aqueous solution
of H2SO4 serving as an electrolyte. Initially, a static voltage of +1 V is applied to
the working electrode, which was later increased to +10 V and kept constant for 30
minutes till the exfoliation process gets completed. Figure 3.5a schematically shows
the experimental setup for the ECE of MoS2. The basic idea behind this exfoliation
is the intercalation of the anionic SO 4 2− and OH− species into the bulk MoS2 crystal
to produce SO2 or O2 gas bubbles, which generate a force for MoS2 to overcome
the weak van der Waal force acting between the MoS2 layers leading to its expan-
sion and fnally the exfoliation to MoS2 NSs. The mechanism of the overall ECE of
MoS2 via ion insertion has been depicted in Figure 3.5b. The exfoliated MoS2 NSs
were then coated on Si substrate covered with 300 nm thick SiO2 by simply dip-
ping the substrate into prepared MoS2 dispersion. Figure 3.5c illustrates the AFM
46 2D Nanomaterials
FIGURE 3.5 (a) Experiment setup for the ECE of MoS2; (b) Schematic diagram illustrat-
ing the mechanism of ECE of MoS2 using ions insertion. (c) Atomic force microscope image
of MoS2 NSs/Si/SiO2 (300 nm). (d) TEM image of exfoliated MoS2 NSs on a carbon grid.
Inset shows the higher resolution TEM image. Adapted with permission from [43]. Copyright
(2014) Elsevier.
image of exfoliated MoS2 NSs on Si/SiO2 substrate, which reveals the average topo-
graphic height of 1.8 nm for the exfoliated MoS2 NSs deposited on Si/SiO2 substrate.
A high degree of crystallinity was confrmed from the TEM image of the exfoliated
MoS2 NSs as shown in Figure 3.5d; inset shows the corresponding higher resolution
TEM image.
A very similar approach for the growth of MoS2 NSs via ECE has also been dem-
onstrated by Liu et al. [18]. They have also reported the growth of large lateral size
(50 μm) atomically thin MoS2 NSs by exfoliation of bulk MoS2 crystal using Pt wire
(counter electrode) and bulk MoS2 as working electrode loaded in 0.5 M Na2SO4
electrolytic solution. At the initial stages, a constant potential of +2 V is applied for
10 minutes to the bulk MoS2 crystal, which was then increased to +10 V for a period
of 0.5–2 hours for the exfoliation of bulk MoS2 crystal to synthesize 2D MoS2 NSs.
The vacuum-fltered exfoliated MoS2 was then dispersed in NMP solvent so that a
uniform MoS2 NS solution can be obtained with a yield of 5%–9%. The overall mech-
anism responsible for such an exfoliation lies in the production of OH and O radicals
and/or SO 4 2− anions, which insert into the bulk MoS2 crystal leading to a lowering
in the van der Waal interaction of MoS2 interlayers. As a result, expansion of MoS2
interlayer takes place causing the detachment of MoS2 fakes from bulk MoS2 crystal.
This method has also been utilized for the 2D growth of h-BN NSs. Wang et al. [19]
have reported ECE of bulk h-BN by applying a constant +10 V DC potential to two
platinum driving electrodes dipped in bulk h-BN dispersed in sodium sulfate, which
acts as h-BN source, supports electrolyte, respectively.
3.2.5 UNZIPPING OF THE NTS

Unzipping of NTs (either single-walled or multi-walled) is one of the fascinating
techniques to synthesize 2D nanomaterials. Graphene, h-BN, or TMDs layers can
be prepared by the unwrapping of their corresponding NTs, e.g., unzipping of car-
bon NTs (CNTs) gives graphene and unrolling of boron nitride NTs produces boron
nitride NS. Unrolling of CNTs has been reported by several authors [44–46] and
warrants the dissociation of C-C bonds either in the axial direction or in the longi-
tudinal direction and hence requires a high level of strain. Hence several routes are
employed for this purpose, e.g., unzipping can be initiated via metal intercalation,
chemical, and plasma etching treatments. In plasma etching treatment, a polymer/
CNT matrix is formed by embedding the CNTs in a suitable polymer. Generally,
polymethyl-methacrylate (PMMA) is employed for this purpose. Once the polymer
is formed, they are deposited on some substrate and then peeled off using KOH solu-
tion and fnally undergoes argon treatment. On the other hand, chemical unrolling
involves the treatment of CNTs with H2SO4 followed by oxidation using KMnO4 to
split the C-C bonds in axial/longitudinal directions. Metal intercalation is one of the
best approaches to rupture the NT walls where the foreign atoms/ions/molecules are
forced to intercalate within the walls of the NTs to produce enough stress leading to
the formation of 2D nanomaterials.
Li et al. [44] have reported an effective intertube and intratube intercalation-
assisted longitudinal unzipping of multi-walled carbon NTs (MWCNTs) for produc-
ing graphene NRs. They have treated the MWCNTs with 1 g KNO3 and varying
concentrations of H2SO4 with continuous magnetic stirring at 300 rpm for 2 hours,
which allows the intertube and intratube intercalation of K+, NO3−, and SO 4 2− ions
within the bundled CNTs. After this, 0.5 g KMnO4 (oxidant) is added slowly with
further stirring for the next 2 hours. This initiates longitudinal unzipping by weaken-
ing the interlayer van der Waals attraction giving rise to graphene layers.
Unzipping process has been further extended for the growth of 2D TMDs (MX 2)
layered nanomaterials. Nethravati et al. [20] have reported the chemical unzipping
of WS2 NT to synthesize 2D WS2 NRs. The WS2 NTs employed were 10 μm long
and 20–80 nm wide. The overall process involves two steps: (a) Lithiation of WS2
NTs to form LixWS2 –NTs and (b) unzipping of LixWS2 –NTs to form WS2 NRs.
Once the LixWS2 –NTs were prepared, they are then dispersed in solvents such as
water, methanol, ethanol, octanethiol, and dodecanethiol and undergo sonication
for 1 minute to form a stable colloidal dispersion. The chemical reaction process
of lithiated LixWS2 –NTs in water and ethanol leads to the formation of WS2
NRs along with the liberation of H 2 gas and can be expressed by Eqs. (3.1) and
(3.2) [20].
Li x WS2 + xH 2 O ° WS2 + xLiOH + x/2H 2 (3.1)

48 2D Nanomaterials
Li x WS2 + xC2 H 5OH ° WS2 + xC2 H 5OLi + x/2H 2 (3.2)
The dispersion was then coagulated by adding acetone followed by fltration and
vacuum drying. To remove the residual Li salts, the obtained mixture was repeat-
edly washed using a mixture of ethanol and water to obtain high-quality WS2 NRs.
Kvashnin et al. [47] have theoretically analyzed the experimental results obtained by
Nethravati et al. [20] on the unzipping of multiwalled WS2 NTs via Li intercalation
using ab-initio calculations.
Recently, Sasikala et al. [48] have also demonstrated the longitudinal unzipping
of 2D TMDs via two-step process. The frst step involves the intercalation of Li+
ions into bulk MX2 to produce Li xMX2, followed by the second process of obtaining
a stable suspension via ultrasonication in oxygenated water due to which Li xMX2
experiences instantaneous longitudinal unzipping.
Figures 3.6a and b depict the SEM images with (scale bars: 0.5 μm (a) and 0.1 μm
(b)) displaying the initiation of unzipping after 5 minutes of ultrasonication from
FIGURE 3.6 SEM images of unzipped 2D MoS2 after 5 minutes of ultrasonication (Scale
bars: 0.5 μm (a) and 0.1 μm (b)). (c) SEM image of MoS2 NRs after complete unzipping of
MoS2 crystal. (d, e) TEM images of isolated MoS2 NRs (Scale bars: 0.2 μm (d) and 0.1 μm (e)).
(f) AFM image of MoS2 NRs (Scale bar: 0.2 μm). (g) Length of NRs versus width obtained
from TEM. (h) STEM image of MoS2 NR with lattice image shown in the inset. (i) Raman
spectra of bulk MoS2, MoS2 sheet with 1Ti crystal structure, and MoS2 NRs. Adapted with
permission from [48]. Copyright (2020) The Authors, some rights reserved; exclusive licensee
[Springer Nature]. Distributed under a Creative Commons Attribution License 4.0 (CC BY)
https://creativecommons.org/licenses/by/4.0/.
the edges of bulk MoS2 crystal. The SEM image after complete unwrapping of
MoS2 crystal to produce MoS2 NRs is shown in Figure 3.6c. Figures 3.6d and 3.6e
show the TEM images (scale bars: 0.2 μm (d) and 0.1 μm (e)) of the unzipped MoS2
NRs. The AFM image of the grown NRs is shown in Figure 3.6f. The variation
of length of the NRs as a function of width obtained from TEM results has been
illustrated in Figure 3.6g. Figure 3.6h displays the STEM image of MoS2 NRs with
a lattice image, which shows Mo-terminated zigzag edge structure. Raman spectra
of bulk MoS2, MoS2 sheet with 1Ti crystal structure, and MoS2 NRs are depicted in
Figure 3.6i.
Similar to the unwrapping of CNTs to obtain graphene, one of the effective ways
to obtain h-BN NSs is via the unwrapping of BN NTs. However, it is worth stressing
here that h-BN is less susceptible to intercalants as compared to graphite and hence
unzipping of BN NTs is quite diffcult. The very frst study of unzipping of BN nano-
tube to form BN NS was reported by Zeng et al. [2] by using the polymer etching
method where BNNT is dispersed in PMMA polymer. They have prepared a disper-
sion of BN NT in PMMA polymer and spin-coated it on Si substrate to form a poly-
mer matrix on a substrate surface. It is then peeled off from the substrate followed
by etching using plasma treatment, which ensures the cutting of BN NT leading to
the formation of BN NS. Erickson et al. [49] have demonstrated the unzipping of BN
NTs by alkali metal intercalation where vaporized potassium metal ions get inserted
within the NT walls to induce lengthwise splitting of the BN NTs. This whole pro-
cess was carried out at 300°C in vacuum ambient for 72 hours and 1 μm along with
5 nm wide h-BN NSs were obtained.
3.3 CONCLUSIONS
In the last two decades, there has been immense progress in the research area of 2D
nanomaterials including graphene, h-BN, and TMDs from fundamental to techno-
logical advancements. Each of these 2D nanomaterials can be synthesized via a wide
range of well-established growth techniques. The properties of these 2D nanomateri-
als can be effectively altered by varying the growth technique as well as the growth
parameters, which may induce several defects, strain, or can vary the surface proper-
ties of these materials. It should be noted that there has been an explosive evolution
in the feld of graphene synthesis; however, there is still immatureness in the devel-
opment of top-down approaches for the synthesis of other 2D nanomaterials beyond
graphene. Therefore, most of the 2D nanomaterials apart from the graphene are
being prepared using the well-developed synthesis methods adopted for graphene-
based nanomaterials. Moreover, for the commercialization of such 2D nanomateri-
als, several challenges arise from the various synthesis techniques such as production
cost, production yield, quality of the growth material, mass production, and produc-
tion rate among these challenges, large scale production without compromising the
quality is one of the major factors to fulfll the requirements from the viewpoint of
device applications. Such device applications generally warrant the fabrication of
hybrid structures and/or homo-/heteronanostructures employing such promising 2D
nanomaterials. Hence more novel approaches are required to be developed, which
will be one of the most promising futures research directions.
50 2D Nanomaterials
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4 Bottom-Up Synthesis of
2D Nanomaterials for
Energy Applications
Felipe de Souza and Ram K. Gupta
CONTENTS
4.1 Introduction .................................................................................................... 53
4.2 Approaches for the Synthesis of 2D Materials ............................................... 54
4.3 Bottom-Up Synthesis of 2D Nanomaterials ................................................... 57
4.3.1 Chemical Vapor Deposition................................................................ 57
4.3.2 Physical Vapor Deposition..................................................................60
4.3.3 Ultra-High Vacuum-Assisted Synthesis ............................................. 63
4.3.4 Hydrothermal/Solvothermal Synthesis...............................................66
4.4 Conclusion ...................................................................................................... 68
References................................................................................................................ 68
4.1 INTRODUCTION
There is an increasing demand for energy storage technologies as the dependence
on electronic devices is becoming more intrinsic to modern society. Such conditions
lead to a higher level of dependence on the materials used to fabricate the compo-
nents and push academia as well as industry to develop new approaches that can
deliver better performance accompanied by lower cost. In this manner, stationary
storage grids, transport systems, and electronic devices are powered by some type of
battery or supercapacitor. Their working principle is based on rechargeable electro-
chemical batteries. In that sense, lithium-ion batteries (LIB) are the dominant tech-
nology, which consists of two electrodes (anode and cathode) that are separated by an
electrolyte. The redox process is carried out based on the electrochemical potential
difference between the anode and the cathode. Because of that, two-dimensional
(2D) materials were brought into the picture to further improve the performance of
current energy storage devices. The 2D structure improves the surface area, which
facilitates the diffusion of ions from the electrolyte as well as the redox process due
to more exposure of active sites and it can facilitate the ionic or electronic trans-
port over its surface. Along with that, the 2D structure can also present enhanced
mechanical properties compared with their bulky counterparts in terms of Young’s
modulus and fexibility. Through that, these types of materials can be used for more
DOI: 10.1201/9781003178453-4 53
54 2D Nanomaterials
robust applications that require a material to be exposed to strain or to be bendable,

which is the current trend of the latest wearable devices. In another sense, 2D materi-
als can be applied as a coating over an electrode’s surface to prevent the formation of
Li metal dendrites or potentially prevent the shuttling effect of polysulfdes, which
are a recurrent challenge on LIB that can cause them to short-circuit. On top of
that, they can play other roles such as improving the surface area for better capaci-
tance, conductibility to facilitate charge transfer, dissipate heat from the battery, and
function as a composite to reinforce specifc properties. Through that, they can be
employed as components for either cathode or anode to increase the cycle stability
along with gravimetric and volumetric capacitances. Based on that, 2D materials are
valuable components to further improve the much-desired performance of the cur-
rent energy storage devices.
Currently, commercially available LIB have their cathode active materials com-
posed of LiCoO2, LiNixMnyCozO2, and LiFePO4 and anode active materials such as
Li4Ti5O12, which provide satisfactory performance, yet still suffer from high polar-
ization, low cycling stability, and safety concerns. A viable option to improve their
overall performance has been widely studied through graphene, which has remark-
able properties such as a high conductibility of 106 S cm−1, a charge carrier mobility
of 200,000 cm2/V.s, chemical stability, and fexibility [1]. Another aspect is that a
lower resistance in the electron transport in the cathode is important to improve the
diffusion of Li+. Based on that, several carbon-based materials alongside graphene
such as carbon nanotubes (CNT), carbon black, and acetylene black can be employed
as additives in electrodes. When graphene was added into LiFePO4 it surpassed other
carbon-based materials such as CNT and acetylene black by a large marge in terms
of the diffusion coeffcient and lower interface resistance reaching 5.9 × 10 −9 cm2 s−1
and 130 Ω cm−2, respectively [2]. In addition, lower amounts of graphene (between
0.2 and 5 wt.%) were required to reach optimal properties. This effect is related to
the uniform dispersion of graphene and its long-range pathway for electron trans-
port, which decreases the overall resistance of the system. In other cases, 2D Ni(OH)2
and V2O5 have delivered high specifc capacitance, fast charge/discharge process, and
low volume expansion due to Li (de)intercalation, which was attributed to shorter
paths for ion diffusion along with a larger number of sites for ion intercalation [3,4].
The architecture of two-dimensional can vary to some degree being completely pla-
nar, puckered, or buckled, which are important to either facilitate electron fow or to
improve the surface area for better adsorption of ions. The representation of some of
the structures of regularly employed 2D nanomaterials is provided in Figure 4.1. With
these concepts in place, the following sessions cover the main synthetic approaches
to obtain 2D materials by briefy showing top-down approaches followed by a more
in-depth discussion of bottom-up synthetic methods.
4.2 APPROACHES FOR THE SYNTHESIS OF 2D MATERIALS

The top-down approach is described as a process in which a bulky material is con-
verted into a single layer while maintaining most of its integrity in the process. It can
be performed in several ways, which roughly include mechanical, chemical, or liquid
exfoliation approaches. It is convenient in the sense of being generally cheaper and
FIGURE 4.1 Widely used 2D materials to compose electrodes for LIB as either anodes or
cathodes depending on the working potential against Li/Li+. Adapted with permission from
reference [5], Copyright (2020), American Chemical Society.
reproducible with the trade-off that it could be some crystallinity disruption or prop-
erty change. The mechanical exfoliation approach consists of breaking weak intermo-
lecular interactions such as van der Waals’ through physical force. Micromechanical
cleavage is one method based on this concept at which a 2D material is fabricated
by using a scotch tape that is adhered to the surface of the bulky material and peeled
off to obtain a single or fewer layer stacked. Since this method functions by weaken-
ing the intermolecular interactions, it maintains the chemical structure of the par-
ent material, its crystallinity along a clean surface. Graphene, for instance, can be
synthesized through this method by using graphite as the bulky parent material. Ball
milling exfoliation is another convenient process that breaks the chemical interac-
tions through shear and compressive force, which can promote chemical reactions in
the absence of solvent. 2D nanolayers of less than 200 nm of materials such as boron
nitride, MoS2, and graphene can be obtained through this approach.
Liquid exfoliation is a method that makes use of organic solvents, surfactants,
and/or ionic liquids. The process can be performed by thinning the bulky materials
through sonication and ball milling. The follow-up process consists of a chemical
etching at which fuoride acid (HF) is largely employed. This approach is widely used
to synthesize MXenes, which consists of a bulky Mn+1AXn material where M is a tran-
sition metal, A is the interlayered atom that can be etched such as Al, and X is usually
C or N. One example for this case is Ta4C3 for instance, which can be obtained from
the chemical etching of bulky Ta4AlC3. Through that, several 2D materials can be
obtained with high effciency with the drawback of the relatively expensive cost of HF.
The mechanical force-assisted technique is another top-down procedure that can
rely on both sonication and shear force. Through this process, ultrasonic waves are
created, which induce liquid cavitation on the bulky material leading to the formation
of bubbles. Once they burst, localized heat is released, which promotes the formation
56 2D Nanomaterials
of either hydroxyl radicals or a pyrolytic process, exfoliating the bulky material into
2D nanolayers. This approach has been used to synthesize MoS2 nanolayers from 5
to 15 nm of thickness and around 40 to 70 nm of length and width [6,7]. The Ion-
intercalation technique is a milder approach that relies on the diffusion of small metal-
lic cations such as Li+, Na+, and K+ within the structure of bulky material and increases
the interlayer spacing between the nanosheets. Then, gentle sonication can be applied
to separate the nanolayers. It is a convenient approach in the sense that water can be
used as a solvent, and requires relatively low-cost materials and instrumentation. The
presence of cations under sonication can lead to the formation of H2, which further
improves the exfoliation [8]. A follow-up ion exchange process can also be adopted, at
which a cation with a larger radius can be used to replace the smaller cation and thus
increase the interlayer spacing, which facilitates the separation of layers.
Oxidation-assisted method or modifed Hummer’s method consists of using strong
oxidizing agents that can introduce oxygenated groups causing the bulky structure
to become more polarized and therefore more soluble in water. After that, sonication
becomes more effective to separate the nanolayers. This approach is commonly used
to synthesize graphene oxide (GO) through the strong oxidative process over graphite
with KMnO4 and concentrated H2SO4. It has a relatively high yield; however, it pro-
motes a drastic change in the chemical structure of the chemically exfoliated nano-
layered material when compared to the bulky parent. Hence, a thermal or chemical
reduction process can be performed to obtain reduced graphene oxide (rGO). Lastly,
cryo exfoliation of 2D quantum dots is a method that relies on low temperature under
the presence of solvents to promote physical exfoliation, with the advantage of pre-
serving the structure of the bulky starting materials since no chemical reactions take
place [9]. Some of the top-down approaches are displayed in Figure 4.2.
FIGURE 4.2 Widely used synthetical approaches for top-down such as mechanical cleav-
age, liquid-phase exfoliation, and ion intercalation. Bottom-up approaches displayed such as
chemical synthesis, physical vapor deposition, and chemical vapor deposition. Adapted with
permission from reference [9], Copyright (2019), Elsevier.
4.3 BOTTOM-UP SYNTHESIS OF 2D NANOMATERIALS

The bottom-up approach consists of the chemical build-up of a nanolayered structure
taking an atom or a smaller molecule as starting reagent, named precursors. It can be
performed through several techniques such as chemical or physical vapor deposition
(PVD), ultra-high vacuum (UHV)-assisted synthesis, hydro or solvothermal, among
other methods. These technologies are valuable in the sense that they provide 2D
nanomaterials through mostly facile, inexpensive, and effcient methods.
4.3.1 CHEMICAL VAPOR DEPOSITION

Chemical vapor deposition (CVD) is a convenient method used to grow thin flms of
organic or inorganic compounds through deposition over a substrate. It allows exper-
imental control as scientists can tune properties such as morphology, phases, number
of layers, doping, insertion of defects, and particle sizes. Such possibility yields 2D
nanomaterials with high surface area and exposed active sites. These properties can
be defned through precise control of parameters such as chamber pressure, tem-
perature, the fow of carrier gas, concentration of reagents precursor, and distance
between the starting materials and substrate. Such control of parameters was studied
by Wu and colleagues, which demonstrated a method that targeted the supply of
gas to a focal point, which created one nucleation site with a carbon precursor that
allowed it to grow up to a few centimeters forming a single graphene crystal [10].
The concentration of precursor, which functions as the reagent for a CVD, defnes
the deposited number of atoms over the substrate, which is usually measured in stan-
dard 1 cm3 minute−1, which can be converted to 7.4 × 10−7 mol s−1. Also, several carrier
gases such as H2, Ar, SiH4, or SiH2Cl2 can be used to control the environment in differ-
ent ways, for example, H2 can be used to reduce undesired reactive groups or dandling
double bonds to obtain samples with high quality. A common example is CVD used to
synthesize graphene through CH4 and H2 as precursors. Hence, through a controlled
ratio of precursor and carrier gas, proper control of size, morphology, and structure
can be achieved. Also, doping with P and N can be performed by adding gases such as
PH3 or NH3. MoS2, MoSe2, WS2, WSe2, among others can also be synthesized through
CVD by using precursors such as MoO3, MoCl5, or WO3 under the presence of S or Se
powders. In another case, precursors such as H2S, CS(CH3)2, or Mo(CO)6 can lead to a
more uniform structure of transition metal dichalcogenides (TMDC) [11].
Temperature infuences the fow of carrier gas, the kinetics of chemical reactions,
and deposition rate as when higher temperatures are employed a faster diffusion is
promoted. This effect can result in a gradient of concentration, which varies the mass
transport. Through that, the uniformity of the deposited 2D material can change.
For the case of TMDC, the temperature has a considerable impact if compared with
graphene, as a small variation in this parameter can cause a change in saturation
pressure, varying the material’s growth. Based on previous experiments it has been
noted that temperatures around 800°C contribute to a higher deposition rate as it can
lead to multilayered materials.
Substrates are the surface at which the precursor materials grow. It plays an impor-
tant role in the catalysis of the process since active Ni or Cu, for instance, possess
58 2D Nanomaterials
active sites that enhance the reaction rate at their surface, which are widely used for
the growth of graphene. For the case of TMDCs substrates such as polyimide, mica,
Si/SiO2, Au, or W can be used. Nucleation sites to start the material’s growth can
also be employed, which include the addition of rGO or compounds such as perylene-
3,4,9,10-tetracarboxylic dianhydride (PTCDA) or perylene-3,4,9,10-tetracarboxylic
acid that have the goal to promote catalytic activity over inert substrates like Si/SiO2.
The substrate’s orientation is also a factor that can change the morphology as a previ-
ous study demonstrated the difference between a CVD performed with the substrate
at vertical rather than horizontal orientation, which promoted a flm with uniform
formation without further need of volatile solvents of higher vacuum [12].
Pressure greatly infuences the reaction progression, and it provides more control
over the system when high vacuum and low precursor concentration are used, enabling
more accurate deposition over the substrate. This effect has been observed by varying
the partial pressure of Mo(CO)6 as a precursor for MoS2 at which under low pressure
the deposition occurs more accurately at the grain boundaries. However, when high
pressure is employed the deposition occurs randomly, which leads to a non-uniform
surface of mono and multilayer nanomaterials [13]. Other variations of CVD can also
infuence the quality of the 2D flms such as inductively coupled plasma CVD, which
can be performed at lower temperatures. It aids to decrease cost and is more effcient
toward the deposition of polymeric flm’s growth over glass substrates [13]. There are
other relevant factors for the optimization for the 2D flm, which can be summarized
in grain size, layers, growth direction, phase, morphology, degree, and effect of dop-
ing, and defects on the structure. During a flm formation, it is expected that it should
be close to a single crystal instead of a structure with several grain boundaries, which
has been performed for several known 2D materials that include MoTe2, WSe2, WS2,
and MoS2. The latter has been studied by employing an Au foil as substrate and WO3
and S2 as a precursor for the formation of the MoS2 flm [14,15]. In this case, Au played
a catalytic role as it dissociates S2 into single S atoms over its surface, which facilitates
the follow-up sulfurization of MoO3. This condition led to the formation of regular
flms over the substrate with an edge length of around 80 μm.
The higher number of layers causes a decrease in the bandgap of most TMDCs.
Based on that, when WS2, MoS2, and MoSe2 reach one layer of dimension there is a
transition from indirect to direct bandgaps. This characteristic allows these materi-
als to be applicable as in photovoltaic cells, laser diodes, and light-emitting diodes.
Hence, properly controlling the stacking of nanolayers is an important step to control
the properties. Based on that, some approaches such as oxygen-plasma treatment and
increase of layer deposition by increasing temperature in the sense that one-, two-,
and three-layered structures of MoS2 were obtained for the temperatures of 750°C,
825°C, and 900°C, respectively, have been employed [16,17].
The orientation of the precursor over an aligned substrate is another parameter that
correlates with the properties as it describes the nucleation model during the grow-
ing process. However, if the precursor is not oriented with substrate there is a higher
tendency of more grain boundaries, uneven distribution of the flm, and more defects.
That is a relevant matter for the flm growth as graphene flms on the scale of meters
have been reported when the deposition process occurred with domains under 60° of
rotation [18]. Yet, an effort to reach such dimension is still being made for TMDCs.
To attain more control of orientation growth it is necessary to use a substrate that can
properly interact with the precursor, usually through van der Waals interaction, match
of lattice between the components, and symmetrical lattices. For that, facet sapphire,
c-plane, has been often employed to obtain crystals of high quality.
The infuence of morphology in the properties of 2D nanomaterials used on sensors,
batteries, supercapacitors, and electrocatalysts is a considerable matter for performance
improvement. In that perspective, the catalytic properties of electrodes for water split-
ting are greatly improved by the density of edge sites [19]. The symmetric threefold
lattice commonly observed in the TMDC’s structure that takes the shape of truncated
triangles, dendritic, hexagons, three- or six-pointed stars are factors that contribute to
the edge effect. The morphology can vary based on several factors such as the ratio
of precursors, fow rate, and temperature. The effect of change in these parameters in
the morphology was studied by Wang et al. [20]. In the study the authors showed that
the distance of that MoO3 precursor is from the substrate for the synthesis of MoS2
provides a relation between the ratio of Mo and S in the flm. This situation led to a
change in growth rate as it followed the order of medium-sized truncated triangles, to
larger sized, again medium-sized, diminishment size of hexagons, and small triangles
as displayed in Figure 4.3a. This variation occurred due to the change in growth rate in
the MoS2’s different facets. Also, a higher concentration of Mo leads to a suggestive Mo
edge denominated as zigzag Mo edge (Mo-zz). A similar phenomenon occurs when S
was in excess leading to zigzag S edge (S-zz) as shown in Figure 4.3b.
Phase control is an important matter for the defnition of properties. For the case
of MX2, there is an arrangement of X–M–X on the X and Y axis, along with those
chalcogen elements that are aligned vertically on the Z-axis forming a trigonal pris-
matic phase, referred to as the 2H phase (semiconductor). In another way, the adjacent
chalcogen atom can align toward each other, forming an octahedral phase, referred
to as the 1T phase (metallic). Hence, controlling the phase change allows controlling
the material’s properties without introducing new atoms. Based on that, recent stud-
ies showed that to obtain metastable TMDC phases some post-synthesis techniques
such as electron beam irradiation, intercalation with alkaline metals, mechanical
force, or plasma treatment as viable options [20,21]. In that sense, Li salts interca-
lated with MoS2 1T phase have been obtained and its stability in the air has been
improved by hydrogenation of the intercalated Li leading to the formation of LiH
[22]. Despite being an important factor for property enhancement, phase change has
not been widely performed by CVD, which still requires further studies.
In another perspective, doping is a process at which a heteroatom is introduced
into the structure to tune the material’s properties. Since the metals are less exposed
and stacked in between chalcogen atoms it deems simpler to dope the chalcogens,
which can be performed through CVD with the current challenge of defning proper
concentration and dopant position during the process [13]. Yet, synthesizing ternary
TMDC by doping with metals has been performed, as Mo1-xWxS2 was obtained by
laser-plasma CVD where the precursors were WCl6 and MoO3 for W and Mo sources,
respectively. The reaction between Mo and S was performed at 700°C [23]. This type
of approach promotes the decrease of the bandgap, facilitating electron transitions
through a relatively simple technique. Based on this discussion several factors infu-
ence the overall properties of 2D materials as CVD is a highly versatile technique in
60 2D Nanomaterials
FIGURE 4.3 (a) Effect of the distance of precursor distance between precursors as a factor
for change in morphology according to the rate of growth. (b) Change in morphology accord-
ing to the cases of higher concentration of Mo or S to form MoS2 flm. Adapted with permis-
sion from reference [20], Copyright (2014), American Chemical Society.
that regard. For that, the key factors for the proper control of CVD to allow optimal
growth of 2D nanomaterials are expressed in Figure 4.4a. Also, Figure 4.4b provides
an overall summary of the effect of the main parameters for CVD synthesis.
4.3.2 PHYSICAL VAPOR DEPOSITION

PVD is a process that has some advantages over CVD such as more reproducibil-
ity, lower temperature, and tendency to cover larger areas of substrate with more
uniformity. It functions under the same principles with the difference that it relies
on the disruption of intermolecular interactions, mostly van der Waals, instead of
the formation of new chemical bonds as it occurs in CVD. The PVD process can be
mainly divided into methods that are sputtering and laser deposition, which is known
to be the most suitable to obtain 2D materials with satisfactory performance [24].
FIGURE 4.4 (a) Correlation between the main parameters for CVD approach such as pre-
cursor, pressure, substrate, and temperature. (b) Key factors for the proper control of CVD
technique for the growth of 2D nanomaterials. Adapted with permission from reference [13],
Copyright (2018), American Chemical Society.
The sputtering PVD consists of exposing the bulky material that already has the
desired composition to vacuum and a large negative potential that can range from
−1,000 to −100 V. Then, after highly pressurized inert or reactive gas is introduced
in the system within the range of 70–7,000 Pa. Ar is commonly used for this purpose
as it is an inert gas that when exposed to both negatively high voltage and pressure it
is ionized releasing electrons and forming cations. The positively charged gas species
are accelerated into a negatively charged substrate in which the bulky material (tar-
get) is placed. Once the cationic species hit the substrate atoms are released, which
vaporize the bulky material. Controlling the voltage infuences the amount of sput-
tered yield, which is the number of atoms on the target that leaves the bulky structure
when bombarded by one cationic gas atom. Yet it is important to note that voltages
above 1,000 V cause the incident cations to be buried too deep into the target and
be unable to sputter other atoms. Hence, usually, voltages of 500 V under 1.3 kPa
are applied, which allow proper control of the kinetic energy of the incident gaseous
cations [25]. The technique is meant to be performed on the bulky equivalent of the
2D desired materials as the fnal composition of the layered product tends to pres-
ent a proportional number of atoms of those of the bulky one. It is an effect since
observed on TMDCs, as the chalcogens present higher vapor pressure than metals as
well as similar size compared to the cationic incident species, which maximizes the
momentum transfer for the ejection of chalcogen atoms. Thus, chalcogens leave the
bulky structure faster than metals, which may cause a stoichiometric imbalance in
the 2D structure. To address that, the deposition pressure can be increased along with
the distance between target and substrate.
Another parameter of study is the mechanism of TMDCs growth, which provides
information on the exposure of active sites. Taking the case of MoS2 for instance
scientists observed that growth occurred through a layer-by-layer mechanism at the
62 2D Nanomaterials
basal planes (002), which are parallel to the surface. The low energy surface toward
the center of the flm and the higher energy surface on the edges, due to the driv-
ing force of atoms in the edge to bond, is what directs this type of flm to grow.
Misalignment of growing flms can occur on the basal plane due to impurities such as
moisture or oxygen, which can disrupt the deposition of other layers. Yet, purposely
introducing defects into an inert basal plane is a convenient strategy to improve the
surface area, which can be performed through incident ions to create anionic vacan-
cies. Another aspects that can be used to control the 2D material’s structure are the
ratio of Mo:S. In the case that more S needs to be introduced due to its defciency in
the flm [26].
Graphene can be synthesized through pulsed laser PVD; however, the energy of
incident particles in this technique is often strong enough to cause damage to the lat-
tice structure, which causes the structure to deteriorate [27,28]. For that, low-energy
electron beam evaporation or thermal treatment is more favorable to induce an advan-
tageous number of defects, and therefore preserves the electron transport properties
of graphene [29]. Another strategy consists of using reactive gases, such as a mixture
of N2 as the reactive species along with Ar, over a metal target that can function as
a cathode. This approach can be employed to synthesize many metal nitrides such
as AlN, ScN, TiN, among others. The other type of PVD can be performed through
pulsed laser deposition, which consists of the incidence of a laser with a wavelength of
248 nm (ultraviolet) as the source of energy, instead of ion bombardment as it occurs
in the case of sputtering. Based on that, this type of approach is suitable to obtain
2D electrically insulator materials from their bulky counterparts. The reason for that
is because conductive materials present higher thermal conductivity and refectivity
leads to a decreased energy adsorption that weakens the effect of the incident laser as
the heat diffuses faster through the structure. The main parameters for this approach
are based on the laser’s energy, length, and absorption on the target material. The
synthesis of boron nitride (BN) through this method has yielded ultrathin flm that
ranged from 5 to 10 nm, which maintained its high dielectric constant, whereas it
can be performed over several substrates such as metals, polymers, or ceramics. BN
has promising applications due to its chemical and thermal stability, which allows it
to be used in devices to prevent the deterioration of other active electrode materials.
TMDC can also be synthesized through this technique, which has been known
to yield high-quality flms. Yet, the same phenomenon of a faster release rate of
chalcogens is observed. To counter that Serrao and colleagues used tetrathiomolyb-
date (MoS4) to compensate for the higher release rate of S as a means to prevent
excessive anionic vacancies that could damage the structure [30]. Through that, thin
MoS2 flms were obtained, which could be deposited over either semiconducting or
insulating flms as the process was performed at 700°C. Based on these concepts
several research areas make proper use of PVD, among them, there is the fabrica-
tion of organic photovoltaics that are promising materials suitable for solar cells.
With recent progress in this area there has been the combination of graphene as
a substrate along with metal phthalocyanines (MP), which present tunable proper-
ties, chemical stability, and a high coeffcient of adsorption in the visible spectrum,
hence highly attractive for this feld [31]. Through that, growing MPs over C-plane
sapphire, graphene substrate can provide a good combination of MP’s properties
along with optical transparency, fexibility, and high conductivity of graphene, for
instance. This idea was tested by Mirabito et al. [32] by performing a PVD of ZnPc
over different substrates such as graphene, Cu, and hexagonal boron nitride (h-BN).
The authors observed that high lengthwise nanowires were formed over graphene,
Cu, or h-BN. Yet, the morphology of ZnPc was highly infuenced by the structure
of graphene as it tended to form continuous flms when single-layered graphene was
used as substrate whereas it formed nanowires when stacked graphene nanolayers
were used. This variation was likely due to the more exposed surface area of single-
layer graphene, which allowed more deposition of ZnPc. For photovoltaic activity, it
is desired that materials deposited over the substrate present a smaller grain size to
facilitate the formation of excitons and electron transfer steps. This process is tunable
and dependent on the substrate in which the MC is grown as it can defne its morphol-
ogy, orientation, and structure. The change in morphology when ZnPc is grown in
the different substrates can be seen in Figure 4.5.
4.3.3 ULTRA-HIGH VACUUM-ASSISTED SYNTHESIS

Both CVD and PVD are widely explored methods due to the 2D material’s proper-
ties that can be obtained and tuned through them. Yet, UHV-assisted synthesis dif-
fers in the sense that it can avoid contaminants as it allows techniques for on-surface
synthesis and molecular beam epitaxy. On top of that, the UHV technique can be
used to synthesize specifc 2D materials. Ogikubo et al. took advantage of this tech-
nique to synthesize a hetero 2D structure based on germanene and stanine [33]. These
compounds present a similar structure compared to graphene. Based on that, fnding
ways to properly synthesize nanolayered compounds from the Group 14 can provide a
new array of opportunities for materials that can potentially surpass graphene’s prop-
erties and perhaps serve as a viable option within several research areas including
energy applications. For this case, the synthesis was performed at UHV adopting both
molecular beam epitaxy (MBE) and atomic segregation epitaxy, which led to a precise
multijunction of Ge and Sn atoms over an Ag (111) flm. The authors observed that
FIGURE 4.5 Scanning electron microscopy (SEM) images for the PVD-grown ZnPc over
different substrates and the changes in ZnPc’s morphology. Adapted with permission from
reference [32], Copyright (2021), American Chemical Society.
64 2D Nanomaterials
both germanene and stanene could be fabricated without intermixing the nanosheets
through scanning tunneling microscopy (STM). The precise control for this type of
approach may provide a satisfactory performance on electronic devices [33].
Another approach that has been frst developed more than 100 years ago is the
Ullmann reaction that consists of C-C coupling performed through the reaction
between an aryl halide along with high surface area Cu at temperatures higher than
200°C to yield a biaryl and a Cu halide byproduct. Despite its complex mechanism, this
approach is still employed today under UHV conditions to grow a thin layer of carbon-
based materials over a Cu substrate, even though this approach does not yield large
molecules. Yet, large polymerizations with highly aligned structures were obtained
through Ullmann’s coupling by using 2,5-diiodo-3,4-ethylene dioxythiophene with
the advantage that when it was performed over Cu (110) substrate there was a Cu-S
interaction that promoted the alignment of the polymer leading to all-cis geometry,
which was also attributed to the anisotropic nature of Cu (110) that created a driving
force for one-directional growth [34]. This approach deems a convenient process as it
can form accurately structured 2D flms over a metallic substrate as it has been used
to synthesize porous graphene. The synthesis was performed by 575 K annealing of
hexaiodo-cyclohexa-m-phenylene (CHP) for 5 minutes. The precise nanostructured
layered material had a pore spacing of 7.4 Å. On top of that, iodine atoms were released
from the structure by thermal treatment at 875 K without damaging the 2D structure.
The reaction that describes this process can be seen in Figure 4.6.
The formation of a regular and atomically precise flm is infuenced by the condi-
tion imposed by UHV but also the substrate. With that in mind, Bieri and colleagues
proposed the synthesis of a 2D polyphenylene over Ag (111), Au (111), and Cu (111)
to form a honeycomb-like structure. Through this study, the authors observed that
substrate plays a major role in the amount of C–C coupling once the optimal activa-
tion temperature is reached. This driving force for the flm growth is based on the
transportation that the metal substrate allows along with its exposure of reactive sites
to promote the reaction. In that sense, Cu presented the most favorable surface for
reactions to carry over, meaning that radicals formed were quickly bonding with
FIGURE 4.6 (a) Represents the CHP’s chemical structure. (b) Chemical structure of the poly-
phenylene network. (c) The chemical reaction between aryl-halides forms an aryl–aryl bond.
Adapted with permission from reference [35], Copyright (2010), American Chemical Society.
each other, that effect also caused a decrease in the mobility as it presented a more
“opened” branched structure. For the case of Ag, the opposite behavior was observed
as this metal allowed faster transport of reactive species, which led to the formation
of denser polymeric networks over Ag’s surface, yet with relatively lower exposure
of active sites. Au on the other hand presented a behavior that was in between that of
Cu and Ag by yielding a mix of compact clustered networks and branched domains.
It is worth mentioning that the annealing temperatures for each of the metals were
475, 525, and 575 K for Cu, Au, and Ag, respectively. The structure growth patterns
for the polyphenylene over the different metals are presented through STM images
displayed in Figure 4.7. These approaches show one of the major advantages of UHV
systems, which allows the formation of C–C bonds under atomic precision to grow
graphene under different structures and porosities as it can be controlled by select-
ing the desired starting halide-aryl. On top of that, the synthesis of this 2D layered
structure is relatively shorter if compared with other methods. The chemistry of C–C
coupling under UHV can be performed in other ways such as cyclodehydrogenation,
which consists of the bond between two C–H bonds through the loss of H2 followed
by cyclization. It can be catalyzed with FeCl3 or AlCl3 [36]. Yet, other approaches
that make use of annealing at 400°C of polyanthrylenes followed up by thermal
treatment at 440°C to perform the cyclization step. The inherent drawback of this
process is that due to the large distance a lower amount of starting material that is
sublimated can reach the substrate, which may account for around 2%.
The use of UHV systems for the synthesis of fullerene (C60) and triazafullerene
(C57N3) was performed over a Pt (111) substrate at 750 K to yield the desired 0D struc-
tures. This type of structure has potential applications for storage energy due to its high
surface area, which may improve the catalytic activity or energy storage properties.
FIGURE 4.7 (a, c, e) The fgures display the overview for STM images and (b, d, f) the fg-
ures display high-resolution STM for the networks of polyphenylene over Cu (111), Au (111),
and Ag (111), respectively. Adapted with permission from reference [35], Copyright (2010),
American Chemical Society.
66 2D Nanomaterials
It can be also envisioned that, if this method is performed under the presence of guest
species, its properties can be functionalized and perhaps obtain enhanced properties
[37]. Based on these examples it is notable that synthesis at UHV condition allows
several types of reactions besides Ullman and dehydrogenation, which also include
Sonogashira, radical (CH2●), imination, amidation, urea linkage, dehydration, esterif-
cation under the presence of boron-based compounds, and amino-fullerenes [36].
4.3.4 HYDROTHERMAL/SOLVOTHERMAL SYNTHESIS

Hydrothermal and solvothermal synthesis are procedures performed under a reactor
that is hermetically sealed or an autoclave. Due to the controlled pressure within the
reaction system, higher temperatures can be achieved without causing the solvents
or components to evaporate. This condition prompts the precursor or monomers to
deposit over the substrate surfaces forming 2D nanosheets. It is a widely used method
due to its low-cost, high yield, and scalable method for the synthesis of several types
of 2D materials, although it tends to form structures that present more than a single
layer of 2D material, it is effective to properly bind the synthesized material over
the substrate’s surface. The process allows the dissolution of the precursor in a sol-
vent that would be poorly soluble under normal conditions. Hence, when the reac-
tion system is submitted to this high temperature and pressurized environment, the
system becomes homogeneous, and the precursor recrystallizes over the substrate
usually presenting a higher degree of crystallinity. Another convenient variation for
this method is the microwave-assisted type, which greatly reduces the reaction time
due to exposure of high frequency. Yet, it applies to polarizable materials that can
absorb microwaves [38]. Such convenience of this method allows it to be adopted for
the synthesis of several types of materials besides thin flms such as simple oxides,
Perovskites, bioceramics, vanadates, garnets, among others.
Based on that, the synthesis of 2D nanomaterials suitable for energy storage appli-
cations can be widely explored through the hydrothermal method. With that insight,
2D nanolayers of MoS2 were synthesized by Huang and colleagues [39]. MoS2 is
a vastly researched material because it presents satisfactory electrochemical prop-
erties whereas relatively lower cost if compared with other materials. Some of its
properties arise from its planar structure that similarly to graphene’s allows a facile
electron transport over its surface, which gives it appreciable optical, physical, and
electrical properties. The synthesis was carried out by dissolving the precursors that
were Na2MoO4·2H2O as Mo source and l-cysteine as S source at pH = 6.5. The high
heat and pressurized environment provided by the hydrothermal reaction yielded
the MoS2 nanosheets that were deposited over Ni foam. The strong interaction that
was formed between the MoS2 nanolayers and the Ni foam improved the overall
electrochemical performance of the electrode, despite the relatively high resistance
of MoS2, which showed a stable capacitance up to 500 cycles with retention of 85.1%.
This effect was likely due to the hydrothermal method approach that provided the
dissolution of both MoO 4 2− and H2S, formed during the decomposition of l-cystine,
under the hydrothermal reactor environment. Through that, the MoS2 was grown
over Ni foam providing a strong interfacial contact between them, which improved
its stability. Because of that, the electrical double-layer mechanism for charge storage
was also optimized as there was a minor detachment of active material from the
electrode’s surface. The MoS2 nanolayers reached 129.2 F g−1 of specifc capacitance,
which were satisfactory values for straightforward adhesion of a TMDC without any
other additive.
The hydrothermal method is constantly used to synthesize composites for energy
storage applications. In the previous case, neat nanolayers of MoS2 were obtained,
which deliver satisfactory properties when considered as a standalone electrode
material. Yet, its properties can be further optimized by introducing other nanoma-
terials such as N-doped graphene (NG) as it was performed by Xie et al. [40]. For
this case, the one-step hydrothermal method was used to obtain nanofowers of MoS2
over NG’s surface. The authors compared the performance of a composite electrode
material based on MoS2 over graphene nanosheets (MoS2/GN) as well as NG (MoS2/
NG). The procedure was based on a typical synthetical approach for the hydrother-
mal method. It was notable that the doped nitrogen in graphene’s structure promoted
a considerable change in the composite’s morphology even though the amount of
precursor, Na2MoO4 and GO, were the same for both cases. On top of that, the load
of MoS2 deposited over graphene’s surface remained nearly unaltered when com-
paring the neat graphene and N-doped. Yet, the ratio of precursors is an important
matter since the high concentration of MoS2 over graphene’s surface decreases the
interfacial contact between graphene and the electrolyte, which partially hinders the
ionic transport for the charge/discharge process. On the other hand, a lower amount
of Mo would lead to a 3D structure as it would facilitate the restacking of graphene
nanolayers. Based on these events, it is also deemed important to understand the
growth of MoS2/Graphene as it takes place through a reductive process where the
chemical driving force is provided by thiourea (NH2CSNH2), which simultaneously
reduced both MoO 4 2− and GO into a layered structure of MoS2 deposited over rGO.
The proper electrostatic interaction between both components promotes a more
even distribution of MoS2. The description of the synthetical process along with the
change in morphology of the GO compared to the MoS2/GN and MoS2/NG is pre-
sented in Figure 4.8. This change in morphology and electrochemical behavior was
observed during the CV analysis as a synergistic effect between rGO providing an
electric double-layer capacitance whereas MoS2 provided a redox process based on
the Mo4+/Mo5+ pair. This process was enhanced due to the presence of N, which
facilitates the electron transfer step. This improvement in electrochemical properties
was suggested by the appearance of a covalent bond of C–O–Mo, which provides
better performance for the electrode. That effect was observed by the electrochemi-
cal analysis results at which MoS2/NG containing 1.5 ratios of Mo source provided
the highest capacitance when compared to NG and MoS2, with the respective values
of 227, 155, and 70 F g−1. Through that, it was notable the infuence of an N-doped
conductive substrate and the proper arrangement of MoS2 over graphene through the
hydrothermal method, which reinforces the convenience of this method. Based on
these concepts, it is notable that the hydrothermal approach is a convenient method
to perform the growth of precursors into larger materials through a convenient and
facile process that yields optimized materials usually with proper adhesion between
the active materials and the substrate. On top of that, it’s a versatile process that can
be widely applied in several cases.
68 2D Nanomaterials
FIGURE 4.8 Schematics for the synthesis of nanosheets of graphene functionalized with
MoS2 (MoS2/NG) and N-doped graphene functionalized with MoS2 (MoS2/GN) under the pres-
ence of thiourea for the chemical reduction of the precursors performed through the hydrother-
mal method. Adapted with permission from reference [40], Copyright (2016), Elsevier.
4.4 CONCLUSION
In conclusion to this chapter, it is notable the bottom-up approaches promote a viable
option to obtain high-performance materials, which were vastly used in the energy
storage feld. That is due to the control over the system that bottom-up methods
offer in comparison to other procedures. For instance, either CVD or PVD allows
accurate control over the amount of material that is deposited over a substrate based
on several parameters such as precursor concentration, carrier gas, temperature, and
distance from the substrate. Even though lower quantities are produced the variation
in these parameters can considerably change properties in terms of morphology and
surface area, which are core aspects for the optimization of electrochemical proper-
ties. Also, UHV-assisted system promoted an atom accurate process as graphene
can be grown over diverse surfaces with its pore size pre-defned. Such prediction
is possible by selecting the desired precursor for the process as well as growing the
2D nanomaterial over a specifc substrate, which are usually metals such as Cu, Ag,
Au, or Pt. The latter plays an important role as it defnes the nanostructure of the
growth flm, which effectively changes the flm’s morphology. Another widely used
method for the synthesis of nanoflms is the hydrothermal or solvothermal method,
which among the other methods presents a relatively lower cost and usually yields
materials with satisfactory electrochemical performances. Based on that, bottom-
up approaches are valuable techniques that allow more control over the reaction
system for the growth of nanoflms, which provides high surface area and exposure
of active sites, which are inherently important aspects for the enhancement energy
storage properties.
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5 Types of Energy Devices
and Working Principles
Yuyan Wang, Yang Liu, Linrui Hou,
and Changzhou Yuan
University of Jinan
CONTENTS
5.1 Solar Cells....................................................................................................... 71
5.1.1 Silicon Solar Cells (SSCs) .................................................................. 72
5.1.2 Thin-Film Solar Cells (TFSCs) .......................................................... 72
5.1.3 Dye Solar Cells (DSCs) ...................................................................... 73
5.1.4 Perovskite Solar Cells (PSCs)............................................................. 73
5.1.5 Organic Solar Cells (OSCs) ................................................................ 75
5.2 Fuel Cells ........................................................................................................ 75
5.2.1 Alkaline Fuel Cells (AFCs) ................................................................ 75
5.2.2 Phosphoric Acid Fuel Cells (PAFCs).................................................. 75
5.2.3 Molten Carbonate Fuel Cells (MCFCs).............................................. 77
5.2.4 Solid Oxide Fuel Cells (SOFCs) ......................................................... 77
5.2.5 Proton-Exchange Membrane Fuel Cell (PEMFCs) ............................ 78
5.3 Rechargeable Batteries ................................................................................... 79
5.3.1 Organic Rechargeable Metal Ion Batteries......................................... 79
5.3.1.1 Alkali Metal Ion Batteries ................................................... 79
5.3.1.2 Multivalent Rechargeable Batteries .....................................80
5.3.2 Aqueous Rechargeable Metal Ion Batteries (ARMIBs) ..................... 81
5.3.3 Metal-Sulfur Batteries (MSBs)........................................................... 81
5.3.4 Metal-Air Batteries (MABs)............................................................... 82
5.4 Supercapacitors............................................................................................... 82
5.4.1 Electric Double Layered Capacitors ................................................... 83
5.4.2 Pseudocapacitors................................................................................. 83
5.4.3 Asymmetric Supercapacitors (ASCs) ................................................. 85
5.5 Conclusion ...................................................................................................... 85
References................................................................................................................ 86
5.1 SOLAR CELLS

As one kind of renewable energy, solar energy is widely distributed, abundant
resources, environmentally friendliness, and sustainable used. And solar cells, which
aim at collecting and converting the solar energy, have become a sustainable energy
device with wide applications and promising prospects. By directly using solar
DOI: 10.1201/9781003178453-5 71
72 2D Nanomaterials
energy to convert into electrical energy through photoelectric effect or photochemi-

cal effect, it is also called solar photovoltaic technology. Generally, solar cells can be
divided into crystalline silicon solar cells (SSCs; the frst generation), thin-flm solar
cells (TFSCs; the second generation), and emerging solar photovoltaic cells (the third
generation).
5.1.1 SILICON SOLAR CELLS (SSCS)

Silicon (Si) is the second (the content only lower than oxygen) abundant reserves in
the earth's crust, and the silicon-based solar cells with a stable, non-toxicity, abun-
dant resources are currently the most mature solar cells, which have occupied about
90% of the solar cell market. And crystalline silicon (C-Si) with an energy bandgap
of 1.12 eV is one of the most appropriate candidates for building multi-junction cells.
Moreover, the current crystalline SSCs with the maximum conversion effciency as
high as 26.7%, which is very close to the theoretical maximum conversion effciency
of 31% [1–3], that is far higher than other types of solar cells in practical application.
Therefore, crystalline SSCs have become widely used and the best commercialized
photovoltaic power generation products.
The core of crystalline SSCs is the PN-junction, and the basic principle is to con-
vert solar energy into electricity based on the photovoltaic effect of the p-n junction,
the working principle is shown in Figure 5.1a. When the P-N junction is irradiated by
sunlight, the photogenerated carriers gather at both ends of the P-N junction under
the action of internal electric feld and generate potential difference. When the exter-
nal circuit is connected, the current fows through the external circuit under the effect
of the potential difference, thus generating the output power.
5.1.2 THIN-FILM SOLAR CELLS (TFSCS)

TFSCs have received great attention because of their wide material sources, good
fexibility, easy modulation function, simple preparation process, low cost, easy to
prepare large area of fexible devices. They are usually formed by deposing a layer or
multiple layers of photovoltaic materials on the substrate to form P-i-N nodes, whose
thickness is usually tens of nanometers to tens of microns. According to the different
deposition materials, the TFSCs can be divided into amorphous silicon (a-Si) and
mono-crystalline silicon (c-Si), indium phosphide (InP), cadmium telluride (CdTe),
copper indium gallium selenium (CIS or CIGS), and dye solar cells (DSCs).
TFSCs are a kind of photodiodes, under the dark and no illuminated conditions,
the current dense-voltage curve satisfes the Shockley Eq. (5.1) [4].
q (V − IRs ) ˆ (V − IRs )
J = Jsc exp ˘ − 1 + (5.1)
˜ k BT ˇ Rp
where Jsc is the reverse saturation current density, kB is the Boltzmann constant, q is
the elementary charge, T is the Kelvin temperature, and η is the ideal factor. However,
there are series resistance (Rs) and parallel resistance (Rp) in practical devices. Rs
Energy Devices and Working Principles 73
includes the bulk resistance, interface contact resistance, etc., which are in series
with load resistance; Rp comes from various leakage paths of the photocell.
When light irradiates the device, a current will be generated in the device, that
is the photogenerated current I. The Shockley under illumination becomes Eq. (5.1):
q (V − IRs ) ˇ (V − IRs )
J = Jsc exp − 1 + (5.2)
(˜ + cV ) k BT ˘ Rp
The active absorbing layer is sandwiched between two carrier-selective interfacial

layers that are deposited from solution or thermally evaporated. Finally, a refective
metal contact is evaporated to complete the device.
5.1.3 DYE SOLAR CELLS (DSCS)

DSCs as a semiconductor photovoltaic device can directly convert solar radiation
into electric current, which have been attracting researcher’s attention due to their
abundant sources, low cost, and easily manufacturing process [5]. Typically DSCs
consists of a semiconductor oxide (TiO2, ZnO, or SnO2) flm, a transparent conduc-
tive substrate, a dye, an electrolyte (iodide/triiodide), and a counter electrode (Pt or
carbon-based materials) coated on transparent conductive substrate [6].
The working principle of DSCs is based on the injection of electrons into nano-
structured metal-oxide (TiO2, ZnO) photoanodes from chemically adsorbed dye mol-
ecules, regenerated by a redox pair in a liquid electrolyte [7]. As shown in Figure 5.1c,
when the dye molecules adsorbed on the semiconductor flm are photoexcited by
the light, the electrons transition from the ground state to the excited state, and the
excited state electrons are injected into the conduction band of the semiconductor,
making the sensitizer in an oxidized state. When the electrons injected into the con-
duction band fow out from the photoanode to the counter electrode, the working
current is generated through the external circuit.
5.1.4 PEROVSKITE SOLAR CELLS (PSCS)

Perovskite is a ceramic oxide with a regular octahedron structure and a general
molecular formula of ABX3. “A” usually refers to the monovalent alkaline or organic
cations, such as CH3NH3+, CH3(NH2)2+, or Cs+; “B” is typically divalent metal ion
Pb2+ or Sn2+; and “X” represents halide ion Cl−, Br−, and I−. Perovskite solar cells
(PSCs) with small bandgaps, high extinction coeffcients, and high carrier mobility
have become a promising new photovoltaic technology [8].
In PSCs, the perovskite material acts as an absorbing layer that can absorb solar
photons to produce both electrons and holes, and the electron–hole pair separation
occurs under the internal electric feld. The electrons transition from the valence
band of perovskite to the conduction band and the corresponding holes are left in the
valence band, and electrons and holes are collected at each electrode, respectively.
Finally, generated the current in the external circuit and completed the conversion of
light energy to electric energy. Its basic working principle is shown in Figure 5.1d.
74
FIGURE 5.1 (a) Schematic diagram of PN-junction for the crystalline silicon solar cells. Adapted with permission from [1]. Copyright (2020) The
Authors, some rights reserved; exclusive licensee [The Royal Society of Chemistry].) (b) The architecture and materials (left) and current density versus
voltage curve (right) for the thin-flm solar cells [11]. Copyright (2016) WILEY-VCH. (c) Structure and schematic diagram of charge transfer in dye solar
cells [12]. (Copyright (2019) WILEY-VCH.) (d) Energy band and component diagram of a typical perovskite solar cells [13]. Copyright (2016) Elsevier.
(e) Working mechanism of organic solar cells [14]. Copyright (2016) Elsevier.
2D Nanomaterials
5.1.5 ORGANIC SOLAR CELLS (OSCS)

Organic solar cells (OSCs) with easy preparation, lightweight, low cost, strong fex-
ibility, environmental friendliness, etc. have been developed rapidly in recent years
[9,10]. And it mainly uses photosensitive organic compounds as semiconductor mate-
rials to generate voltage and current by photovoltaic effect.
OSCs absorb light energy and convert it into electricity. As shown in Figure 5.1e,
the main working principle can be divided as (a) light absorption, (b) exciton trans-
port, (c) exciton dissociation, and (d) charge transport and collection [10]. When the
OSC device is exposed to the sunlight, the donor material in the active layer absorbs
photons and produces excitons. The exciton diffuses to the interface of the donor and
dissociates, and the electron jumps into the acceptor material and the holes remain in
the donor material. The electrons and holes then migrate to the cathode and anode,
respectively, and eventually form a photocurrent in an external circuit.
5.2 FUEL CELLS

Fuel cells are a variety of galvanic cells with an open system, where the electrode
(both anode and cathode) is just the charge transfer media and the active materials
for the redox reaction are transported from outside. Using pure hydrogen as the fuel
that successful converts the chemical energy into electric energy while causing little
pollution. Usually, fve major types of fuel cells can be distinguished by the type
of electrolyte: alkaline fuel cell (AFC), phosphoric-acid fuel cell (PAFC), molten-
carbonate fuel cells (MCFCs), solid-oxide fuel cells (SOFCs), and proton-exchange
membrane fuel cell (PEMFC).
5.2.1 ALKALINE FUEL CELLS (AFCS)

The AFCs were the frst type of fuel cells to be put into the practical service. By
employing liquid alkaline solution as electrolytes (aqueous KOH), hydrogen as fuel,
inexpensive Ni or Ag as catalysts, the AFCs can convert the H2 gas directly into elec-
tricity [15,16]. As shown in Figure 5.2a, the H2 directly reacts with OH− to generate
water and electrons (hydrogen oxidation reaction) on the anode, and the electrons gen-
erated at the anode are transferred to the cathode through an external circuit, where
the oxygen reduction reaction of O2 reacts with H2O to generate OH−. The direction
of the reactions on the electrodes is opposite to that in alkaline water electrolysis.
The overall reactions are given by:
Anode: H2 + 2OH− → 2H2O + 2e−

Cathode: 1/2O2 + H2O + 2e− → 2OH−
The overall reaction: H2 + 1/2O2 → H2O
5.2.2 PHOSPHORIC ACID FUEL CELLS (PAFCS)

PAFCs are one of the most practical fuel cells, which used concentrated phosphoric
acid (95% ~ 100%) as electrolyte, Pt or Pt alloy supported on carbon as catalyst, natu-
ral gas or methanol conversion gas as raw material, and the working temperature is
76
FIGURE 5.2 (a) The essential structures of alkaline-based fuel cells. Adapted with permission from [27]. Copyright (2021) The Authors, some rights
reserved; exclusive licensee [Elsevier].) (b) The structure and working principle of the PAFCs [17]. Copyright (2020) Elsevier. (c) A schematic diagram
of molten-carbonate fuel cells [20]. (Copyright (2012) Springer-Verlag.) (d) The schematic of three-type SOFCs according to the different types of the
electrolyte ion conduction: (a) oxygen ion conductor (O-SOFC); (b) proton conduction (H-SOFC); and (c) mixed ion conductor [21]. Copyright (2020)
Springer-Verlag. (e) The essentials structure of proton-exchange membrane fuel cells [28]. Copyright (2020) Elsevier.
2D Nanomaterials
150°C ~ 210°C, the power generation effciency is about 40% [17,18]. Commonly, the
PAFCs consist of bipolar plants, gas diffusion layers, catalyst layers, and a phosphate
acid electrolyte layer (Figure 5.2b).
The working process is as follows: hydrogen fuel is frst added to the anode, and
then oxidized into protons under the catalyst. Two free electrons are released at the
same time. Hydrogen protons combine with phosphoric acid to form phosphoric acid
protons and move to the anode electrode. At the same time, electrons move to the
anode electrode, while hydrated protons move to the cathode through phosphoric
acid electrolyte. Therefore, on the anode electrode, electrons, hydrated protons, and
oxygen generate water molecules under the action of catalyst [18]. The specifc elec-
trode reaction is expressed as follows:
Anode: H2 + 2OH− → 2H2O + 2e−

Cathode: 1/2O2 + H2O + 2e− → 2OH−
The overall reaction: H2 + 1/2O2 → H2O
5.2.3 MOLTEN CARBONATE FUEL CELLS (MCFCS)

Generally, the MCFCs are composed by a porous Ni/Al(Cr) as anode, NiO as cath-
ode, and bicarbonate or alkaline carbonate as electrolyte. Compared with low-
temperature fuel cells, the MCFCs operate at 600°C–700°C, which eliminates the
need for the noble catalysts such as Pt [19].
The essential working process of MCFCs is the fuel oxidation and redox process
as shown in Figure 5.2c [20]. CO2 is used to produce carbonate ions in the cell, i.e.,
the ionic conductor in the electrolyte. The fuel and oxidant gases fow through the
anode and cathode channels. The electrochemical reaction includes the formation of
( )
the carbonate ion CO3 2− at the cathode and transporting the carbonate ion to anode
through the molten carbonate mixture.
At the cathode, O2 and CO2 in the oxidant react with electrons to produce CO3 2−.
CO3 2− in the electrolyte moves directly from the cathode to the anode, and H2 react
with CO3 2− at the anode to generate CO2, H2O, and electrons. The electrons are col-
lected by the collector and fowed through the external circuit to complete the reaction.
Cathode: 1 / 2O2 + CO2 + 2e − ° CO3 2−

Anode: H 2 + CO3 2− ° CO2 + 2e − + H 2 O
Overall reaction: H2 + 1/2O2 → CO2 + H2O
5.2.4 SOLID OXIDE FUEL CELLS (SOFCS)

SOFCs are a kind of electrochemical power generation device with all-ceramic struc-
ture. Generally, cermet oxides with fuorite structure and perovskite structure are
used as electrolytes, which can avoid the possible loss or corrosion of the electrolyte
[21,22]. The ions conducted by electrolytes can be oxygen ions and protons, and the
working temperature of the SOFCs is as high as 400°C–1,000°C, and many fuels can
be used directly as fuel without precious metals as catalysts, such as pure hydrogen,
methane, alcohol, natgas, and marsh gas [23].
78 2D Nanomaterials
According to the different types of electrolyte ion conduction, SOFCs can be

divided into three categories: oxygen ion conductor (O-SOFC), proton conduction
(H-SOFC), and mixed ion conductor in Figure 5.2d [21,24]. And the electronic con-
ductivity of the electrolyte needs to be negligible to avoid voltage loss and the pos-
sibility of short circuit.
For the O-SOFCs transportation mode, O2 from the air is adsorbed on the cathode
surface and electrons are reduced to oxygen ions, and O2− is transferred to the anode
through the electrolyte layer, while the fuel is oxidized at the anode to generate elec-
trons, and then transferred to the cathode via the external circuit. When the fuel gas
is hydrogen, the corresponding electrochemical reaction is:
At the anode:
H2 + O2− → H2O + 2e−
At the cathode:
1/2O2 + 2e− → O2−
The overall reaction:
H2 + 1/2O2 → H2O
For H-SOFCs transportation mode, the protonation reaction of water and hydrogen
occurs at the anode, and hydrogen ions are transferred to the cathode through the
electrolyte, and react with oxygen ions to produce water. The corresponding electro-
chemical reaction is as follows:
At the cathode:
H2 → 2H+ + 2e−
At the anode:
1/2O2 + 2H+ + 2e− → H2O
The overall reaction:
1/2O2 + H2→H2O
For mixed ion conductor, the ions conduction occurs that depend on the different
conducting medium.
5.2.5 PROTON-EXCHANGE MEMBRANE FUEL CELL (PEMFCS)

PEMFCs have attracted signifcant attention as a promising clean energy source due
to their excellent characteristics of low operating temperature (typically from 25°C
to 90°C), fast start, no electrolyte loss, easy water discharge, long life, high specifc
power, and specifc energy [25].
For the PEMFCs system, hydrogen is oxidized at the anode and protons enter
into the electrolyte and are transported to the cathode [26]. As shown in Figure
5.2e, hydrogen gas fows and diffuses into the anode along with the collector
channel, then split into two hydrogen protons and two electrons. Protons penetrate
through the electrolyte membrane and reach the cathode, oxygen reacts with pro-
tons to form water, and electrons generate current in the process of arriving from
the cathode to the anode. In this process, the electrolyte membrane provides the
reaction place, both the effective contact between the electrode and the electrolyte
membrane and the catalyst are the guarantee of the fowing of the proton and
electron.
At the anode, hydrogen gas (H2) is separated into two hydrogen protons (H+) and
two electrons:
H2 → 2H+ + 2e−
At the cathode, the supplied oxygen reacts according to:
O2 + 4e− → 2O2−
Electrons fow in the external circuit during these reactions. The oxygen ions react
with protons to form water:
O2−+ 2H+ → H2O
5.3 RECHARGEABLE BATTERIES

The increasing energy crisis and environmental pollution caused by fossil fuel
combustion have prompted people to deeply explore effcient and renewable
sources [29]. Clean and renewable energies (such as water, wind, or sunlight) play
an important role in resolving the increasingly serious environmental problems.
However, renewable energy is inherently intermittent, and limited by time and
place. To improve the intermittency of renewable energy production, rechargeable
secondary batteries as the green energy resources have been considered as a prom-
ising option for grid-level stationary energy storage systems and transportation
technology [30,31].
5.3.1 ORGANIC RECHARGEABLE METAL ION BATTERIES

5.3.1.1 Alkali Metal Ion Batteries
Alkali metal ion battery mainly includes lithium-ion battery, sodium-ion battery,
and potassium ion battery. Compared with the traditional commercial batteries,
such as lead-acid, metal hydride, and alkaline batteries, LIBs have the advan-
tages of long cycle life, high charge–discharge voltage and energy density, and
have been widely employed in portable electronic products, electric vehicles, and
large energy storage power stations [32,33]. However, the uneven distribution
and limited lithium resources have restricted the future application of lithium-ion
battery technology. The content of sodium (2.74wt %) and potassium (2.09wt %)
in nature is much higher than that of lithium (0.0017wt %), which reduces the
production cost to a certain extent. Moreover, the standard potential of sodium
(−2.71V vs. SHE) and potassium (−2.93V vs. SHE) is not very different from that
of lithium (−3.04V vs. SHE), ensuring the high specifc energy of sodium ion and
potassium ion batteries [31]. Therefore, the concept of sodium ion battery and
potassium ion battery has been put forward and studied as a potential substitute
for lithium ion battery.
Similarly with Li-ion batteries, sodium-ion batteries/potassium-ion batteries
(NIBs/KIBs) are also composed of positive and negative electrodes, electrolyte, and
80 2D Nanomaterials
FIGURE 5.3 (a) Schematic illustration of the commercial Li-ion battery (LiCoO2/graphite).
Adapted with permission from [32]. Copyright (2013) The Authors, some rights reserved;
exclusive licensee [American Chemical Society]. (b, c) The molar and weight salt/solvent
ratios in NaOTF-H 2O binary system [39]. Copyright (2017) WILEY-VCH. (d) The typical
schematic illustrations of Li-S batteries. Adapted with permission from [43]. Copyright
(2015) The Authors, some rights reserved; exclusive licensee [The Royal Society of
Chemistry]. (e) Schematic principle for metal-air batteries. Adapted with permission from
[45]. Copyright (2017) The Authors, some rights reserved; exclusive licensee [American
Chemical Society].
they use the same “rocking-chair”-type mechanism like LIBs do. Typically, a com-
mercial LIB is using graphite anode and transition metal oxide-based cathodes and
uses the “rocking-chair”-type mechanism [32]. And the corresponding process is
shown in Figure 5.3a.
During the charging process, Li+ was frst escaped from the LiCoO2, then fow
through the electrolyte to the electrolyte at the other end, and fnally inserted into
the layered graphite anode material. To achieve charge balance, electrons must pass
through an external circuit from the positive electrode to the negative electrode. At
this time, a large number of lithium ions gathered on the anode material temporarily
formed a lithium-rich state, while the positive electrode is in a lithium poor state.
The whole charge and discharge process can be summarized as follows:
Cathode: LiCoO2 → Li1-xCoO2 + xLi+ + xe−

Anode: 6C+ xLi+ + xe− → LixC6
Overall reaction: LiCoO2 + 6C → Li1−xCoO2 + Li xC6
5.3.1.2 Multivalent Rechargeable Batteries

The rapid development and urgent demand for consumer electronics, electric trans-
portation technologies, and grid-scale energy storage have forced the enhanced
improvement capacity storage for rechargeable batteries. Multivalent rechargeable
batteries (Zn/Mg/Ca/Al) are considered as another promising alternative energy stor-

age advice that has gained considerable attention due to their abundant resources,
high volumetric energy density, and multielectron redox capability [34].
5.3.2 AQUEOUS RECHARGEABLE METAL ION BATTERIES (ARMIBS)

Aqueous rechargeable metal ion batteries (ARMIBs) have recently attracted exten-
sive attention as promising energy storage systems due to their high safety, low cost,
easy-to-assemble, high ionic conductivity, and environmental friendly [35]. These
features ascribe to the use of aqueous electrolyte with non-fammability, high ionic
conductivity, low interface resistance, and stable voltage window [36,37]. According
to the different ionic valence states, the ARMIBs can be roughly divided into two
types: aqueous monovalent metal ion batteries (M = Li+, Na+, K+ and Cl−) and aque-
ous polyvalent metal ion batteries (M = Zn2+, Mg2+, Ca2+, Al3+).
The fundamental mechanism of ARMIBs is similar to the commercial recharge-
able organic metal ion battery systems, which transfers electrons through an external
circuit between two electrodes and metal ions through the electrolytes [37]. However,
the narrow electrochemical stability window of aqueous electrolyte restricts the selec-
tion of electrode materials, the side reactions between the active electrode materials
and the aqueous solution to generate hydroxide and H2 tremendous affect cycle abil-
ity of ARMIBs, and metallic dendrite formation also made the metal ion extraction/
insertion process more complicated [37,38].
To solve conventional hydrogen evolution for the ARMIBs, the development of
the “water-in-salt” electrolyte systems has successfully expanded the electrochemi-
cal voltage window up to 3 V by using high concentration electrolytes to avoid the
direct interaction between electrode and water, and eliminates the free water mol-
ecules in the solution [38,39].
5.3.3 METAL-SULFUR BATTERIES (MSBS)

Metal-sulfur (Metal = Li, Na, K, Mg, Al) batteries (MSBs) are the most promising
battery technologies due to high energy density, abundance of elements, low costs,
and less toxic [40,41]. Sulfur is considered as a promising cathode material because
of their earth abundant resources, a high theoretical specifc capacity of 1,675 mAh
g−1 (based on a two-electron-transfer reaction mechanism), which has promoted the
rapid development of MSB systems [42].
Li-S batteries are the most studied feld for a long time, in which the lithium metal
anode offers a high energy density (3,681 mAh g−1), and the sulfur cathode provides
a theoretical energy density (1,675 mAh g−1), respectively. So the theoretical capacity
of Li-S battery is as high as 1,167 mAh g−1. Here, we take Li-S batteries as example
to explore the mechanism.
The mechanism of Li-S battery is between LIBs and Li-O2 battery to some extent
[42,43], which is based on a conversion or integration reaction of S8 and Li+ at the
cathode interface. As shown in Figure 5.3d, in the discharging process, lithium ions
and electrons are produced by oxidation reaction of lithium anode. The positive sul-
fur gains electrons and the reduction reaction forms lithium sulfde. In the positive
82 2D Nanomaterials
electrode reduction process, the S8 molecule frst opens the ring long chain Li2S8
molecule. With the progress of reduction reaction, the long chain Li2S8 molecule
is further reduced to the short chain polysulfde ion Li2Sx (4 ≤ x ≤ 6), and fnally
is reduced to Li2S2/Li2S. In the charging process, on the contrary, Li2S2/Li2S goes
through multiple steps of oxidation reaction to fnally generate elemental sulfur
and generate electrons and lithium ions. The electrons return to the lithium anode
through external circuit, and the lithium ions are also transferred to the metal lith-
ium anode through electrolyte, where they get electrons and are reduced to lithium
elemental.
5.3.4 METAL-AIR BATTERIES (MABS)

Metal-air batteries (MABs; metals such as Li, Na, K, and Zn) with an open cell struc-
ture, large storage capacity have received revived interest recently. These systems
combine the design characteristics of conventional rechargeable secondary batteries
and fuel cells in which used a metal as negative electrode, neutral or alkaline solvents
as electrolytes, oxygen as cathode active materials that breathed from ambient atmo-
sphere. As the cathode material is directly replaced by O2 in the air, the total weight
of the MABs can be greatly reduced, thus greatly improving the energy density of the
battery. Different types of MABs can be found in recent researches, including Li-air,
Na-air, K-air, Zn-air, Mg-air, and Al-air batteries [44,45].
Generally, the reaction for the MABs is considered as a redox process (Figure 5.3e).
During the discharging process, the metal element is oxidized at the anode, and O2
from the surrounding atmosphere is reduced on supported electrocatalysts in the
cathode as illustrated in Figure 5.3d, and the corresponding reaction equations are
as follows:
Anode: M ↔ Mn+ + ne−

Cathode: nO2 + 4ne− + 4Mn+ ↔ 2M2On
where M presents the metal and n is the oxidation number of the metal ion.
5.4 SUPERCAPACITORS
Supercapacitors as high electrochemical energy storage devices are widely used in
heavy electric vehicles and other types of hybrid batteries, which require high power
due to their fast charge/discharge rates (charging times ranging from seconds to
minutes), excellent electrochemical performance, high reversibility, and long cycle
life [46].
Like batteries, supercapacitor is also composed of two electrodes (an anode and a
cathode), an electrolyte (usually is aqueous or organic solution), and a separator that
allows ions to transfer and stores the charge through adsorption of ions from electro-
lytes on electrode surfaces. Generally, the supercapacitors can be divided into three
types including electric double-layered capacitors (EDLCs), pseudocapacitors, and
asymmetric supercapacitors (ASCs) [47].
5.4.1 ELECTRIC DOUBLE LAYERED CAPACITORS

EDLCs are the simplest and most commercial supercapacitor in which stores charge
at the interface between electrode and electrolyte via electrostatic charge adsorption,
thus forming the electrical double layers [48].
As we all know, the electrode materials play an important role in providing excel-
lent electrochemical performance for supercapacitors. For EDLC electrodes, carbon-
based materials (including the active carbon, carbon nanotubes, carbon aerogels,
porous carbon, grapheme, and grapheme oxide) are the commonly used materials due
to their high specifc surface area, appreciable electrochemical stability, nontoxicity,
open porosity, and high electrical conductivities [49]. The specific capacitance of an
EDLC is strongly dependent on the accessible surface area of the electrode materials
and surface properties of the carbon materials, which stored energy at the interphase
between electrode and solution to form an electrical double-layer (Figure 5.4a) [49].
The capacitance of EDLCs can be estimated as following Eq. (5.3):
˜r˜ 0
C= A (5.3)
d
where εr is the relative electrolyte dielectric constant, ε0 is the permittivity of vac-
uum, A is the specifc surface area of the electrode, and d is the effective thickness of
charge separation distance layer (the Debye length). According to the physical elec-
trostatic processes, the formation and relaxation of the electric double layer (EDL)
occur within 10 −8 s, which is shorter than that of in pseudocapacitor (10 −2–10 −4 s). The
charge/discharge process of EDLCs only store charge at the interface between elec-
trode and electrolyte via charge rearrangement without any redox reactions (Faradaic
reactions). Thus, the EDL can respond to change of potential immediately.
5.4.2 PSEUDOCAPACITORS
Pseudocapacitors (known as Faraday capacitors or gold capacitors) have a signifcant
contribution in the energy storage felds, which can store charge by a fast and revers-
ible redox reaction on the surface or near the surface of the material. Compared with
EDLCs, pseudocapacitors perform higher capacitance due to the additional charges
transferred within the defned potential. Generally, metal oxides and conductive
polymers are the commonly used electrode materials for pseudocapacitors due to
their high energy densities and high capacitance.
Commonly, the pseudocapacitors are classifed into three types: (a) underpoten-
tial deposition, (b) redox pseudocapacitance (such as MnO2, RuO2, V2O5, or con-
ductive polymer), and (c) intercalation pseudocapacitance (Nb2O5), corresponding
processes are illustrated in Figure 5.4b [50]. The mechanism of pseudocapacitors
can be summarized as a reversible redox reaction at the interface of the electrode/
electrolyte, which is accompanied by the charge transfer, thus achieving the charge
storage. During the energy storage process of the pseudocapacitor, a rapid redox
reversible reaction will occur on the surface of the electrode active substance, and
a large amount of charge or ion transfer can be carried out in a short time [51].
84
FIGURE 5.4 (a) The construction of the electric double-layer capacitors [56]. Copyright (2006) Elsevier B.V. (b–d) Three types of reversible redox
mechanisms for the pseudocapacitance: (b) underpotential deposition, (c) redox pseudo-capacitance, and (d) intercalation pseudocapacitance. Adapted
with permission from [50]. Copyright (2014) The Authors, some rights reserved; exclusive licensee [The Royal Society of Chemistry]. (e) The typical
schematic construction of an asymmetric supercapacitor [55]. Copyright (2017) WILEY-VCH.
2D Nanomaterials
Different physical processes and with different types of materials determine these
three different mechanisms, detailed processes are as below:
When metal cation is higher than its redox point, it forms a monolayer adsorption
on the surface of another metal, which is the occurrence of underpotential deposi-
tion. And one typical example of underpotential deposition is the deposition of Pb2+
on the surface of Au [52]. Redox pseudocapacitance occurs when the electrolyte ions
or electrons adsorbed on the surface or near the surface of materials, the metal oxides
materials are often accompanied by redox reactions, while conductive polymer mate-
rials, charge storage is realized by absorbing N-P type doping or dedoping process
through the abrupt conjugate effect of polymer chain [53]. The third intercalation
pseudocapacitance can be accompanied by rapid Faraday charge transfer when ions
are embedded on the surface, interlayer, or channels of an active material without
phase transformation reactions.
5.4.3 ASYMMETRIC SUPERCAPACITORS (ASCS)

ASCs (also known as hybrid capacitors) are devices composed of two electrical lay-
ers with complementary electrochemical windows and pseudocapacitor electrode
material. It covers a wider working voltage window that can signifcantly improve
the energy density [54,55].
According to the defnition of pseudocapacitor behavior, the discussion between
“asymmetric” and “hybridization” only involves devices, not electrodes [47,54]. The
term “hybrid capacitor” is generally considered to describe a situation in which the
electrodes have two different storage mechanisms: a capacitive storage mechanism
and a battery-type storage mechanism (Figure 5.4e). Unlike traditional supercapaci-
tors, ASCs assembled using two different electrode materials, namely battery-type
Faradaic cathode electrode and capacitor-type anode electrode. Based on the differ-
ent electrode materials, the charge storage behaviors can be divided into three types:
EDLC//pseudocapacitive type, reversible redox type, and EDLC//battery type.
5.5 CONCLUSION
Electrochemical energy storage technologies can effectively reduce the traditional
energy consumption of fossil fuels, avoid the restriction of renewable resources by
geographical and environment, which can provide electricity directly when it is
needed. Electrochemical energy devices (EEDs) are considered as an alternative
energy resource in making renewable energies effective and effcient, while creating a
more sustainable and environmentally friendly society. Commonly, the EEDs include
solar cells, fuel cells, rechargeable batteries, and supercapacitors. The energy storage
and conversion mechanisms are different: solar cells collecting and converting the
solar energy into electric current, fuel cells and rechargeable batteries generated the
electrical energy via redox reaction (fuel cells are operated in an open system, and
batteries are closed system), and supercapacitors delivered the energy via adsorp-
tion or redox reaction. Currently, the solar cells are the most pollution-free in energy
storage devices and have the largest market space, but so far limited by the energy
conversion rate and stability. Rechargeable batteries are the most application markets’
86 2D Nanomaterials
energy storage device with the widest market share and have established a certain
market position. Whereas supercapacitors with their fast charge/discharge character-
istics have occupied a certain market in some electronic devices, electric vehicles,
shape memory applications, and light rails. Fuel cells are still in the development
process and are looking for applications that are suitable for entering the market.
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6 Theoretical
Considerations of 2D
Materials in Energy
Applications
Harsha Rajagopalan
Vellore Institute of Technology
Sumit Dutta and Sourabh Barua
Birla Institute of Technology
Pawan Kumar Dubey

Ariel University
Jyotsna Chaturvedi
Indian Institute of Science
Laxmi Narayan Tripathi

CONTENTS
6.1 Introduction ....................................................................................................90
6.2 Calculation of Electronic Properties of Transition Metal
Dichalcogenides (TMDCs) from First Principles........................................... 91
6.2.1 Density Functional Theory or First Principles Calculation................ 91
6.2.2 Computational Details ........................................................................92
6.2.3 Results and Discussions......................................................................92
6.3 Finite-Difference Time-Domain (FDTD) and Application for Field
Enhancement in Two-Dimensional Materials ................................................ 95
6.3.1 The Finite-Difference Time-Domain Method.................................... 95
6.3.2 Field Enhancement in General in Nanogap Antennas........................96
6.3.3 Application of Field Enhancement for Energy Application
Using 2D Materials............................................................................. 99
6.4 Applications of 2D Materials in Piezoelectric Devices.................................101
6.5 Applications of 2D Materials in Hydrogen Production:
Photoelectrochemical Cell and Photocatalytic Water Splitting.....................102
DOI: 10.1201/9781003178453-6 89
90 2D Nanomaterials
6.5.1Solar Energy to Chemical Energy Effciency, η without

External Bias......................................................................................104
6.5.2 Solar Energy to Chemical Energy Effciency, ηw/o with
External Bias......................................................................................104
6.6 Conclusion .................................................................................................... 105
Acknowledgements................................................................................................ 105
References.............................................................................................................. 106
6.1 INTRODUCTION
The feld of two-dimensional (2D) materials got much attention after the discovery
of graphene leading to a noble prize.1 Bulk 2D materials can be used to prepare thin,
mono/few-layer thick transition metal carbonitrides (MXenes), carbides, nitrides,
oxides, and transition metal dichalcogenides (TMDCs).2,3 TMDCs are a class of 2D
materials with the chemical formula MX2, where M represents a transition metal
and X represents a chalcogen.4,3 TMDCs are one of the most studied materials that
have been isolated in monolayer form and show promising results like direct band-
gap, which is a desired optoelectronic property.5,6 Molybdenum- and tungsten-based
TMDCs are quite popular as semiconductors, with bandgap ranging from visible to
near-infrared.7 Different types of 2D materials are widely used for the study of energy
storage and energy conversion devices. They mainly include solar energy storage,
photovoltaics, piezoelectric, and thermoelectric devices.8,9 Nanostructured 2D mate-
rials possess unique properties like high surface areas, tunable bandgap leading to
superior optoelectronic properties. The fact that the 2D materials can mechanically
be exfoliated from bulk single crystal and transferred to any desired substrates2,10
make them invaluable. Raman spectroscopy is an important tool to characterize the
number of layers of 2D materials.11 Graphene is one of the heavily used 2D materials
for the energy application industry due to its unique properties like large surface area
and a high electrochemical performance rate. The discovery of graphene, experi-
mentally by Andre Geim and Konstantin Novoselov in 200412 highlighted the 2D
materials for various applications. Since graphene doesn’t have any bandgap, much
effort has been made to fnd 2D materials that have a bandgap.5
In this work, we introduce several theoretical tools and theoretical principles for
energy applications of 2D materials. To understand the electronic properties, we
discuss the density functional theory or the frst principle approach. We then dis-
cuss the Finite-Difference Time-Domain method (FDTD) or Yee’s method (named
after Kane S. Yee). The FDTD is simple yet conceptually elegant and frequently
used full-wave techniques to solve problems in electromagnetics.13–15 It incorporates
the time-domain method technique, unlike the others, for a wide frequency range.
Maxwell equations can characterize electromagnetic waves. Therefore, to solve an
electrodynamical problem, we need to solve the four Maxwell equations. Finally,
we review the piezoelectric and H2 evolution reaction (HER) due to photoelectro-
chemical (PEC) applications of 2D materials. Under mechanical stress, piezoelectric
materials undergo electrical polarization. We have illustrated this by an example of a
piezoelectric device consisting of metal electrodes and a monolayer of MoS2.16 Thus,
piezoelectric application of 2D materials opens new avenues for energy application.
2D Materials in Energy Applications 91
Hydrogen is a source of clean energy and has tremendous potential to replace the
fossil fuels. It could be a sustainable and environment-friendly source of energy.
Recently, 1D and 2D nanostructures were used as a catalyst for the generation of H2
from water or organic molecules. This process of generation of H2 where the genera-
tion of H2 is facilitated by 2D materials in the presence of UV/visible radiation is
known as photocatalysis.17 The hydrogen evolution can easily happen through water
splitting. The separation of H2 and O2 in water requires a Gibbs free energy change,
∆G0 of 237 kJ mol−1 or wavelength, 1,100 nm corresponding to energy 1.23 eV.18 The
photocatalytic water splitting has great potential as an up-scaled, cost-effective, and
green source of energy in the form of H2. The only requirement for the semicon-
ductors to be used as photocatalysts is the appropriate bandgap (1.6–2.4 eV), cor-
rosion resistance, stability, and recyclability.19 A photocatalytic water splitting is
important due to the presence of water as an abundant, clean, renewable, and natural
source. The solar to chemical energy conversion effciency in the water splitting
can be enhanced signifcantly by the application of heterogeneous and non-precious
metal electrocatalysts such as metal selenides and metal sulfdes.20 Furthermore, for
upscaled usage, integrated PEC cell devices can be made scalable to large areas such
as 64 cm−2.21
6.2 CALCULATION OF ELECTRONIC PROPERTIES OF TRANSITION

METAL DICHALCOGENIDES (TMDCs) FROM FIRST PRINCIPLES
Here we choose tungsten selenide (WSe2) as a representative material to demonstrate
how density functional theory (DFT) can be used to obtain important results, e.g.,
the evolution of the electronic band structure with thickness in TMDCs. For the DFT
calculations, we have chosen the open-source code, Quantum ESPRESSO (QE),22,23
which uses the plane wave method of DFT and pseudopotentials.
6.2.1 DENSITY FUNCTIONAL THEORY OR FIRST PRINCIPLES CALCULATION

Ab initio/DFT calculations are based on the fact that the electron density contains
all the necessary information about the ground state of any electronic system. This
was shown by Hohenberg and Kohn in two theorems,24 which form the basis of DFT.
According to the two theorems, any many-body problem with N electrons, involving
3N spatial coordinates, can be reduced to a simple problem involving only three spa-
tial coordinates when expressed in terms of the electron density. Thus, in DFT, rather
than solving the practically unsolvable many-body Schrodinger equation, the single-
particle Kohn–Sham equations are solved. Once these single-particle wave functions
are found out, the electron density and from it, all properties of the solid can be
known. The Kohn–Sham equations require an exchange-correlation functional to
obtain the exact electric potential for which the equations are to be solved. This
exchange-correlation functional is key to DFT and different methods exist to fnd the
best possible exchange-correlation functional, like the Local Density Approximation
and the Generalized Gradient Approximation (GGA). One such example of a GGA
exchange-correlation functional is the Perdew-Burke-Ernzerhof (PBE) exchange-
correlation functional,25 which we have used here in our calculations.
92 2D Nanomaterials
Therefore, by using DFT, calculating the electronic properties of any solid, e.g.,
the Fermi energy, bandgap, and density of states, is possible, even before the solid is
developed in the laboratory. So, as new materials such as TMDCs were discovered,
scientists could study them extensively using DFT and arrive at important conclu-
sions only by computation.
Using DFT, we can fnd the band structure of complex molecules and solids and
account for the changes in the band structure while varying other physical proper-
ties associated with the system such as strain, electric feld, and doping. For exam-
ple, the effect of strain on the bandgap in WSe2 and WS2 flms, and its conversion
from indirect to direct bandgap due to wrinkle formation caused by strain have been
reported.26
6.2.2 COMPUTATIONAL DETAILS

All the electronic structure calculations in this text are performed within the DFT
framework, using the open-source code Quantum ESPRESSO.22,23 The code uses
the Projector Augmented Wave method along with pseudopotentials. We use the
PBE exchange-correlation functional for the calculations. The energy cut-off for the
wavefunction has been set to 40 Ry and 80 Ry for bulk and monolayer calculation,
respectively. The k-point mesh size is set to 9 × 9 × 9 for the bulk and 9 × 9 × 1 for
the monolayer self-consistent (SCF) calculations. For the monolayer calculations, a
supercell with a vacuum of 15 Å is used. The vacuum is required so that interactions
between monolayers of repeating units are minimized otherwise this can lead to
artefacts in the calculated properties.
6.2.3 RESULTS AND DISCUSSIONS

Figure 6.1a shows the layered structure of bulk WSe2. The electronic band struc-
ture of bulk WSe2 is calculated using the unit cell shown in Figure 6.1b. The bulk
band structure is calculated from the frst principles along the k-path Γ-M-K-Γ of the
Brillouin zone and is shown in Figure 6.1c. The band diagram depicts the conduc-
tion band and the valence band separated by a signifcant bandgap. The bandgap is
the energy gap between the minima in the conduction band and the maxima in the
valence band. It is clear from the diagram that the minima in the conduction band
and the maxima in the valence band are not at the same k-point. This implies that the
bandgap is indirect in bulk WSe2. Semiconductors with an indirect bandgap are not
ideal for optoelectronic devices. In Figure 6.2a we show a monolayer of WSe2, and in
Figure 6.2b, we show the supercell used for the ab initio calculation of the properties
of WSe2. The electronic band structure of the monolayer WSe2 is calculated along
the k-path Γ-M-K-Γ of the Brillouin zone and is shown in Figure 6.2c. From the band
diagram in the monolayer, the minima in the conduction band and the maxima of
the valence band occur at the same point in k-space, which is the high symmetry K
point in this case. Thus, monolayer WSe2 is a direct bandgap semiconductor, which
makes it suitable for optoelectronic devices. The bandgap in our calculation comes
out to be 1.63 eV.
2D Materials in Energy Applications
FIGURE 6.1 (a) Bulk WSe2 showing multiple layers. The grey atoms are tungsten (W), and the green atoms are selenium (Se). (b) The unit cell of bulk
WSe2 used for the DFT calculations. Bulk WSe2 has a 2H structure, i.e., the structure repeats after every two layers in the vertical (c-axis) direction. (c)
Electronic band structure of bulk WSe2. The Fermi level (FL) is set to zero in the band structure.
93
94
FIGURE 6.2 (a) Monolayer of WSe2 showing a layer of W atoms (grey) sandwiched between two layers of Se atoms (green). (b) The unit cell (super-
cell) of monolayer WSe2 used for the DFT calculation. A vacuum of 15 Å was added above the WSe2 layer in the supercell to prevent artifacts arising
from the interaction between two repeating monolayers. (c) Electronic band structure of monolayer WSe2. The Fermi level (FL) is set to zero in the band
structure. From the band diagram, the conduction band minima and valence band maxima are at the same k point, which is the K point here. (d) Plot of
the electrostatic potential (ionic potential plus Hartree potential) inside the supercell of the monolayer WSe2. The green line shows the fuctuation of the
potential with position along the c-axis of the supercell. The vertical magenta lines indicate the location of the ions in the supercell, which are shown in
2D Nanomaterials
the superposed image of the supercell at the top. The potential is plotted as energy and the Fermi energy is subtracted from it. Since the work function
of a semiconductor is the difference between the potential energy in the vacuum and the Fermi level, it can be read directly from our plot.
The work function of a semiconductor material is the separation between the

vacuum energy level and the Fermi energy in the semiconductor. The work func-
tion is a relevant quantity in semiconductors that are required for the calculation of
various properties, e.g., Schottky barrier height. Using DFT it is possible to calculate
the work function quite simply. After the self-consistent calculation, post-processing
allows the plotting of the electrostatic potential (sum of the ionic potential plus the
Hartree potential) in the supercell. We plot this for the monolayer WSe2 supercell in
Figure 6.2d.
The green line shows the variation of the potential with the position along the
c-axis in the supercell. For a guide to the eye, the positions of the various ions in
the supercell are marked by vertical magenta lines. Furthermore, we also superpose
the supercell structure on this plot to help understand the variation of the potential
with position better. Inside the cell, the potential varies periodically with the posi-
tions of the ions. In the vacuum region, it is fat as expected. The potential is plotted
in terms of energy, and we subtract the Fermi energy from the potential energy in
the plot. So, the zero lines on the energy scale signify the Fermi level. Since the
work function of a semiconductor is defned as the difference between the vacuum
potential energy and the Fermi level, this can be read from the graph in our case and
comes to be 4.65 eV.
6.3 FINITE-DIFFERENCE TIME-DOMAIN (FDTD)

AND APPLICATION FOR FIELD ENHANCEMENT
IN TWO-DIMENSIONAL MATERIALS
6.3.1 THE FINITE-DIFFERENCE TIME-DOMAIN METHOD
FDTD or Yee’s method incorporates the time-domain method technique, which
provides advantages over other methods because it can be used for a wide frequency
range. Maxwell equations can characterize electromagnetic waves. Therefore, to
solve electrodynamics, we need to solve the four Maxwell equations. The Maxwell
equation is continuous, but there is no general way of solving the Maxwell equa-
tion; rather, one needs to be more precise about the problem and the inputs. In
other words, one needs to solve the Maxwell equation on every point, even for the
most straightforward geometry to study, how the feld components are propagat-
ing with time (or how fast the felds are changing at each point). Thus, there is
no closed-form solution of the Maxwell equation. Here FDTD simulation tech-
nique comes into the picture, which simplifes the equation solving methodology
by discretizing the Maxwell equation using central-difference approximations to
space and time partial derivatives. Thus, using the FDTD method for Maxwell's
equations, any arbitrary media types (either in 2D or 3D) can be modeled, includ-
ing inhomogeneous and lossy, frequency-dependent (dispersive), anisotropic, bi-
anisotropic, chiral, or nonlinear media. Mathematically 1D Maxwell’s equation can
be written as13–15
˜E x 1 ˜H y
= (6.1)
˜t  ˜z
96 2D Nanomaterials
°H y 1 °E x
=− (6.2)
°t µ °z
Here, symbols have their usual meaning. The two equations represent a plane wave
traveling on the z-axis. Considering a central difference approximation of the deriva-
tives and shifting E x and H y by half cell in space and half time in the time domain,
we get:
ˇ 1 nˇ 1
H yn k + − H y ˘ k −
E xn+1/ 2 ( k ) − E xn−1/ 2 ( k ) 1 ˘ 2 2
=− (6.3)
˝t  ˝z
˙ 1˘ n˙ 1˘
H yn+1 ˇ k + − H y ˇˆ k +
ˆ 2
n +1/ 2
2 = − 1 Ex ( k + 1) − Exn +1/ 2 ( k )
(6.4)
t µ Z
Here, superscript ‘n’ indicates time and means a time t = °t ˛ n. The term ‘n + 1’
means a one-time step later. The term in parenthesis ‘k’ indicates distance with
actual distance z = °x ˛ k . These two equations assume that E and H are interleaved
in both time and space. In particular, the left-hand side term in Eq. (6.3) says that the
derivative of the E feld at time n ˜ °t can be expressed as a central difference using
( ) ( )
E feld values at times n + 1 2 ˝ ˙t and n − 1 2 ˝ ˙t . The right-hand side term in Eq.
(6.3) approximates the derivative of the H feld at point k ˜ °x as a central differ-
( ) ( )
ence using H feld values at points k + 1 2 ˝ ˙x and k − 1 2 ˝ ˙x. This approximation
obliges us to calculate the value of E and H at the central and neighboring steps of
time ( n ˛ ˝t ) and space ( k ˛ ˝x ). Thus, this algorithm by Allen Tafov and JJ Simpson14
helps us calculate many values of E and H within the modeled geometry, and the
result after the simulation is collected in data form, which can be visualized as some
form of map or graph.
6.3.2 FIELD ENHANCEMENT IN GENERAL IN NANOGAP ANTENNAS

Characteristic properties of a single or array of nanoholes and nanoslit apertures in
metals for microwave, terahertz, and infrared frequency regions have long been pur-
sued subject, not only for its fundamental importance in spectroscopy (for instance,
in surface-enhanced Raman and extreme-ultraviolet generation) but also for bio-
molecule detection and next-generation photovoltaics. Recently, due to innovation
in nanotechnology, several metal nanostructures of different shapes and sizes have
been studied for surface plasmons.27 Phenomena like feld enhancement due to the
interaction of electromagnetic light with metallic nanostructures have gained atten-
tion from almost every aspect of the active research feld related to light-matter
interaction. Such metal nanoparticles are subwavelength scattering elements or can
be used as nearfeld antennas that can be effciently coupled to the material due to
increased effective absorption cross-section. Such phenomena can be observed in
different nanostructure arrangements, consisting of adjacent Nobel metal (gold and
silver) structures like nanorods or nanosphere separated by a nanoscale gap. Such a
system can strongly scatter, absorb, and even confne or squeeze the optical feld in
the nanometer dimension. The study of such light-matter interaction, which deals
with the generation, manipulation, and transmission of this excitation, is known as
‘plasmonics’. It is crucial to study the fundamental mechanism and theoretical model
of these interactions. One can explain the basic phenomena behind plasmonic by
considering localized surface plasmon resonances (SPRs; in simple terms, charge-
density oscillations) on the closed surfaces of the particles. Surface charge plasmons
are oscillatory charge waves in a thin metallic flm that can be excited by coupling
light into this metal flm at a suitable angle. When conduction electrons oscillate
coherently in response to incident light, they displace the nuclei's electronic arrange-
ment, giving rise to surface charge distribution. Here the Coulomb force between
positive and negative charges is acting as a restoring force. The frequency of the
oscillation is called the plasmon frequency.28
1
˙ 4˝Ne 2 ˘ 2
˜p = ˇ (6.5)
ˆ ° m*
Here, e is the electronic charge, N is the carrier density (number electron per unit
volume), and m* is the effective mass of the carrier. Each collective oscillation of dif-
ferent surface charge distribution has its resonant mode known as SPR. The electron
density, effective mass, particle’s shape, size, and the dielectric function of the mate-
rial determine the number of modes and the frequency of the oscillation.27 Under the
quasi-static limit, we assume that the particle size is much smaller than the wave-
length of the incident light.27
Here it is worth mentioning that some applications like enhanced nonlinear opti-
cal microscopy or near feld Raman microscopy need suffciently large feld enhance-
ment. For such cases, aperture-less and sharp tip nanostructures like nanorods tips
or bow-tie-shaped structures are more valuable than structures like nanosphere.30 An
elongated structure like a metal nanorod has surface plasmons confned in two dimen-
sions, one along the length and the other across the width. When the light of proper
polarization is incident on it, the surface plasmons are excited in both directions,
giving rise to a longitudinal and transverse mode of oscillation (Figure 6.3b). Hence,
they have non-zero absorption coeffcients at two different wavelengths. A shift in
peaks was also observed if the aspect ratio of the nanorods was varied.31 As evident
1
from Eq. (6.5) ˜ p ° N 2 surface plasmons absorption effciency is affected by the
nanoparticle size. In a study related to UV–Vis absorption spectra of colloidal solu-
tions, it was observed that if we increase the particle size in the case of the gold nano-
sphere, the absorption is red-shifted.32 Ward et al. studied the theoretical approach of
variation of feld enhancement with gap width and found that the intensity increases
as the decrease in gap width ‘d’.33 This result was later confrmed by Garcia et al.,34
in which they studied the intensity variation with the gap width between the tip of
gold nanorods (similar to structure as shown in Figure 6.3d). Here we present a simi-
lar result in which we have observed that the feld intensity decreases exponentially
as we go away from the point of feld enhancement. The simulation was performed
using the FDTD package from Lumerical inc. Figure 6.3f(II) shows the variation
98
FIGURE 6.3 (a–d) represents a schematic diagram of the standard nanostructure shape used to study plasmons enhanced light-matter interaction.
Figures (a) and (b) are adapted with permission from Dubey et al.,29 Copyright (2019) Elsevier. (e) The schematic of simulated nanoslit to study the
effect of feld enhancement dependence on gap width. (f) Normalized intensity of incident light vs gap width for visible frequency range (I and II) and
terahertz frequency range (III and IV).
2D Nanomaterials
of normalized feld intensity with the distance away from the gap and for different
gap widths (2, 5, 10, and 50 nm) between the metallic (silver) slit. Figure 6.3f(I) was
simulated for the visible frequency range. On the other hand, Figure 6.3f(IV) was
simulated for the terahertz frequency range. In both cases, for suffciently larger gap
width (50 nm and 1 micrometer), there is minimal feld enhancement, and it is almost
constant as we go away from the surface of the slit.
6.3.3 APPLICATION OF FIELD ENHANCEMENT FOR ENERGY

APPLICATION USING 2D MATERIALS
Conventional solar cells were designed signifcantly thick to increase the absorption
path of incident light in the material. Such designs have not successfully created eff-
cient solar cells as the short minority carrier diffusion length compared to the over-
all thickness of material signifcantly reduced device effciency. Modern technology
leaped forward with the advent of 2D material like TMDCs, graphene as the photo-
voltaics (PV) material that has dramatically reduced the thickness of solar cell devices
with improved effciency. Utilizing Plasmonic nanoparticle for improved incident light
absorption is another milestone scientist has achieved recently. The hybrid structure
of 2D materials with metallic nanostructure uses phenomena like thermo-plasmonic
effect, scattering, absorption enhancement, and near feld enhancement for effcient
light energy harvesting. Such light-matter interaction has the potential to extend the
detection capabilities of semiconductors beyond their bandgap. For example, in the
thermo-plasmonic effect, plasmonic nanostructure generates plasmon-generated hot
electrons, moving in the semiconductor material, transferring their energy to other
electrons. Suppose these electrons have enough energy to overcome the Schottky bar-
rier of the metal-semiconductor boundary, in that case, the electron will inject into
the semiconductor's conduction band to generate current for photodetection.32 Authors
have suggested several designs in which nanoparticles can be embedded on the mate-
rial’s surface or within the semiconducting material to increase the coupling of the
incident light.33 The nanoantenna embedded on the surface of the semiconducting PV
material (Figure 6.4c) acts as a subwavelength scatterer that scatters the sunlight into
the thin absorber layer of the PV cell at some angle, thus increasing the path length
and absorption. Mathematically, we can illustrate this phenomenon using lamberts
beers law as follows: Let I fe be the intensity due to feld enhancement and L fe be the
distance travelled by the light inside the semiconductor material after the scattering
from the plasmonic nanoparticle, then the intensity I at the later distance is given by29
I = I fee −° ˝ L fe (6.6)
where α is the absorption coeffcient of the material. Let us further assume that I w , fe
is the intensity without any feld enhancement (in the absence of any plasmonic nano-
antenna). For the same fnal intensity I (assuming that most of the intensity has been
absorbed in the end of the path) and Lw , fe as the path length traveled by the incident
light, we get:
I = I w , fe ° e −˛ ° Lw , fe (6.7)
100
FIGURE 6.4 (a) The schematic diagram shows embedded silver nanoparticles on the material's surface. The nanoparticles scatter the light deep into
the medium, effectively increasing the path length and absorption. (b) This structure utilizes the near feld enhancement to couple light into the mate-
rial due to an increase in effective absorption cross-section. (c) Here corrugated metal back surface has been used instead of spherical nanoparticle.
When longer wavelength light penetrates the material, they interact with a tip-like metallic nanostructure giving comparatively more signifcant feld
enhancement and effcient coupling into the semiconductor material. (d) This fgure depicts the layer integration of silver nanoparticles with the material
and how the optical and electrical effects together improve the effciency of solar cell technology. Figure (d) is adapted with permission from Higgins
2D Nanomaterials
et al.35 Copyright (2018) AIP publishing.

Dividing Eq. (6.6) by (6.7), we get:
1 ˝ I fe ˇ
L fe − Lw , fe = ln (6.8)
˜ ˆ˙ I w , fe ˘
The term L fe − Lw , fe is the difference in path length. Since I fe > I w , fe the right-hand
side of the Eq. (6.8) is always greater than one, proving that plasmonic particles' use
facilitates more signifcant absorption within the material.
In addition to the hybrid structure mentioned above, the plasmonic ‘tandem’
geometry-based solar cell has also proven to be very effcient.36 In the plasmonic
tandem geometry, the different semiconductor material is stacked on the top of each
other separated by the metal flm with the plasmonic nanostructure. Some other
designs involve the coupling of sunlight into surface plasmon in quantum dot solar
cells.37 Such techniques are handy since it has fexibility in bandgap engineering of
the semiconductor by controlling the size of the semiconducting particle. Plasmonic
structures are becoming more and more involved in solar cell technology; hence,
we should expect to see several other plasmonic facilitated effcient hybrid solar cell
designs that may or may not be based on 2D materials.
6.4 APPLICATIONS OF 2D MATERIALS IN

PIEZOELECTRIC DEVICES
Piezoelectric current and voltage can be generated in 2D materials such as MoS2
after application of mechanical stress along x-direction.16 The authors16 found that
the voltage and current were positive (negative) with an increase(decrease) of strain.
When strain was applied in the x-direction with an increase of strain, positive volt-
age and current output are obtained. When the strain was decreasing negative output
was observed. This is an example of the conversion of mechanical energy to elec-
trical energy using 2D materials. The voltage response and current response were
found to be increased with the increase of the magnitude of the applied strain. The
peak current reached 27 pA at the applied strain of 0.64%. The output current and
voltage as a function of load resistance show constant output current for a load resis-
tance. Few kΩ till 1 MΩ while it decreases after a further increase of load resistance.
The mechanical to electrical energy conversion was stable for cyclic loading up to
0.43% strain at 0.5 Hz for 300 minutes.16 The piezoelectric output decreases with an
increase in the number of layers. We can conclude that the piezoelectric output (cur-
rent) is maximum for monolayers MoS2.
The piezoelectric charge polarization strongly depends on the direction of applied
strain in 2D materials. The coupling between polarization (Pi) and strain tensor (εijk)
can be quantifed to the frst order by the third-order piezoelectric tensor, eijk16
eijk = ( ˙ Pi / ˙˜ jk ) (6.9)
Here i, j, k are 1, 2, 3, corresponding to x, y, z axes, respectively.

102 2D Nanomaterials
6.5 APPLICATIONS OF 2D MATERIALS IN HYDROGEN

PRODUCTION: PHOTOELECTROCHEMICAL CELL
AND PHOTOCATALYTIC WATER SPLITTING
Electrochemical water splitting is inspired by natural light-driven chemical reactions,
i.e., photosynthesis (Figure 6.5). The evolution of O2 through photosynthesis follows
the Calvin–Benson cycle where light-driven (absorption of light (1.76–2.47 eV)) elec-
tron and proton transfer happen in the chloroplast (Figure 6.5b). Natural photosyn-
thesis happens to be the frst example of water splitting through light.
Figure 6.5 shows a comparative diagram for the mechanism of H2 evolution using
photochemical water splitting as opposed to O2 generation in photosynthesis. Both
processes occur in the presence of solar energy. In the classical photochemical cell
(Figure 6.5a), used for water splitting by Honda and Fujishima,38 a TiO2 electrode
was connected with a platinum electrode. When the surface of the TiO2 was irradi-
ated with visible light, a current was detected in the external circuit. Honda and
Fujishima suggested that the water could be decomposed into hydrogen and oxygen
by the visible light without any external voltage. They39 suggested the following reac-
tion pathways.
1. The generation of electron (e−) and hole (p+) pairs by absorption of photons
TiO 2 + 2h° ˛ 2e − + 2p+
2. The oxidation of water at the TiO 2 electrode
1
2p+ + H 2 O ° O 2 + 2H +
2
3. Reduction of Hydrogen at a platinum electrode
2e − + 2H + ° H 2
The overall reaction was
1
H 2O + 2h° ˛ + O 2 + H 2
2
A current of few mA fowed when the TiO2 electrode was irradiated with a 500 W
Xe lamp. The TiO2 electrode surface area illuminated by the authors38 was 1 cm2.
The estimated quantum effciency, i.e., the number of electrons generated per pho-
tons absorbed was 10%. The free energy change that occurred during the change
of one molecule of water to H2 and ½ O2 under standard conditions was given by
˜G = 237.2 kJ/mol, which corresponds to an energy of 1.23 eV.39 Therefore, to drive
this reaction with the help of a semiconductor, the materials must absorb solar energy
of more than 1.23 eV, i.e., wavelength less than or equal to 1,000 nm of light. This
solar energy is further converted into H2 and O2. This process requires the generation
of two electron–hole pairs per molecule of H2, i.e., 2 × 1.23eV = 2.46eV of energy.39
2D Materials in Energy Applications
FIGURE 6.5 (a) Pictorial representation of a classical photochemical cell; (I) absorption of irradiation of light (UV/Visible) (II) Absorption of photons
by the photocatalyst leads to the generation of electron/holes in the conduction and valence band (III). (b) Photosynthesis process in plants driven by
Calvin–Benson Cycle. The light-induced electron/proton transfer inside the chloroplast.
103
The photo-induced charge carriers (electrons and holes) must travel in the liquid.
The electron transfer process at the semiconductor/liquid junction suffers losses due
to kinetic overpotential and concentration needed to drive the HER.39 Therefore, the
energy needed to drive the HER reaction due to photoelectrolysis at a semiconductor
electrode is 1.6–2.4 eV. Thus, a water-splitting reaction needs semiconductors having
a bandgap of 1.6–2.4 eV.
6.5.1 Solar Energy to Chemical Energy Efficiency,

η without External Bias
The efficiency of conversion of solar energy to chemical energy39 is given by, η
J g µex Φ conv
η=
S
where Jg is the absorbed flux, µex is the excess chemical potential generated by
absorption of light, Φ conv is the quantum yield for absorbed photon, and S is the total
incident solar radiation (mWcm−2)
6.5.2 Solar Energy to Chemical Energy Efficiency, ηw/o with

External Bias
Some photoelectrode devices require an external bias to drive water electrolysis. In
PEC water splitting, photoelectrode devices require an external bias for water elec-
trolysis. The efficiency of such water splitting39 is given by
Jmp (1.23V − Vapp )

ηw / o = (6.10)
Pin
where Jmp is the externally measured current density and Vapp is the applied voltage
between the photoanode and the photoelectrode. The Pin is the power density dur-
ing illumination. The two criteria for good evolutions of hydrogen are (a) the cata-
lyst must generate more electrons and hole pairs and (b) catalyst must work for a
longer time scale, i.e., must be robust over a longer period for commercial applica-
tions. HER catalyst such as TMDC,40 which have been used as high-performance
materials to satisfy three main criteria—(a) They have active sites (e.g., edges), (b)
intrinsic catalytic activity, and (b) high conductivity. We can increase the number
of active sites by an increase of a load of materials on the electrode and improved
structuring exposes more active sites per gram.40 Furthermore, the efficiency of
H2 evolution can also be enhanced by the intrinsic activity of each site.41,42 The
use of plasmonic nanoparticles enhances the PEC water-splitting reaction.43,44
Relatively high overpotential of TMDC as compared to Pt electrodes possesses
a serious problem. This was overcome by doping of Mn in MoSe2 nanoflowers by
Vasu et al.45 The authors also claim that doping also enhanced the charge transfer
kinetics.
6.6 CONCLUSION
2D materials have an immense potential for application in a wide variety of felds.
DFT is very instrumental in understanding many of the properties of 2D materials.
It can calculate a wide variety of properties like the thickness dependence of band
structures, phase stability, catalytic properties for hydrogen evolution reactions, work
function, Schottky barriers, and so on. Moreover, it allows calculating properties
of new materials even before they are synthesized in the laboratory thus offering
a unique perspective to material scientists in designing new materials. Besides, 2D
materials are playing the lead role in modern thin and ultralight solar energy conver-
sion devices. For the lowest per watt cost and lowest gram consumed per watt power
generation, the commercial players are shifting their focus from crystalline solar
cell material to 2D materials. Experimental designs incorporating metallic nanopar-
ticles in these 2D materials have dramatically improved 2D material-based solar
energy conversion device effciency. Due to excellent carrier mobility and electron
transport properties, not graphene but other direct bandgap monolayer materials such
as TMDCs have tremendous potential for designing low-cost, fexible photovoltaic
devices. The next-generation concept, such as tandem and hot carrier photovol-
taic devices, has been made possible by the advent and utilization of 2D materials.
On-chip integrated design using these concepts can utilize almost the entire energy
of the incident photon. Such solar cell devices can be made very compact to be
installed in miniature next-generation advanced miniature devices.
2D materials are the wonder material exhibiting high electrochemical perfor-
mance and are very useful for photovoltaics, piezoelectric materials, and energy pro-
duction in the form of hydrogen. 2D material-based energy devices can be improved
by combining different 2D materials. The individual components in a composite can
introduce the characteristics like high porosity, large surface area, increased active
sites, enhanced cyclic stability. 2D materials are suitable for solar to chemical energy
conversion and thus can become a nature-friendly, low-cost source of energy. In pho-
tocatalytic water splitting, the 2D/2D interface has an important role since the 2D
cocatalysts on 2D semiconductors create a large interface that helps for the separat-
ing electron–hole pairs. It promotes the movement of electron–hole pairs between
the 2D semiconductors and cocatalysts. Doping plays an important role in the forma-
tion of active sites in 2D materials. In the case of MoSe2 Mn doping enhances the
HER activity of MoSe2.
ACKNOWLEDGEMENTS
Sourabh Barua acknowledges the Ministry of Human Resource Development
(MHRD), Government of India for fnancial support through the NPIU TEQIP-III
CRS scheme (CRS Application ID: 1-5743255881), and Birla Institute of Technology
Mesra.
Ranchi for fnancial support under the NPIU TEQIP-III seed money scheme 2018.
Jyotsna Chaturvedi acknowledges the department of science and technology (DST)
for fnancial support through women scientist scheme A (WOSA) with fle no: SR/
WOSA-A/CS-26/2019.
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7 2D Nanomaterials Using
Thin Film Deposition
Technologies
Kwadwo Mensah-Darkwa and
Daniel Nframah Ampong
University of Science and Technology
Daniel Yeboah
Institute of Industrial Research - Council for
Scientific and Industrial Research
Emmanuel Acheampong Tsiwah

University of Science and Technology Of China
Ram K. Gupta
CONTENTS
7.1
Introduction................................................................................................... 110
7.2
Synthesis of 2D Materials.............................................................................. 112
7.2.1 Synthesis Approaches........................................................................ 112
7.2.1.1 Top-Down Approach........................................................... 112
7.2.1.2 Bottom-Up Approach.......................................................... 114
7.2.2 2D Materials Using Thin Films Deposition....................................... 115
7.2.2.1 Physical Deposition............................................................. 115
7.2.2.2 Chemical Deposition........................................................... 116
7.3
Characterization of 2D Materials.................................................................. 117
7.3.1 Optical Microscopy........................................................................... 117
7.3.2 Scanning Probe Microscopy.............................................................. 117
7.3.2.1 Atomic Force Microscopy.................................................. 117
7.3.2.2 Scanning Tunneling Microscopy........................................ 118
7.3.2.3 Raman Spectroscopy.......................................................... 118
7.3.2.4 X-ray Photoelectron Spectroscopy...................................... 118
7.4
Energy Applications of Thin Films Based 2D Materials.............................. 118
7.4.1 Thin Film-Based Supercapacitors..................................................... 118
7.4.1.1 Graphene-Based Supercapacitors....................................... 118
DOI: 10.1201/9781003178453-7 109

7.4.1.2 Transition Metal Oxides and Hydroxides-Based

Supercapacitors .................................................................. 120
7.4.1.3 Transition Metal Dichalcogenides (TMDs)-Based
Supercapacitors .................................................................. 120
7.4.1.4 MXenes-Based Supercapacitors ........................................ 122
7.4.2 Thin Films-Based Batteries.............................................................. 124
7.4.2.1 Lithium (Li)-Based Batteries............................................. 124
7.4.2.2 Zn-MnO2 Battery ............................................................... 124
7.4.2.3 Nickel-Metal Hydride ........................................................ 125
7.4.2.4 Flow Batteries .................................................................... 125
7.4.3 Thin Film-Based Solar Cells ............................................................ 126
7.4.3.1 Amorphous Silicon ............................................................ 126
7.4.3.2 Cadmium Telluride (CdTe) Solar Cells.............................. 128
7.4.3.3 Dye-Sensitized Solar Cells (DSSCs) ................................. 128
7.4.3.4 Perovskite Solar Cells (PSCs) ............................................ 129
7.4.4 Thin Film-Based Fuel Cells.............................................................. 129
7.4.4.1 Alkaline Fuel Cells ............................................................ 129
7.4.4.2 Solid Oxide Fuel Cells (SOFCs) ........................................ 131
7.4.4.3 Microbial Fuel Cells (MFCs)............................................. 131
7.4.4.4 Direct Methanol Fuel Cells (DMFCs) ............................... 131
7.5 Conclusion .................................................................................................... 133
References.............................................................................................................. 133
7.1 INTRODUCTION
Over the last several decades, rapid economic growth has led to an increase in energy
demand and consumption. The majority of this demand is met by non-renewable
energy sources including petroleum, natural gas, coal, oil shale, and so on. Our over-
reliance on traditional energy sources has prompted severe concerns about resource
distribution inequity, intermittent fossil fuel supply, and environmental concerns.
Because of the paucity and the depletion of non-renewable energy and the wors-
ening environmental condition, environmentally friendly energy conversion/stor-
age technologies are receiving more attention in research and development. In this
regard, solar cells, supercapacitors, batteries, fuel cells, and other innovative sustain-
able energy conversions/storage technologies have evolved as a viable technology
that has reduced our reliance on fossil fuels while also protecting the environment.
Nevertheless, new technologies must be developed to synthesize and fabricate mate-
rials that have unique properties to enhance the performance of these technologies.
Through extensive interdisciplinary research, new functional materials have been
developed and applied to several emerging technologies, to develop environmentally
clean and renewable energy conversion/storage systems.
Nanomaterials have demonstrated exceptional properties and have been accepted
for application in energy conversion/storage systems, as well as a variety of other
material discoveries. It is widely reported in the literature that, nanomaterials can
exhibit a wide range of material properties based on particle size and shape. For
example, a particular element or compound can exhibit unique properties depending
Thin Film Deposition Technologies 111
on the crystal structure and composition. Depending on the manipulation of particle

size and dimensions, nanomaterials can exhibit tunable physical and chemical proper-
ties. These materials’ physical and chemical properties make them more attractive in
applications such as photovoltaic cells, batteries, and supercapacitors. Nanomaterials
are materials that have a length scale of 1–100 nm in at least one dimension. In regards
to their dimensions, they are categorized as zero-dimensional (0D), one-dimensional
(1D), two-dimensional (2D), and three-dimensional (3D) structures. 0D nanomateri-
als tend to have spherical shapes due to the restrictions in all dimensions (x, y, z) in
the nanoscale (a dot). The restrictions limit it to atomic/molecular-scale structures
such as quantum dots and nanoparticles. On the other hand, 1D nanomaterials have
one dimension outside the nanoscale length scale. These usually exhibit needle-like-
shaped structure, which includes nanotubes, nanorods, and nanowires.
2D nanomaterials, on the other hand, have two dimensions that aren't confned to
the nanoscale. Nanocoatings, thin flms, and nanolayers are all 2D nanomaterials.
Finally, 3D nanomaterials (also known as bulk nanomaterials) are nanomaterials that
are not constrained in all dimensions. This defnition is ambiguous, leaving room for
other interpretations; however, it is important to note that these materials must have a
nanocrystalline structure as one of their main features at the nanoscale. Based on the
defnition, 3D nanomaterials can include dispersions of nanoparticles (0D), bundles
of nanowires and nanotubes (1D), and multi-nanolayers (2D). The concept of 2D
nanomaterials has inspired considerable research interest since Novoselov et al. [1]
discovered graphene in 2004. When compared to other types of nanomaterials, 2D
nanomaterials have been used in a variety of energy conversion/storage technologies
due to their outstanding physical and chemical properties, including large surface
to volume ratio versus shape and remarkable electrical and thermal characteristics.
Many 2D materials have been fabricated and a lot more have been theoretically pre-
dicted. Because recent studies have focused on the unique features of 2D nanoma-
terials, we will begin by discussing 2D nanomaterials, thin flms, and the properties
that distinguish them for next-generation energy conversion and storage applications.
Thin-flm nanomaterials have superior property stability due to their inherent
structure and large surface area when compared to other types of nanomaterials. Most
thin-flm fabrication processes will necessitate the use of a substrate as support. This
means that the substrate can be used as a seed to facilitate growth, or it can provide
the necessary support to prevent aggregation during the fabrication process. This is
especially problematic for 0D nanomaterials during the fabrication process, where
aggregation/agglomeration can occur, causing the material to be unstable. Thin-flm
materials are commonly used in applications that require a large exposed surface area
or interface. Because of these inherent properties, thin flms are better suited for elec-
trochemical energy conversion/storage applications that require more active sites and
a larger contact surface area, such as batteries and supercapacitors. Recently, 2D TiO2
[2], MXene/TiO2 [3], reduced graphene oxide [4], Bi2Te3 [5], and BiFeO3 [6] thin flm
have been widely reported in applications for energy conversion/storage.
Chen et al. [7] reported on the use of In2S3 nanosheet arrays fabricated on TiO2
thin flms using molecular precursor solution. The 2D nanosheet arrays were used
for a heterojunction solar cell, which exhibited a power conversion effciency (PCE)
of 2.58% depending on the height of the array. In another work, 2D WO3 nanosheets
were prepared by a controlled hydrothermal method [8]. The fabricated CdTe solar
cell using the nanosheets as back contact exhibited improved thermal stability and
device effciency. 2D nanomaterials exhibit more stable structure and performance
compared to the other types of nanomaterials because of the lateral exposed area
(sheet-like structure), which could also be tuned to vary its properties. For instance,
Malek et al. [9] prepared MoS2 nanosheets on indium tn oxide (ITO) substrate as an
electron transfer layer for perovskite solar cells (PSCs) application. The PCE was
found to increase with the decrease in the number of MoS2 nanosheets. These are just
a few examples of how 2D nanoparticles could improve the performance of materials
in energy conversion/storage applications.
The most recent advancements in 2D nanomaterials for energy conversion/
storage applications will be discussed in this chapter. First, we begin by review-
ing the most common synthesis methods for 2D nanomaterials and then focus
on methods for fabricating 2D materials using thin-flms deposition, followed
by a brief overview of characterization techniques for 2D materials fabrication.
Second, we will look at 2D thin flms and their applications in various energy
conversion/storage systems.
7.2 SYNTHESIS OF 2D MATERIALS

7.2.1 SYNTHESIS APPROACHES
2D nanomaterials have found their way into modern optoelectronic, catalytic, pho-
tovoltaic, imaging, sensing, and energy applications. Their use owes to the inher-
ently high surface to volume ratio, structure, quantum size effect, and morphological
(e.g., shape, size, and surface porosity of individual particles) attributes they possess.
An attribute of particular importance for many of these applications is large sur-
face area, as it facilitates fast (chemical and charge) transport phenomena. Another
is, morphology that dictates how well they adhere, absorb, refract/refect, and also,
whether or not they are printable. These key attributes, among others mentioned,
hinge on both synthesis and deposition techniques used. As a result, varied proce-
dures and thus setups have been applied in synthesizing and depositing 2D nanoma-
terials as thin flms for their required use in the applications of research and industry.
Among the techniques include chemical vapor deposition (CVD), nanolithography,
chemical/mechanical exfoliation, sol–gel, solvothermal, and others. The two types of
synthesis/deposition procedures are top-down and bottom-up synthesis/deposition.
Thus, entailed in this section is a discussion of such techniques explored in research
and industry under these categories.
7.2.1.1 Top-Down Approach

Top-down methods involve disintegrating bulk material to obtain nanoscale forms
of the material. It can be done by machining, etching, or breaking down successively
the bulk material to atomic crystal lattices. For 2D materials, this is achieved by
targeting and severing weak interlayer forces. Some examples are the mechanical
exfoliation method, chemical exfoliation method, laser ablation method, and nano-
lithography (Figure 7.1).
FIGURE 7.1 Examples of popular top-down and bottom-up approaches used to synthesize
2D nanomaterials.
7.2.1.1.1 Mechanical Exfoliation Method

The scotch tape approach is popular for mechanical exfoliation where the scotch
tape is stuck onto the surface of bulk material and peeled off repeatedly to obtain
thin sheets of material. It is a simple method and gives clean surfaces with minimum
defects. The downside to this approach is that parameters cannot be controlled to
produce specifc quality. Also, it is not suited for mass production and has low yields.
It has been used to synthesize graphene, antimonene, NbSe2, TiS2, WS2, WSe2, and
TaSe2 [10–13]. A shear exfoliation method has also been explored, which yielded
graphene sheets in organic solvent without any defects.
7.2.1.1.2 Chemical Exfoliation Method

This involves, frst of all, the intercalation of bulk material by chemical species
followed by either a mechanical (e.g., ultrasonication and stirring) or electric (e.g.,
microwave irradiation and electric current probes) means of exfoliation. Chemical
species like bromine, glycolic acid, hydrogen peroxide, and perchloric acid have
been used [14–16]. The approach was successfully used to synthesize graphene,
boron nitride nanosheets, and molybdenum disulfde having large lateral size (up
to 256.8 μm 2) and high quality; few structural defects hence showing outstand-
ing electrical conductivity [16,17]. Compared to mechanical exfoliation, this has
higher yields, better quality, and takes less time. The downside is that it is not
benign and requires high energy input if corrosive acids or high-boiling solvents
are used, respectively.
7.2.1.1.3 Laser Ablation Method

In laser ablation, short wavelength, high fuence laser irradiation is used to remove
bulk material and by severing Van der Waal forces. The laser irradiation can be
continuous or pulsed. The method has wide use in processing ceramic, metallic, and
polymeric materials. Noble metal nanoparticles have been synthesized in liquid solu-
tion through laser ablation [18]. In recent research, laser ablation, mainly pulsed laser
deposition (PLD), has been explored in synthesizing 2D materials. WS2 flms have
been grown on sapphire substrates using a pulsed KrF excimer laser [19]. Others like
Bi2Te3, SnSe, SnS, MoS2, and Mo0.5W0.5S2 with mono-/few layer(s) have also been
prepared via PLD [20–23]. The thickness of 2D flms deposited by PLD is precisely
controlled by varying the number of laser pulses.
7.2.1.1.4 Nanolithography
It involves imprinting a pattern of nano-size onto a sacrifcial substrate and thereaf-
ter, transferring the pattern onto an underlying substrate surface for its application.
The process starts with cleaning a substrate, then deposition of resist onto its surface
followed by baking. Afterward, the resist material is etched by light, electrons, or
ions. The pattern is developed via the removal of unexposed resist portions. Finally,
it is pressed onto an underlying substrate. Examples are photolithography, electron
beam lithography, atomic force microscopy (AFM) manipulation, ion beam lithog-
raphy, dip-pen lithography, and x-ray lithography. Graphene flms were manipulated
at the nanoscale through anodic oxidation to structure isolating trenches into single-
layer graphene fakes of sizes less than 30 nm via the AFM technique [24].
7.2.1.2 Bottom-Up Approach

This method involves using chemical means to self-assemble smaller units, such as
atoms or molecules, into bigger nanomaterials with desired chemical composition,
size, shape, stacking order, crystal structure, and edge/surface defects. Examples in
this category are solvothermal synthesis, CVD, and the sol–gel method.
7.2.1.2.1 Solvothermal Synthesis

It is a wet-chemical process that occurs at elevated temperatures and pressures. An
organic or inorganic solvent is mixed with precursor materials and transferred into a
reaction chamber. The solvent catalyzes the growth of nanoparticles. Hydrothermal
synthesis is a similar process that uses water as a solvent. It is particularly used for
the crystal growth of substances that are insoluble at normal temperatures yet soluble
in water at high temperatures and pressure. This method has been used to fabricate
2D nanosheets such as metals, metal oxides, and metal chalcogenides. It is a low-cost
process, can produce various morphologies, has high yields, and is green.
7.2.1.2.2 Chemical Vapor Deposition

In this technique, gas precursors are introduced into a chamber, and the substrate
is heated to high temperatures, causing a reaction that results in the formation of
the desired flm. Low-pressure, atmospheric pressure, and plasma-enhanced CVD
methods are all variations of this process. Parameters that affect the chemical and
physical properties of thin-flm material of varying sizes include substrate type, the
concentration of the gas mixture, temperature, and pressure. This process yields a
stable, homogeneous flm with low porosity and high purity. It does, however, have
signifcant drawbacks, such as the need for expensive equipment and the release of
toxic gaseous by-products during the reaction process.
7.2.1.2.3 Sol–gel Method

Sol–gel method uses high chemically active compounds as precursors. They are
mixed in the liquid phase, hydrolyzed, and condensed via chemical reactions to form
a stable sol system in solution. The hydrolysis reaction causes an active monomer to
polymerize forming a sol, and then a gel with a 2D spatial structure. The gel is dried,
heat-treated, and prepared into required nanoparticular materials. It provides flm
homogeneity, facilitates uniform doping, synthesizes at lower temperatures, and is
adapted to various new materials [25]. Synthesis of some 2D nanomaterials such as
graphene and its composites via the sol–gel method is a challenge because graphene
has low solubility in commonly used solvents.
7.2.2 2D MATERIALS USING THIN FILMS DEPOSITION

7.2.2.1 Physical Deposition
Physical vapor deposition happens in a highly evacuated chamber and coats sub-
strate by transferring atoms from a source material via its evaporation or sputtering
(Figure 7.2a–c).
FIGURE 7.2 Schematic diagrams of deposition techniques for 2D thin flms; (a) thermal
evaporation, (b) pulsed-laser deposition, (c) electron beam evaporation, and (d) sputtering.
7.2.2.1.1 Evaporation Techniques

Deposition by evaporation takes place either in a vacuum or under controlled atmo-
spheric conditions. The fundamental principle underlying this approach is to trans-
form the material from a solid to a vapor phase and back to solid once it reaches the
substrate surface [26]. Evaporation of the material can be achieved thermally, by
electrons, laser, as well as ion-beam. CdSSe, MnS, and Ge-Te-Ga thin flms were
deposited by the vacuum thermal evaporation technique [26]. The thin-flm quality
depends on laser wavelength, energy, gas pressure ambient, pulsed duration, and the
distance of the target to the substrate in the PLD evaporation technique. PLD depos-
its fast, use less time and are compatible with oxygen and other inert gases.
7.2.2.1.2 Sputtering Techniques

In a sputtering set-up, target material (acting as the cathode) supplied with either
direct current or radio-frequency (RF) power is placed in a vacuum chamber at a dis-
tance from the substrate (acting as the anode). A sputtering gas (e.g., argon, neon, and
krypton) is let into the chamber to cause a glow discharge, which releases ions from
the target, bombarding the substrate thereby producing dense thin flms (Figure 7.2d).
By bleeding small amounts of oxygen with the sputtering gas, TiO2 thin-flms can be
deposited from the metallic Ti. The method is suitable for high melting point materi-
als and ultrahigh vacuum applications. Conversely, it is diffcult to achieve uniform
deposition on complex shapes [27].
7.2.2.2 Chemical Deposition

7.2.2.2.1 Chemical Vapor Deposition (CVD)
In conventional CVD, volatile gaseous precursors are allowed into a chamber con-
taining a substrate. The reaction of the precursors takes place on the surface of the
substrate, which is covered by a thin flm. High-quality monolayer graphene flms
are easily grown by a self-limited growth mode employing a metal substrate as a
catalyst in the process. Advantages of using this method include tunable physical and
chemical properties and reduced porosity of flms formed. CVD that makes use of
liquid precursors also exists. Graphene-like flms have been deposited on sapphire
and SiO2/Si from acetone and isopropanol liquid precursors and showed superior
properties in terms of carrier mobility [28].
7.2.2.2.2 Sol–gel Technique

This is an appropriate method for producing 2D nanomaterials from the liquid
phase. The method employs a low-temperature synthesis to allow the incorpora-
tion of organic molecules into the matrix while avoiding the degradation associ-
ated with a high-temperature synthesis. A challenge in using this synthesis approach
is the uncontrolled aggregation side reactions observed in the precursor sol [29].
Graphene-titania nanocomposites have been prepared to harness the photocatalytic
properties of graphene. A variety of techniques have been used to integrate graphene
into mesoporous titania, silica, and other nanocomposites. Also, the graphene-silica
sol–gel system was prepared as transparent nanocomposites and assessed for their
optical applications [26].
7.3 CHARACTERIZATION OF 2D MATERIALS

After 2D nanomaterials are synthesized, peculiar properties such as flm size,
thickness, crystallinity, composition, and others are measured via characterization
techniques. Based on the synthesis/deposition approach taken, different 2D materi-
als tend to have different morphological and structural traits. Hence there is a need
to accurately understand how the growth mechanism contributes to the structure,
how the structure affects and relates to the functionality of the synthesized mate-
rial, which could ultimately aid in the design of 2D materials with desired features
for specifc applications. As a result, a wide range of characterization techniques
has been used in probing 2D materials to understand such correlations. This sec-
tion explores the working principle, the strengths, and the limitations of some of
these techniques.
7.3.1 OPTICAL MICROSCOPY

This technique is affordable and facilitates the study of 2D materials without the
need for sophisticated imaging instrumentation. Generally, the interference of
refected light at the flm/substrate interface is responsible for the generation of
the image. Information on the location, thickness, and shape is obtained by gen-
erating a contrast between the substrate and the 2D nanomaterial. Mechanically
exfoliated graphene has been probed via this technique with monochromic light
[30]. The method is adapted to materials with good optical properties to obtain
an estimated thickness of the 2D material according to color and contrast. The
limitation this method has is that most insulating 2D nanomaterials have a small
refractive index, as a result, a few layers might lack the contrast needed to be
notable in refected light [31].
7.3.2 SCANNING PROBE MICROSCOPY

This consists collectively of methods for studying the surface morphology of nano-
materials at high resolutions. By using a probe to interact with the surface, the
topography and electronic band structures of 2D materials can be obtained and
interpreted.
7.3.2.1 Atomic Force Microscopy

This method, when combined with other techniques like photoluminescence spec-
troscopy, can measure the thickness of 2D materials. Thickness measured via this
method can be affected by contaminants on substrate or chemical contrast between
thin flm and substrate leading to some discrepancies in thickness relative to the-
oretical values. For that reason, appropriate precautionary steps have to be taken
[32]. Additionally, AFM can be used to monitor changes in morphology over time
to reveal degradation activity in unstable 2D thin flms. Nanosheets of black phos-
phorus, for example, have been found to degrade rapidly in ambient conditions due
to a chemical reaction with oxygen. This observed dissolution of the reactants was
studied with AFM [33].
7.3.2.2 Scanning Tunneling Microscopy

This method provides resolved atomic morphologies of materials. It can also give
information on the localized electron density of states. Recently, it has been used to
probe 2D materials to study band structure and the effects of doping. It reveals band
alignment of Van der Waal heterostructures [34]. The particle bandgap of MoS2 has
been obtained through this method. Band structure of MoS2-WS2 heteroflms has also
been reported. Aside from that, the position of Fermi level in a material can be deduced
by this approach. It has been discovered that the Fermi levels of metallic substrate met-
als such as Ti, Au, or Pd exhibit intrinsic defects close to their conduction band [35].
7.3.2.3 Raman Spectroscopy
This method gives information about the structural and electronic properties of a
material with high spatial and spectral resolution. It is non-destructive and fast. It
can reveal crystalline orientation and phases, the number of layers, strain, and doping
effects of 2D materials [36]. Raman spectroscopy has further been used to investigate
perturbations like doping effect and strain in 2D materials. Changes in peak intensi-
ties and positions were observed for MoS2 nanosheets during gradual stretching or
via the application of gate voltages. In addition, slight shifts in Raman peaks can be
linked to substrate effects that can show the effects of doping in 2D nanomaterial [37].
7.3.2.4 X-ray Photoelectron Spectroscopy
X-ray photoelectron spectroscopy is useful for qualitative and quantitative elemental
and chemical analysis, respectively. This method can be used to identify the elements
that comprise a material because each element is represented by a peak that also
represents distinct binding energy. The electronic confguration within the atoms
corresponds to the position and shape of the peak and hence can be used to extract
parameters such as chemical composition and atomic bonding of the material. This
technique measures information within 10 nm of the material surface thus, making
it well suited for thin-flm 2D materials as their thicknesses are usually <5 nm [38].
7.4 ENERGY APPLICATIONS OF THIN FILMS BASED 2D MATERIALS

The ever-rapid world development, industrialization, and increase in the standard of liv-
ing of modern societies have necessitated the need for effcient, reliable, cost-effective,
and eco-friendly energy conversion and storage systems. The development of alternative
clean energy generation and storage sources is critical, given the growing concern about
the global carbon footprint caused by the use of conventional fossil fuels. Batteries and
supercapacitors are prominent energy storage devices, whereas fuel cells and solar cells
provide clean energy generation; these technologies are discussed in the subsequent sec-
tions. To meet the demand for portable, lightweight, and energy-effcient requirements
for certain device applications, thin-flm nanostructures are crucial for this realization.
7.4.1 THIN FILM-BASED SUPERCAPACITORS

7.4.1.1 Graphene-Based Supercapacitors
Graphene-based electrodes are attractive for supercapacitor applications due to
their improved charge mobility and surface area on the electrode surface. To study
the performance of supercapacitors, thin flms of graphene oxide/tungsten oxide

(GO/WO3) were fabricated using the chemical bath deposition (CBD) technique
by employing different substrate materials [39]. The fabricated device recorded a
maximum specifc capacitance (Csp) of 268.5 F g−1 and energy intensity of 52.2 W
kg−1 on the Glass/GO/WO3 with the specifc capacitance increasing with decreas-
ing scanning rate as shown in Figure 7.3a and b. This performance was attributed
to the graphene oxide’s large surface area. A simple hydrothermal process was
adopted to produce thin-flm binder-free GO-nickel sulfde nanoplates to inves-
tigate its pseudocapacitance behavior [40]. Using the three-electrode system, a
maximum Csp of 1,745.50 F g−1 at a current density of 5 mA cm−2 was recorded.
This performance was due to the enhanced specifc surface area and higher electri-
cal conductivity.
Another cost-effective electrodeposition approach was adopted to produce a fex-
ible thin-flm RuO2 electrode on a substrate of copper and graphene-coated Cu foil
[41]. The electrochemical performance was studied for supercapacitor applications
and a Csp of 1,561 F g−1 was recorded at 5 mV s−1 scan rates for the RuO2/Gr/Cu elec-
trode, with 98% retention improvement under bending conditions (Figure 7.3c and d).
Thin flms of reduced graphene oxide (GO) used in supercapacitor applications with
a solid-state electrolyte recorded an optimum electrode capacitance of 8.55 mF cm−2
FIGURE 7.3 (a) Csp-R curves for GO/WO3 on different substrates. (b) Csp-V curves for
Glass/GO/WO3. Adapted with permission from [39]. Copyright (2020) Elsevier. (c) Csp of
the RuO2/Cu and RuO2/Gr/Cu electrodes at different scan rates in the bent and unbent states.
(d) Capacitance retention for the RuO2/Gr/Cu electrode for 500 cycles in the bent and unbent
states. Adapted with permission from [41]. Copyright (2017) Elsevier.
as compared to the liquid-based Na2SO4 electrolyte (10.67 mF cm−2). Here, the GO

thin flms fabricated on ITO substrates were reduced electrochemically to obtain the
reduced GO (rGO). This performance is encouraging for the possible integration of
solid-state thin-flm rGO supercapacitor electrodes in portable electronic devices [42].
7.4.1.2 Transition Metal Oxides and Hydroxides-Based Supercapacitors

Transition metal oxides and transition metal hydroxides offer great pseudocapacitive
performance for supercapacitors due to enhanced charge separation at the interface
of the electrode and electrolyte. Thin flms of cobalt hydroxide [Co(OH)2]-based elec-
trode for symmetric supercapacitor was successfully fabricated utilizing 1 M KOH as
the electrolyte onto stainless steel (SS) substrate by potentiodynamic electrodeposi-
tion process (Figure 7.4a and b) [43]. The performance of the device was evaluated
and maximum specifc energy and specifc power of 3.96 Wh kg−1 and 42 kW kg−1
at 5 mV s−1 scan rates were recorded respectively, as shown in Figure 7.4c. A Csp of
1,727 F g−1 at 5 mA cm−2 has been reported with about 91% capacitance retention
after 2,000 cycles for NiO/multiwalled CNTs (MWCNTs) fexible SS electrode using
ionic layer adsorption and reaction [44].
Temperature is critical in supercapacitor applications if the energy storage device
is to be employed in operations that need high-temperature variations. The device’s
electrochemical performance strongly depends on the operating temperatures. The
performance of the thin-flm silver oxide (Ag2O) electrode in an aqueous solution was
evaluated in a temperature range of 35°C–75°C for supercapacitor applications [45].
The capacitance increased with an increase in temperature with higher stability as
shown in Figure 7.5a and b. This improved electrochemical performance was attrib-
uted to the resistance reduction in charge transfer, an enhancement in ionic conduc-
tivity, and quick adsorption/desorption of ions at elevated temperatures. The effect of
temperatures on the electrochemical performance of nanostructured hydrous copper
oxide/hydroxide [CuO/(OH)2] deposited onto SS substrate by CBD method has been
reported [46]. The binder-free solid-state electrode used for supercapacitors recorded
a maximum Csp of up to ~340 F g−1 at 1 mA cm−2 for 105°C (Figure 7.5c). Figure 7.5d
shows the capacitance retention of the (CuO/(OH)2)-based supercapacitor electrode
up to about 91% after 1,000 cycles.
7.4.1.3 Transition Metal Dichalcogenides (TMDs)-Based Supercapacitors

Higher specifc area and better conductivity of 2D nanostructure materials are
necessary for enhanced supercapacitor performance. Several 2D transition metal
dichalcogenides (TMDs), for example, MoS2, MoSe2, and WS2 have been studied for
electrochemical energy conversion/storage applications due to good metal ion coor-
dination and high electrical conductivity. Electrochemical intercalation of ions such
as H+, K+, Li+, and Na+ is possible in nanosheets of MoS2, which contains a greater
concentration of metallic 1T phase. This results from the chemical exfoliation of the
material to achieve excellent effciency and capacitance values. This material also
showed good power density values as well as better cycling stability [47]. A simple
and resizable spray-painting technique and a further laser-patterning can be adopted
to fabricate and optimize thin-flm 2D MoS2 nanosheets for micro-supercapacitors to
obtain high area capacitance (8 mF cm−2) with improved cycle stability [48].
Thin Film Deposition Technologies
FIGURE 7.4 Symmetric Co(OH)2-Co(OH)2 supercapacitor (a) test cell and (b) charging–discharging mechanism, (c) Variations of specifc energy and
power as the function of current densities. Adapted with permission from [43]. Copyright (2013) Elsevier.
121
FIGURE 7.5 (a) Charge–discharge and (b) stability test of thin-flm Ag2O electrode at dif-
ferent temperatures. Adapted with permission from [45]. Copyright (2021) Elsevier. (c) Graph
of Csp with different current densities of CuO/(OH)2 electrode at different temperatures. (d)
Cyclic stability of CuO/(OH)2 electrode (prepared at 105°C) at 2 mA cm−2 charging current
density over 1,000 cycles. Adapted with permission from [46]. Copyright (2017) Elsevier.
2D-tungsten disulfde (WS2) possesses enormous active sites that enhance charge
accumulation. Incorporating WS2 with rGO nanosheets (Figure 7.6a) as the electroac-
tive material through a simple molten salt technique improves the electrochemical per-
formance for supercapacitor applications. A higher Csp of 2,508 F g−1 at 1 mV s−1 scan
rate can be achieved, with excellent stability of 98.6% retention after 5,000 charge/
discharge cycles as shown in Figure 7.6b [49]. TMDs can be engineered with defects
to create active sites for enhanced electrochemical performance. A facile moderate
solution reduction technique was adopted by a group of Chinese researchers to fab-
ricate high-performance supercapacitors comprising of reduced CoNi2S4 (r-CoNi2S4)
nanosheets as shown in Figure 7.6c [50]. A specifc capacitance of 1,117 C/g at 2 A/g
was obtained as compared to 882 C/g for the pristine CoNi2S4 (Figure 7.6d) due to the
generation of sulfur vacancies of the reduced nanosheets, which enhanced conductivity.
7.4.1.4 MXenes-Based Supercapacitors

2D MXene (Ti3C2Tx) flms can be derived from MXene inks for higher electron trans-
fer for purposes of manufacturing electrodes for portable thin-flm supercapacitors.
The main problems hindering its real-life application are the dismantling of MXene
components and oxidative instabilities when contacted with water. To control this,
FIGURE 7.6 (a) SEM images of WS2/RGO hybrid. (b) The capacitance retention and the Coulombic effciency as the function of the charge/discharge
cycle for the SC electrodes with WS2/RGO. Adapted with permission from [49]. Copyright (2016) Elsevier. (c) Schematic illustration of the synthesis of
123
r-NiCo2S4 nanosheets. (d) Specifc capacity at different current densities for the r-CoNi2S4 and CoNi2S4 nanosheets electrodes. Adapted with permission
from [50]. Copyright (2018) Elsevier.
tartaric acid can be added to the MXene composite to impede oxidation and frmly
hold the assembly units together [51]. Incorporating TMOs such as Fe3O4 [52] into
MXene interlayers to form sandwiched electrodes (MXene/Fe3O4/MXene) by laser
crystallization technique improves the areal capacitance and cycling stability of the
device. MXene-based electrode flms (PANI/MXene) can be fabricated by simple
blade-coating technique by intercalating PANI into interlayers of MXene nanosheets
for improved electrochemical performance, fexibility, and structural stability. By so
doing, the operating potential window, volumetric energy density, and volumetric
capacitance can also be enhanced [53]. Annealing treatment can also be used to mod-
ify 2D MXene thin flms, which affect the electrochemical and structural proper-
ties [54]. Direct annealing techniques help to improve the strength of the structures,
cycling stability, and electrochemical performance due to structural and chemical
variations on the surface of the flm. Polystyrene microspheres can be incorporated
into MXene flms to generate porous interconnected structures (3D) to promote ion
transport and obtain higher electrochemical performance. The 3D channels promote
electrolyte accessibility for high-performance thin-flm supercapacitors [55].
7.4.2 THIN FILMS-BASED BATTERIES

7.4.2.1 Lithium (Li)-Based Batteries
The high capacity and lightweight requirement of many microelectronics require
thin-flm power sources and lithium-ion batteries (LIBs) have been promising in that
regard. The electrode materials have a signifcant impact on the performance of these
devices. Thin flms of RuOx nanocrystals deposited (sputter deposition) at room tem-
perature on SS were employed as cathodes for use in thin-flm micro batteries (MBs).
The device showed enhanced cycling stability and excellent electrochemical proper-
ties. The oxygen content in the sputter gas contributed signifcantly to this perfor-
mance, which makes it possible for integration into microsystems [56]. There is a need
to understand the diffusion barriers of Li in thin-flm batteries to enable its integration
on silicon substrates since it can cause damage to surrounding units, device separa-
tion, and loss of battery capacity. For the frst time, the thermal atomic layer deposi-
tion (ALD) technique was used to fabricate ultrathin flms of titanium nitride (TiN)
as a current collector and bifunctional Li-ion diffusion barrier. The device recorded
the lowest specifc resistance and high electrical conductivity, which is a requirement
for current collectors [57]. PLD was also employed to produce a thin flm of TiO2
nanoparticles to be used as Li-ion MBs’ negative electrodes. Post-deposition anneal-
ing improved the electrochemical activity whereas additional carbon layer PLD onto
the flms enhanced the Li+ transport properties and battery capacity retention [58].
7.4.2.2 Zn-MnO2 Battery

The units of LIBs are poisonous and highly fammable, making them unfeasible power
sources for implantable and wearable electronics close to the body. Zn-MnO2 batteries
have several qualities such as high fexibility, low cost, eco-friendliness, high electro-
chemical performance, and abundance, making them desirable candidate materials for
making wearable storage systems. Free-standing electrode materials are crucial to attain-
ing higher device performance. Figure 7.7 shows the mechanism of charge/discharge
FIGURE 7.7 Charge-transfer mechanism during battery operation of a unit cell. Adapted
with permission from [59]. Copyright (2021) Elsevier.
cycles during the operation of the Zn-MnO2 unit battery. The thickness of the current
collector, Ag coating, and the amount of carbon contents in the carbon current collector
have proven to be the major factors that contribute to the device’s maximum discharge
capacities and conductivity. These factors were optimized in the current collector for its
application in thin-flm Zn-MnO2 battery with high fexibility [59]. A one-step electrode-
position technique was employed by Huang et al. [60] to deposit nanofakes of MnO2 onto
CNT flm, which enhanced the electrochemical kinetics when used in Zn-MnO2 bat-
tery. The device recorded high capability rate of 105.6 mAh g−1 at 3mA cm−2 outstand-
ing cycling stability even after 1,000 cycles, and mechanical robustness during bending.
Recently, Liang and colleagues [61] integrated nanosheets of graphite with little surface
defects in MnO2 to suppress Zn-MnO2 batteries in situ electrodeposition to investigate the
factors that affect the system’s stability. The fabricated electrode device showed enhanced
cycling stability over 600 cycles with high columbic effciency (~99.8%).
7.4.2.3 Nickel-Metal Hydride

Thin-flm nickel-metal hydride (Ni-MH) batteries are advantageous over the LIBs
due to their competitive price and power density making them ideal candidates for
power supply in microsystems. Surface modifcation of the MH electrode used in
Ni-MH batteries can improve the conductivity and reduce the ohmic resistance of
the battery. Yang et al. [62] employed a vacuum evaporation plating technique to
plate thin Ag flm on both sides of the electrode and observed appreciable durability,
improved effciency, and stability of the battery. Tsai et al. [63] also utilized a cost-
effective and effcient process to fabricate thin flm and fexible buckypapers derived
from MWCNTs to be used for Ni-MH batteries anode. An improved electrochemical
performance was observed, thus, the buckypaper could be used as a replacement for
the metal substrate in Ni-MH battery anode for miniature storage systems.
7.4.2.4 Flow Batteries

Redox fow batteries (RFBs) demonstrating a lot of advantages such as long cycle
life, low cost, high energy effciency, and safety are considered as one of the best
electrochemical energy storage devices. To obtain higher performance of the device,
thin-flm electrodes are required, aside from the membrane being the major compo-
nent. A two-layer thin-flm electrode was developed by Wu et al. to be used for vana-
dium RFB [64]. The electrode comprised of electrospun fber mat (EFM) as catalyst
layer and carbon cloth, carbon paper, and graphite felt as the backing layer as shown
in Figure 7.8a. From Figure 7.8b, the energy effciency of 76.1% at 240 mA cm−2 was
recorded for the carbon cloth/EFM electrode. After operating for 800 cycles, no sig-
nifcant decay was observed and hence, the battery showed higher stability. Teng
et al. [65] used interfacial polymerization to prepare and optimize thin-flm composite
(TFC) of polypyrrole (PPy) to enhance the porous membrane for vanadium RFB. A
coulombic effciency of 98.1% was recorded for the device with minimal deteriora-
tion upon cycling tests. The enhanced performances of these TFC materials suggest
a great potential for large-scale energy storage systems.
7.4.3 THIN FILM-BASED SOLAR CELLS

7.4.3.1 Amorphous Silicon
A well defect passivated c-Si surface by intrinsic amorphous silicon (i-a-Si:H) layer
prior to deposition of the n/p-doped layers is critical to achieve high effciency for sil-
icon heterojunction (SHJ) solar cells, as the i-a-Si:H layer can signifcantly reduce the
surface defect related to recombination losses. Ru et al. introduced a low deposition
rate, approximately 2 Å s−1, i-a-Si:H (i1) buffer layer grown prior to the bulk i-a-Si:H
layer, both deposited with RF-PECVD to improve c-Si surface passivation and thus
the effciency of SHJ solar cell was improved 25.11%. The fabrication process and
device performance have been shown in Figure 7.9 [66]. Ruan et al. also deposited a
high CH buffer layer (i1) with pure silane plasma, followed by deposition of intrinsic
bulk layer. The i1 layer suppressed the epitaxial growth at interface, while low-defect
i2 bulk layer further promoted passivation quality [67]. Cho et al. then used plasma-
enhanced chemical vapor deposition (PECVD) to create bifacial and semitranspar-
ent a-Si:H thin-flm solar cells with bifacial transparent conducting oxide (TCO)
contacts, obtaining PCE values of 6.39%–6.62% and 4.95%–5.15% using front and
rear lighting, respectively [68]. Wu et al. reported the implementation of trimethyl
boron B(CH3)3 (TMB) doped p-type a-Si:H (a-Si:H(p)) flm as hole transport layer
FIGURE 7.8 (a) Schematics of the dual-layer electrode structured fow cell. (b) Energy
effciency of batteries as a function of cycle index. Adapted with permission from [64].
Copyright (2019) Elsevier.
FIGURE 7.9 Schematic illustration of the SHJ solar cell structure: (a) RF-PECVD-prepared intrinsic layer with i1 buffer layer, (b) RF-PECVD-
prepared normal intrinsic layer, (c) VHF-PECVD-prepared intrinsic layer. (d) I–V characteristics of a 25.11% effciency SHJ solar cell on a total area of
127
244.5 cm2. Adapted with permission from [66]. Copyright (2020) Elsevier.
contacting with indium-free aluminium-doped zinc oxide (AZO) in SHJ solar cells.
The optimized low-resistivity a-Si:H (p)/AZO contact enables a fll factor above 81%
and an effciency of 23.6% for M2 SHJ solar cells [69]. Sedani et al. also studied
the solid-phase crystallization of boron-doped non-hydrogenated amorphous Si flms
fabricated by electron beam evaporation equipped with effusion cells (e-Beam EC)
on silicon nitride-coated glass substrates [70].
7.4.3.2 Cadmium Telluride (CdTe) Solar Cells

Because of its high absorption coeffcient, nearly optimum optical bandgap, and
ease of manufacturing, CdTe is an excellent candidate for thin-flm PV solar cell
applications. To deposit the CdTe absorber layers, several growth methods have been
developed. The effciencies of CdTe cells grown on commercial fuorine doped tin
oxide (FTO)-coated substrates were signifcantly lower. A lot of methods have been
developed but their results are signifcantly below the results from world-record cells
grown on non-commercial TCO glass substrates. Paudel et al. recently focused on
optimizing the fabrication and characterization of high-effcient CdTe solar cells
grown on commercial TCO glass substrates using the close space sublimation (CSS)
system developed in their lab, and effciencies of greater than 15% were achieved [71].
Hu et al. attempted to minimize absorption loss from the CdS:O window layer, which
is one of the challenges in the development of CdTe-based thin-flm solar cells, by
using a post-annealing process to further reduce the CdS:O thickness to 30 nm while
still achieving 18% effciency. The device performance is shown in Figure 7.10 [72].
Major et al. incorporated ZnO NWs deposited by a low-temperature electrochemical
deposition route, which achieved up to 9.5% effciency [73].
7.4.3.3 Dye-Sensitized Solar Cells (DSSCs)

Many materials, including TiO2, ZnO, Al2O3, MgO, and others, have been depos-
ited using various thin-flm deposition techniques, including sputtering, ALD, spin
coating, thermal oxidation, spray pyrolysis, and electrochemical methods for use in
dye-sensitized solar cells (DSSCs). Pham et al. recently addressed the use of SnO2-
based photoanodes in aqueous dye-sensitized PV solar cells, as well as a new liquid
deposition strategy for forming SnO2@TiO2 surfaces. The device achieved an overall
FIGURE 7.10 (a) J–V and (b) EQE curves of the cell with 18% effciency (with AR coating).
Adapted with permission from [72]. Copyright (2021) Elsevier.
solar conversion effciency of 0.66% [74]. Fu et al. also proposed a simple method
for fabricating effcient panchromatic DSSCs with a photoelectrode composed of bi-
layered TiO2 thin flms coated with one or two dyes. A screen-printing process was
used to create the bottom layer of the TiO2 thin flm on an FTO glass electrode [75].
RF-sputtered ZnO and TiO2/ZnO play an important role in the charge dynamics.
7.4.3.4 Perovskite Solar Cells (PSCs)

For high-performing PSCs, the quality of the fabricated perovskite flm is very essential.
The PCEs of PSCs have been improved over the past decade with lead-based perovskite
having the highest of them (25.5%) as shown in Figure 7.11 [76]. To provide a full picture
of realizing high-performance PSCs, the focus has been on the strategies for preparing
high-quality perovskite flms (including antisolvent, additive engineering, scalable fabri-
cation, bandgap adjustment, and strain engineering). A Gallium-doped zinc oxide (GZO)
layer was used as TCO flm for low-cost Cu2O/CH3NH3PbI3/SiO2 structure to improve
the heterojunction planar PSCs [77]. Ayad et al. used the well-known SCAPS-1D soft-
ware to simulate a planar structure (CuI/CH3NH3PbI3-xClx/ZnO/TCO). Also, CuI like
transport layer of the holes was used, which can be deposited by simple techniques at
low temperature. A three-step fabrication method at ambient atmospheric conditions
was presented by Zanca et al. involving an initial step to fabricate MAPbI3 thin flms
directly on conductive and optically transparent substrates [78]. Chen et al. reported the
thin-flm deposition of a representative Ti-based HP, Cs2TiBr6, and provided insights
into the flm-formation mechanism. The optical bandgap of the as-deposited Cs2TiBr6
HP thin flms was 1.8eV, making them highly suitable for tandem PV applications [79].
7.4.4 THIN FILM-BASED FUEL CELLS

7.4.4.1 Alkaline Fuel Cells
A signifcant attempt is being made to design high-utilization, low-loading electrodes
for target performance. The electrode fabrication method and substrate material have
a signifcant impact on this development. Electron beam physical vapor deposition was
used to create thin-flm anodes with low catalyst loading on both Ni foam and carbon
paper as electrode substrates. [80]. Although Ni foam performed better than carbon
paper as an electrode substrate, it was less effcient. The anode was made entirely of
Ni foam, which produced a peak power density of 174 mW cm−2 at 60°C. As a result,
nickel foam had both a positive (electro-oxidation of NaBH4) and a negative (hydroly-
sis) effect on the performance of the fuel cells. Liu et al. fabricated Cu2O-Cu compos-
ite catalyst by a facile laser-irradiation method. The addition of Cu2O-Cu composite
in activated carbon air-cathode greatly improved the performance of the cathode [81].
Takahashi et al. then investigated the catalytic activity of the Pt oxide thin flm for the
ethanol oxidation reaction (EOR) in alkaline media. The Pt oxide thin flm showed
high activity for the EOR in alkaline media, and it was possible to approach the real-
ization of direct ethanol fuel cells (DEFCs) that use a safe fuel with high energy den-
sity. The Pt oxide thin flm and Pt thin flm were prepared by reactive sputtering and
the electrocatalytic activity of the ethanol oxidation reaction and it was investigated in
a KOH solution for developing the alkaline direct ethanol fuel cells [82].
130
2D Nanomaterials
FIGURE 7.11 Improvement of PCE of various PSCs in the last decade. Adapted with permission from [76]. Copyright (2021) Elsevier.
7.4.4.2 Solid Oxide Fuel Cells (SOFCs)

A solid oxide fuel cell (SOFC) is a form of high-temperature fuel cell constructed of
solid oxides, such as ceramic materials (generally over 700°C). Fuel fexibility, high
effciency, and high power density/specifc power are all advantages of this method.
A unit cell was successfully manufactured using a 2-inch sputtering system, indicat-
ing that signifcantly larger cells can be fabricated using larger sputtering equipment.
Despite these accomplishments, there have been concerns raised because the tech-
nology used to fabricate the multiscale-architecture SOFC was PLD, which has well-
known commercialization constraints. Kang et al. introduced the anode functional
layer on the surface of the substrate to stably deposit the thin-flm electrolyte and addi-
tional design parameters including the roughness and density were also introduced.
The fabrication process and device performance are shown in Figure 7.12 [83]. Seo
et al. also demonstrated how Al2O3 layers coated through ALD effectively suppress
the degradation of nanoporous Pt thin-flm electrodes [84]. These results suggested
that a simple and scalable coating strategy enables the implementation of TF-SOFCs
with ideal performance and durability outcomes. Normal butane was selected as the
fuel by Thieu et al. and multiscale-architectured thin flm-based SOFCs were oper-
ated in direct butane utilization mode at a temperature of 600°C. They tried to secure
fuel fexibility at lower operating temperatures (≤600°C), to employ low temperature
solid oxide fuel cells (LTSOFCs) as portable and mobile power sources [85].
7.4.4.3 Microbial Fuel Cells (MFCs)
A microbial fuel cell (MFC) is a device that converts chemical energy to electrical
energy through the catalytic reaction of microorganisms. MFCs open up new oppor-
tunities for generating sustainable energy from biodegradable compounds. MFCs
have also gotten a lot of attention because of their inherent advantages in both funda-
mental studies (particularly of anodes) and applications as high-throughput platforms
(compared to the cultivation and hydrogen production of algae). There has been a lot
of research on MFCs. Recently, Lee et al. modifed the anodic electrodes of MFCs
with Rhodobacter sphaeroide-imprinted polymers by using various polymer concen-
trations to perform micro-contact imprinting of bacteria [86]. Park et al. also investi-
gated electricity generation in MFCs using e-beam deposited Pt electrodes to improve
effciency and minimize Pt loading [87]. Narayanasamy et al. then reported a carbon
cloth-based composite material with effectively improved electrochemical properties
resulting from surface modifcations with two redox species, namely nickel cobaltite
(NiCo2O4) and a conductive polymer (PANI), through a hydrothermal method and the
electro-polymerization technique, respectively [88]. Ying et al. prepared a TiO2 thin
flm-modifed SS mesh (SSM/TiO2-H) by an electrochemical method and applied it
as an anode in an MFC to enhance their power output. A maximum projected current
density of 69.5 ± 1.2 A m−2 was obtained from the SSM/TiO2-H electrode [89].
7.4.4.4 Direct Methanol Fuel Cells (DMFCs)

Membranes commonly used in a direct methanol fuel cell (DMFC) are expensive and
show a great permeability to methanol which reduces fuel utilization. Santiago et al.
developed sulfonated styrene-ethylene-butylene-styrene-modifed membranes with
zirconia silica phosphate sol–gel phase and studied them to evaluate their potential
132
FIGURE 7.12 (a) Schematic of the developed anode-supported thin-flm SOFC fabrication process. (b) Current–voltage curves of the fabricated large-
sized thin-flm SOFC. Adapted with permission from [83]. Copyright (2020) Elsevier.
2D Nanomaterials
use in DMFC applications [90]. Nanocellulose composite membrane was success-

fully synthesized by the phase inversion method and investigated its properties for
DMFC [91]. Suhaimin et al. synthesized SPEEK/GO membrane using a simple and
facile method. The carbonaceous fller, GO was incorporated into the SPEEK matrix
for improving the physical and chemical properties of the fabricated membrane [92].
A novel fexible gas diffusion layer was prepared by vacuum fltration of a suspension
of carbon fbers and highly-dispersed multiwall carbon nanotubes in a polytetrafuo-
roethylene binder and water repellent [93].
7.5 CONCLUSION
To meet the rising energy demand, it is critical to creating energy generation and stor-
age systems that are sustainable, effcient, eco-friendly, and low-cost. Faced with the
massive energy demands against the increasing carbon footprints and an impending
energy crisis, innovative ways to develop clean and renewable energy materials and
systems are extremely eminent. This is possible with microfabrication techniques.
The merits of utilizing microfabrication techniques such as thin flm deposition for
2D nanomaterials stern from the ease to control the product quality to the creat-
ing of enormous electron confnements in the 2D planes, which enhance electronic
properties. Thin-flm 2D materials feature excellent electrical, thermal, and optical
properties as compared to their bulky ones, which render them fexible and make
them suitable for wearable electronics. The effciency, behavior, and response of a
material in service can be infuenced by its surface characteristics. It is believed that
these surface features can be modifed and tuned to fulfll a specifc application for
greater performance, and this method has been widely used in a variety of felds. The
focus of this chapter is on the most recently evolved thin flm deposition techniques
for high-tech energy applications, particularly in advanced microelectronic device
production which necessitates the most enhanced performance for its applications.
Attention is paid to the materials, synthesis methods, and characterization techniques
employed in thin-flm 2D nanomaterials. The advantages and limitations of using the
various synthesis methods and characterization techniques have been reported.
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8 Wafer-Scale Growth
and High-Throughput
Characterization
of Ultrathin 2D
Transition Metal
Dichalcogenides
(TMDCs) for Energy
Applications
Shraddha Ganorkar
Sungkyunkwan University
Mangesh Diware
Seoul National University
CONTENTS
8.1 Introduction .................................................................................................. 140
8.2 Wafer-Scale Growth of Ultrathin TMDC Films .......................................... 141
8.2.1 Metal-Organic Chemical Vapor Deposition..................................... 142
8.2.2 Vertical-Ostwald Ripening Method ................................................. 142
8.2.3 Self-limiting Growth Method Using Atomic Layer Deposition ....... 144
8.2.4 Layer-Resolved 2D Material Splitting Technique ............................ 146
8.3 High-throughput Characterization of Wafer-Scale Ultrathin MoS2
Using Spectroscopic Ellipsometry................................................................ 149
8.3.1 Basics of Spectroscopic Ellipsometry .............................................. 150
8.3.2 Data Analysis.................................................................................... 152
8.3.3 Uniformity of Wafer-Scale MoS2 Monolayer ................................... 153
8.3.3.1 SE Measurement ................................................................ 153
8.3.3.2 Thickness-Dependent Dielectric Functions
Ultrathin MoS2 Films......................................................... 154
DOI: 10.1201/9781003178453-8 139

8.3.3.3 Thickness Mapping of MOCVD and ALD

Grown Wafer-Scale MoS2 Ultrathin Films........................ 154
8.4 Conclusion .................................................................................................... 156
References.............................................................................................................. 157
8.1 INTRODUCTION
An imminent threat for exhausting natural fossil fuels, climate change, and global
warming is lingering over our heads. A new era of ‘green energy’ is already started
where various innovative techniques have been tried and tested for sustainable energy
generation and developed strategies for its wise use. The challenge with energy utili-
zation is to use it effciently and consistently through smart and low-energy devices
with high performance. For example, massive data centers run by big tech giants use
nearly 1.15% of total global electricity consumption and are predicted to increase up
to 1.89% by 2030, which is ~ 658 TWh [1]. The design of energy-effcient devices
is a long-waited quest, and billions of dollars are being invested every year search-
ing for novel materials that can fulfll this task. The discovery of graphene, a two-
dimensional (2D) array of carbon atoms in a hexagonal pattern, surged a massive
interest in exfoliable layered materials, searching for a new degree of freedom whose
control can give the new exciting properties. 2D electronic materials have gained
momentous attention with the rise of graphene, realizing the lack of bandgap making
it unsuitable for smart electronics devices. Graphene has led the path for 2D materi-
als, and transition metal dichalcogenide (TMDC) has been born. TMDC is a family
of 2D layered materials with the general formula MX2, where M is transition metal
and X is chalcogenide. There are more than 40 TMDC possible combinations with
2D structure and increasing.
A typical 2D layered TMDC structure comprises a hexagonal plane of metal
(M) sandwiched between two hexagonal planes of chalcogenide (X) atoms with a
valance of +4 and −2, respectively [2]. Like graphene, each 2D layer with a thick-
ness of 6–7 Å has a strong M-X-M in-plane covalent bond and weak out-of-plane
Van der Waals interactions. The 2D TMDC stabilizes in two structural polytypes
– trigonal prismatic (2H) (Dh3 point group) and octahedral (1T) (D3d point group)
in the honeycomb and centered-honey comb motif, respectively, based on the posi-
tion of M relative to X in the M-X-M structure [2,3]. The irreversible transition of
2H to 1T polytype in a few TMDC is tunable via chemical processing [4]. Owing
to the confned movement of electrons in 2D layers, TMDC has remarkable prop-
erties such as direct bandgap in the visible-near infrared (IR) range, which can
be engineered with the number of layers, high carrier mobility, and high on/off
ratio, spin–orbit coupling (SOC), and ultra-strong Coulomb interaction linked to
the valley degree of freedom [5]. The semiconducting monolayer of TMDC is
successfully molded in green energy applications [6] such as energy generators,
energy storage, energy generator catalysis, electronic devices, and solar energy
harvesting. Strong interactions with light give rise to a series of emerging elec-
tronic and optoelectronic device applications [7], not limited to strong piezoelec-
tric coupling, feld-effect transistors, heterostructure junctions, photodetectors,
Characterization of Ultrathin 2D TMDCs 141
photovoltaics, and sensors with the advantage of ultrafast responses, compact,

light-weighted and energy-effcient. 2D TMDC has revolutionized the electronic
industry. However, most of the applications mentioned above are in the lab-based
research phase. These devices need to reach the batch-processing capability for
practical applications.
8.2 WAFER-SCALE GROWTH OF ULTRATHIN TMDC FILMS

Large area with a uniform thickness of ultrathin TMDC flms are prerequisites for
batch processing to meet the commercial application standards. The pivotal top-
down synthesis methods such as mechanical exfoliation for layered TMDC materi-
als give very high-quality pristine 2D sheets, useful for lab-scale research purposes
but suffer spatial and structural uniformity, including intrinsic defects. The exfoli-
ated size is limited to the quality of 3D precursor and impossible to achieve wafer-
scale 2D single crystal. The bottom-up approach facilitates large-area uniformity
by layer engineering via parametric control of vapor-phase deposition. However,
the conventional epitaxial thin flms suffer from lattice mismatch due to the strong
bonding nature of two surfaces (layer–substrate (LS)) resulting in intrinsic strain
in the thin flms, deteriorating the quality of the thin flms. On the contrary, due
to the high anisotropic atomic bonding and advantage of dimensionality, 2D mate-
rials are privileged with weak substrate interactions; hence, lattice mismatch and
growth mechanism have an insignifcant correlation. Theoretical studies by den-
sity function theory show the typical strength of interlayer interaction is 0.03 eV
atom−1 (layer–layer, LL) and LS is 0.2eV atom−1 for most of the 2D materials [8,9],
much lower than typical chemical bonds strength (2–8 eV atom−1). According to
the theory of thin-flm growth [10], the LL and LS interactions lead to three differ-
ent mechanisms. The Frank–van der Merwe (FM) growth facilitates layer-by-layer
growth through surface nucleation due to stronger LS and weaker LL interaction.
On the other hand, in Volmer–Weber (VW) growth, the clusters form without nucle-
ation due to stronger LL interaction comparatively weaker LS interactions lead-
ing to island formation. Stranski–Krastanov growth is transitional through surface
nucleation similar to FM followed by VW type over the critical thickness of the
flm [11]. Following the growth models, 2D materials with very weak LL interaction
and weak LS interaction must follow the FM growth mechanism enabling selec-
tive growth of mono or few layers of 2D materials [12]. After nucleation in the FM
mechanism, there are three possible scenarios for large-scale growth of 2D material:
frst, forming a single large nucleus on a substrate, which then grows to wafer-scale.
Second, the formation of multi-nucleus orientated in the same direction grows big-
ger fawlessly to form a large-scale single crystal. Third, differently oriented nano-
crystallites are grown into a large-scale polycrystalline 2D flm with unrestrained
grains and grain boundaries. Enormous efforts have been dedicated to the synthesis
of large-area ultrathin TMDC flms, including chemical vapor deposition (CVD)
[13], metal-organic chemical vapor deposition (MOCVD) [12], and micromechani-
cal cleavage [5]. In this section, the most effective wafer-scale synthesis methods for
ultrathin TMDC are described.
8.2.1 METAL-ORGANIC CHEMICAL VAPOR DEPOSITION

The MOCVD technique uses the metal-organic sources (i.e., Mo(CO)6, W(CO)6,
(CH3)2Se, (C2H5)2S), and H2S) that are generally preferred due to cost-effective-
ness and precise control over the concentration of gases. MOCVD facilitates several
degrees of freedom such as temperature, pressure, carrier gas, and chalcogen/transition
(X/M) metal ratio to precise control of grain size, nucleation density, structure, etc. In
showerhead-type MOCVD, the precursor gases are inserted into the reactor through the
showerhead across the entire substrate area (wafer). The gas inlet is equipped with an
array of multi-tube assemblies to spread the individual gases. The gases are introduced
in the reactor separately for even distribution during the reaction. The substrate (wafer) is
mounted on a rotating susceptor, which is heated by the resistance heater. The advantage
of MOCVD over CVD is the temperature for the process that can be as low as 250°C.
Figure 8.1a shows schematics of a typical MOCVD with a mass fow controller
connected to various gases. The top inset of Figure 8.1a shows an SEM image of MoS2
island that is eventually grown to 8-inch MoS2 ultrathin polycrystalline flm using
MOCVD, with 30 sccm H2S gas, chamber pressure of 10 Torr, growth temperature
of 400°C, and S/Mo, Ar/H2S, and H2/H2S molar ratios of 200, 5, and 5, respectively,
with an optimum growth time of 9 hours [14]. The growth mechanism for the poly-
crystalline large-scale ultrathin flm follows the FM growth. The parametric studies
of MOCVD grown MoS2 show a critical balance of control parameters for wafer-scale
growth [14]. Ar fow rate has a signifcant infuence on MOCVD. Figure 8.1b indicates
the effect of growth pressure on nucleation density. The nucleation density increases
with an increasing fow rate, which could be due to the effective temperature of the
substrate, as the higher fow rate will lose the temperature equilibrium in the reactor.
The ambient gas, H2, acts as a catalyst for the nucleation site and prevents inter-grain
coupling. This results in a higher lateral growth rate by blocking bilayer formation.
Comparing the effect of the fow rate of two gases, higher H2 facilitates the growth
of quasi monolayer formation of MoS2. In contrast, a higher Ar fow rate deteriorates
the quality of MoS2 crystal and leads to the formation of multilayer, confrmed by
Raman spectra [14]. The growth pressure is the most important parameter to produce
wafer-scale MoS2 via optimizing the higher lateral growth rate. The parametric varia-
tion study under the growth pressure 0.3–9 Torr results in decreasing nucleation site
and increasing grain size (with constant parameters: T = 400°C, X/M = 300) due to
competing driving forces of crystallization with increasing the pressure. The grain
size is inversely proportional to nucleation density for 2D TMDC and increases with
the X/M ratio due to the higher diffusivity of M compared to X. The MOCVD is
one of the promising techniques for industrial production of wafer-scale 2D TMDC,
enabling the easy and precise control of growth parameters. The major drawback of
MOCVD is that it is a time-consuming process. The temperature equilibrium of the
chamber is very sensitive to growth and needs to optimize in the future.
8.2.2 VERTICAL-OSTWALD RIPENING METHOD

The MOCVD method is a promising technique to grow wafer-scale TMDC ultra-
thin flms, as mentioned above. The major drawback is its slow growth rate due to
the use of needed low precursor pressure to avoid the secondary nucleation over
Characterization of Ultrathin 2D TMDCs
FIGURE 8.1 (a) Schematics of MOCVD and (b-d) SEM images for parametric study MoS2 ultrathin flm growth. Inset of Figure (a) and Figure (b-d)
are adapted with permission from Ref. [14]. Copyright 2017 Institute of Physics Publishing.
143
pre-deposited TMDC. Large-area growth of monolayer will require several hours,

not a cost-effective way. The higher partial pressure of precursors is essential to
increase the growth rate, but it favors the island-type growth. Secondary nucleation
over pre-grown monolayer should be regulated to achieve fast wafer-scale mono-
layer growth. The modifed-MOCVD method introduced by Seol et al. is called
pulsed MOCVD for the rapid growth of wafer-scale MoS2 and WS2 monolayer [15].
Schematic of TMDC monolayer growth via the vertical-Ostwald ripening process is
illustrated in Figure 8.2a. Nano-TMDC (e.g., MoS2) crystallites grow over the entire
wafer surface during the initial stage of the growth process. Secondary nucleation
could start on these pre-deposited MoS2 nanocrystals unless suddenly precursor sup-
ply cuts off, stopping the MoSx cluster from reaching critical nuclei size. As shown
in Figure 8.2b, adatoms energetically favor the edge than the basal plane of the pre-
deposited MoS2 nanocrystals. Both adatoms and unstable MoSx clusters diffuse from
surface to edge of the pre-deposited MoS2 nanocrystals, called vertical-Ostwald rip-
ening. Seol et al. observed that Mo adatoms can survive for 5.9 μs and travel up to
65 nm at 900°C before desorption [15]. So, cutting precursor supply provides enough
time for adatoms to diffuse from surface to edge of the pre-deposited MoS2 nano-
crystals. Accordingly, pulsating precursor injection, shown in Figure 8.2d, subdues
the vertical growth and helps to achieve wafer-scale MoS2 monolayer.
Seol et al. used the showerhead-type cold wall reactor to facilitate the uni-
form and controlled precursor supply over the entire substrate surface, as shown
in Figure 8.2c-i. Figure 8.2c-ii shows the reaction cycles; gas phase (Mo(CO)6) or
(W(CO)6), ((C2H5)2S2), and H2 precursors were injected for 2 minutes using N2 carrier
gas followed by purging the chamber with N2 for 1 minute after stopping precur-
sor supply. Thus, four of such reaction cycles were enough to grow MoS2 and WS2
monolayer over a 6-inch quartz wafer. The total growth time was only 12 minutes.
Raman line-scan across the wafer and photoluminescence peak intensity map con-
frms the uniformity of the grown MoS2 monolayer, shown in Figure 8.2e and f,
respectively [15].
8.2.3 SELF-LIMITING GROWTH METHOD USING ATOMIC LAYER DEPOSITION

In the previous sections, we have discussed vapor depositions of ultrathin 2D TMDC
flms that indicate the sensitivity of deposition parameters on the growth of the large-
area ultrathin flm. The change in the control parameters or the thermodynamics
equilibrium in the reactor can lead to multilayer deposition. The self-limiting growth
of ultrathin flms is an effective and effcient way to grow wafer-scale 2D TMDC
materials. Atomic layer deposition (ALD) is known for the self-limiting growth
technique for 2D TMDC flms using a layer-by-layer deposition approach via alter-
nate precursor exposure. ALD consists of four major steps – (a) precursor exposure,
(b) purge/evacuating precursor/byproducts, (c) precursor/reactant exposure, and (d)
purge/evacuate reactants/byproducts. Contrary to CVD, the growth in ALD does
not depend on the fow rate; rather, it depends on the kinetics of surface reaction
leading to self-limiting growth. The self-limiting growth technique is important for
industrial production since critical control of precursor gases is no longer required to
avoid multilayer formation. Eventually, wafer-scale growth time can be dramatically
FIGURE 8.2 Pulsed MOCVD facilitates the vertical-Ostwald ripening process to grow
wafer-scale TMDC monolayer. Growth of wafer-scale monolayer TMDCs. a) Schematic of the
growth mechanism by pulsed MOCVD. After nucleation in the early stage (i), lateral growth
is induced by repeating the precursor injection and interruption steps (ii), which results in
continuous monolayer TMDCs (iii). b) Calculated reaction energy diagram of Mo adsorbed
on the basal plane of MoS2. c) Schematic illustration of the reactor geometry (i) and injection
sequence of precursors (ii) for growing wafer-scale monolayer TMDCs. A shower-head-type,
cold-wall reactor system was used with MO precursors. d) Photograph of wafer-scale mono-
layer MoS2 and WS2 grown on 6-inch quartz glass wafers. e) Color-coded rendering of the
spatially resolved Raman spectra for MoS2 flms. The data were collected from 300 positions
(with an interval of 500 µm along the horizontal direction of the entire 6-inch wafer). Inset:
Raman spectrum of the MoS2 flm. f) PL peak intensity mapping of the MoS2 flm on the
wafer scale. The spatial resolution is 1 cm. Inset: PL spectrum of the MoS2 flm. Adapted with
permission from Ref. [15]. Copyright 2020 Wiley-VCH GmbH.
shortened. The frst step in the self-limiting process is the adsorption of precursor
molecules on the surface, achieved by the ligands bonded to the metal atoms in the
precursors (halogen or organic ligands), resulting in the growth of the frst mono-
layer. Consequently, after forming a fully covered monolayer, no further catalytic
surface is available for the additional decomposition of ligands. This process limits
the adsorption of the precursor by passivating the adsorption sites after the saturation
coverage is reached, i.e., self-limiting. Excess exposure of precursor gases will not
take part in the formation of layers. Large-scale 2D MoS2 and WS2 are successfully
grown by this self-limiting method [16,17]. The self-limiting technique can be tuned
to control layer thickness by varying the number of ALD cycles, temperature, or
fow concentration [16]. Nevertheless, the self-limiting method can be engineered
to be completely temperature-dependent (cycle independent) by using liquid-phase
organic precursor in place of the gaseous H2S reactant. Park et al. [18] used WCl2
and C4H10Se as precursor and reactant, respectively, with temperature as an effcient
parameter for controlling the number of layers of WSe2. The pre-heated precursor
was carried into the tubular furnace by a pure Ar carrier gas. H2 gas was used with
C4H10Se for reducing WCl6.
Figure 8.3a shows a schematic of the ALD self-limiting process, including the
four steps: precursor exposure for 4 s, Ar purge 5 s, reactant exposure for 3 s, and a
fnal 5 s Ar purge. The ultrathin WSe2 flms are synthesized with 100 ALD cycle
at a temperature ranging from 600°C to 800°C with the precise controlling thick-
ness from mono- to penta-layer as shown in Figure 8.3b and c. The quality of the
flms is confrmed by photoluminescence, X-ray photoelectron spectroscopy, and
Raman spectroscopy, shown in Figure 8.3d–j. The uniformity of tri-layer WSe2 on
the 6-inch wafer strip was confrmed by measuring Raman spectra line-scan along
the wafer length (shown in Figure 8.3h–j). The temperature sensitivity of the self-
limiting mechanism can be understood from the surface potential difference of the
used precursor. First, the surface of TMDC is inherently inert for physical adsorp-
tion over the substrate. Second, the surface potential depth of the WCl6 precur-
sor decreases with the increasing thickness of WSe2 2D layers due to screening
from the electric feld of the pre-deposited layer [18]. Hence at the given growth
pressure, the number of layers can be terminated by lowering the potential depth
of WCl6 via manipulating the growth temperature. This method has the potential
for industrial-scale production of wafer-scale 2D TMDC flms using liquid-phase
organic reactants.
8.2.4 LAYER-RESOLVED 2D MATERIAL SPLITTING TECHNIQUE

Exfoliation of 2D layers is one of the pioneer methods, which gives pristine 2D
layer materials. The vapor deposition methods can lead to contamination due to
precursors, reactants, and the carrier gas used during the process, thereby affect-
ing the properties of 2D TMDC. Nevertheless, the exfoliation with adhesive tape is
time-consuming, and wafer-scale exfoliation is impossible. The size of exfoliated
gains highly depends on the quality of the 3D crystal used. Recently, Shim et al.
[19] introduced the layer-resolved spitting (LRS) technique by integrating with pre-
liminary wafer-scale deposition methods such as MOCVD and vapor phase epitaxy.
The steps involved in the LRS technique are illustrated in Figure 8.4a. A thick 2D
TMDC flm is deposited on a wafer using vapor phase deposition, followed by a
capping layer of 600 nm thick Ni. A thermal releasing tape is used as a handler to
peel off 2D TMDC/Ni layer completely from the 5 cm diameter wafer to giving a
TMDC/Ni/Tape stack. Another Ni layer is deposited on the bottom of the TMDC/
Ni/Tape stack to form strong adhesion to the 2D TMDC layers; these give the Ni/
FIGURE 8.3 (a) Schematic of self-limiting process, (b-d) AFM images of 1L, 3L, and 5L of WSe2 flms showing their thickness with growth tem-
peratures of 600C,700C, and 800C, respectively. (e) Photoluminescence as a function of a number of layers and (f) XPS spectra show the quality of the
grown layers, (g) number of ALD cycles with temperature, and (h-j) uniformity investigation of tri-layer WSe2 deposited SiO2/Si substrate by Raman
spectroscopy. The intensity ratio of characteristic Raman peaks is used to quantify thickness uniformity. ((a) Adapted with permission from Ref. [17]
Copyright 2013 American Chemical Society and (b-j) adapted with permission from Ref. [16] Copyright 2016 Springer Nature.)
147
148
2D Nanomaterials
FIGURE 8.4 (a) Schematic of layer-resolved spitting method, (b)–(e) schematic of Au-assisted large-scale exfoliation of TMDC with optical image
and feck area count. Figures (b)–(e) adapted with permission from Ref [20]. Copyright 2016, John Wily & Sons.
TMDC/Ni/Tape stack. A second thermal tape handler was used on the bottom Ni.
The stack is then split, followed by transfer on Si/SiO2 substrate (Si/SiO2/TMDC/
Ni/Tape). The transferred stacking was then heated to 110°C to release the tape.
The Ni flm was etched in the solution of FeCl3 followed by rinsing with DI water.
The above steps can be used for multiple splitting. The key parameter of the LRS
process is the interfacial toughness (Γ) between Ni-TMDC-substrate and TMDC
interlayer. The ΓTMDC - ΓTMDC < ΓTMDC - Γsapphire < ΓTMDC - ΓNi, (0.26, 0.45, and 1.4
Jm−2), respectively. Shim et al. claim that LSR is the universal method applicable to
all TMDC. The underlying mechanism is explained on the basis of external force
triggered bending moment torque applied across a small distance in the sample that
initiates spalling mode fracture and cracks formation. The LSR method is a modi-
fed version of metal-assisted TMDC exfoliation described by Desai et al. [20,21] as
depicted in Figure 8.4b. The large-scale Au-assisted exfoliated MoS2 fake is shown
in Figure 8.4c. The metal-assisted exfoliation has dramatically enhanced the fack
area compared in Figure 8.4d and e.
8.3 HIGH-THROUGHPUT CHARACTERIZATION

OF WAFER-SCALE ULTRATHIN MoS2 USING
SPECTROSCOPIC ELLIPSOMETRY
Mechanical exfoliation of TMDC single crystals can give defect-free TMDC mono-
and multilayers very easily but limited to a small area, suitable for research pur-
poses. On the other hand, commercial applications demand wafer-scale production
of ultrathin TMDCs flms with precise thickness control for batch processing. Also,
there should be easy access to crucial information about these large-area flm quality
and thickness uniformity. Various attempts were made to grow wafer-scale TMDCs
flms [12,22–25]; poor thickness control and limited deposition scale are a few limi-
tations of these methods. Recently, Kim et al. [14], Park et al. [18], Shim et al. [19],
and Seol et al. [15] developed effcient recipes using MOCVD and ALD methods to
grow wafer-scale TMDC monolayer flms with precise thickness control by single
deposition parameter; details are in the above section. Usually, the thickness and
quality of TMDC ultrathin flms are characterized by atomic force microscopy
(AFM), tunneling electron microscope, and X-ray photoelectrons spectroscopy,
which are inadequate for large-area samples. However, Raman spectroscopy and
photoluminescence are being used for large area samples, but an intense laser beam
could damage the underlying material. Therefore, a fast and non-destructive method
is needed to quantify thickness uniformity and quality of wafer-scale TMDC ultra-
thin flms.
Ellipsometry can provide that option; it has come a long way since the frst appear-
ance of the commercial instrument in the frst half of the 19th century due to the
advancement of automation and computation power and expanded in a wide applica-
tion area. Specifcally, it became a valuable measurement technique and real-time
feedback control in the semiconducting industry. This section will discuss spectro-
scopic ellipsometry (SE) basics, data analysis, and application for wafer-scale char-
acterization of ultrathin TMDC materials.
8.3.1 BASICS OF SPECTROSCOPIC ELLIPSOMETRY

Details about the ellipsometry technique are given in the standard books [26,27].
However, essential terms needed for discussion are explained in brief. Figure 8.5a
illustrates the working principle of ellipsometry. SE measures the change in a polar-
ization state of incident light after interaction with the sample surface. Spectroscopic
means several wavelengths of light are used. The polarization state of light is
defned in terms of coordinates of the waves propagating along two orthogonal
axes: parallel (p-) and perpendicular (s-) to the plane of incidence. For example,
linear polarized light is defned in Figure 8.5a where incident light is in the frst
quadrant, oriented at −45° with-respect-to Eip = Eis; is incident electric feld vec-
tor for p- and s- polarization. It means the amplitude of electric vectors for both
the polarization is the same, and the phase difference between them is zero. In the
same way, other polarization states can be defned from amplitude and phase differ-
ences between p- and s-polarization vectors. The most common polarization state
is elliptical hence the name. The p- and s-polarized components of the incident
beam behave differently after interacting with the sample, and amplitude refection
coeffcients are different. Therefore, change in polarization state is measured from
modifed refected light in terms of two ellipsometric angles Ψ: amplitude ratio and
Δ: phase difference between refected p- and s-polarizations. The complex refec-
tance ratio is given below:
˜=
( Erp / Eip ) rp
= tan ˙ exp ( −iˇ )
( Ers / Eip ) = rs (8.1)
rp
°= , ˝ = ˜ rp − ˜ rs (8.2)
rs
where E is the electric feld vector, ‘r’ is for refection, and ‘’ for incidence.
SE instruments in various confgurations are available depending on optical com-
ponents and the modulation type used [26,27]. Rotating-analyze type SE (RASE)
with simple optical confguration and automated data acquisition was frst devised by
Aspens et al. in 1975 [28]. To overcome the limitations of RASE, which is it cannot
measure the complete range of Ψ and Δ, more complicated versions are invented.
The most popular and accurate confguration is the rotating compensator SE (RCSE).
The compensator is a quarter-wave plate that generates a phase difference between
p- and s-components of the electric vector of the light. The RCSE measures the full
range of Ψ and Δ (0° ≤ Ψ ≤ 90° and 0° ≤ Δ ≤ 360°). Complete Stokes parameter can
be measured, allowing uniform measurement sensitivity and depolarization from a
sample.
Figure 8.5a shows the schematics of rotating compensator type SE (RCSE), con-
sisting of light source – polarizer (P) – rotating compensator (C) – sample – analyzer
(A) – detector. A combination of P and C convert the unpolarized incident beam into
circularly polarized light. Therefore, the light of known polarization is incident on the
sample surface, generating elliptically polarized refected beam, passed through the
FIGURE 8.5 (a) Schematic of rotating compensator spectroscopic ellipsometer (SE) explaining the basic principles of ellipsometry technique. (b)
Analysis procedure of SE data. (c) SE data analysis of MoS2 ultrathin flms: (c-i) Ψ and (c-ii) Δ spectra of mono-, bi-, tri-, tetra-, and hexa-layer MoS2
flms on SiO2 (100 nm)/Si substrate. (c-iii) Four-layer (ambient/MoS2/SiO2/Si) optical model used for data analysis. (c-iv) Calculated (lines) and mea-
sured (symbols) data for MoS2 monolayer show the good ft. (c-v) Thicknesses of MoS2 thin flms obtained from SE analysis, compared with values
obtained using AFM. (d) Extracted dielectric functions of MoS2 ultrathin flms. (d-i) Imaginary part of the dielectric function of monolayer MoS2 grown
by MOCVD and ALD, compared with CVD grown Ref. data [29]. The (d-ii) ε 2 and (d-iii) ε1 of MOCVD grown mono-, bi-, tri-, tetra-, and hexa-layer
151
MoS2 flms.
analyzer and fnally to the detector to measure the polarization change. It is advised
that measurements should be done at multiple angles around the Brewster angle for
ex situ measurements. For an in situ application, suppose an ellipsometer is attached
to the deposition chamber, there is a restriction of fx angle. In that case, it should be
aligned at the Brewster angle where p- and s-polarization have the highest sensitivity.
Proper calibration should be performed to initialize the optical components before
measurements. Also, chromatic errors from optical elements should be corrected for
spectroscopic measurements.
8.3.2 DATA ANALYSIS

The bitter truth about ellipsometry is that if you don’t have a complete description
of a sample to construct an optical model as close as an actual sample, you cannot
fgure out what you have measured despite being the most surface-sensitive tech-
nique known today. Measured SE data contain the information of the whole sample
structure accessed by the entire penetration depth of the probing light. Therefore,
to make sense of measured data, a proper analysis procedure should be followed, as
shown in Figure 8.5b. The frst step is the construction of an optical model, which
can regenerate measured data and separate the optical response of the thin flm
from substrates using Fresnel’s equations [26]. An optical model is the structure of
stacked fat layers representing an actual sample as close as possible. Each layer used
in the optical model is defned by thickness and dielectric function ( ˜ = ˜1 + i˜ 2 ).
For example, to represent the measured SE data for silicon wafer requires a three-
layer optical model: the frst layer is silicon, the second layer is SiO2, which grows
naturally over silicon, and the third layer is ambient. Analytical oscillator models
(AOMs) are used to represent the ε of material if it is not known. Various AOMs are
available and can be used concerning the properties of the material. For example,
the Cauchy model is for transparent material, Drude model represents the free-
electron response. For absorbing materials, Lorentz or Tauc-Lorentz models can be
used [30]. An important point to remember is that the ε of the substrate should be
known in advance to analyze a flm. So measurement of the substrate is advisable
before flm deposition.
The next step is to match the calculated data with experimental data via ftting
some parameters representing the layers in the optical model. We can ft any SE
data if many ftting parameters are used, but results may be unphysical. So, we
need to use a minimum number of ftting parameters that show no correlations. The
microstructure and thickness of the flms should be checked using AFM, SEM, or
TEM; their advanced knowledge can ease the ftting process and may lead to accu-
rate extraction of thin flm's dielectric function. Multi-wavelength, multi-angle, and
multi-sample measurements generate an extensive data set, which will help to extract
reliable results from the analysis. Finally, ftting results can be improved by correct-
ing the model appropriate to the real sample, i.e., adding interference effect, surface
roughness, and an interface layer. Physical properties like dielectric function, funda-
mental bandgap, and thin-flm thickness can be extracted by achieving an excellent
ft between calculated and measured data. Dielectric function is related to complex
refectance ratio as
ˇ ˇ1 − ˛
2
˜ = sin 2 ° 1 + tan 2 ° (8.3)

˘ ˘ 1 + ˛
where θ is the angle of incidence. The ˜ is a dielectric function of a whole sample

accessed by a probing beam. The ε of the thin flms is obtained from Eq. (8.3) using
Fresnel’s equations. Other optical functions can be easily obtained as ˜1 = n 2 − k 2
and ˜ 2 = 2nk, where n is the refractive index, k is absorption coeffcient, ˜1 and ˜ 2 are
real and imaginary parts of the ε. The thickness of a thin flm is obtained from phase
thickness as ˜ = 2° dN cos˛ /˝ , where β is phase thickness, d is a flm thickness,
N = n + ik is a complex refractive index, and λ is the wavelength of probing light. For
a detailed derivation of these quantities, please refer to these books [26,27].
8.3.3 UNIFORMITY OF WAFER-SCALE MOS2 MONOLAYER

In this investigation, MoS2 ultrathin flms with varying thickness (mono- (1L), bi-
(2L), tri- (3L), tetra- (4L), and hexa-layer (6L)) were grown on 2 × 2 cm2 SiO2(100 nm)/
Si substrate to optimize the MoS2 thickness extraction process from SE data. Actual
large-area MoS2 monolayer and multilayers samples were grown on an 8-inch
SiO2(300 nm)/Si wafer. SiO2 was grown from wet thermal oxidation of Si wafer.
Therefore, SE data are represented as [31]:
˜ = f ( ° air , ° MoS2 , ° SiO2 , ° Si ,dSiO2 ,d MoS2 , E,˛ ) (8.4)
Measured Ψ and Δ spectra are the function of eight parameters: dielectric functions
of air ( ˜ air ), MoS2 ( ˜ MoS2 ), SiO2 ( ˜ SiO2 ), Si ( ˜ si ), thicknesses of SiO2 ( dSiO2 ), MoS2
( d MoS2 ), the energy of probing beam (E), and angle of incidence (θ). We need to
reduce the unknowns from Eq. (8.4) to avoid the complications in the analysis due
to correlations among ftting parameters and for accurate extraction of the proper-
ties of ultrathin MoS2 like thickness and ˜ MoS2 from SE data. The E, θ, and ˜ air = 1
are known. Si and SiO2 are well-known materials, and their ε is available with good
precision. The dSiO2 value can be obtained by prior measurement of a substrate before
deposition. The ˜ MoS2 , d MoS2 are the only remaining unknown parameters. The ˜ MoS2
is thickness dependent [32], so its knowledge is essential for analyzing wafer-scale
MoS2 ultrathin flms and mapping the thickness.
8.3.3.1 SE Measurement
Ellipsometric measurements were performed using M200D RCSE from J.A Woollam
Co. inc. The M2000D model is equipped with an automated goniometer for vari-
able angle measurement, XY stage for precise multi-sport measurement, and a laser
system for sample alignment. This automation is necessary to measure wafer-scale
samples. The measured energy range was 1.24–3.50 eV. Angles of incidence were
60°, 65°, 70°, and 75°. The 1L, 2L, 3L, 4L, and 6L MoS2 flms were measured at
multiple spots. This extensive data set for every sample is helpful to accurately obtain
the ˜ MoS2 . Similar measurements were performed at 950 spots over an 8-inch wafer
of MOCVD grown samples and at 51 spots for 1.5 x 20 cm2 of ALD grown samples
to map the thickness uniformity.
8.3.3.2 Thickness-Dependent Dielectric Functions Ultrathin MoS2 Films

Figure 8.5c-i,ii show the measured Ψ and Δ spectra of 1L, 2L, 3L, 4L, and 6L MoS2
flms, clearly shows the effect of the thickness variation of these ultrathin flms. Raw
SE data can be used to detect the difference between a number of layers of MoS2.
Aex and Bex optical features are excitonic transitions from split valence band due to
SOC to excitonic ground state. Four-layer (ambient/MoS2/SiO2/Si) optical model,
shown in Figure 8.5c-iii, was used for data analysis. Thicknesses of the ambient
and Si are taken as infnite and dSiO2 =~ 100 nm, measured previously. The ˜ SiO2 and
˜ Si are taken from the literature [33]. The d MoS2 was measured using AFM, and
used as the initial guess and refned during ftting. Only unknown parameter is
˜ MoS2 . Wavelength-by-wavelength (w-b-w) ftting approach was used to match the
measured data. Measured and calculated Ψ and Δ spectra of monolayer MoS2 on Si
substrate is plotted in Figure 8.5c-iv. Used known parameters in Eq. (8.4) are avail-
able with good accuracy, results in that simple w-b-w ft provide better results [34].
Otherwise, we had to use AMO to represent the ˜ MoS2 . Care should be taken that
˜ MoS2 obtained from w-b-w ft is not necessarily Kramer–Kronig (KK) consistent.
In our case, ε1 and ε 2 follow KK relations, suggest the accuracy of our model. The
obtained d MoS2 values from SE analysis were compared with measured using AFM,
shown in Figure 8.5c-v.
Extracted ˜ MoS2 from the above procedure is plotted in Figure 8.5d. The ε2 spectra
of ALD and MOCVD grown MoS2 1L are compared with reported data by Lee et al.
[29], which were measured on CVD grown 1L MoS2. Line shapes are nearly similar.
Peaks Aex and Bex are the excitonic transitions from split valence band minimum due
to SOC to the excitonic ground state at the K point of the Brillouin zone. The SOC
splitting is 0.12 ± 0.02 eV. High energy absorption peak E1 is from high energy inter-
band transitions due to the presence of the Van Hove singularities in joint density of
states at high-symmetry points and saddle-points from band nesting. It is observed
that the ˜ MoS2 depends on the thickness of the ultrathin flms, shifts to the lower
energy with an increasing number of layers, plotted in Figure 8.5c-ii,iii. Therefore, it
is critical to know accurate ˜ MoS2 to calculate other dependent properties like device
performance.
8.3.3.3 Thickness Mapping of MOCVD and ALD Grown
Wafer-Scale MoS2 Ultrathin Films
As we mentioned above, if we want to extract one desired property from Eq. (8.4),
the remaining seven parameters should be known with the required accuracy. An
8-inch wafer was used for MOCVD growth, and a 1.5 cm × 20.0 cm strip was used
for ALD due to instrument restrictions. Commercially available 8-inch silicon wafers
are with thermally grown 300 nm SiO2 that was used to deposit MoS2 flms. Si wafers
from two different manufacturers were used for MOCVD and ALD, their provided
value dSiO2 = 300 ± 5nm. We have observed that dSiO2 is not uniform over an 8-inch
wafer, should be measured before deposition. Si wafers were measured with the same
procedure mentioned above and obtained the map of the SiO2 thickness using the fol-
lowing analysis. A three-layer (ambient/SiO2/Si) optical model was used, as shown
in Figure 8.6a. Figure 8.6b and c show the ˜ SiO2 and ˜ Si , respectively, used as the fx
parameter and only dSiO2 was varied during ftting.
FIGURE 8.6 Characterization of substrate (SiO2 (300nm)/Si) before MoS2 deposition. (a) Three-layer optical model, and (b) ˜ SiO2 and (c) ˜ Si . Thickness
map of SiO2 over (d) 8-inch wafer used in MOCVD and (e) 1.5 cm × 20.0 cm strip used in ALD growth of MoS2 ultrathin flms. Thickness map of wafer-
scale MoS2 (f) monolayer grown by MOCVD and (g) bilayer grown by ALD.
155
The SiO2 thickness map of both the wafers is given in Figure 8.6d and e. The 8-inch
Si wafer has 308.9 ± 1 nm SiO2 layer (Figure 8.6d), which suggests good quality wafer.
While Si wafer used for ALD shows the non-uniform SiO2 formation, edge to the cen-
ter has ~ 5 nm thickness difference (Figure 8.6e), which may cause an error in d MoS2
estimation. Therefore, it is highly advisable to measure substrates before deposition.
Finally, we have collected all the necessary parameters in Eq. (8.4) to estimate
the thickness uniformity of wafer-scale MoS2. We limit the use of energy range
between 1.3 and 3.0 eV where the substrate is transparent, which will be helpful
for easy converge of ftting data. Also, the high energy optical response of MoS2 is
unpredictable due to the complicated nature of its band structure; two samples with
the same thickness show slightly different values of ε, which may induce an error
in uniformity analysis. The same four-layer was used and plugged all the obtained
parameters in Eq. (8.4), only d MoS2 was the unknown parameter. Thickness maps
are obtained from the above procedure for wafer-scale MoS2 flm grown over 8-inch
wafer by MOCVD and 1.5 cm × 20.0 cm wafer strip by ALD, plotted in Figure
8.6f and g, respectively. It is observed that MOCVD-grown MoS2 flm has an aver-
age thickness of 0.65 ± 0.05 nm (monolayer), and ALD-grown flm's average thick-
ness is 1.25 ± 0.05 nm (bilayer). This precise thickness control growth of MoS2 was
achieved by controlling the partial pressure of precursor gases and growth tempera-
ture, explained in detail in the synthesis section.
Thickness uniformity (U) was quantifed using the following expression [31],
U=
( davg − dˆ )
davg × 100 (8.5)
where davg is the average thickness of ultrathin MoS2 flms, dσ is the standard devi-
ation in the measurement. Wafer-scale MoS2 monolayer grown using MOCVD
shows ~ 92%, and ALD grown bilayer shows ~ 96% thickness uniformity.
8.4 CONCLUSION
This chapter introduces the different methods for wafer-scale growth, which have
the potential of mass production, and a non-destructive way to characterize the
wafer-scale samples to quantify the uniformity and quality of ultrathin TMDC flms.
Wafer-scale production of high-quality 2D TMDC materials is necessary for batch
processing to meet the criteria of practical commercial applications. Four different
approaches, namely MOCVD, pulsed MOCVD, ALD with self-limiting approach,
and layered resolved splitting, are summarized, which showed uniform wafer-scale
growth of ultrathin TMDC flms. The frst three methods use vapor phase precur-
sors and control the thickness of flms via vapor pressure, precursors injection time,
growth temperatures, and reactant gas ratio. However, the fourth method uses metal-
assisted controlled crack initiations and propagation in wafer-scale artifcially grown
thick TMDC flms. Pulsed MOCVD with the vertical-Ostwald ripening process to
control the secondary nucleation over pre-deposited TMDC nanocrystals and sur-
face diffusion to cover the entire surface is the most promising method for mass
production. However, further investigations are required to reach that goal.
SE, a non-destructive optical technique, is a powerful tool that can optimize the
growth process of wafer-scale ultrathin TDMCs flms, leading to practical device
development. This chapter explains the basics of SE and the data analysis procedure. It
is observed that rotating compensator SE is a good choice for high-speed data acquisi-
tion and can be used for a variety of materials with high accuracy and precision. The
optical properties of sensitive materials like TMDCs strongly depend on growth tech-
niques and substrates. Therefore, we frst build the database of thickness-dependent
dielectric functions (ε) of MoS2 ultrathin flms, which will be used as a fxed parameter
or as the initial guess during accurate thickness mapping. We build the extensive SE
data set for each measured point using 370 wavelengths and 5 angles of incidences,
which helps to reduce any correlation in ftting parameters. Using pre-measured
parameters, which defne the SE data of MoS2 monolayer on SiO2(300 nm)/Si sub-
strate, the thickness map of MoS2 was obtained, shows 96% uniformity. The capabil-
ity of SE to measure the high-speed thickness and the parameter that could defne the
material's quality help to bring the proposed technologies from lab to production lines.
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9 Morphological Aspects
of 2D Nanomaterials for
Energy Applications
Jing Ning, Maoyang Xia, Dong Wang,
Jincheng Zhang, and Yue Hao
Xidian University
CONTENTS
9.1 Introduction .................................................................................................. 162
9.2 Graphene....................................................................................................... 162
9.2.1 Morphology and Synthesis Method.................................................. 162
9.2.1.1 Graphene Nanosheet .......................................................... 162
9.2.1.2 Porous Graphene................................................................ 163
9.2.2 Application of Graphene as Electrode.............................................. 164
9.2.2.1 Supercapacitor.................................................................... 164
9.2.2.2 Lithium-Ion Batteries......................................................... 165
9.2.2.3 Sodium-Ion Batteries ......................................................... 165
9.2.2.4 Potassium-Ion Batteries ..................................................... 165
9.3 Transition Metal Dichalcogenides (TMDCs) ............................................... 166
9.3.1.1 TMDC Nanofakes............................................................. 166
9.3.1.2 TMDC Nanorod and Nanofower ...................................... 167
9.3.1.3 TMDC Nanofber............................................................... 167
9.3.1.4 Porous TMDC.................................................................... 167
9.3.2 Application of TMDCs as Electrode ................................................ 167
9.3.2.1 Supercapacitor.................................................................... 167
9.4 MXene .......................................................................................................... 168
9.4.1.1 MXene Nanofake .............................................................. 168
9.4.1.2 Porous MXene ................................................................... 169
9.4.2 Application of MXene as Electrode ................................................. 169
9.4.2.1 Supercapacitor.................................................................... 169
DOI: 10.1201/9781003178453-9 161


9.5 Conclusions and Perspectives ....................................................................... 170
References.............................................................................................................. 171
9.1 INTRODUCTION
In the information age of the rapid development of the Internet of Things connec-
tion, self-developed smart chips for various applications have become a problem
to be solved in all countries. The energy supply system integrated with microelec-
tronic devices is required for fast charging and discharging, high power density, long
cycling lives, and good stability. Selecting the appropriate electrode material is the
key to ensuring high energy density for the micro-energy storage system. So far,
two-dimensional (2D) nanomaterials have shown promising prospects in the feld of
energy storage due to their excellent physical and chemical properties.
Since the preparation of graphene, many atomic-layer materials including 2D
TMDCs and MXene have also been implemented in laboratories. These materi-
als present layered structures with a dimensional constraint in one direction. The
micron-scale lateral size and nanoscale thickness endow the 2D nanomaterials with
ultra-high specifc surface areas and exposure of the surface atoms, which make them
suitable for surface modifcation. Due to their lower dimension, the open channels for
ion diffusion and the presence of active sites enable the fast transport and effcient
storage of ions. The strong covalent bonds in the 2D nanosheets result in prominent
mechanical strength and fexibility for individual sheets. Therefore, excellent and
unique physicochemical properties of 2D materials lead to high mobility and high
energy density, making them very promising candidates for energy storage devices.
Although 2D materials have a larger theoretical capacity than other traditional
bulk materials, their self-pseudocapacitance is limited because of poor processability.
During micro-energy devices fabrication process, 2D materials nanosheets are easy to
aggregate and restack, which seriously impedes rapid diffusion of electrolyte ions and
affects the full utilization of the active surface of the electrodes. Converting the planar
structure of 2D materials nanosheets into an interpenetrating network with open or
porous structures is an effective way to construct high-performance micro-electrodes.
In the past few years, a large number of reviews are on the application of 2D materi-
als as electrode materials for energy storage devices. This chapter will focus on the
morphological aspects of 2D nanomaterials and their energy applications.
9.2 GRAPHENE
9.2.1 MORPHOLOGY AND SYNTHESIS METHOD
9.2.1.1 Graphene Nanosheet
Graphene nanosheets are generally prepared by mechanical stripping of graphite,
chemical vapor deposition (CVD), or chemical oxidation or stripping of graphite.
Each method has advantages and disadvantages in terms of the quality and yield of
the prepared graphene.
Morphological Aspects of 2D Nanomaterials 163
Liquid-phase exfoliation (LPE). Graphite is dispersed in organic solvents or spe-

cifc surfactants. Single or multiple layers of graphene are peeled off from the graph-
ite surface by ultrasound. The graphene dispersion was obtained by centrifugation.
Finally, graphene can be deposited on different substrates. Telkhozhayeva Madina’s
group [1] reported that monolayer graphene fakes are directly exfoliated from graph-
ite using ethanol as a solvent by bath sonication. A total of 77% of the graphene fakes
have a thickness below three layers with an average lateral size of 13 μm.
Chemical vapor deposition (CVD). Using carbon-containing gas (such as meth-
ane) as raw material, in an environment above 1,000°C, through chemical reaction,
carbon is precipitated and grown on copper and other substrates to form graphene
fakes. Kim et al. [2] developed a CVD device for producing high-quality (about 252
Ω per square) and large area (over 16 inches) graphene.
Redox method. Natural graphite is oxidized by strong acids and strong oxidants
such as sulfuric acid, potassium permanganate, and hydrogen peroxide to obtain gra-
phene oxide. It is then dispersed by physical stripping and high-temperature expan-
sion to obtain graphene oxide. Finally, it is reduced to obtain reduced graphene oxide.
Wang et al. [3] used hydroquinone to reduce graphene oxide in an aqueous solution to
prepare graphene nanosheets.
9.2.1.2 Porous Graphene

At present, the preparation methods of porous graphene include the template method
and colloid drying method.
Template-assisted methods are common methods for preparing the structure and
morphology of specifc nanomaterials. The template-assisted method mainly includes
three steps: (a) Combine the precursors of the reaction to impregnate or infltrate the
template; (b) Form a solid state on the template through reaction, nucleation, and
growth; and (c) The fnal product can be obtained after removing the template.
Metal Template-Assisted Chemical Vapor Deposition. Graphene is directly grown
using nickel foam as a catalytic metal and template. Self-supporting porous graphene
can be obtained by etching the nickel foam. Ning’s group [4] reported that pore-
adjustable copper-nickel alloy was prepared on nickel foam by electrochemical depo-
sition and etching. Compared with commercially available Cu or Ni foams, graphene
grown on alloy foams also has smaller and variable pore size and larger surface area.
The specifc surface area of graphene can reach 0.096 m2 cm−3, which is four times
larger than that of commercial templates.
Colloidal sphere synthesis. The photoresist method using polystyrene or silicon diox-
ide spheres as templates has been used to prepare various porous graphene. The struc-
ture prepared by this method has ordered aperture and controllable size. Self-assembled
polystyrene micro-sphere templates and chemically modifed graphene (CMG) have
been reported to prepare self-supported network graphene [5]. In this method, self-
supported polystyrene spheres/graphene are mixed with hydrocolloid suspended
graphene and polystyrene spheres for vacuum fltration, and then polystyrene sphere
templates are removed with toluene to obtain porous graphene. The resulting graphene
pore diameter is the diameter of the polystyrene ball, so it is easy to control its pore size.
Interferometric lithography template method. The multilayer graphene prepared
by converting the prepared 3D pyrolysis photoresists [6]. Its specifc surface area
is two orders of magnitude smaller than that of graphene grown directly on nickel
foam. It consists of three steps: frst, fabricating a 3D porous carbon face-centered
cubic structure by interferometric lithography; then, 3D porous carbon was annealed
at 750°C for 50 minutes and converted into 3D graphite material. Finally, the 500-nm
pore size is obtained after etching the nickel foam.
Hydrothermal template method. Porous graphene was prepared by combining hydro-
thermal synthesis with nickel foam template method. The main method is to deposit
chemically peeled graphene oxide onto nickel foam by hydrothermal synthesis. The
deposited nickel foam was then reduced by vapor etching in ethylene to obtain porous
graphene. This method is simpler than the foam nickel template CVD method. However,
graphene has many stacking defects and its thickness is diffcult to control [7].
Hydrothermal gel synthesis method. Self-supporting porous graphene can be pre-
pared by graphite oxide or organic oxide graphite. But the stability and uniformity
of graphene depend on gel molecules and polymers. When the gel and polymer are
dried, small holes will form on the surface of the porous graphene. These small
holes communicate with each other to form a 3D structure, not just connected on the
surface. Shi et al. [8] reported that graphene oxide (GO) sheets could form complex
hydrogels with poly(vinyl alcohol) (PVA). The role of GO sheets is similar to that of
2D macromolecules. The formation of the hydrogels depends on the assembly of GO
sheets and the cross-linking effect of PVA chains.
Freeze-dry method. Freeze the graphene solution below the freezing point, con-
vert the water to ice, and then remove the ice by converting it to steam under a higher
vacuum. Material can be frozen in the freezer before drying. But it can also be frozen
directly in a drying chamber by pumping it into a vacuum quickly. The water vapor
generated by sublimation is removed by means of a condenser. The voids that remain
form a porous material. Xu et al. [9] organized GO into 3D networks with a cylindri-
cal structure by hydrothermal treatment of a GO suspension (1 or 2 mg ml−1) at 180°C.
9.2.2 APPLICATION OF GRAPHENE AS ELECTRODE

9.2.2.1 Supercapacitor
When used in supercapacitors, graphene stores energy through an electric
double-layer capacitance. Due to its high conductivity and high specifc surface
area, graphene can provide high-performance energy storage. The theoretical
specifc capacitance is 21 μF cm−2 (550 F g−1).
Ruoff et al. [10] reported the work of CMG as electrode material for supercapaci-
tors in 2008. CMGs are made from 1-atom thick carbon sheets by Hummer method.
The specifc capacitances in aqueous (5.5 M KOH) and organic electrolytes (TEABF4/
AN) are 135 and 99 F g−1, respectively. Further, Ruoff et al. [11] also reduced GO by
microwave heating and activated the product to obtain porous graphene. The surface
area achieves 3,100 m2 g−1. The specifc capacity in TEABF4/AN increases to 166 F
g−1, and the energy density increases to 70 Wh kg−1.
Kim et al. [12] prepared micron-scale graphene nanolayers (GNMs) with nano-
manipulation by catalytic carbon gasifcation. The pore size and density distribution
of GNMs are controlled by adjusting the size and fraction of metal oxides. GNM
electrodes show high capacitance (253 F g−1 at 1 A g−1).
Tang et al. [13] used polystyrene balls as templates to assemble graphene nanosheets
into spherical shells. Compared with stacked planar graphene, the prepared graphene
spherical shell has a larger free space between the spheres. Graphene hollow spheres
show high specifc capacitance 273 F g−1 and excellent electrochemical stability.
9.2.2.2 Lithium-Ion Batteries

Graphene has lithium storage activity in the low potential range (<1.5V) and is usually
used as a negative electrode material for lithium-ion batteries (LIBs). Lithium can be
stored on both surfaces and edges of graphene, resulting in two layers of lithium per gra-
phene sheet, with a theoretical capacity of 744 mAh g−1 by forming Li2C6. At the same
time, graphene has a large interlayer spacing and abundant pores, and Li-ion can quickly
diffuse through the interlayer spacing, which has good multiplication performance.
Wang et al. [14] prepared 2–3 layered graphene nanosheets from bulk graphite via
Hummer method. The graphene nanosheets as anodes of LIBs exhibit an enhanced lith-
ium storage capacity (650 mAh g−1). Yoo et al. [15] reported that graphene layer spacing
was extended from 0.365 to 0.42nm by the incorporation of macromolecules of CNT
and C60. The capacity was increased from 540 to 784 mAh g−1. Zhao et al. [16] synthe-
sized mesoporous graphene nanosheets by a controlled low concentration monomicelle
close-packing assembly approach. Mesoporous graphene provides high surface area for
Li-ion adsorption and intercalation and enables effcient ion transport. Mesoporous gra-
phene exhibited an excellent reversible capacity of 1,040 mAh g−1 at 100mA g−1.
9.2.2.3 Sodium-Ion Batteries

The size of Na-ion is large (102 pm) and the bonding to the graphite surface is weak,
so graphite cannot be directly used as negative electrode material of sodium-ion bat-
teries (SIBs). The replacement of graphite by 2D graphene as a cathode material for
SIBs is considered to be an effective strategy.
Wen et al. [17] reported expanded graphene as an SIB anode. Expanded graphene
has a 4.3 Å expanded interlayer lattice distance, but retains a similar long-range
ordered layered structure. Expanded graphene can provide a high reversible capacity
of 284 mAh g−1 at a current density of 20 mA g−1.
The sodium storage properties of porous graphene depend on appearance, sur-
face defects, and pore size. Lee et al. [18] prepared activated wrinkled graphene by
CVD. For sodium storage, the reversible capacity is 280 mAh g−1 at 40 mA g−1. The
enhanced electrochemical performance stems from the adsorption of ions on various
defects such as the Stone–Wales defect.
9.2.2.4 Potassium-Ion Batteries

For potassium-ion batteries (PIBs), the electrochemical properties of pure graphene
materials are still unsatisfactory. One of the optimization principles of graphene-
based electrodes is to design novel structures that can introduce more point defects,
edges, grain boundaries, and doped atoms [19].
Share et al. [20] developed several layers of N-doped graphene, which provides
a higher potassium storage capacity (more than 350 mAh g−1) than KC8 (278 mAh
g−1). N-doped uniformly distributed in the carbon matrix serves as the active sites
for local storage of K-ions. Ju et al. [21] synthesized nitrogen-doped graphene from
dicyandiamide and coal tar pitch. The electrode shows a high specifc capacity (320
mAh g−1 after 60th cycle at 50 mA g−1), and long-term cycling capability (over 150 mAh
g−1 after 500 cycles at 500 mA g−1) in PIBs. Ju et al. [22] using polyvinylidene difuoride
(PVDF) as a single source reactant, prepared several F-doped graphene foams with a
thickness of about 4 nm and high surface area (874 m2 g−1) by a high-temperature solid-
state method. The F-doped graphene shows a high initial capacity of 863.8 mAh g−1.
9.3 TRANSITION METAL DICHALCOGENIDES (TMDCs)

“Top-down” and “Bottom-up” are used in the synthesis of 2D materials [23]. “Top-
down” is the preparation of large-size materials into nanostructures through physical
or chemical means, including mechanical stripping and LPE. “Bottom-top” is to self-
assemble small structural units (such as molecules, atoms, and nanoparticles) into
nano-sized structures through weak interactions, including CVD and hydrothermal/
solvent thermal synthesis methods.
9.3.1.1 TMDC Nanofakes

TMDC nanofake is generally prepared by the mechanical exfoliation and LPE of
bulk TMDC, and CVD.
Mechanical exfoliation is the simplest physical method to synthesize 2D TMDCs
nanofake in a short time. This method of preparing ultra-thin TMDCs by mechanical
exfoliation is fast and simple. It does not need the conditions of high temperature and
high pressure. Ultra-thin TMDCs can be prepared only through special tape, and the
yield of stripped products is high. However, the sample size is small, the yield is low,
and the thickness of sample layer cannot be controlled. Late et al. [24] successfully
prepared single-layer and few layer WS2 thin flms on SiO2/Si substrate by mechanical
stripping of large WS2 crystals and transparent tape technology at room temperature.
LPE method is to disperse TMDC crystal powder into liquid medium and provide
external force assistance for stripping through ultrasonic, microwave, shear force,
thermal stress, and centrifugation. Solvent-assisted stripping and ion intercalation-
assisted stripping are commonly used in LPE. Coleman et al. [25] placed bulk
TMDC in organic solvent for ultrasonic treatment to obtain monolayer nanosheets.
The experimental results show that 1-methyl-2-pyrrolidone (NMP) is the most effec-
tive organic solvent for removing bulk TMDC. Yu et al. [26] placed the bulk WSe2
in NMP solvent for ultrasonic treatment, and WSe2 thin flms were prepared. The
treatment of TMDCs by solvent exfoliation method will not signifcantly interfere
with its crystal structure. Fan et al. [27] found that ultrasonic treatment can help
n-butyl lithium intercalate bulk TMDC in hexane solution. MoS2 nanosheets can fall
off after ultrasonic treatment in aqueous solvent for 5 minutes.
Through CVD technology, single layer or several layers of TMDCs can be grown
on a variety of substrates, which is also one of the most practical methods for large-
area synthesis of materials. Lee et al. [28] used MoO3 and S powder as reactants and
N2 gas as protective gas to form large-area MoS2 flms on SiO2/Si substrates through
CVD for the frst time.
9.3.1.2 TMDC Nanorod and Nanofower

Hydrothermal/solvothermal method is a common wet chemical synthesis method,
which has low cost and large amount of products. By adjusting the ion concentra-
tion, temperature, and reaction time in the hydrothermal process, the morphology
and crystal structure of the products can be further regulated and a large number of
active sites can be provided.
Ning et al. [29] used a one-step hydrothermal method to form sodium intercala-
tion nanofower 1T-2H MoSe2-graphene. The insertion of Na-ions not only expands
the distance between layers but also provides space for electrolyte Na-ions.
9.3.1.3 TMDC Nanofber

Electrospinning depends on the electrostatic repulsion between surface charges
to continuously prepare viscous fuids into nanofbers with diameters up to tens
of nanometers. In Kumuthini et al. [30] MoS2/CNFs composite was successfully
fabricated by electrospinning technology. The diameter of the composite was
200–300 nm.
9.3.1.4 Porous TMDC

Hydrothermal gel synthesis method. Li et al. [31] prepared a polysulfde molybde-
num gel (MoS12) with (NH4)2Mo3S13 as a precursor and then obtained porous MoS2
through critical point drying technology. The porous MoS2 has a wide pore size.
A specifc surface area is 315 m2 g−1 and a pore volume is 1.9 cm3 g−1.
9.3.2 APPLICATION OF TMDCS AS ELECTRODE

The two common structural phases of TMDC are 2H and 1T, which are charac-
terized by trigonal prismatic and octahedral coordination of the transition metal
atoms, respectively. The 2H Phase TMDC is semiconductor, which shows double
electric layer energy storage properties in aqueous electrolyte. Conversely, 1T
phase TMDC is metallic material, which shows pseudocapacitance energy storage
properties. In addition, the electron mobility of 1T phase TMDC is higher than
that of 2H phase TMDC. Therefore, 1T phase TMDC is widely used in the feld of
energy storage.
Habib et al. [32] reported CVT technique is used to form a layered single crystal
of WS2 and WSe2. The TMDC electrodes exhibit excellent cycle stability and high
capacitance retention of 80 and 99% for WS2 and WSe2 after 20,000 cycles, respec-
tively. Ning et al. [33] synthesized gypsophila-like 1T-WSe2/graphene via ammonia-
assisted hydrothermal treatment. The 1T-WSe2/graphene electrode shows a large
specifc capacitance (1,735 F g−1 at 1 A g−1), and the energy density of all-solid-state
supercapacitor reaches 48.2 Wh kg−1 at 250 W kg−1. Tu et al. [34] used molten salt
process to prepare WS2 reduced graphene oxide (rGO) nanosheets. WS2/rGO elec-
trodes reach a high specifc capacitance of 2,508.07 F g−1 at 1 mV s−1. The hybrid
WS2/rGO achieves an excellent cycling stability, and the capacitance retention is as
high as 98.6% after 5,000 cycles.

The layered structure of TMDCs is conducive to the rapid diffusion of Li-ions in the
electrode. At the same time, due to the very loose stacking structure, few layer TMDCs
can greatly adapt to the structural changes before and after Li-ion insertion, and the
volume expansion rate is low. It is considered an ideal cathode material for LIBs.
Guo et al. [35] synthesized MoS2 nanospheres with a diameter of about 200nm by
hydrothermal method as the cathode electrode of LIBs, and the frst discharge specifc
capacity reached 1,272 mAh g−1. Du et al. [36] obtained restacked MoS2 by Li-ion chem-
ical exfoliation and hydrothermal treatment. Through stripping and restacking process,
the c lattice parameter and surface area of MoS2 were increased. Restacked MoS2 shows
high reversible lithium storage capacity (750 mAh g−1 after 50 cycles) as anode for LIBs.

The large interlayer distance in TMDCs favors the adaptation of Na-ion. However,
because of their low electrical conductivity, the overall performance, especially the
high-rate performance, still far exceeds satisfaction. Therefore, opening TMDCs and
introducing agents and good conductivity are expected to solve the problem.
Bai et al. [37] developed a layered yarn spherical MoS2 nanosphere structure
coated with an N-doped carbon layer. As the anode material for SIB, the MoS2-
PVP@NC electrode exhibits an excellent cycling performance of 410.2 mAh g−1 at
1 A g−1 after 200 cycles. Ye et al. [38] reported that metal-semiconductor mixed-
phase twinned hierarchical (MPTH) MoS2 nanowires. The expanded interlayer spac-
ing accelerates Na-ion insertion/extraction kinetics, and the metal-semiconductor
mixed-phase enhances electron transfer ability. The MPTH MoS2 electrode delivers
high reversible capacities of 200 mAh g−1 at 0.1 A g−1 for 200 cycles.

In non-aqueous electrolytes, the standard redox potential of K is lower than that of
Na (or even Li). Compared with SIBs and LIBs, K can be converted into a potentially
higher battery voltage for PIBs.
Guo et al. [39] reported single crystalline metallic graphene-like VSe2 ultrathin
nanosheets as anode materials. The large-sized ultrathin wrinkle-like nanosheets
show a large surface-area-to-volume ratio, ultrafast electron/K-ion transport, lim-
ited self-aggregation, and excellent structural stability. The ultrathin VSe2 nanofakes
exhibit high reversible capacity (366 mAh g−1 at 100 mA g−1).
9.4 MXene
9.4.1.1 MXene Nanofake
MXene is usually obtained by etching MAX materials with different concentrations
of HF, NH4HF2, and the mixture of fuoride and concentrated HCl. Single layer or
few layers MXene is usually obtained from multi-layer MXene etched by liquid phase
stripping HF in various polar organic solvents. Hydrazine, urea, dimethyl sulfoxide,
isopropylamine, or organic base molecules can be embedded between MXene layers,
and single or few layers of MXene is obtained by mechanical vibration such as ultra-
sound and ball milling. Gene et al. [40] achieved one-step etching exfoliation of MAX
pretreated with low concentration HF using TMAOH to obtain a single layer of MXene
with Al(OH)4− functional groups on the surface. Li et al. [41] prepared large monolayer
MXenes without F functional groups by etching and exfoliation at 180°C for 24 hours
with inorganic alkali KOH solution.
9.4.1.2 Porous MXene

After the porogen is removed by a specifc method, the interconnected scaffold can
be retained and a porous MXene material is formed. These methods mainly include
freeze-drying, spray drying, hard template strategy, and also chemical reduction.
Freeze-drying has been widely used to create porous 2D materials by discharg-
ing nanofake precursors into the boundaries of ice crystals. Wang et al. synthesized
porous MXene with a large surface area by freeze-drying and used the product as the
substrate to prepare porous MXene/Fe2O3 composites.
Spray drying is an alternative method to prepare porous 2D materials by capil-
lary forced crumpling and self-assembly. Recently, Qiu et al. used spray drying to
prepare porous MXenes. First, MXene dispersion is transferred into aerosol droplets.
Second, directly calcined at a high temperature to remove solvents. Then, the inward
capillary force leads to the isotropic compression of MXene nanofakes and rapid
assembly into 3D structures with fuffy shape after the solvent completely evaporated.
Hard templating strategy is another effective method for preparing porous materi-
als, which depends on the pre-deposition of 2D materials on the surface of the hard
template and then removing the hard template. For instance, Gogotsi et al. synthe-
sized MXene-coated polymethyl methacrylate (PMMA) spherical composite mate-
rial based on the interactions between their surface hydroxyl groups and then vacuum
fltered them into independent flms. After removing the PMMA hard template, the
hollow MXene spheres and 3D macroporous MXene flms are obtained.
The chemical reduction method can produce pores in the dense MXene flm
through the foaming process induced by the removal of surface functional groups.
For example, Yu et al. treated dense MXene flms via hydrazine to prepare MXene
foam. Hydrazine reacts with oxygen-containing groups to quickly release a large
amount of gaseous substances, such as CO2 and H2O, which generate high pressure
between MXene sheets and overcome the van der Waals force that holds the fakes
together. Therefore, the dense hydrophilic Ti3C2Tx flm is transformed into a hydro-
phobic porous Ti3C2Tx flm with a honeycomb structure [42].
9.4.2 APPLICATION OF MXENE AS ELECTRODE

In neutral aqueous electrolyte or organic electrolyte, the energy storage mechanism
of Ti3C2Tx may behave as electric double-layer capacitance. When Ti3C2Tx is in
the H2SO4 electrolyte, the storage mechanism of pseudocapacitance is dominant.
The embedding of hydrogen ions protonated the oxygen functional groups on the sur-
face to form hydroxyl groups, and the oxidation state of Ti changed. The reversible
change of Ti oxidation valence from +3 to +4 follows the bonding and bond breaking
of oxygen functional groups, respectively. Similar to acidic electrolytes, KOH can
provide ion intercalation without the reaction of surface functional groups.
Zhang et al. [44] fabricated the free-standing, fexible 3D porous MXene Ti3C2Tx/
CNTs flm via freeze-drying MXene Ti3C2Tx -based water membranes without post-
treatment. The 3D porous Ti3C2Tx/CNT electrode shows the excellent specifc capac-
itance of 372 F g−1 at a scan rate of 5 mV s−1.

MXenes can be a very suitable anode material for LIBs because of their large inter-
layer spacing (0.7–1.1 nm), excellent ionic and electronic conductivity, and adjustable
elemental composition.
In 2012, Gogotsi et al. used a 2D Ti2C-based material with an oxidized surface
(prepared from Ti2AlC by using HF etching Al at room temperature) as anode mate-
rial for LIBs. When current rate is 0.1 C, the specifc capacity stabilizes at 160 mAh
g−1 after fve cycles [45]. In addition, Gogotsi et al. fabricated porous MXenes with
in-plane pores and then used carbon nanotubes (CNTs) flter it into an independent
fexible flm [46]. When used as an anode for LIB, the activated P-Ti3C2/CNT flm
provides high capacity approximately 1,250 mAh g−1 at 0.1 C.

Layered MXene is considered an ideal electrode material due to its obvious interlayer
spacing, which can promote the insertion and removal of sodium ions. Constructing
2D MXene nanosheets into 3D structure can inhibit the stacking between MXene
sheets, improve the utilization of surface active sites, and then improve the electro-
chemical performance.
Zhang et al. [47] synthesized 3D carbon-coated Ti3C2Tx by realizing self-
polymerization of dopamine on the surface of original Ti3C2Tx nanosheets followed
by freeze-drying and carbonization under an inert air atmosphere. The 3D architec-
ture exhibits a high capacity of 257.6 mAh g−1 at 0.05 A g−1 after 200 cycles for SIBs.

The radius of K-ion is much larger than that of Li-ion and Na-ion, which leads to
slow reaction kinetics and large volume expansion of active substance during charge
and discharge. Therefore, expanding the MXene layer spacing and constructing a 3D
structure is an effective strategy to improve the performance of PIBs.
Zhao et al. [48] designed PDDA-NPCN/Ti3C2 hybrids as PIBs anodes via an elec-
trostatic attraction self-assembly approach, while N-rich porous carbon nanosheets
(NPCNs) came from metal-hexamine frameworks. The hybrids possess a synergetic
effect, resulting to a reversible capacity of 358.4 mAh g−1 after 300 cycles at 0.1 A g−1.
9.5 CONCLUSIONS AND PERSPECTIVES

In this chapter, we discussed the preparation of 2D materials from exfoliated layer
materials, assembling them into 2D flms/flms or 3D powdered samples/macrostruc-
tures, and the latest applications of solution-treated 2D materials in energy applica-
tions (including supercapacitors and batteries).
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10 Effect of Exfoliation
on Structural and
Electrochemical
Properties
Gibin George
SCMS School of Engineering and Technology
Deepthi Panoth
Kannur University
Brijesh K
National Institute of Technology Karnataka (NITK) Surathkal
Anjali Paravannoor
Kannur University
Nagaraja Hosakoppa
National Institute of Technology Karnataka (NITK) Surathkal
Yu-Hsu Chang
National Taipei University of Technology
Centre for Nano and Soft Matter Sciences (CeNS)
CONTENTS
10.1 Introduction .................................................................................................. 176
10.2 Electrochemical Sensors............................................................................... 177
10.3 Water Splitting and Fuel Cells...................................................................... 179
10.3.1 Hydrogen Evolution Reaction (HER) ............................................... 180
10.3.2 Oxygen Evolution Reaction (OER) and Oxygen Reduction
Reaction (ORR)................................................................................. 181
10.4 Supercapacitors............................................................................................. 184
DOI: 10.1201/9781003178453-10 175

10.5 Lithium-Ion Battery...................................................................................... 186

10.6 Conclusions................................................................................................... 188
References.............................................................................................................. 188
10.1 INTRODUCTION
The term exfoliation represents a process during which the layered bulk materials are
expanded through a chemical or physical method to overcome the weak inter-layer
forces that hold the layers together. Generally, the stacked layered materials seized
together by van der Waals forces can be easily intercalated or exfoliated by solution
methods or simple physical means such as shear or ultrasonic vibrations to form 2D
nanosheets. The exfoliated 2D nanosheets are often composed of single or few lay-
ers of atoms, and most importantly several of their properties are largely deviated
from the bulk. Such materials fnd applications in electronics, photonics, catalysis,
supercapacitors, fuel cells, batteries, etc. [1]. The success of graphene triggered the
development of other 2D structured nanomaterials, especially by the exfoliation of
layered bulk inorganic materials. Unlike bulk materials, 2D nanosheet counterparts
exhibit unique electron and phonon transport characteristics, which leads to several
fascinating properties such as thermal conductivity, ion transport, and charge carrier
concentration, besides the structural and mechanical properties.
Many of the 2D nanosheets are non-toxic and can be handled easily, and they can
be cast to any substrate as a thin flm for device fabrication [2]. Over the years, exfo-
liated 2D nanolayers have become an essential part of electrochemistry, mainly in
sensing, energy, and environmental applications. 2D carbon allotropes such as gra-
phene and 2D porous carbon are not electrochemically active by themselves; there-
fore, they are often doped/modifed by heteroatoms such as B, P, and N or transition
metals. The high charge conductivity of the 2D carbon materials is highly favorable
for several electrochemical applications such as batteries, supercapacitors, sensors,
and catalysis. The stability of several inorganic 2D nanosheets in acidic and basic
media makes them attractive for the aforesaid applications and they are considered as
the immediate replacement for expensive noble metal electrocatalysts [3].
MXenes are 2D nanolayers of metal carbides, carbo-nitrides, and nitrides, an
important class of electroactive 2D nanomaterials that are developed lately. Ti3C2Tx
is the frst MXene discovered in 2011. So far about 50 different types of MXenes with
wide chemical and structural variations are synthesized by exfoliating MAX phases by
selective etching and mechanical shearing. MAX phases represent a family of ternary
carbides and nitrides. MXenes are unstable in oxygen-containing environments. The
hydrophilic nature and high surface charge of MXene nanosheets make them stable in
polar solutions for device printing. The ability of MXenes to intercalate various cations
including multivalent ions and polar organic molecules between its 2D layers makes
them apt for non-lithium-ion batteries and supercapacitors [4]. Alike graphene, MXene
exhibits excellent electronic conductivity and can be functionalized, hybridized, and
doped for tuning the properties to meet the requirements of a specifc application.
Many non-noble metal electrocatalysts are inactive and unstable in acidic mediums.
The reaction in an acidic medium is highly effcient at a high current density. Transition
metal dichalcogenides (TMDs) are highly active electrocatalysts for sensing, batteries,
Effect of Exfoliation 177
supercapacitor, water splitting, etc., especially in acidic and harsh environments. TMDs
have the general formula MX2, where M is the transition metal and X is the chalcogen
(X = S, Se, and Te), having a similar layered structure to those of graphene. Alike any
other 2D layered nanosheets, TMDs can be doped, functionalized, and hybridized for
improving various operating parameters such as selectivity, sensitivity, and affordabil-
ity in sensing and effciency, stability, and life span in catalysis. Additionally, TMDs
have good electronic and mechanical properties favorable for electrode materials [5].
2D nanosheet of layered hydroxides (LDHs) and oxides are also an important class of
electrochemical materials, starting from sensing to fuel cells. The presence of oxyl and
hydroxyl groups allows the effcient transport of ions when they are used as electrodes in
energy storage. The possibility of intercalation of ions other than Li+ makes them a prom-
ising candidate for non-lithium-ion batteries. The electronic conductivity of LDHs and
oxides are poor, therefore these materials are often hybridized with carbon-containing
conductive materials as an effective strategy to increase the intrinsic catalytic activity.
In this chapter, the electrochemical applications of the exfoliated 2D nanosheets in bat-
teries, supercapacitors, biological sensing, and water splitting are discussed concisely.
The underlying mechanism of electrochemical activity of different classes of 2D layered
nanosheets is different. Such unique characteristics of different classes of 2D nanosheets
favorable for the respective applications are also explored in this chapter.
10.2 ELECTROCHEMICAL SENSORS

A large number of sensors are used in our daily life to monitor and modify ourselves
and our surroundings in a positive way. Electrochemical sensors have the largest share
among all the chemical sensors, which use an electrochemical reaction (parameters such
as a change in current and impedance) of the analyte to quantify the concentrations.
Analytes electrochemically interact with the active material to produce signals and the
sites on which such interactions happen are known as electrochemically active sites.
Usually, the concentration of electrochemically active surface area increases with the
surface area of the active material. Interestingly, exfoliation of 2D materials increases the
surface area and exposes active sites, which may not be active otherwise. Often, exfoli-
ated materials take part in the electrochemical reaction or act as a host to molecules such
as enzymes that catalyze the reaction. Exfoliation, being a top-down approach results in
defects that can also have a positive infuence on the electrochemical reactions because
of their very high activity. Apart from this, the extend of exfoliation, lateral size, etc. is
also critical in deciding exfoliated material's electrochemical activity [6].
Graphene, which is a carbon allotrope, is the frst known material to be exfoliated
into atomically thin layers from its bulk counterpart graphite. Graphite can be eas-
ily exfoliated by mechanical cleaving. This can be used as an advantage in sensing
where the fouling of the electrode material is a serious concern. The detection of
material like bisphenol-A involves the polymerization of the analyte molecules and
results in the deposition of the material on the surface of the electrode, which results
in the electrode fouling. Exfoliated graphite helps in tackling this issue wherein a
mild polishing results in the removal of the polymerized products from the surface as
described by Ndlovu et al. [7]. Figure 10.1 schematically represents how exfoliation
acts as a tool to challenge the fouling issues in electrochemical sensing.
Graphite oxide samples are usually exfoliated using thermal shock to achieve high
quality and are electrochemically active for the detection of hydrogen peroxide and this
is extensively reported by many researchers. Moolayadukkam et al. in 2020, in detail,
explained the effect of solar exfoliation on the H2O2 sensing performance. Exfoliated
graphene sheet has more defect concentration, which acts as the electrocatalytically
active sites by adsorbing the analyte molecules. These adsorbed analyte molecules are
electrocatalytically oxidized and corresponding signals can be recorded with a tech-
nique such as chronoamperometry. Figure 10.2 schematically shows graphene layers
with defects/pores and their activity in adsorbing H2O2 molecules (analyte) [8].
Non-carbonaceous materials are electrocatalytically more active and their exfo-
liation has revolutionized electrochemical sensing research and developments.
Layered 2D TMDs offer a wide variety of materials that can be exfoliated and
having electrical properties varying from metallic to semiconducting nature. The
peculiar arrangement of each atomic layer in TMDs offers a variety of active sites
for the analyte adsorption in each layer after the exfoliation process. This property
is widely used in the effcient detection of biomolecules. MoS2 is one of the most
widely used TMDs for sensing and other applications. Ashwathi et al. studied the
relation between the analyte affnity and the active material by taking MoS2 and Hg
(II) ions as an example. In this particular example, Hg (II) ions have a high affnity
toward S-containing groups. Exfoliation leaves S on both the surfaces of nanosheets
exposed while the Mo layer at the center acting as the backbone. This arrangement
of atoms improves the sensitivity by many folds clearly showing exfoliation of 2D
TMDs could be used as an effective method for fne-tuning sensing capabilities [9].
FIGURE 10.1 Shows how exfoliation of the material helps tackle the fouling issues in sensing.
FIGURE 10.2 Schematic representation showing the importance of defects in adsorbing the
analyte molecules on the graphene surface.
LDHs are another class of materials that can be exfoliated to form molecular lay-
ers with metal as the center layer. Compared to TMDs, LDHs have the advantage
that there may be more than one metal in the metallic center layer, and varying
the ratios of metals at the center and the metals themselves can tweak the sensing
properties [10]. Sahoo et al. studied the sensing properties of ultrasonically exfoli-
ated Ni2Co-LDH with dopamine, an important biomolecule. The electron transfer
rates are reported to be improved on moving from bulk to the monolayers of the
LDH. Going from bulk to monolayers could help decrease the electron scattering
at the active material, which can have a positive impact on the sensing properties
[11]. Strong dependence of the exfoliation on the sensing properties is also reported
by Chia et al., Authors explained the effect of exfoliation using enzymatic glucose
sensing as a tool. Exfoliated 2D sheets show better sensing properties because of
the high surface area and thin nature. Thinner sheets result in a decreased distance
between adsorbed enzyme and the electrode, which facilitates effcient electron
transfer. Polymeric 2D material, graphitic carbon nitride also shows similar sensing
properties upon exfoliation. Kesavan et al. exfoliated graphitic carbon nitride using
ultrasonication technique and demonstrated the futamide (FLT) sensing properties.
With the help of impedance spectroscopic studies, they have shown that active sites
and conductivity are increased as a result of exfoliation. Along with this, the affn-
ity of FLT and nitrogen on the graphitic carbon nitride played an important role in
improving the sensing properties [12].
Irrespective of the layered material, exfoliation is observed to have a signifcant
infuence on the sensing properties. Exfoliation results in exposing active sites and the
reduction in thickness resulting in better absorption of the analyte molecules and better
electron transfer characteristics. Apart from this, the method of exfoliation induces dif-
ferent types of defects on the 2D crystal, the electron density on these defects such as
edges and pores have an impact on the electrocatalysis of the analyte molecule. Carefully
altering the method of exfoliation, sensing capabilities of the materials could be extended.
10.3 WATER SPLITTING AND FUEL CELLS

Water is an abundant source of energy and splitting water in a most economic route is
a serious research concern in recent years for the production of hydrogen and oxygen.
Hydrogen is considered the most advantageous renewable source of energy and the
availability of oxygen is critical for the treatment of patients affected with COVID
19. Oxygen is also important for the complete combustion of any fuel, including
hydrogen. The commercial electrocatalysts containing noble metals are currently
used in fuel cells as hydrogen evolution reaction (HER), oxygen evolution reaction
(OER), and oxygen reduction reaction (ORR) catalysts. The involvement of noble
metals in crucial energy-related applications such as a fuel cell increase the installa-
tion and operation cost tremendously. Recently, several non-noble metal electrocata-
lysts are introduced as a replacement for noble metals and their derivatives. Several
2D layered nanosheets prepared by intercalation/exfoliation are subjected to HER
and OER/ORR. Many are identifed as potential replacements for noble metals in
their respective applications. A list of widely studied exfoliated 2D materials as elec-
trocatalysts are discussed in this session.
10.3.1 HYDROGEN EVOLUTION REACTION (HER)

The evolution of hydrogen by electrochemical water splitting can be a feasible way
of storing hydrogen for energy-related applications, especially for fuel cells. Over
the years, noble metals are broadly used as an effcient catalyst for HERs. However,
the high cost of noble metals limits their extensive use as a catalyst at a large scale.
To overcome the high cost of noble metal catalysts, electroactive materials that are
available in abundance are proposed as catalysts. However, the major challenges of
most non-noble materials used in HER are (1) the low effciency, well below the
thermodynamic limits of the water-splitting reaction and (2) the short lifetime [13].
Materials containing transitions metals are very active for HER. Though HER can be
performed either in an acid ( 2H + + 2e − ˝ H 2 ) or basic ( 2H 2O + 2e − ˝ H 2 + 2OH − )
medium, a basic medium is commonly preferred due to the short-term stability of
many materials in the acid medium. Similarly, due to stability issues, pure metals are
avoided for HER reactions. To improve the performance of electroactive materials
par to the noble metals several strategies are adopted. The suitability of a nanostruc-
tured material as an electrocatalyst depends on the surface area, presence of defects
such as oxygen vacancies, availability of active sites on the surface, and dopants. The
surface area plays an important role in HER since HER is a surface-active reaction.
Materials with the layered structure are identifed as a suitable candidate for the
HER since the layered materials are often characterized by the presence of multiva-
lent transition metals in their crystal structure and the synergic interaction of these
elements can augment the catalysis by offering many active sites for catalyzing the
reaction. Interestingly, the conductive fexible 2D nanosheets enable the easy access
of the electron from the catalyst substrate to the surface through intimate contact. As a
result, the interfacial electron transfer resistance can be reduced and electrons can cir-
culate through the external circuit effciently [14]. The most active sites of exfoliated
2D materials for HER are located along the edges of the layers, but its performance is
currently limited by the density and reactivity of active sites. The unprecedented HER
activity of the layered materials is observed when they are exfoliated by intercalating
a charged ion such as Li and Na, and thereby surface area is increased enormously
in addition to the increased electrical conductivity. The overall HER activity is deter-
mined by how well hydrogen atoms can be adsorbed on the catalyst surface [14].
Among the layered materials, the introduction of exfoliated TMDs is a break-
through in the history of non-noble metal catalysts for HER. Chemically exfoliated
layers of dichalcogenides such as MoS2, WS2, CoS2, VS2, and NiS2 are extensively
studied as a promising electroactive HER catalyst. The above materials exhibit a
low overpotential in the range of 100–250 mV vs reversible hydrogen electrode in
an acidic medium. Overpotential is the measure of the effciency of a material for a
water-splitting reaction and it represents the loss of the applied voltage. The overpo-
tential of platinum/carbon commercial electrodes are ~30–50 mV. The layered materi-
als without exfoliation or intercalation are often inactive as in the case of MoS2. The
ultra-thinning and 2D nanosheet formation create an abundance of HER active sites at
the edges [15]. Moreover, the planar mobility of electrons along the 2D layer guaran-
tees rapid electron transfer from the substrate to active sites. The exfoliated transition
metal selenides and tellurides are also reported as electroactive materials for HERs.
For instance, exfoliated WSe2, MoSe2, MoS2(1−x)Se2x, MoTe2, WTe2, MoSe2/WSe2,

VSe2, etc. 2D nanosheets exhibited a superior performance than the bulk counter-
parts. Doping noble metals such as Pt and Ru to the 2D chalcogenides can increase the
catalytic activity tremendously. MoSe2 is an n-type semiconductor, converting MoSe2
to a p-type semiconductor by Nb or Ta doping reduces its activity toward HER [16].
MXene (layered metal nitrides and carbides) is a new family of exfoliated mate-
rials and potential electrocatalyst for HER, MXene adopts a general formula of
Mn+1XnTx (n = 1–3), where M is a transition metal such as Mo, V, or Ti, X is C and/
or N, and Tx represents surface functional groups such as H or OH. Despite the high
surface area, MXenes are characterized by excellent hydrophilicity and conductiv-
ity. Interestingly, the active HER sites for MXene are located on the O* basal plane,
which makes them ideal for HER [17]. The HER activity of MXene is enhanced by
modifying the transition metal, during which the Gibbs free energy for hydrogen
adsorption is improved, subsequently, one can obtain a decreased barrier energy for
hydrogen production [18]. MXene combined with nanostructured platinum is widely
used as the electrocatalyst. Mo2TiC2Tx, Ti3C2Tx, V4C3Tx, Mo2TiC2Tx, etc. are some
representative MXene electrocatalysts for HER.
Layered carbon allotropes such as graphene and its oxide exhibit poor adsorp-
tion toward hydrogen; therefore, they are not effcient catalysts for HER. However,
these materials are extensively used as supporting materials for electroactive ele-
ments and nanostructures. The graphene decorated with electroactive nanostructures
of Pt, Ni-Mo-N, Ni, CoP, MoS2, ReSe2, WS2, etc. is identifed as excellent catalysts
for HER in a basic medium. In addition to the large surface area, the high conduc-
tivity of the graphene/graphene oxide signifcantly reduces the interfacial electron
transfer resistance between the catalyst support and the active sites, which ultimately
improves the effciency toward HER.
10.3.2 OXYGEN EVOLUTION REACTION (OER) AND

OXYGEN REDUCTION REACTION (ORR)
The electrochemical generation of oxygen through water splitting is critical in metal-
air batteries and fuel cells. The electrochemical OER (2H2O → O2 + 4H+ + 4e−) and
ORR (O2 + 4H+ + 4e− → 2H2O) are four-electron transfer reactions. Due to the com-
plicated multi-electron transfer steps, the ORR/OER suffers from sluggish kinetics.
Similar to HER, noble metals and their derivatives exhibit low overpotential for both
ORR (e.g., Pt) and OER (e.g., IrO2 and RuO2) applications. 2D nanolayers are unique
due to a large number of surface atoms as compared to the internal atoms, which makes
them highly electroactive for a variety of applications. Exfoliated 2D materials like
graphene and graphene oxide, inorganic monolayer materials such as metal oxides,
TMDs, LDHs, MXenes, diatomic hexagonal boron nitride, and black phosphorous
(BP or phosphorene) are studied as potential candidates for OER and ORR applica-
tions. In addition to the planar strength, exfoliated 2D materials are fexible with an
atomic or few-layer thickness. Interestingly, the most single or few layers of graphene,
carbon nanosheets (CNS), TMDs, LDHs, and MXenes are exfoliated from their bulk,
and these are the most extensively studied 2D materials for OER application.
To overcome the scarcity of OER electrocatalysts for acid medium the transition
metal dichalcogenides (TMD) are proposed. The exfoliated 2D nanosheets of MoS2,
TaS2, WS2, MoSe2, etc. either in 1T and 2H polymorphic forms are the common elec-
troactive catalysts for OER. The performance of the above materials for OER is par
to stable IrO2. Liquid phase and ion intercalation are the most common routes for the
exfoliation of TMDs nanosheets from the bulk by overcoming the weak van der Waals
interaction among layers. The step-by-step exfoliation of bulk TMDs using Isopropyl
alcohol and the preparation of electrodes using exfoliated nanolayers are shown in
Figure 10.3. Alike HER, the dominant active sites of TMDs for OER are on the edges
rather than the surface [19]. The dichalcogenides of noble metals such as Rhenium-,
Ruthenium-, and Iridium- exhibit exceptional activity toward OER and ORR.
Unlike in the HER, MXenes themselves are not directly active for ORR or OER
electrocatalysis; however, they serve as excellent supports for various electroactive
materials. MXenes are better catalyst support for Pt nanoparticles or Pt/Pd atoms
than carbon as in the commercial Pt/C electrode for OER due to the strong inter-
action between Pt and the respective MXene layers. Likewise, other electroactive
materials such as metal-organic frameworks, carbon nitride, LDHs, oxides, borate,
sulfdes, and metals bound to the surface of MXenes also exhibited superior OER
activity par to the commercial noble metal catalysts. Hybrid TMD–MXene-like
materials are recently introduced as OER catalysts. The heterostructure of the above
hybrids allows the synergistic interactions between TMDs and MXenes and one can
achieve a signifcant improvement in the OER activity.
Carbon allotropes themselves are not active for OER or ORR, though when doped
with heteroatoms (B, S, N, P, F, and O) or transition metals (Ni, Co, Fe, etc.), they
become excellent ORR and OER catalysts. The conductivity of graphene, 2D porous
FIGURE 10.3 Schematic representation of step-by-step electrode fabrication process using

exfoliated TMDs. (a) Starting TMD, (b) Insertion water and IPA, (c) Sonication and exfolia-
tions, and (d) application for OER (Wu et al. 2016). Reprinted with permission from © 2016
John Wiley and Sons.
carbon, and graphitic carbon nitride (g-C3N4) layers can significantly reduce the
interfacial resistance between the electroactive materials or the active sites and the
current-carrying substrate. Additionally, as discussed in the case MXenes, the exfo-
liated 2D carbon layers are commonly used as a support for nanosized or atomic
catalytic materials. MoS2, Fe3O4, FeP, Ni2P, CoP2, CoOx, NiO, etc. are some represen-
tative nanoparticles grown on 2D carbon materials for OER. Nevertheless, the long-
term stability of carbon-based electrocatalysts is inferior to MXenes. Both MXenes
and 2D carbon allotropes are mostly sought for OER and ORR in a basic medium.
Among the OER catalysts, layered double hydroxides (LDHs) are extensively stud-
ied as a potential replacement for noble metal catalysts due to their compositional and
structural flexibility in addition to the simple preparation routes. Often LDHs adopt
x M1− x ( OH )2 ( A ) x . yH 2 O or M x M1− x ( OH )2 ( A ) x . yH 2 O;
n− n−
a formula either M2+ 3+ 1+ 4+
n n
where M is a metal and A is the intercalating anion. In LDHs, every single layer is
composed of edge-sharing octahedral MO6 moieties (M stands for metal) as shown in
Figure 10.4. The color code used in the figure are: purple for metals, red for oxygen, and
grey for inter-layer anions and water molecules. If d1 is the inter-layer distance before
intercalation, the inter-layer distance increases after intercalation to d2 and d2 > d1.
One can observe the change in interlayer spacing under an electron microscope and
the subsequent change in the crystal structure from X-ray diffraction. The transition
metal oxides (TMOs) with d-orbitals can effectively bind oxygen species on its surface,
which is an essential requirement for OER/ORR catalyst. The substitution of elements
in M2+ and M3+ sites can fine-tune the electronic as well as the catalytic properties of
LDHs. Exfoliated LDHs formed by a combination of the transition metals, Ni-Co,
Ni-Fe, Co-Fe, Co-Co, Ni-Mn, Co-Mn, etc. are some representative low overpotential
electrocatalysts for OER in a basic medium among the non-noble metal catalysts.
Exfoliated layered perovskite with the general formula ABO3 (A and B can be
occupied by a large number of elements in the periodic table) and delafossite with
the general formula AMO2 is also studied as potential OER catalysts [20]. The
above oxides with transition metals such as Co, Ni, and Fe at one of the sites are
excellent OER catalysts. Such oxides are stable than the carbon-containing catalysts
under oxidative environments and offer a competitive catalytic property compa-
rable to noble metals.
FIGURE 10.4 (a) Structure of layered hydroxides, (b) LDHs intercalated with a layer of
anions and water molecules, and (c) exfoliated LDH monolayers in a colloidal solution (Song
and Hu 2014). Reprinted with permission from © 2014 Springer Nature.
10.4 SUPERCAPACITORS
Supercapacitors bridge the gap between rechargeable batteries and conventional
capacitors. But one of the major restrictions of supercapacitors is their lower energy
density than the rechargeable batteries. There are several reported attempts to
improve and enhance the energy density of supercapacitors. Supercapacitors mainly
consist of electrodes, electrolytes, current collectors, sealants, and separators. The
selection and design of the electrode materials have a major role in the overall perfor-
mance of a supercapacitor as it determines the ionic conductivity, surface area, and
chemical and thermal stability [21].
Supercapacitors are categorized mainly into two, based on their charge storage
mechanism, one is electric double-layer (EDLC) or faradaic capacitor where energy
is stored via non-Faradaic electrostatic interaction and the other one is pseudocapaci-
tor where the energy storage is accomplished through Faradaic redox charge trans-
fer reactions [22]. When 2D layered nanomaterials are used as electrodes in both
Faradaic and non-Faradaic storage systems, the charge is mainly stored at the basal
plane of the layered nanosheet, i.e., with the larger planar area. Additionally, the
presence of active edge sites and the weak van der Waals gap between the nanosheet
layers of 2D nanomaterials offer enhanced and suitable electrochemical perfor-
mance in supercapacitors. Here in this section, the most commonly used exfoliated
2D nanosheets of both carbon-based and non-carbon-based are discussed in detail.
Graphene is one of the most common 2D layered carbon sheets with a hexagonal
lattice structure, widely investigated for supercapacitor applications. The kinetics of
an electrode material mainly depends on the transportation and diffusion of electro-
lyte ions. Due to the lack of enough edge planes and surface charges, monolayer gra-
phene is considered one of the most chemically and electrochemically inert materials
[23]. During the charge storage process, graphene acts as a superior active material as
the electrolyte ions like Na+, K+, etc., can be stored electrostatically on the electrode.
But the agglomeration of graphene nanosheets due to the strong van der Waals inter-
action limits the full utilization of graphene surface for ion adsorption. The agglomer-
ated structure extremely limits the direct access to the charge-storage surfaces, which
fnally leads to the increase in ionic resistance at the electrode [24]. Higher agglom-
eration, hydrophobicity, and the random orientation of graphene nanosheets restrict
the availability of ions on the active surface. Thus, the morphology of the electrode
materials plays a vital role in the charge storage mechanism of supercapacitors.
Stoller et al. developed chemically modifed graphene (CMG) electrodes with
good electrical conductivity and a specifc surface area of 705 m2 g−1, by chemical
functionalization of monolayer graphene. The CMG electrode materials exhibited
a specifc capacitance of 135 F g−1 in aqueous electrolyte (5.5 M KOH) and 99 F g−1
in the organic electrolyte [25]. Most reported graphene-derived electrode materials
exhibited lower specifc surface area than their theoretical value (2,630 m2 g−1). But
the Ruoff group reported KOH-activated thermally exfoliated graphene oxide and
microwave exfoliated graphene oxide (MEGO) electrode material, which exhibited
an ultrahigh specifc surface area value of 3,100 m2 g−1, a high electrical conductivity
(~500 S.m−1), high content of sp2-bonded carbon, and low hydrogen content. The KOH-
activated MEGO electrode exhibited a notable high energy density (~70 Wh kg−1)
and power density (~250 kW kg−1) at a current density of 5.7 A g−1 [26]. El-Kady et al.
fabricated a graphene-based supercapacitor via laser irradiation of a graphene oxide
flm coated on a fexible substrate mounted in a LightScribe DVD optical drive. The
graphene oxide sheets stacked in the flm were reduced and exfoliated simultane-
ously upon laser irradiation and this structure restricts the agglomeration of graphene
sheets and also the open pores in them facilitate the easy accessibility of electrolyte
on the electrode surface. The resultant laser-scribed graphene sheets exhibited a high
specifc surface area of 1,520 m2 g−1, good mechanical fexibility, and high electrical
conductivity (1,738 S.m−1) [27]. Miller and his group fabricated supercapacitor elec-
trodes using radio frequency plasma-enhanced chemical vapor deposition in which
vertically oriented graphene nanosheets were deposited on a heated Ni-substrate.
They showed a specifc surface area of ~ 1,100 m2 g−1 and effective fltering of 120 Hz
current with a resistance-capacitance time constant value less than 0.2 ms. With the
exposed edge planes the vertically aligned graphene nanosheets showed enhanced
charge storage as compared to the fat graphene nanosheets [28]. The exceptional
properties and promising application of graphene in energy storage devices have trig-
gered a remarkable interest in exploring other non-carbon 2D layered nanostructures
with versatile properties.
Non-carbon-based 2D layered nanomaterials have been considered as a poten-
tial candidate for supercapacitor electrodes owing to their unique physical and
chemical properties such as high electronic conductivity, tunable surface chem-
istry, more surface-active sites, dual non-faradaic and faradaic electrochemical
performances, and larger mechanical strength. 2D non-CNSs include TMDs
(MoS2, WS2, TiS2, ZrS2, MoSe2, WSe2, etc.), layered metal-oxides, hexagonal
boron nitride (h-BN), LDHs, graphitic carbon nitride (g-C3N4), and MXenes
(Ti3C2, V2C, Ti2AlC, TiAlC, Ti3CN) [29]. Among TMDs, 2D MoS2 nanosheets
are a potential supercapacitor electrode material that exhibits large electrical
double layer capacitance (EDLC) owing to their stacked sheet-like structure, and
large pseudocapacitance due to the different Mo oxidation states (+2 to +6). Tour
and his co-workers developed vertically aligned/edge-oriented MoS2 nanosheets
that offer a high capacitive property with more van der Waals gaps and rendered
reactive dangling bonds sites for the electrolyte ions. Areal Capacitance of 12.5
mF cm−2 was obtained for sponge-like vertically aligned MoS2 electrodes [30].
Layered 2D TMOs exhibit exceptionally high surface area and high conductivity
as they are capable of holding charged ions on their surface without intermix-
ing. Supercapacitors based on layered TMOs feature superior cyclic stability, high
energy density, and high discharge currents. Commonly used 2D layered TMOs
include MnO2, NiO, Co3O4, and RuO2. MnO2 possesses low conductivity and thus
they require a conductive matrix of graphene or metal foam. Peng et al. fabricated
a supercapacitor electrode integrating 2D graphene and 2D MnO2 into a planar
capacitor design that was highly fexible [31].
2D LDH sheets are a class of multi-metal clay materials that consist of metal
cations brucite layers octahedrally surrounded by hydroxyls forming M2+(OH)6/M3+/
M4+(OH)6 octahedra. Their high redox activities can be attributed to their unique
properties like cations, easy tenability in their host layers and they are capable of
exchanging anions without disturbing the structure. In NiAl-LDH, its electrochemical
property is due to a mixed mechanism comprising of ‘electron hopping’ along with

the layers of LDH and the migration of protons from the host layer to the solution
[32]. MXenes have become a widely accepted supercapacitor electrode material with
their impressive electrochemical properties due to their unique 2D structure and
well-defned geometry. MXenes are one of the fast-growing materials among 2D
materials, which include metal carbides, nitrides, and carbonitrides. One of the prom-
ising features of MXene is the exceptionally large interlayer spacing, which helps
in the de/intercalation of ions like Na+, Li+, etc. Mainly hydrogen bonding and van
der Waals bonding interactions act between the MXene layers. To produce MXene
single fake suspensions, water, cations, tetrabutylammonium hydroxide (TBAOH),
dimethylsulfoxide (DMSO), etc. are intercalated into the MXene interlayer spacing
followed by the sonication process. In the H2SO4 electrolyte, Ti3C2Tx shows a high
volumetric capacitance of ~1,500 F cm−3 (380 F g−1), and the conductive, transparent
Ti3C2Tx flms are used to fabricate solid-state transparent supercapacitors [33].
10.5 LITHIUM-ION BATTERY

Lithium-ion batteries (LIBs) are the answer to many of the energy storage-related
challenges. LIBs become an essential part of everyday life. LIBs work by the rocking
chair mechanism wherein the lithium ions are moved between the anodes and cath-
odes. The electrodes play an important role in storing the lithium ions by the inter-
calation and deintercalation reactions. Historically, layered materials have played an
important role in the development of LIBs by allowing the layered structures of the
electrodes like graphite to intercalate lithium ions. Currently, LIBs use a wide variety
of electrodes having mechanisms such as insertion, alloying, and conversion reac-
tions [34]. Electrodes with higher rate capability, higher charge capacity, and (for
cathodes) suffciently high voltage can improve the energy and power densities of Li
batteries and make them smaller and cheaper. The fast-paced life around the globe
is forcing researchers to focus on materials that can be charged faster and hold more
energy per volume and weight. Layered materials are often helpful in achieving faster
lithium-ion diffusion and have a higher capacitive contribution. Owing to compelling
electrochemical and mechanical properties, exfoliated 2D nanomaterials have been
propelled to the forefront in investigations of electrode materials in recent years.
Exfoliated 2D nanomaterials are exceedingly desirable as anodes and cathodes.
As anodes, the famous candidates are graphene and graphene-based composite mate-
rials, including carbon nanotubes/graphene, nonmetal/graphene, TMOs/graphene,
sulfde/graphene, and salts/graphene. As cathodes, exfoliated 2D nanomaterials have
remarkable electron transport velocity, high theoretical capacity, and excellent struc-
tural stability. The exfoliation of bulk material and Li+ insertion was represented in
Figure 10.5, which shows easier paths for lithium-ion storage.
Graphite is the most traditionally used anode in LIBs, which is a layered material.
Expansion and exfoliation of the graphite are well reported by various researchers.
Graphite as such shows a theoretical capacity of 372 mAh g−1. Due to good electri-
cal conductivity, high surface area, and greater mechanical fexibility, graphite exfo-
liation has attracted the most attention for fabricating high-performance electrode
material for LIB. Lithium may bond both graphene sheet sides as well as edges and
FIGURE 10.5 Sketch of the exfoliated layered material as a cathode for Li+ insertion in LIBs.
covalent sites. Recent studies demonstrated that the small lateral sizes of narrow gra-
phene nano-ribbons can accommodate Li+ ions at the edges sites more effciently than
basal sites, thus leading to maximum Li-storage in the form of Li4C6. The probable
defects formed during the exfoliation process become an advantage in such cases.
Apart from this, graphene nanosheets are widely used to make composites with other
electrode materials. In materials like silicon, graphene sheets are also used to give
cushioning effect to accommodate the high volume change during the lithium uptake.
Exfoliated carbons are trustable electrodes for lithium battery electrodes but lack
high capacity, which restricts the overall capacity of the batteries. Exfoliated 2D
group V nano-crystals have a greater theoretical capacity than graphite. Exfoliation
of these metallic electrodes is challenging because of the stability issues. Among
them, layered 2D antimony has the potential as electrode material for LIBs, owing to
their large interlayer distance in their layered structure, high capacity, long mean free
path, and environmental friendliness. The theoretical capacity of antimony is mod-
erate therefore other 2D materials are also explored as LIB electrodes. The layered
transition metal oxides (LTMOs) require a special mention in LIBs. The exceptional
feature of these materials is the presence of an interlayer region that serves as the host
for ion intercalation. The extensive interlayer spacing and weak interlayer bonding
of LTMOs permit the intercalation of an enormous variety of guest species, like cat-
ions, polymers, and anions. LTMO has excellent electronic and ionic conductivity, the
attainability of interlayer sites for the intercalation of cations from the electrolyte, and
the ability to undergo redox reaction property for high energy density LIB. Several
mechanisms are possible when LTMO is in contact with an electrolyte like intercala-
tion, conversion, double layer capacitance, conversion, and pseudocapacitance [35].
2D TMDs consist of greater specifc capacity and larger interlayer spacing, which
permit a quick Li+ insertion/extraction process without persuading noteworthy volume
changes [36]. Exfoliated layers of chalcogenides such as MoS2, NbSe2, WS2, MoSe2,
TaSe2, and MoTe2 nanosheets are widely used for the LIB. Among them, MoS2 is an
exciting electrode material for LIBs due to its high theoretical capacity. MoS2 nano-
layers allow intercalation of Li+ ions into the structure without noteworthy volume
change and charging and discharging prevent the disintegration of active material.
Based on the reaction MoS2 + 4Li+ + 4e− ↔ 2Li2S + Mo, the electrochemical reaction
of Li with MoS2 involves 4 moles of Li per mole of MoS2. The main concern of MoS2
layered nanomaterial is low electronic conductivity and poor cyclic stability [37].
Another class of materials that is gaining recent attention is MXenes, which pos-
sess 2D layered structure. The main advantage of MXene as electrode material for the
energy storage device is the separation between MXene layers that can be controlled
systematically. MXenes usage as anode for LIBs was frst reported by Naguib et al.
[38]. The MXenes prepared by Naguib showed improved surface area by ~10-fold as
compared with graphene since MXenes exhibit improved specifc capacity. Layered
morphology of the electrodes always had a positive impact on LIBs by facilitating the
rocking chair mechanism. Fast charging and higher capacities are repeatedly reported
as a result of exfoliation. Structural changes during the exfoliation are usually acting
in favor of the intercalation of more lithium ions to the electrodes. Therefore, exfoli-
ated 2D materials are going to have a large impact on the future development of LIBs.
10.6 CONCLUSIONS
Exfoliated 2D nanosheets have gained considerable attention from the research com-
munity in recent years. The development of various 2D nanosheets of different ori-
gins allows the researchers to resolve numerous bottlenecks associated with many
electrochemical devices, especially in sensors, fuels cells, supercapacitors, and bat-
teries. Though exfoliation is a top-down approach, it can produce reasonably good
quality nanosheets in large quantities, which is essential for device fabrication at a
large scale. Interestingly the defects generated during exfoliation favor electrochemi-
cal activity than the ones prepared by chemical vapor deposition with fewer defects.
The exfoliated 2D materials are expected to play an important role in the further
advancements in electrochemical devices in the coming years.
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11 Tuning of Bandgap and
Electronic Properties for
Energy Applications
Maoyang Xia, Jing Ning, Dong Wang,
Jincheng Zhang, and Yue Hao
Xidian University
CONTENTS
11.1 Introduction .................................................................................................. 192
11.2 Graphene....................................................................................................... 192
11.2.1 Structure and Electronic Properties.................................................. 192
11.2.2 Control Method of Bandgap and Electronic Properties ................... 192
11.2.2.1 Non-Metallic Doping of Graphene .................................... 193
11.2.2.2 One-Dimensional Graphene Nanoribbons......................... 193
11.2.2.3 Chemical Modifcation ...................................................... 194
11.2.3 Application of Graphene as Electrode.............................................. 194
11.2.3.1 Supercapacitor.................................................................... 194
11.3 Transition Metal Dichalcogenides (TMDCs) ............................................... 196
11.3.2 Control Method of Bandgap and Electronic Properties ................... 197
11.3.2.1 Phase Control Engineering ................................................ 197
11.3.2.2 Heteroatoms Doping .......................................................... 198
11.3.3 Application of TMDCs as Electrode ................................................ 198
11.3.3.1 Supercapacitor.................................................................... 198
11.4 MXene .......................................................................................................... 199
11.4.2 Control Method of Bandgap and Electronic Properties ...................200
11.4.2.1 Surface Control ..................................................................200
11.4.3 Application of MXene as Electrode .................................................200
11.4.3.1 Supercapacitor....................................................................200
DOI: 10.1201/9781003178453-11 191


11.5 Conclusions and Perspectives ....................................................................... 201
References..............................................................................................................202
11.1 INTRODUCTION
In the information age of the rapid development of the Internet of Things connection,
the large demand for mobile electronic devices has stimulated intensive research
on energy-storage devices. With the wearability of mobile electronics, the matching
energy systems need not only intelligence, miniaturization, and stretchability but
also fast charging and discharging, high power density, long cycling lives, and good
stability. Selecting the appropriate electrode material is the key to ensuring high
energy density for the micro-energy storage system. So far, 2D nanomaterials have
shown broad application prospects in the feld of energy storage because of their
outstanding physical and chemical properties.
Since its discovery, 2D materials have attracted extensive research attention
because of their excellent and controllable physical and chemical properties. The
2D materials are mostly bonded by strong ionic or covalent bonds in layers, and the
layers are stacked together by van der Waals forces, so that few or single-layer 2D
materials can be stripped. The weak interaction between 2D materials layers also
makes it possible to use van der Waals gaps to adjust the electronic structure of the
system and further optimizing the material properties. The introduction of intercala-
tor in van der Waals gap can signifcantly change the layer spacing of host materials
and regulate the van der Waals coupling between layers, so as to optimize the physi-
cal and chemical properties of 2D materials.
In recent years, a large number of studies have proposed many effective methods
to prepare 2D materials, and studied its electronic structure and energy band regula-
tion, in order to solve the bottleneck problem in the application. This chapter sys-
tematically summarizes the research progress in the electronic structure and energy
band regulation of 2D materials and further discusses the energy application felds
and prospects of 2D materials.
11.2 GRAPHENE
11.2.1 STRUCTURE AND ELECTRONIC PROPERTIES
Graphene is a 2D crystalline ultra-thin material with 2D sp2-hybridized carbon nano-
structure and a honeycomb lattice. Graphene exhibits a large theoretical specifc sur-
face area (2,600 m2 g−1), high electrical conductivity (106 S cm−1), and low bandgap
(0 eV). Because of these advantages, graphene is selected as one of the most promis-
ing candidates in energy storage devices electrode [1].
11.2.2 CONTROL METHOD OF BANDGAP AND ELECTRONIC PROPERTIES

The electronic structure and energy band of graphene determine its applications in
the felds of electronics, optoelectronics, and energy storage. Generally speaking, the
Energy Applications 193
methods to control the bandgap structure of graphene include doping, preparation of

1D graphene with quantum effect, and chemical modifcation.
11.2.2.1 Non-Metallic Doping of Graphene

Doping non-metallic atoms in graphene is an effective way to change their proper-
ties [2]. The introduction of nitrogen (N) or boron (B) atoms into graphene to replace
the position of carbon atoms can enable graphene to exhibit the properties of N- or
P-type semiconductors. Because N, B, and C atoms differ by only one valence elec-
tron and have similar size and electronic structure, N and/or B doping of graphene
can avoid large stress, maintain the integrity of graphene structure, and make the
intrinsic graphene change from metallic to semiconductor through changing the
energy bandgap structure.
At present, the main methods to prepare N-doped graphene (NDG) are chemical
vapor deposition (CVD), ion-nitriding, arc discharge, and fame method.
CVD method. Graphene was prepared and doped via high-temperature decompo-
sition of ammonia and methane, mutual solubility of catalysts, and cooling precipita-
tion. Wei et al. [3] deposited a layer of Cu nanocrystalline flm with a thickness of
about 25 nm on the Si wafer and then prepared N-doping graphene in a mixed atmo-
sphere of CH4, H2, and NH3 at 800°C by the CVD method. N atoms are embedded
in graphene by introducing NH3 during the growth process. The incorporation of N
atoms transforms graphene from a conductor to an n-type semiconductor.
Ion-nitriding method. Carbon ring structure in graphene is destroyed by nitrogen
ion bombardment, and N atom is introduced to fll the vacancy defect of C atom.
Dai et al. [4] treated graphene oxide with NH3 between 300°C and 900°C to achieve
reduction and doping of graphene oxide at same time.
Arc discharge method. In carbon-nitrogen-hydrogen atmosphere, the carbon
source and nitrogen source are decomposed by arc discharge to prepare NDG.
Hydrogen is used to avoid the curling of graphene nanosheets to form carbon nano-
tubes. Shi et al. [5] prepared a large number of NDG sheets by DC arc evaporation
graphite electrode in NH3 atmosphere. The doping concentration of N element is
adjusted by controlling the concentration of NH3.
Flame method. The mixed fuel is used as a fuel to provide reaction energy, and
as a material to provide reactants, with Ni as a catalyst. According to the different
solubility of C and N atoms in Ni, NDG was prepared. Zhang et al. [6] mixed amine
and ethanol in 7:3 ratio as fuel, coated a layer of Ni nanocrystalline flm on Si wafer,
putted it on fame for 1–3 minutes. NDG nanosheet layer is obtained on Ni surface.
11.2.2.2 One-Dimensional Graphene Nanoribbons

The electronic structure and energy band of graphene are related to its width and
boundary geometry. The 2D graphene sheet is cut into 1D graphene nanoribbons
with fnite size in the transverse direction. The quantum confnement effect and
boundary effect will limit the movement of electrons in the transverse direction of
graphene nanoribbons so that the energy gap is opened. At the same time, the width
of 1D graphene nanoribbons can be accurately controlled to tune its energy gap. So
far, the preparation technologies of 1D graphene nanoribbons mainly include carbon
nanotube slitting, organic synthesis, and mask etching.
Carbon nanotube slitting method. Carbon nanotubes replace graphite as the start-
ing material, break the bonding on the surface of carbon nanotubes through sulfuric
acid and potassium permanganate oxidation treatment or plasma etching treatment,
and cut longitudinally to form graphene nanoribbons.
Organic synthetic method. Cai et al. [7] reported atomically precise graphene
nanoribbons with different topologies and widths, which utilize surface-assisted cou-
pling of molecular precursors to linear polyphenylenes and their subsequent cyclode-
hydrogenation. The topology, width, and edge periphery of the graphene nanoribbon
products are determined by the structure of the precursor monomers, which can be
designed for various graphene nanoribbons.
Mask etching method. Bai et al. [8] fabricated graphene nanoribbons with a width
of less than 10 nm via using chemically synthesized nanowires as the physical pro-
tection mask for oxygen plasma etching. Banded or branched or crossed graphene
nanostructures can be produced.
11.2.2.3 Chemical Modifcation

Graphene has a large specifc surface area and strong adsorption capacity. The energy
gap of multilayer graphene can be opened by adsorbing metal atoms on the one side.
Chemical modifcation method is to place graphene in a space rich in adsorbents.
Chemical modifcation adjusts the size of the energy gap by altering the electronic
structure of graphene. Chemical modifcation of graphene can also destroy the sym-
metry of graphene to open its energy gap. For example, restore graphene prepared by
graphite oxide has a certain bandgap because of the large number of oxygen-containing
functional groups and defects on the surface. Its bandgap can be adjusted with the
change of oxygen content. Mathkar et al. [9] found that the bandgap of graphene is
adjusted from 1 to 3.5 eV via changing the degree of oxidation and oxidation region.
11.2.3 APPLICATION OF GRAPHENE AS ELECTRODE

Graphene is the most promising electrode material in supercapacitor because of its
high electronic conductivity and outstanding mechanical stability. The self-doping
defect structure is controllably introduced on the surface of graphene to improve the
energy storage performance by doping and introducing functional groups.
Wu et al. [10] synthesized the 3D structure of graphene aerogel and assembled
all-solid-state supercapacitors. The power density and energy density reach 62 Wh
kg−1 and 1,600 W kg−1, respectively. Chen et al. [11] deposited the graphene hydrogel
inside the nickel foam to open the pore structure of the electrode and allow the elec-
trolyte ions to pass smoothly, so it has excellent rate performance.
Ogata et al. [12] reported a fexible solid-state reduced graphene oxide (rGO)/gra-
phene oxide (GO)/rGO supercapacitor. High ionic concentration and fast ion conduc-
tion in the H2SO4-intercalated GO electrolyte/separator and abundant CH defects,
which serve as pseudocapacitive sites on the rGO electrode, were responsible for
the high capacitance (14.5 mF cm−2) of the device. Moon et al. [13] fabricated 3D
porous stretchable supercapacitor with wrinkled-structure poly(3,4-ethylenedioxy-
thiophene)- poly(styrenesulfonate) on a 3D porous reduced graphene oxide-coated
elastic substrate under pre-strained conditions via solution process. The stretchable
supercapacitor exhibits an electrochemical energy capacity up to 82.4 F g−1 and
85.1% capacitance retention at 300% strain.
Dong et al. [14] reported defect-enriched graphene block with a low specifc surface
area of 29.7 m2 g−1 and high packing density of 0.917 g cm−3 performs high gravimetric,
volumetric, and areal capacitances of 235 F g−1, 215 F cm−3, and 3.95 F cm−2 at 1 A g−1,
respectively. Zhang et al. [15] fabricated N-doping graphene paper using GO-ethanol
dispersion fltration. NDG papers maintain good foldability with improved electric
conductivity and porous structure. When the NDG paper is fabricated as fexible
device, this device also demonstrates a high charge/discharge capacitances 312.5 F g−1.

Carbon/graphite is a commercially available lithium-ion battery (LIB) anode mate-
rial because of low cost and stable performance. The theoretical specifc capacity is
376 mAh g−1. Every six carbon atoms are combined with one lithium atom to store
energy in LiC6. The doping and modifcation of graphene can increase the active sites
and improve the energy storage performance of LIBs.
Wei et al. [16] reported all-solid-state LIB is made of monolayer graphene grown
by CVD directly onto Cu foil. The total thickness of the resulting battery was 50 mm.
Graphene LIBs showed the highest energy density of 10 W h L−1 and the highest
power density of 300 W L−1. Yin et al. [17] reported a self-assembly strategy to create
bioinspired hierarchical structures composed of functionalized graphene sheets. The
electrodes with multilevel architectures simultaneously optimize ion transport and
capacity, leading to a high performance of reversible capacity of up to 1,600 mAh g−1,
and 1,150 mAh g−1 after 50 cycles.
Liu et al. [18] reported graphene paper is made from a graphene aerogel, which
is prefabricated by freeze-drying a GO aqueous dispersion and subsequent thermal
reduction. The graphene paper is free-standing and fexible. When used as electrodes
for a LIB, this graphene paper can reach 557 mAh g−1. Mukherjee et al. [19] reported
photofash and laser-reduced free-standing graphene paper as high-rate capable
anodes for LIBs. Photothermal reduction of graphene oxide yields an expanded
structure with micrometer-scale pores, cracks, and intersheet voids. At charge/dis-
charge rates of 40 C, the anodes delivered a steady capacity of 156 mAh g−1.
Liu et al. [20] synthesized sandwich architecture of N-carbon/rGO by simple
pyrolysis of a polypyrrole/GO nanosheet precursor. The N-carbon/rGO exhibits
the N-doping of 15.4% and a specifc surface area of 327 m2 g−1. The N-carbon/rGO
shows a high initial reversible capacity of 1,100 mAh g−1 at 100 mA g−1. Mo et al. [21]
reported the synthesis of nitrogen-doped, mesoporous graphene particles through
CVD with magnesium-oxide particles as the catalyst and template. Such particles
possess structural and electrochemical stability, electronic and ionic conductivity,
enabling their use as anodes with reversible capacity (1,138 mAh g−1 at 0.2 C).

Carbon-based materials have signifcant advantages such as low price, convenient
operation, low toxicity, and high effciency. However, due to the uniform shrink-
age of C = C bond, narrow layer spacing, and weak surface bond cooperation,
layered graphite still has a bottleneck in the application of sodium-ion battery (SIB).
Therefore, the modifcation of graphene and the increase of layer spacing are condu-
cive to improve the performance.
Lee et al. [22] reported the ion storage capacity of activated-crumbled graphene
(A-CG) for fast charging and extended cyclability. A-CG was synthesized by low-
temperature spraying of graphene oxide slurry, reduction annealing, and air activa-
tion. For Na storage, the reversible capacities are 280 mAh g−1 at 0.04 A g−1.
Wang et al. [23] produced boron-functionalized reduced graphene oxide (BF-rGO),
with expended interlayer spacing and defect-rich structure, thereby effectively
accommodating to sodiation/desodiation and providing more active sites. The Na/
BF-rGO half cells exhibit unprecedented long cycling stability, with 89.4% capacity
retained after 5,000 cycles at current density of 1,000 mA g−1.
Dan et al. [24] produced the NC/RGO by pyrolyzing the cellulose, chitosan, and
GO. Nitrogen doping not only improved the conductivity but also increased layer
spacing and promoted the insertion of Na-ions. The NC/RGO shows a sodium stor-
age capacity of 395 mAh g−1 at 0.1 A g−1.

In K-insertion/extraction and the corresponding potassium storage mechanism, KC36
(Stage III) was frst observed between 0.3 and 0.2 V, followed by KC24 (Stage II)
between 0.2 and 0.1 V. Finally, the pure KC8 (Stage I) was decomposed near 0.01 V.
No KC24 (Stage II) was detected during potassium-depotassiation, and KC8 (Stage I)
was replaced by KC36 (Stage III) until around 0.3 V.
Ju et al. [25] prepared few-layer nitrogen-doped graphene (FLNG) by bottom-up
synthesis using Dicyandiamide and Coal tar pitch as raw materials. The FLNG with
high surface area (479.21 m2 g−1) and nitrogen content (14.68 at%) exhibits excellent
K-ion storage performances (320 mAh g−1 at 50 mA g−1).
Dong et al. [26] synthesized carbon dots-modifed reduced graphene oxides (LAP-
rGO-CDs) via a microwave-assisted method. Due to the introduction of carbon dots,
the interlayer space of LAP-rGO-CDs increase and ion transfer rate become faster.
As a potassium-ion battery (PIB) electrode, LAP-rGO-CDs showed a specifc capac-
ity of 299 mAh g−1 at 1 A g−1.
Qiao et al. [27] synthesized columnar graphene nanosheets with expanded inter-
layer spacing via an in situ growth strategy. It is confrmed by kinetics that the
extended interlayer spacing can accelerate ion transport. The graphene nanosheet/
NiO-500 composite anode provides ultrahigh reversible capability 416.1 mA h g−1 at
0.1 A g−1.
11.3 TRANSITION METAL DICHALCOGENIDES (TMDCs)

Transition metal dichalcogenide (TMDC) is a layered compound similar to gra-
phene, and its molecular formula is generally MX2, where M represents a transition
metal atom (Mo, W, etc.) and X represents a chalcogen atom (S, Se, etc.). Single-layer
X-M-X has a sandwich structure. Similar to other 2D materials, TMDC layers are
connected by van der Waals force. TMDCs exist in several structural phases accord-
ing to different coordination modes of the transition metal atoms. The three common
structural phases are 3R, 2H, and 1T, which are characterized by rhombic, trigonal
prismatic, and octahedral coordination of the transition metal atoms, respectively.
Different crystal forms also give different properties to multilayer TMDCs: the con-
ductivity of 1T phase is 107 times that of 2H phase. Both 3R phase and 2H phase have
trigonal prismatic structure, but their stacking order is different, and their application
range is narrow. Due to their similar crystal structure, TMDCs are easy to construct
heterostructures. The heterogeneous interface not only exposes more active sites of
electrochemical reaction but also helps to improve the properties of ion transport and
electron conduction. The combination of different 2D TMDCs provides an oppor-
tunity for the design of artifcial layered materials and widens the application of
TMDCs in the feld of electrochemistry [28].

11.3.2.1 Phase Control Engineering
2D TMDCs are composed of more than 40 compounds. Complex metal TMDCs
assume a 1T phase in which transition metal atoms are coordinated as octahedrons.
The 2H phase is stable in semiconductor TMDCs, where the coordination of metal
atoms is triangular prism. Phase transitions in TMDCs involve transformations by
chemistry at room temperature and pressure. 2H phase 2D TMDCs can be converted
to 1T phase, or 1T phase can be patterned locally on 2H phase.
1T phase was realized in alkali metal (Li and K) intercalated TMDC decades ago.
The embedding of TMDC leads to a signifcant expansion of layer spacing, so that
the solvation and the reduction of embedding agent lead to stripping into a single
layer. These monolayer nanosheets consist of most of the 1T phase. The conversion
of 2H phase to 1T phase in the embedding process is attributed to the charge transfer
from alkali atoms to nanosheets. This additional charge leads to the density of states
of Fermi level, which makes the material metallic. In addition to alkali doping by
intercalation, substitution doping with elements with more valence electrons than
transition metal ions (e.g., Re and Mn) in TMDC can also lead to the formation of
1T phase.
Although the transition from 2H to 1T phase requires additional electrons from
dopants, the presence of such impurities is undesirable. The removal of dopant will
destroy the stability of 1T phase. In lithium-embedded TMDCs (e.g., LixMoS2), butyl
lithium is used. Organic butyl and Li-ions can be removed from MoS2 nanosheets by
careful washing with hexane and water. Surprisingly, the 1T phase still exists after
the removal of organic and alkali impurities. The “Dry” flms of the chemically pure
1T phase TMDCs in multilayer and monolayer forms have been proved. The stability
of these flms is attributed to the presence of protons or other immobile, positively
charged ions on the surface of the nanosheets, which counteract the additional charge
provided by the dopants. After annealing to ~ 300°C in a controlled environment,
the 1T phase relaxes to 2H phase, which supports the existence of positively charged
counter ions adsorbed on the nanosheets [29,30].
11.3.2.2 Heteroatoms Doping

Doped heteroatoms are an effective way to change electron structure especially the
d-band of TMDCs-based material. The layer spacing of 2D materials can be effec-
tively changed by doping heteroatoms and intercalation with metal ions, small mole-
cules, metal atoms, and organic molecules. Heteroatom doping usually causes charge
transfer or other interactions with the matrix material while changing the interlayer
coupling.
The presence of heavy atoms will also increase the spin–orbit coupling, resulting
in changes in superconducting properties, thermoelectric properties, or spin polar-
ization. It is also found that the interlayer coupling of multilayer 2D materials can be
effectively decoupled by inserting other 2D monolayers or organic molecules into the
layers of 2D materials to form superlattices [31].
11.3.3 APPLICATION OF TMDCS AS ELECTRODE

TMDC-based supercapacitors can store energy through three different mechanisms;
in addition to EDLC and pseudocapacitance (caused by the redox reaction of metal
atoms), the large layer spacing of 2D TMDC can also accelerate the rapid revers-
ible insertion of electrolyte ions between layers, which can help some embedded
pseudocapacitance.
Cao et al. [32] fabricated 2D MoS2 flm-based micro-supercapacitors via spraying
MoS2 nanosheets on Si/SiO2 chip and subsequent laser patterning. The best MoS2-
based micro-supercapacitor exhibits electrochemical performance for energy storage
with aqueous electrolytes, with a high area capacitance of 8 mF cm−2 (volumetric
capacitance of 178 F cm−3).
Acerce et al. [33] have shown that chemically exfoliated nanosheets of MoS2 con-
taining a high concentration of the metallic 1T phase can electrochemically embed
ions with extraordinary effciency and achieve capacitance values ranging from simi-
lar to 400 to similar to 700 F cm−3 in a variety of aqueous electrolytes.
Ning et al. [34] synthesized W-doped MoSe2/graphene heterojunctions by a one-
step hydrothermal catalysis. The insertion of a small amount of W (~ 5%) into the
MoSe2/graphene heterostructure leads to the change of its lattice structure. The
W-doped MoSe2/graphene composite achieved excellent capacitance of 444.4 mF
cm−2 at 1 mV s−1.

TMDCs have many advantages, such as high theoretical specifc capacity, high natu-
ral reserves, and environmental friendliness. It has attracted people’s attention and is
widely used as cathode material for LIBs. However, TMDCs also have some short-
comings, such as low conductivity and structure instability. Therefore, it is necessary
to design the TMDC structure to improve the lithium storage performance.
Dong et al. [35] synthesized tremella-like nitrogen-doped carbon encapsu-
lated few-layer MoS2 (MoS2@NC) hybrid via a strategy with simultaneously poly-
dopamine carbonization, and molybdenum oxide specifes sulfurization. The MoS2@
NC exhibits enhanced high rate performance with a specifc capacity of 208.7 mAh
g−1 at a current density of 10 A g−1.
Chan et al. [36] synthesized MoS2/PANI-rGO composite by self-assembling
1T-MoS2 2D sheets on PANI-rGO through an electrostatic interaction. The fower-
like aggregate of 1T-MoS2 with increased interlaminar distance favors diffusion
and intercalation of Li-ions. The electrode has specifc capacities of 812 mAh g−1 at
0.1 A g−1.

Based on multi-electron conversion reaction, layered TMDCs are considered to be a
promising Na-ion anode material, but they usually show poor cycle and rate perfor-
mance due to their low conductivity and large volume changes during charge and dis-
charge. Therefore, how to design and prepare metal chalcogenide cathode materials
with stable structure and excellent sodium storage performance is still a challenge.
David et al. [37] reported layered free-standing papers composed of few-layer
MoS2 and rGO fakes exfoliated by acid, used as a self-supporting fexible electrode
in SIBs. The electrode showed good Na cycling ability with a stable charge capacity of
approximately 230 mAh g−1 with Coulombic effciency reaching approximately 99%.
Yousaf et al. [38] pointed a 3D three-layer design that sandwiched MoSe2 as the
TMDC layer between the internal CNT core and external carbon layer to form a
CNT/MoSe2/C framework. The heterostructure produces a capacity of 347 mAh g−1
at 500 mA g−1.

Potassium and lithium have similar standard redox potentials, however, potassium
has an abundant storage in the crust (1.5 wt.%), which leads to low cost of PIBs. At
the same time, K-ion has fast ion transport kinetics in electrolyte, which makes PIB
have excellent prospects.
Jiang et al. [39] showed that creating suffcient exposed edges in MoS2 via con-
structing ordered mesoporous architecture is benefcial to improving kinetics. The
engineered MoS2 with edge-enriched planes has the characteristics of 3D bicontin-
uous frameworks and shows a high reversible charge capacity of 506 mAh g−1 at
0.05 A g−1.
Soares et al. [40] studied electrochemical performance of WTe2 as a working elec-
trode for a PIB half-cell. WTe2 has a high frst cycle-specifc charge capacity—each
WTe2 molecule stores up to 3.3 K-ion, a stable capacity of 143 mAh g−1 at 10th cycle
number.
11.4 MXene
Metal carbides/nitrides (MXenes) appear as a new 2D materials family with a gen-
eral formula Mn+1XnTx (n = 1,2,3), where M stands for an early transition metal (Ti,
Zr, Hf, V, Nb, etc.), X stands for the C and/or N, and Tx stands for a large number of
surface-terminating moieties (–O, –F and –OH), due to its excellent inherent physical
and chemical properties, such as superb intrinsic electrical conductivity, tunable sur-
face chemistry (various functional groups), and tunable layer structure, have shown
great potential to increase capacitance of micro-supercapacitors [41].

11.4.2.1 Surface Control
Conventional etching methods involving HF or fuorine-containing salts will result
in the termination of F and oxygen-containing functional groups. The content of
functional groups can be adjusted due to the concentration of the etchant, the etching
time, or by different post-treatments (such as annealing in different atmospheres and
hydrazine treatment). Therefore, the engineering of MXenes surface terminals with
various properties has attracted great attention.
Physical properties of MXenes highly rely on the surface terminations and the
electronic properties of Ti3C2Tx. Through annealing at 380°C in vacuum, the work
function of sample would increase from 3.9 to 4.8 eV, which is mainly due to desorp-
tion of water, contaminations, and OH species. With desorption of fuorine at higher
temperatures from 500°C to 750°C, the work function of Ti3C2Tx decreased to 4.1 eV
again. In addition, the tunable electronic structure of MXenes turned by surface ter-
minations shown broad prospects in energy storage. If possible, surface terminations
of -H, -F, and -OH should be avoided to improve the energy storage performance and
M2C with non-functional groups (extremely diffcult to achieve) or -O termination
would provide the most promising performance [42].
11.4.3 APPLICATION OF MXENE AS ELECTRODE

The electrochemical energy storage performance of MXene is greatly affected by
surface functional groups. On the one hand, the F-/OH- and other groups adsorbed
on the surface are not conducive to the rapid migration of electrolyte ions between
layers. On the other hand, they affect the redox reaction of active site transition metal
M in MXene layer. Therefore, F-/OH- and other groups adsorbed on the surface are
one of the main reasons affecting the performance of MXene material as superca-
pacitor electrode material.
Wu et al. [43] reported SA-MXene was dispersed via in situ synthesis and with
sodium ascorbate (SA) terminated of Ti3C2Tx MXenes. The in situ synthesis pro-
cess increases the interlayer spacing of SA-MXene sheets and improves their energy
storage effciency. The all-solid micro-supercapacitor exhibits capacitance of 108.1
mF cm−2.
Levitt et al. [44] reported that MXene fakes are added into PAN solutions at a
weight ratio of 2:1 (MXene:PAN) in spinning coatings, resulting in fber mats with
up to 35 wt% MXene. The electrodes have high areal capacitance, up to 205 mF cm−2
at 50 mV s−1.
Cao et al. [45] synthesized Ti3C2/TiO2-nanowires via room temperature oxidation
methods. When used as electrodes for supercapacitors, Ti3C2/TiO2-nanowires
exhibit enhanced supercapacitive properties. The specifc capacitance of Ti3C2/TiO2-
nanowires electrode is 143 F g−1 at 2 mV s−1. After 6,000 cycles, the 80% of the initial
capacitance is retained for Ti3C2/TiO2-nanowires.

MXene is a 2D material with excellent electronic conductivity, low Li-ion diffusion
barrier, and good mechanical properties. It is widely used for energy storage.
Naguib et al. [46] reported Li insertion into a 2D layered Ti2C-based material
(MXene) with an oxidized surface, formed by etching Al from Ti2AlC in HF at room
temperature. The steady state capacity was 225 mAh g−1 at C/25.
Liu et al. [47] synthesized an N-doped 2D Nb2CTx MXene. The introduction of
nitrogen into MXene nanosheets increases c-lattice parameter of Nb2CTx MXene
from 22.32 Å to 34.78 Å. The N-doped Nb2CTx shows an increased reversible capac-
ity of 360 mAh g−1 at 0.2 C.

Ti3C2 has high rate capacity and good long-term cycle stability, which is most suitable
for SIBs. The pillaring effect of Na-ion captured by MXene can effectively maintain
the stability of layer spacing, which is conducive to the realization of rapid reversible
sodium denaturation process.
Wei et al. [48] studied Mn2+ intercalation strategy to optimize the sodium stor-
age performance of V2C MXene. The intercalated Mn2+ formed a V-O-Mn covalent
bond, which was benefcial to stabilize the structure of V2C. The V2C@Mn electrode
showed a high specifc capacity of 425 mAh g−1 at 0.05 A g−1.
Zhu et al. [49] reported the use of Ti3CN as anode material in SIBs. Introducing
more electronegative nitrogen into the lattice grid of Ti3C increases the electron
count of MXenes. The Ti3CN electrode provides a high specifc capacity of 211.5
mAh g−1 at 20 mA g−1.

Because of the low cost, high element abundance and intrinsic safety, PIBs have
attracted a surge of interest in recent years. Currently, the key challenge to the devel-
opment of PIBs is to fnd suitable anode materials with large capacity, high rate
capability, and small lattice changes during the charge/discharge process.
Zhao et al. [50] designed PDDA-NPCN/Ti3C2 hybrids as PIBs anodes via an elec-
trostatic attraction self-assembly approach. The hybrids afford enlarged interlayer
spacing and 3D interconnected conductive networks to accelerate the ionic/electronic
transport rates. The hybrids exhibit a high capacity of 358.4 mAh g−1 at 0.1 A g−1.
11.5 CONCLUSIONS AND PERSPECTIVES

In this chapter, we systematically describe a series of works on adjusting the bandgap
and electronic properties of 2D materials. The electronic and bandgap structures of
2D materials are regulated by doping, atom insertion, and chemical modifcation, so
as to change its electrical properties. It is of great signifcance to the development and
application of 2D materials, especially in the felds of energy storage. However, there
are still some problems in the study of 2D materials band regulation. For example, how
to effectively and accurately control the bandgap width of 2D TMDC materials so that
it will not cause a signifcant reduction in electron mobility in the process of changing
from semiconductor attribute to metallicity, and how to control the stability of semi-
conductor TMDC. We believe that, while using intercalation to control the properties
of materials, further application of heteroatom doping and strain control to optimize the
properties of materials may break through the limitation of a single method to control
the properties of materials, avoid or compensate for some performance degradation that
may be caused by intercalation, resulting in better or more comprehensive materials.
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12 Electrolyte Membrane
for 2D Nanomaterials
S. Mohanapriya
Periyar University
S. Vinod Selvaganesh
Indian Institute of Technology-Madras
P. Dhanasekaran
CSIR-Central Electrochemical Research
Institute-Madras Unit
CONTENTS
12.1 Introduction ..................................................................................................205
12.2 Advantages of 2D Materials in Electrolytic Membrane...............................206
12.2.1 How 2D Fillers Differ from Other Nano Filler Materials................207
12.3 Important Parameters for Improving Membrane Properties........................207
12.4 Graphene/Graphene Oxide Their Composites for Electrolyte Membrane
Applications ..................................................................................................208
12.4.1 Synthesis, Characterization, and Properties of Graphene/
Polymer Electrolyte Membranes ......................................................209
12.5 Boron Nitride Nanosheet/Polymer Membrane Synthesis and Properties .... 212
12.6 Modifed MoS2/Polymer Membranes for Energy Applications ................... 214
12.7 2D MXene/Polymer Composite Membranes for Energy Applications ........ 217
12.8 Future Scope for 2D Framework in Electrolyte Membrane-Based
Application.................................................................................................... 217
Acknowledgment ................................................................................................... 219
References.............................................................................................................. 219
12.1 INTRODUCTION
Two-dimensional (2D) materials have been reported widespread use in condensed
matter science, chemistry, biotechnology, materials engineering, and nanotechnol-
ogy, among other disciplines [1]. Graphene and its derivative 2D materials such as
transition metal dichalcogenides (TMDs), carbon nitride (g-C3N4), boron nitride
(h-BN), black phosphorus, MXenes, and silicene used as catalysts and additives for
membranes have captivated the research world for decades [2]. Meanwhile, 2D struc-
tures were believed to be thermodynamically unstable, the innovation of graphene
DOI: 10.1201/9781003178453-12 205

and its special properties culminated in a technological uprising. TMD materials,

which are layered compounds with substantial in-plane interaction and weak out-of-
plane interactions, may be exfoliated into 2D layers with single unit-cell thickness.
2D thin-flm sheets have been investigated for years, current progress in nanoscale
materials categorization and product processing has brought about a paradigm shift
[3,4]. 2D electron confnement, for example, gives 2D materials intriguing electri-
cal characteristics, which has inspired the development of next-generation electrical
gadgets.
2D metals, unlike 2D layered materials, are usually made up of non-directional
metallic bonds and have non-layered structures. Besides, 2D materials have outstand-
ing mechanical stability and optical clarity due to their atomic thickness and elevation
in anisotropy, which come up with new possibilities for designing 2D material-based
optoelectronic systems and wearable devices. Furthermore, heterostructures can be
formed by assembling disparate 2D materials without regard to lattice matching or
processing compatibility [5]. There is a revival of technical and industrial curiosity
in 2D structures with an atom thickness, thanks to recent advancements in sample
processing, optical identifcation, conversion, and manipulation of 2D materials. As
graphene and TMDs are packed into a few layers, van der Waals bonds form a weak
force of attraction between the layers. The stacking series of bilayer 2D materials
changes the crystal symmetry and equilibrium size, affecting physical properties
such as band difference, phonon vibration frequency, and superconductivity. The
combination of their electronic and optical properties, which can be engineered by
chemical functionalization, makes 2D materials appealing in diverse felds.
Non-covalent interactions may cause physical adsorption, or physisorption, of
molecular units onto the basal planes of 2 sheets, or chemical adsorption, or chemi-
sorption, of reactive species undergoing chemical reactions. The heavy intra-layer
covalent bonding and comparatively weaker interlayer van der Waals interaction of
the analogous bulk materials, which facilitates their exfoliation to 2D layers, result in
a layered structure that assists their 2D layer exfoliation. In layered materials, elec-
tronic mobility and hence conductivity are often 3- to 4-fold more effective across
the layers than between the layers. This is due to good charge carrier localization
between individual layers and charge carrier transport across several layers simulta-
neously at the same time.
12.2 ADVANTAGES OF 2D MATERIALS IN

ELECTROLYTIC MEMBRANE
A solid-state electrolyte is a solid ionic conducting electrolyte material, and it is
mainly utilized in electrochemical devices like fuel cells and solid-state batteries,
besides wide their utility for molecular separation [6,7]. The most commonly used
methods for solid-state electrolyte formulation are (a) polymer doping with organic
or inorganic salts, resulting in so-called polymer electrolytes like those based on and
(b) the use of a polymer network as mechanical reinforcement for an ion-conducting
matrix, referred to as a composite electrolyte.
2D materials like graphene, MoS2, MXene, metal-organic frameworks, and cova-
lent organic framework nanosheets are fast getting prominence in fabricating high
Electrolyte Membrane for 2D Nanomaterials 207
and permeability membranes. 2D-based membranes can generate highly selective

separations due to their balanced tunability and specifc mechanism of interlayer
lengths and openings at nanoporous surfaces. Due to their ultra-thin thickness and
remarkable mechanical and chemical stability, recent discoveries have revealed 2D
fllers in composite materials are desirable components for modifying and enhanc-
ing membrane properties [8,9]. Nanoscale 2D materials have intriguing possibilities
for enhanced molecular separations and transport. MXenes are 2D materials that
have been extensively researched and applied to high-performance molecular separa-
tions and ionic/molecular transport. Because of its remarkable fexibility, hydrophilic
surface, strong mechanical strength, and good electrical conductivity, the MXene
family of materials has grown in prominence. 2D materials that possess good trans-
port characteristics are incorporated into membrane microstructure because their
physical and chemical properties drastically fne-tune the membrane characteristics.
The larger surface area and more chemically active external surface structure 2D
materials integrated composite membranes exhibit facile proton transport rate due to
the creation of additional conducting channels for ion mobility. The planar structure
of 2D materials is a more appropriate nano-confguration for the fabrication of thin
selective layers, as 2D allows the full exploitation of their features, even at low fller
loadings.
12.2.1 HOW 2D FILLERS DIFFER FROM OTHER NANO FILLER MATERIALS

The membrane is composed of semi-crystalline glassy or elastomeric polymers.
These polymers’ structural and dynamical behavior differs, leading to a wide vari-
ety of molecular permeability characteristics. Cussler et al. developed an analyti-
cal model for calculating gas permeability and selectivity in composite membranes,
including selective fakes, to anticipate layered material’s impact on composite mem-
brane separation performance [10]. Membrane nanoscopically thin fakes, according
to the authors, is best described as nanoscale composite structures that cannot be
explained by analytical models that assume bulk permeation action in the fakes.
Because of its stability and intrinsic ability to be functionalized, graphene-based 2D
materials are preferred over nanomaterials for membrane modifcation. Due to the
barrier feature of the nanoplatelets, they are increasing the fller loading. With the
use of 2D materials, rational design of predefned interlayer channels, reasonable
functionalization, membrane nanopores, and new design of polymer structure is pos-
sible because 2D materials are easily tunable with several functional groups. In addi-
tion, incorporating 2D materials, interface design could be controlled that greatly
facilitates improving selectivity and permeability of the membranes for dynamic
liquid–liquid/liquid–gas separation.
12.3 IMPORTANT PARAMETERS FOR IMPROVING

MEMBRANE PROPERTIES
The mechanism of transport or separation through 2D material incorporated mem-
branes greatly infuenced by the factors, namely (a) Membrane interlayer channels,
(b) Membrane interposes, (c) Surface functionalization, (d) Membrane microdomains,
and (e) Balancing hydrophilic/hydrophobic domains. The redesigned membranes’

increased separation performance may be achieved because of their 2D structure,
high hydrophilicity, tunable interlayer spacing, and superior mechanical strength.
Finally, the infuence of substrate chemical functional groups on the binding char-
acteristics of 2D stacked materials with their underlying support should always be
addressed. To assemble 2D nanosheets into ordered laminates, several methods
namely polymer induction, vacuum suction, or external-force-driven techniques can
be utilized predominantly. The rate of penetration and selectivity of membranes can
both be improved by intelligently selecting the aperture size and permeability of
in-plane nanopores. 2D nanosheets may be readily aggregated into laminar mem-
branes having intermediate pathways for selective molecular transport, in addition
to the in-plane intrinsic holes. It was shown for the frst time by Geim et al. that gra-
phene oxide (GO) membranes could enable unlimited water penetration while being
impervious to liquids, vapors, and gases [11]. They discovered that the practically
zero friction surface of the non-oxidized section of GO nanosheets improves the fast
movement of water based on theoretical simulations. To provide frm and discern-
ing transport channels in 2D materials-based membranes, three major approaches
for creating nanostructures and regulating the chemical composition during mem-
brane construction were proposed: (a) building laminar structures, (b) modifcation
of interlayer transport pathways, and (c) directing superfcial morphology. Herein,
we have focused on recent and advanced 2D nanomaterials (current literature, novel
methodology, and characterization) like graphene, Boron nitride, MoS2, and MXene
nanosheet used as effective fller for base electrolyte membranes and its Physico-
chemical properties toward energy community application.
12.4 GRAPHENE/GRAPHENE OXIDE THEIR COMPOSITES

FOR ELECTROLYTE MEMBRANE APPLICATIONS
The new technology using graphene-based or composite 2D nanostructured elec-
trolyte membrane offers incremental development such as scaling the size of the
product or improving the order of magnitude. The new universal technology of
graphene-based materials is better to change the product effciency and is also envi-
ronmentally friendly. As far as the graphene properties are considered, it undoubt-
edly has higher potential. Nobel laureates in Physics for 2010, A. Geim, and K.
Novoselov, have acknowledged the excellent/intriguing novelty of the physical prop-
erties that could be exhibited in graphene nanostructured. Especially graphene has a
higher Brunauer, Emmett and Teller (BET) surface area, a thin layer or monolayer,
transparent like plastic, high electrical conductivity, superior thermal conductivity
water-resistant membrane, elastic flm, chemically inert, and superior stability, which
are more useful for improving electrolyte membrane properties.
Graphene alone is not suitable or recommended materials for, especially electro-
lyte membrane applications such as storage and conversion applications. However,
an optimum level of nanostructured graphene, when introduced into electrolyte
membrane or separator, can signifcantly improve membrane properties like tensile
strength, proton conductivity water uptake, Young modulus, and water permeability
resulting in the overall enhanced performance of the designated membrane/separator
in conversion, storage, gas sensor, and separation applications. In addition, it is more

important to have a basic understanding of synthesis methodology, forming a stack-
ing layer or monolayer, and constructing better composition or composite and physi-
cal characterization, which may further expand the electrolyte membrane properties.
12.4.1 SYNTHESIS, CHARACTERIZATION, AND PROPERTIES OF

GRAPHENE/POLYMER ELECTROLYTE MEMBRANES
An optimum graphene/graphene oxide powder was used as an effective additive/
fller in the SPEEK electrolyte membrane in current decades because it allows acces-
sible water uptake properties, gas permeability, and proton transport due to its larger
BET area. Dai et al. synthesized an innovative composite membrane-like graphene-
SPEEK via the conventional solution casting technique. First, an optimum level of
graphene (15 mg) was dispersed in 10 mL of DMF followed by sonication. Followed
by it, a required amount of SPEEK (1.5 mg) was gradually added to the above admix-
ture and then stirred for 24 hours. Finally, the resultant admixture was transferred
into a fat glass plate followed by evaporation at two different temperatures (60°C
and 100°C) overnight. While introducing graphene 2D nanostructure into SPEEK
membrane, physicochemical properties are improved, the vanadium ions reduced
cross-overrate toward redox fow battery. Especially, the swelling ratio (15.2%) and
ion exchange capacity (1.98 mmol g−1) have been ameliorated as compared to pristine
SPEEK membrane (21.2% and 2.0 mmol g−1) [12].
Self-humidifed composite membrane fabrication via solution casting techniques
uses carboxyl-functionalized graphene and terminal anionic oxygen from phospho-
tungstic acid (PWA) to turn the composition into the SPEEK framework. The opti-
mum composition of the SPEEK-PWA-graphene improves self-humidify behavior
at 60°C. PWA and graphene with different compositions were mixed into SPEEK
matrix, and the admixture was stirred for 48 hours. PWAs terminal and anionic
oxygen species are highly reactive sites and could interact with graphene nanostruc-
ture and SPEEK network. The combination composition improves the proton con-
ductivity (5.19 × 10 −2 S cm−1) and methanol uptake (91.2%), resulting in improved
self-humidifying behavior for fuel cell application [13]. Suhaiman et al. observed
that few-layer enriched graphene oxide incorporated into the SPEEK matrix showed
solid interfacial interaction between surface groups (-O, -OH, -COOH) of graphene
oxide and sulfonic group SPEEK, which resulted in improved proton conduction
than SPEEK matrix. This result indicates that the accessibility of graphene oxides
fllers developed with different surface oxygenated reactive groups has intensely
infuenced the electrostatic interaction and hydrogen bonding with the SPEEK elec-
trolyte membrane [14].
Considering direct methanol fuel cell (DMFC), methanol permeability, and pro-
ton conductivity are important parameters for improving DMFC application. At the
same time, the incorporation of graphene oxide nanosheet fllers into the SPEEK
electrolyte membrane leads to retaining hydrophilic property via the hydrogen bond-
ing network. Similarly, proton conductivity has tremendously enhanced while intro-
ducing an optimum amount of GO into the SPEEK electrolyte membrane. Moreover,
incorporating layer-by-layer assembly of graphene oxide nanosheet in the SPEEK
electrolyte membrane gradually decreases methanol permeability. The bilayer or

layer-by-layer membrane was formed that is more helpful in blocking the methanol
molecules and enhanced more than 50% fuel activity than SPEEK.
According to Cai et al., Zeolitic imidazolate-graphene oxide 2D SPEEK nanohy-
brid nanocomposite show superior membrane behavior and improved cell activity.
First, 250 mg of SPEEK matrix is dissolved in DMF, then an optimum composition
of ZIF-L@GO 2D nanostructured materials added dropwise followed by sonication
for 4 hours and stirred overnight. Next, the above admixture was cast on a fat glass
plate and dried for 16 hours at 80°C in the vacuum oven. The cross-linked struc-
ture of the ZIF-L@GO/SPEEK framework is illustrated in Figure 12.1. The cross-
linked ZIF-L@GO/SPEEK bond formation was studied through X-ray Photoelectron
Spectrometer (XPS) measurement. The optimum composition of ZIF-L@GO/SPEEK
was found to retain the physical properties equivalent to SPEEK and improved stabil-
ity than the SPEEK matrix [15].
Thimmappa et al. cast a thin layer of 2D Graphene oxide solution alone on a glass
slide and then air-dried, effectively used as a membrane for the low temperature
polymer electrolyte fuel cells (LT-PEFC) application. The as-prepared 2D graphene
oxide showed improved H+ conductivity of 0.001 mS cm−1 at atmospheric tempera-
ture. However, a thin layer of graphene oxide membrane has lower electrolyte resis-
tances than Nafon 211, especially the LT-PEFC confguration. When the graphene
oxide membrane thickness is reduced, the ion transport properties are superior at
room temperature [16].
Similarly, Kumar et al. observed that free-standing graphene oxide exhibited
higher proton conductivity 4–8 × 10 −2 S cm−1 at different temperatures ranging
between 25°C and 90°C, showed a fuel cell performance of 8 mW cm−2 when tested
in DMFC confguration [17]. Besides, the oxygen-containing surface group and sul-
fonic acid on the edges and basal plane are ascribed to the in-plane proton transport.
FIGURE 12.1 Schematic diagram of the formation of SPEEK/ZIF-L@GO. Adapted with

permission from [15]. Copyright (2021) Elsevier publishing Ltd.
Kuila et al. explored an effective and simple technique for the fabrication of water-
dispersible graphene-(SPEEK) electrolyte membrane used for energy storage appli-
cation. According to Kuila et al., 0.1 g of graphite oxide was dispersed in 0.2 L of
water, followed by sonication and centrifuged (remove unexfoliated graphite oxide).
Separately, 0.3 g of SPEEK was dissolved in water and stirred at 60°C. The superna-
tant of SPEEK was slowly added to graphene oxide and stirred for 24 hours at 70°C.
A required amount of hydrazine was added dropwise to the above admixture and
refuxed at 100°C for 12 hours. Finally, SPEEK-Graphene (SPG) was fltered using
a cellulose acetate membrane. The macromolecules nature of the SPEEK membrane
is adsorbed on the graphene surface via π−π interactions. This modifed nature of
the SPEEK-graphene electrolyte was found to be highly stable even up to 6 months.
Figure 12.2a and b represents AFM micrographs image of graphene oxide and
SPEEK-SPG. The AFM images indicated that graphene oxide has a thickness of
0.84 nm while SPG exhibited a higher thickness (1.34 nm). This is mainly due to
the SPEEK membrane adsorption on a graphene surface and the development of the
single-layer graphene sheet. SPG membrane shows larger rectangular areas repre-
senting its higher EDLC and superior capacitive behavior [18]. The Nafon-based
perfuorinated membrane is generally used for LT-PEFC and HT-PEFC applications.
However, Nafon suffers from deterioration even under standard polymer electrolyte
fuel cells (PEFC) operating conditions, especially at higher temperatures. An opti-
mum level of sulfonic acid-functionalized graphene is a promising fller for Nafon
electrolyte membrane for improved proton-conducting in polymer electrolyte fuel
cells. S-graphene-Nafon hybrid composite is achieved via embedding S-graphene in
Nafon, which gives higher absorption water molecules and superior proton transport
FIGURE 12.2 Atomic force microscopy of (a) graphene oxide and (b) SPEEK-Graphene
composite (SPG). Adapted with permission from [18]. Copyright (2012) ACS publishing Ltd.
through the overall membrane under low relative humidity conditions. 1 wt.% of
S-graphene-Nafon hybrid composite was observed to be 17 mS cm−1, which is
almost fve times greater than recast Nafon membrane. This recast membrane shows
a maximum of 300 mW cm−2 power density at 760 mA cm−2 under 20 RH conditions
at 70°C [19]. Moreover, sulfonated graphene nanosheet was highly spread into Nafon
structure resulting in hydrophilic domains and enhanced surface roughness, thus
strengthening the proton conduction properties in a composite membrane. Similarly,
0.7 wt.% of graphene fller spread into the poly(vinyl alcohol) (PVA) matrix has a
higher tensile strength (76%) and Young’s modulus (62%) compared to PVA [20].
Sulfonated graphene nanoplates have naturally fascinated the ionic species of Nafon
monomer to their region, which is rotated and polarized underneath the electric feld,
and rearranged proton channels in the solidifed membrane. As a result, the trans-
plane conductivity of the composite electrolytic membrane was observed to be 0.155
S cm−1 at 80°C, which is more than 48% higher than cast Nafon. Consequently,
PEFC comprising composite electrolyte membrane delivered more than 15% higher
fuel cell performance than Nafon at 80°C [21].
Yan et al. prepared a monolayer of thin graphene nanosheets sandwiched between
Nafon membranes via chemical vapor deposition. Nafon ionomer spin-coated
on graphene/copper surface, and then the Cu foil was an etching by FeCl3-based
materials. Finally, Graphene-Nafon flm was transferred onto a Nafon electrolyte
membrane and hot-pressed [22]. As a result, the graphene-Nafon formation reduced
methanol permeability up to 68%, and the graphene monolayer was selectively
allowed to protons than the Nafon membrane. Similarly, an optimum level of 5 wt.%
reduced graphene oxide nanosheet in Nafon matrix has shown better proton con-
ductivity. The optimum composition was synthesized via solution cast and hot press
thermal reduction techniques. The composite active membrane showed increased
proton conductivity more than 30 times from the recast Nafon membrane.
Su et al. fabricated GO-Nafon hybrid membranes via spin-coating techniques.
The hybrid Nafon-graphene oxide composite shows inferior vanadium ion perme-
ability than the Nafon. The ultrathin graphene oxide layer suppressed the vanadium
cross-over and enhanced the proton conduction throughout the membrane. As a result,
the composite membrane has a higher energy effciency of 81%–88% and coulom-
bic effciency of 92%–98% than the Nafon membrane (energy effciency 68%–79%
and coulombic effciency 73%–90%). Accordingly, as prepared composite membrane
shows excellent battery stability even after 200 charge–discharge cycles, and the
capacity decay rate is much lower (0.23%) than the Nafon membrane (0.44%) [23].
12.5 BORON NITRIDE NANOSHEET/POLYMER

MEMBRANE SYNTHESIS AND PROPERTIES
In general, hydrocarbon-based or composite membranes have conjugated a more
signifcant percentage of sulfonic acid. Sulfonic acid groups can prompt proton con-
ductivity and hence enhancing ion exchange capacities based on the hopping mech-
anism. Through membrane stability test dry–wet cycles, hydrocarbon-based solid
membranes signifcantly change volume shrinkage/expansion behavior. Thereby,
the initial bond interfaces among the membrane and electrodes become weakened
during stability tests (wet-dry cycles), damaging the membrane. Hence, reducing
hydrocarbon-type membrane swelling and stability is a serious and challenging topic
in the energy conversion application.
To overcome the above issues, 2D boron nitride (BN) has begun enhancing the
mechanical strength when incorporated in a minimal amount within the composite.
The additional advantages of BN nanosheet have low density, excellent chemical and
thermal stability. Keun-Hwan et al. explored the intrinsic mechanical strength of
boron nitride nanosheet and the marginal amount of (0.3 wt.%) boron nitrides nano-
fakes (BNNF) signifcantly enhanced mechanical stability. The 1-pyrenesulfonic
acid (PSA)-BNNF/SPEEK composites membrane fabricate via a solution casting
method with a thickness of ~40 μm. The optimum composition of 0.3 wt.% of PSA-
BNNF composites delivered a higher tensile strength of about 47.2 MPa, correspond-
ing to 41% higher than bare SPEEK [24].
An optimum level of functionalized boron nitride is incorporated into the Nafon
(N) membrane synthesis. Wu et al. via the vacuum fltration method. The optimum
composition of boron nitride nanocomposites (NBNM) exhibits higher stability at fully
humidifes conditions and a redox environment. The proton conductivity shown is 0.44
S cm−1 at 95% RH condition at 80°C than Nafon (0.13 S cm−1). The higher proton
conductivity might be attributed to the maximized availability of the microchannel and
physicochemical environments in composite membranes. The composite membrane
enhances proton conductivity rapidly at higher RH conditions because of the presence
of water molecules as the H+ carrier achieves the loosely arranged boron nitride sheet
in the membrane and simplifes the state. In addition, the formation of long-range ionic
channels and quasi-isotropic architecture simplifes the proton conduction [25].
Akel et al. explored the different amounts of 3, 5, 10, and 15 wt.% of nano-
hexagonal boron nitride (NhBN) was added to Nafon polymer. The effect of NhBN
was examined in terms of swelling property, thermal stability, methanol permeabil-
ity, and proton conductivity. Generally, hydrocarbon-based membranes have a larger
affnity to agglomerate, which is attributed to weakening mechanical and physico-
chemical behavior. While incorporating NhBN nanosheet improves water content
throughout the membrane, it may considerably impact ionic channel or conductivity
and thermal stability [26].
Hence, functionalized boron nitride-polymer composite membrane was found to
improve the H+ conductivity by order of magnitude with the increase in the tem-
perature. Besides, nitrogen groups in the BN structure play a vital role in improv-
ing H+ conduction and HSO3− group functionalization. In addition, the fBN-Nafon
composite membrane exhibits lower weight than the Nafon membrane at the same
temperature, which may lead to the discomfture of breaking S-C bond due to the
presence of hydrogen bond existing between the sulfonate group of Nafon and nitro-
gen atom of BN nanosheets. Moreover, the presence of functionalized BN limits the
methanol permeation rate [27]. Similarly, hexagonal BN nanosheet combined with
Sulfonated polyvinyl phosphonic acid and polysulfone (PVPA-SPSU) polymer, the
resulting better thermomechanical stabilities. The uniform distribution of hexagonal
BN nanosheet in polymer framework increases proton conduction. Incorporation of 5
wt.% h-BN into SPSU-PVPA results in a composite membrane that exhibits excellent
proton conductivity of 9 × 10 −3 (S cm−1) at 150°C under anhydrous conditions [28].
According to Liu et al., reports wafer-scale hexagonal BN monolayer deposited

on copper rolls via space confned CVD techniques (Figure 12.3). Further Nafon
layers are functionalized on hexagonal BN nanosheets and then effectively transfer
as grown Nafon-hexagonal BN flms to SPEEK electrolyte membrane. During, self-
discharge operating condition, Nafon/h-BN/SPEEK composite membrane exhibited
higher long-term stability of ~78 hours than Nafon-SPEEK (51 hours) and SPEEK
membrane (46 hours) [29]. The presence of monolayer h-BN nanosheet resulted in a
positive effect on vanadium redox fow battery performance, and three times better
selectivity is achieved than that of pure SPEEK membrane.
12.6 MODIFIED MOS2/POLYMER MEMBRANES

FOR ENERGY APPLICATIONS
Transition metal chalcogenides, predominantly molybdenum-based chalcogenides,
have gained researchers’ attention owing to their interesting physicochemical prop-
erties. MoS2 has been the focus of various research groups, mainly attributed to its
fascinating behavior like high anisotropy, distinct crystal structure, and low cost. The
inter-layer distance calculated for MoS2 is around 0.615 nm as compared to 0.335 nm
for graphite. This is primarily attributed to the less strong physical affnity between
the freely suspended S–Mo–S sheet [30]. This makes MoS2 a promising alternative,
eco-friendly nanomaterial to be implemented in diverse energy conversion and stor-
age systems.
2D MoS2 nanosheets in pristine form or composite have shown remarkable capaci-
tance attributed to their high conductivity, larger surface area, and graphene-like mor-
phology. Three-dimensional frameworks comprising 2D MoS2 nanosheets exhibited
enhanced stability that retains the integrity of the suspended ultrathin sheets having
a large available surface area. This is considered a major advantage of using 2D
MoS2 ultrathin nanosheets as fllers. MoS2 nanosheets polystyrene composite mem-
brane was prepared through simply blending and casting technique. It was observed
that the exfoliated sheets of approximately 3–4 layers remarkably enhanced Young’s
modulus up to 0.8 GPa as compared to 0.2 GPa observed for pristine polystyrene. In
addition, the tensile strength also noticeably showed up to three-fold enhancement
even with a very low-level loading of exfoliated MoS2-nanosheets.
Hou et al. prepared a series of innovative quaternized poly(vinyl alcohol)/chitosan/
molybdenum disulfde (QPVA/CS/MoS2) membranes for alkaline DMFC. The opti-
mum composition of QPVA/CS/MoS2 was enhanced by the mechanical stability,
which may be due to the incorporation of MoS2. According to these authors, the
addition of 1.0 wt.% of MoS2 resulted in the lowest methanol permeability [31]. Wu
et al. has adopted an innovative approach of in situ growing of MoS2 to fabricate
MoS2-Nafon-based hybrid membranes showing superior selectivity for its applica-
tion in DMFCs. He surmised that the judicious selection of the precursor for Mo,
that is, (NH4)2MoS4, and solvent media led to a strong interaction of Mo-precursor
with sulfonic groups present in the Nafon. This resulted in the selective growth
of MoS2 fakes mostly surrounding the ionic clusters in the obtained MoS2/Nafon
hybrid membrane, which resulted in improved connectivity between the existent
ionic clusters and consequently enhanced the ionic conductivity [32]. It is noteworthy
FIGURE 12.3 (a and b) Represents the membrane selectivity with respect to relative humid-
ity for Nafon and 0.1−1.0 wt.% MoS2/Nafon composite at 25°C and 50°C. Adapted with
permission from [32]. Copyright (2013) ACS publishing Ltd.
that membrane selectivity has been enhanced by nearly two orders of magnitude for
the designated MoS2/Nafon composite membrane than with that of the Nafon when
tested under stringent DMFC operation at 50°C and high methanol concentration.
Figure 12.3 shows the comparative membrane selectivity for recast Nafon and vari-
ous compositions of MoS2/Nafon composite membranes at 25°C and 50°C.
Similarly, Wu et al. adopted Nafon in water as a medium to exfoliate MoS2.
According to his fndings, strong non-covalent bonding interactions between 2D
MoS2 and Nafon were brought about by hydrophilic sulfonic acid groups and hydro-
phobic polytetrafuoroethylene backbone in stabilization and functionalization of
Nafon–MoS2 (N-MoS2) nanocomposites. Figure 12.4 clearly illustrates the synchro-
nized exfoliation of MoS2 and functionalization of 2D MoS2-nanosheets over Nafon.
Interestingly, these interactions were found to be highly independent of the pH of the
solvent/media. However, the extent of exfoliation and the size of the obtained MoS2
nanosheets were severely infuenced by the Nafon concentration [33].
Besides, an optimum composition of sulfonated poly (ether sulfone) (sPES)
composited with sulfonated-MoS2 was explored toward application in DMFC by
FIGURE 12.4 Illustration of the synchronized exfoliation of MoS2 and functionalization

of 2D MoS2-nanosheets over Nafon. Adapted with permission from [33]. Copyright (2018)
Springer publishing Ltd.
Kulshrestha and co-workers [34]. In this study, hydrothermally prepared 2D MoS2

was synthesized by adopting a hydrothermal method and functionalized using 1,
3-propane sulfone as sulfonating media. Notably, the methanol cross-over from
anode to cathode was drastically reduced due to the methanol permeation barrier
created by s-MoS2, which simultaneously offered a proper path for proton transport.
5 wt.% of s-MoS2 into the composite membrane resulted in a reduction in methanol
permeation up to 91% and four times higher electrochemical selectivity than sPES
membrane, which further increased the cell performance as compared to sPES.
Exfoliated molybdenum disulfde (E-MoS2) 2D nanosheets incorporated into
chitosan membrane reveal superior IE capacity, water absorption, and proton con-
ductivity than pre-chitosan-based electrolyte membrane. Composite membranes
comprising 0.75% exfoliated MoS2 showed better ionic conductivity and membrane
selectivity. Besides, the presence of MoS2 nanosheets in the membrane channels pre-
vented methanol cross-over to a greater extent [35]. In a similar approach, Chen et al.
have synthesized a chitosan-based composite membrane employing MoS2-nanosheets
with the primary intention of boosting membrane stability [36]. In this study, chemi-
cal conjugation of the exfoliated MoS2-nanosheets was brought about by using thio-
glycolic acid to functionalize the exfoliated MoS2 2D structure chemical conjugation
with thioglycolic acid prior to the preparation of composite membrane. Blending with
functionalized exfoliated MoS2-nanosheets provided better thermal and mechanical
stability to the chitosan membrane. The effect is primarily attributed to the strong
interaction between the former and the latter. Thermogravimatric analysis (TGA) plot
for pristine and composited chitosan membrane is shown in Figure 2.5.
FIGURE 12.5 Comparative TGA plots for pristine and composited chitosan membrane with
functionalized exfoliated MoS2-nanosheets. Adapted with permission from [36]. Copyright
(2016) Springer publishing Ltd.
12.7 2D MXene/POLYMER COMPOSITE MEMBRANES

FOR ENERGY APPLICATIONS
MXenes are captivating materials comprising 2D transition metal nitrides or car-
bides obtained from the MAX phases via the selective chemical etching method.
An optimum level of MXene-based fllers is recognized as the most promising fller
material for enhancing the proton conduction behavior and thermo-mechanical sta-
bility of polymer matrix. MXene-based fller was used in polybenzimidazole (PBI)
membrane for intermediated polymer electrolyte membrane fuel cell application.
Interestingly, 3 wt.% of Ti3C2Tx -MXene 2D nanosheet incorporated into polybenz-
imidazole membrane that resulted in better physicochemical behavior, like Young’s
modulus and tensile strength for PBI membrane. According to the reports by Fei et al.
about 3 wt.% of Ti3C2Tx -MXene incorporated in the PBI membrane when employed
in high temperature-proton-exchange membrane fuel cells (PEMFC) resulted in
improved performance of 200 mW cm−2 than to 130 mW cm−2 for pristine PBI mem-
brane [37]. Besides, it was observed that the incorporation of Ti3C2Tx -MXene also
resulted in the enhanced mechanical and thermal stability of PBI-based electrolyte
membranes.
Cheng et al. reported an optimum level of Ti3C2Tx nanosheet is used as an addi-
tive for quaternized polysulfone (QPSU) matrix and formed complex membrane for
alkaline polymer electrolyte fuel cells (APEMFC). The designated composite mem-
brane showed two-fold higher ionic conductivity and increased peak power density
when tested in APEMFCs. This clearly shows that the quaternary ammonium group
facilitates the OH− conductivity [38]. Wang et al. adopted a quick solution casting
technique to prepare a hybrid composite membrane by dispersing Ti3C2Tx nanosheets
into Nafon ionomer solution. The as-prepared hybrid membrane exhibited remark-
able properties like thermal stability, mechanical strength, and water uptake [39]. In
addition, 2D Ti3C2Tx -nanosheets were also investigated as an effective fller for the
Nafon membrane. It is surmised that the incorporation of 2D MXene nanosheets
as fller into the Nafon matrix resulted in a decrease in elongation properties. It is
noteworthy that as-prepared hybrid membrane, when employed in PEMFCs, a power
density of 200 mW cm−2 is achievable.
As proof of the thermal stability of 2D MXene-based materials, there are also
reports wherein these materials are employed as fllers, even in solid oxide fuel cells
(SOFCs). Xian et al. dispersed about 5 wt.% of Ti3C2Tx -MXene into Sm0.2Ce0.8O1.9,
and observed an improvement in the ionic conductivity. In addition, the performance
of the SOFC cell was also observed to be doubled with the incorporation of Ti3C2Tx
into Sm0.2Ce0.8O1.9-based membrane [40].
12.8 FUTURE SCOPE FOR 2D FRAMEWORK IN

ELECTROLYTE MEMBRANE-BASED APPLICATION
2D material-based membranes have demonstrated remarkably high separation per-
formance along with good transport properties that are desirable in sectors like
nanofltration, energy material device components, desalination, gas separation, and
solvent dehydration. In current decades, several key concerns have been resolved.
Because of high-quality nanosheets and fne-tuning of the transport channel with

the incorporation of single atomic layer thickness 2D materials, these membranes
exhibit well-transport properties with good thermos-mechanical stabilities. Previous
studies have demonstrated these membranes as building blocks for high-performance
separation as well as better transportation. It is possible to highlight the use of 2D
membrane materials for effcient separation, with an emphasis on two key issues:
(a) membrane stability through extended times of operation and (b) the construction
of large-area, effective uniform membranes. The structural stability of 2D mem-
branes in water is one of the most complicated issues to resolve. Considering GO
membranes as an example, water molecules will intercalate into interlayer channels
due to the hydrophilic nature of GO nanosheets distributed with oxidized functional
groups, breaking the previously formed barrier. As a result, it’s essential to avoid 2D
membrane swelling in order to improve durability. In an aqueous solution, the swell-
ing of 2D material extends interlayer channels and reduces sieving property, result-
ing in 2D material disintegration and impeded long-term operation.
Constructing molecular bridges to enhance both the linkages between 2D materi-
als and the interactions between the 2D material layer and the substrate has to be
improved for constructing better-performing membrane. In addition to this, increas-
ing the interfacial adhesion between the 2D material layer and the substrate is also
desirable for fabricating stable 2D material-based membrane. Another issue with 2D
material-based membranes in terms of practical use is membrane-scalable manu-
facturing. As a result, synthesis methodologies with a larger membrane area and
their separation performance should be offered. 2D material-based membranes as
a new family of superior membranes are capable of overcoming many challenges
with their improved microdomain structure and phase well-separated composition
with minimal thickness. However, the uneven distribution of pathways present in
the membrane microdomains has to be regularized for better results along with
exploring the fundamental mechanism behind nanochannel characterization and
transport mechanism. Furthermore, there are no theoretical models for describing
mass-transfer behavior happening within 2D membranes. The transport mechanism
may be explored through theoretical calculations, and theoretical models must be
constructed to envisage the impact of membrane assembly on the transport mech-
anism, such as pore size, molecular structure, electrical characteristic, and so on.
Also, because the thickness of 2D material membranes is 1–2 orders of magnitude
less than that of traditional membranes, specialized membrane modules are nec-
essary to maintain structural integrity and, as a result, separation performance. In
this line, the cost-efficient engineering of structurally robust, defect-free membranes
for molecular transport/separation applications remains inspiring. Once integration
methods with traditional porous supports have been refned, higher production scal-
ability will be possible, leading to lower manufacturing costs. However, to attain
higher industrial viability, cost reductions of at least 1–2 times higher are necessary,
most likely infuenced by economic forces. Such commercial forces often lead to
further design optimization and process refnement in both research and industrial
production. Materials development, essential knowledge acquisition, and the creation
of analytical simulation and experimental techniques are all essential to adopt 2D
material-based membranes for a diverse range of electrochemical technology.
ACKNOWLEDGMENT
S. Mohanapriya, P. Dhanasekaran, and S. Vinod Selvaganesh thank CSIR-for Senior
Research Associateship (Scientist’s Pool Scheme 9037-A, -9123-A, and 9178-A,
respectively).
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13 Nanocomposites of 2D
Materials for Enhanced
Electrochemical
Properties
Nitika Devi
Shoolini University
Alok Kumar Rai

University of Delhi (North Campus)
Rajesh Kumar Singh

Central University of Himachal Pradesh
CONTENTS
13.1 Introduction ..................................................................................................224
13.2 Composites of 2D Materials ......................................................................... 225
13.2.1 Metal-Matrix Composites of 2D Materials ...................................... 225
13.2.2 Ceramic-Matrix Composites ............................................................ 226
12.2.3 Metal-Organic Matrix/2D Polymer/Carbon Composites ................. 226
13.2.4 Heterostructure Composites of 2D Materials................................... 229
13.3 Supercapacitor .............................................................................................. 231
13.3.1 Mechanism........................................................................................ 231
13.3.2 2D Material Composites as a Supercapacitor................................... 231
13.4 Batteries ........................................................................................................ 233
13.4.1 Mechanism........................................................................................ 233
13.4.2 2D Material Composites as a Battery............................................... 235
13.5 Sensor ........................................................................................................... 237
13.5.1 Mechanism........................................................................................ 237
13.5.2 2D Material Composites as a Sensor................................................ 237
13.6 Conclusions................................................................................................... 239
References..............................................................................................................240
DOI: 10.1201/9781003178453-13 223

13.1 INTRODUCTION
Nanotechnology has provided a new world to material science, which not only helps
in exploring the new applications in this area but also imparting the new profciency in
already existing approaches. Dimensions play a vital role in describing the particular
type of nanomaterials and depending upon that they are classifed as 0-dimensional,
1-dimensional, 2-dimensional, and 3-dimensional materials means at least one of
their dimensions is in the nanometer range (1–100 nm). After the discovery of gra-
phene, 2D materials found great attention because of their exceptional properties
[1]. Later, it was found that beyond graphene there are other 2D materials that are
also exceptionally good. These materials are MoS2, WS2, MoSe2, and WSe2 collec-
tively known as transition metal dichalcogenides (TMDs), layered double hydrox-
ides, LAPONITEs clay, hexagonal boron nitride (h-BN), black phosphorous (BP), a
family of monoelemental compounds (Xenes), metal oxides, graphitic carbon nitride
(g-C3N4), metal nitrides/carbides (MXenes), transition metal halides (e.g., PbI2 and
MgBr2), transition metal oxides (e.g., MnO2 and MoO3), perovskite-type oxides (e.g.,
K2Ln2Ti3O10 and RbLnTa2O7 (Ln: lanthanide ion)), and 2D polymers. Although these
materials are suffcient enough for particular use, many applications need to evolve
their composite forms for overcoming some drawbacks associated with pristine form
[2]. Usually, composite classifcation is done by making matrix material as a refer-
ence for classing the composites. Depending upon that we can have metal-matrix
composites, organic-matrix composites, ceramic-matrix composites. Polymer com-
posites and carbon matrix composites are two subclasses of organic-matrix com-
posites. Another type of composite is heterostructure composites of 2D materials
based on their structural features. Each composite type has its advantages as well
drawbacks associated with them. For example, polymer composites have advantages
like ease of formation, lightweight but for an application of high corrosive environ-
ment ceramic and metal-matrix composites are found to be more stable due to their
nature of bonding that is either covalent or ionic. In addition to this, high strength
and toughness of the metal-matrix composites provide a good mechanical strength
to the composite [3–6].
Different approaches are employed for the synthesis of various types of 2D com-
posites materials. But in general, it can be broadly divided into two types that are in
situ approaches and ex situ approaches. In case of in situ approaches, examples are
hydrothermal and solvothermal methods. In ex situ methods a specifc composition
and dimensions of 2D materials are fabricated then it is being combined with the
other part of composite with covalent and non-covalent interactions [7]. Chen et al.
[8] reported an in situ approach for the synthesis of graphene-reinforced Cu-matrix
composites. In this work, ball milling is followed by the hot pressing sintering for
obtaining the fnal product. Another report by Santalucia et al. [9] gave a com-
parison of in situ and ex situ approaches for synthesizing MoS2/TiO2 nanoparticles
sheets composites. It was concluded that depending upon the particular synthesis
approach, it is possible to incorporate a specifc type of interactions, also in situ
approach results in thinner and more defective MoS2 slabs. The dimensionality
of MoS2 slabs is also lower as compared to the same product obtained by ex situ
synthesis.
Nanocomposites of 2D Materials 225
The abovementioned 2D-materials composites can be further utilized in different

areas such as energy storage applications [10,11], sensing [12–14], and EMI shielding
[15,16].
13.2 COMPOSITES OF 2D MATERIALS

Composite is a combination of two materials in specifc composition so that resulting
product has entirely different properties as compared to the individual components.
Composites have been extensively used in material science for almost all applica-
tions so that either properties of the materials got enhanced or some drawbacks get
improved. One component of the composite acts as a matrix and other component
acts as reinforcement [17]. There are different types of possible 2D material compos-
ites based on the matrix.
13.2.1 METAL-MATRIX COMPOSITES OF 2D MATERIALS

These types of composites metal and alloys are used as a matrix and 2D materials
act as reinforcement. In order to achieve required properties of metal-matrix com-
posites, the incorporation and dispersion of the reinforced material should be done
in good manner so different techniques have been developed for the synthesis of this
class of composites. In the case of graphene, techniques like metal alloying, spray
forming, electrochemical deposition, and selective laser melting [18] are used. The
development of these techniques is the result of the constant efforts for removing
the agglomeration problem and increasing the interface binding between matrix and
reinforcement material. All these factors signifcantly affect the mechanical strength
of the material. Six main techniques that are used for forming the metal-matrix com-
posites are ball milling, hot press sintering, stir casting, hot extrusion, wet chemis-
try, and compress shearing [4]. All the mentioned techniques have been successfully
applied for the synthesis of various 2D material composites. Out of these techniques,
milling, sintering, and casting are the most effcient ones for 2D materials composite
synthesis. Nautiyal et al. [19] used ball milling for synthesizing copper matrix com-
posites reinforced by reduced graphene oxide (rGO)-MoS2. The advantage of using
ball milling is uniform distribution but the associated drawback is that it can cause
defects in the materials. In the hot press sintering process, high pressure and tem-
perature are used for pressing and sintering. Usually graphite material die is used for
compacting the materials as it is stable at high temperatures [18]. Liu et al. [20] used
hot press sintering method for fabricating Ni-nanoparticles decorated graphene rein-
forced in Al matrix composites. Merit associated with this method is that no damage
occurs to the material but the problem is contamination, which is mostly unavoidable
in hot pressing sintering. Stir casting is also a metallurgical process like the sintering
and ball milling; the difference is that in this process reaction occurs in liquid phase.
A mechanical stirrer is used for mixing reinforcing and matrix material, which as
a fnal product results in composite formation. In addition to already discussed pro-
cesses stir casting offers some advantages related to the material size and yield and
is also found to be cost-effective [18,20]. Sekar et al. [21] prepared MoS2 and Al2O3
nanoparticles composites by using stir casting techniques. The method successfully
synthesized the composite and was also capable of controlling the reinforcement
percentage to a minimum of 0.5 wt.% for MoS2. Other than the mentioned processes
wet chemistry, hot extrusion, and compression shearing are also the possible routes
for synthesis, etc. Microwave-assisted synthesis processes are also being used for
composite formation as it provides a fast and effcient way of synthesis [22,23]. Many
times two or more processes may be combined to get useful results. Such a synthesis
of graphene reinforced in Cu matrix composite was reported by Nie et al. [24]. In
this process, graphite oxide is synthesized by Hummer’s method and then molecular
level mixing of Cu matrix and RGO is done and in the last step hot press sintering is
used for forming the compact mass of Cu-RGO composites. Schematic of the process
is shown in Figure 13.1.
13.2.2 CERAMIC-MATRIX COMPOSITES

This class of composites is similar to the metal-matrix composites; the only differ-
ence is that the metal matrix is replaced by the ceramic matrix. Also, similar type of
approaches has been used by the researchers for synthesizing the ceramic composites
like mechanical mixing, colloidal dispersion, and solid-state sintering [25]. In the
formation of ceramic-matrix composites the main problem is the high temperature of
reaction, which sometimes result in diffusion and non-useful reactions. So, the need
is to develop such methods, which can synthesize the 2D ceramic-matrix composites
at low temperature or without forming any extra reaction by products. One such work
is done by Guo et al. [26] in which formation of nanocomposites of 2D MXene with
zinc oxide is done using a cold sintering process (schematic shown in Figure 13.2).
This developed process is capable of synthesizing the composite material with uni-
form distribution with relative density of 92%–98% without any oxidation and inter-
diffusion [26]. Colloidal dispersion mixing process has also been used for ceramic
matrix-2D materials composite. In this process, both the phases are dispersed in
the same type of colloidal solution and then both solutions are mixed for obtaining
the fnal product. Surface treatment of material is important as oppositely charged
surfaces will strongly bond as a result there will be strong binding in the component
of composite [27]. Fan et al. [28] prepared ceramic matrix few layer graphene com-
posite by using colloidal mixing. This method gave freedom for manipulating the
doping and concentration level of the matrix and reinforced material. Liu et al. [29]
prepared in situ Ni-nanoparticle decorated graphene reinforced in Al matrix, which
results in improved mechanical properties and can be successfully used for different
applications.
12.2.3 METAL-ORGANIC MATRIX/2D POLYMER/CARBON COMPOSITES

These 2D material composites used polymer/carbon materials as a matrix. Such
composites result in the enhancement of the properties of polymer materials with
respect to strength, thermal stability, and conductivity. In some cases, mechanical
properties of the polymer get enhanced by 200 times than the pristine polymer [6].
Synthesis of 2D-polymer composites involves two steps; the frst one is exfoliation of
the 2D material and then dispersion of this material into polymer matrix. Exfoliation
Nanocomposites of 2D Materials
FIGURE 13.1 (a) Schematic representation of RGO-Cu matrix composites. (a) Graphite; (b) Hummer’s method synthesis procedure for graphite oxide;
(c) Cu2+ absorbed on the surface of GO; (d) oxidation of Cu2+; (e) Cu-GO obtained by reducing Cu2+ with ascorbic acid; (f) small Cu particles aggregated;
(g, h) Cu-RGO power with low and high content of RGO; (i) bulk Cu-RGO composite consolidated by hot-press sintering; (j, k) spatial distribution of
RGO in copper matrix [24]. Adapted with permission from [24]. Copyright (2018) MDPI.
227
FIGURE 13.2 Schematic illustration showing: (a) the grain boundary of (1-y)ZnO -yTi3C2Tx
nanocomposites and (b) the fabrication process via cold sintering. Adapted with permission
from [26]. Copyright (2018) Wiley.
is a process used to synthesize 2D material, which was established after the discov-
ery of graphene. In exfoliation, the interaction between the two layers of material is
decreased either by functionalizing it or by ball milling. The exfoliation can be of
several types depending upon the methods used such as electrochemical exfoliation
and etching-assisted exfoliation [6]. Dispersion of 2D material in polymer matrix is
done in some organic solvents. Interactions of matrix with fllers are very crucial as
larger loading doesn’t necessarily mean the enhanced properties. Many steps may
be included in the synthesis method depending upon the product requirement. Song
et al. [30] fabricated the composite of graphene with cellulose-derived carbon aero-
gels and polydimethylsiloxane (PDMS) polymer. Different steps involved in synthe-
sis are shown in Figure 13.3. Resulting composites have been used for EMI shielding
and found to have excellent EMI shielding capacity and thermal conductivity coef-
fcient. Composite synthesis can be described in three main steps that is preparation
FIGURE 13.3 Schematic illustration of the fabrication procedure for CCA@rGO/PDMS

EMI shielding composites (a) illustration of the fexibility (b) and resilience (c-c’’) of CCA@
rGO aerogel. Adapted with permission from [30]. Copyright (2021) Springer.
of cellulose aerogel, formation of cellulose doped graphene, and in the last step the
CCA@rGO/PDMS composite. Calculated composite mechanical strength is found to
be 4.1 MPa and hardness was 42 HA.
Black phosphorous/polyaniline hybrid composites were developed by Moghaddam
et al. [31] for supercapacitor applications. Composite showed a high specifc capaci-
tance of 354 F g−1 at 0.3 A g−1 current density. In situ polymerization of black phos-
phorous nanosheets and aniline is used for their composite formation. Fabrication of
h-BN-rGO@PDA nanohybrids is also an example of polymer composites. Composite
can be used as anti-corrosion fller for polyvinylbutyral (PVB) and showed a two-
order higher performance than pristine PVB [32].
13.2.4 HETEROSTRUCTURE COMPOSITES OF 2D MATERIALS

2D materials have a layered structure so diverse 2D materials can be stacked in dif-
ferent orientations in order to give a heterostructure composite. Synthesis methods for
developing the heterostructure composites are similar to those used for synthesizing
the individual layer of composite like mechanical exfoliation, chemical vapor depo-
sition (CVD), and molecular beam epitaxy (MBE). Depending upon the orientation
of stacking layers, mainly two types of heterostructure are formed; vertical or lateral
confgured heterostructures. CVD synthesis is widely used for creating different het-
erostructure due to better control on orientation, no. of layers, and interface of different
layers of 2D materials [3]. Schematic of vertically and laterally aligned heterostructure
composites are shown in Figure 13.4. Mechanical exfoliation is capable of synthesiz-
ing 2D materials due to weak van der Waals forces interplay between the layers of
2D materials. Similar interactions are also responsible for the heterostructure forma-
tion. Heterostructure can signifcantly affect the properties of the individual sheets by
combining the characteristics of two dissimilar materials. If we particularly discuss
graphene, then it has a zero bandgap, which restricts its use in electronics applications.
But TMDs are such 2D materials in which bandgap can be tailored, so heterostructures
of graphene and TMDs provide effcient materials for electronics [33].
Cho et al. [35] fabricated a heterostructure device of 2D graphene/MoS2 for NO2
sensing. Two methods have been used for heterostructure device formation, i.e.,
mechanical exfoliation and CVD. Yamaguchi et al. [36] evaluated tunneling trans-
port in a few monolayer-thick WS2/graphene and MoS2/graphene heterojunction. In
this work, both TMDs and graphene were prepared by mechanical exfoliation and
heterostructure was obtained by dry transfer process. Black phosphorous/ultrathin
Ti3C2/ultrathin g-C3N4(BQ/TiC/UCN) composite fabrication and performance as
a photocatalytic hydrogen production is reported by Song et al. [37]. Presence of
MXene increases the charge transfer due to photoinduced charge carriers. In this
report, UCN and TiC were prepared by the furnace heated melamine at 550°C
for 4 hours and constant stirring of 72 hours Ti3AlC2 in HF solution, respectively.
Dispersion of UCN and TiC is done in distilled water and then xBQ/TiC/UCN com-
posite is formed by grinding and sonication in milli-Q water with 2D black phos-
phorous (BP) powder. Black phosphorus@laser-engraved graphene heterostructure
is developed for the electronic skin application sensor. This heterostructure exhibits
the high strain sensitivity (2,765), low detection (0.023%) limit, which is the result
230
FIGURE 13.4 (a) CVD synthesis of Graphene and h-BN (i) Ammonia borane is used as a precursor for h-BN growth (ii) graphene is decorated on
the h-BN grown surface. (b) Individual 2D sheets are prepared either by CVD or MBE then one layer is directly transferred to the other type of 2D
material. (c) (i) Vertically aligned heterostructure (ii) Controlled twist heterostructure. (d) Different methods for synthesizing lateral heterostructures
(i) After fabricating a 2D layer seeding is done on this layer (ii) Second layer is developed by using suitable precursor (iii) different shape like zig-zag,
donut-like, linear can be grown by proper placement of seeds using processes like etching. (e)(i) h-BN/graphene heterostructure formation (ii) Scanning
2D Nanomaterials
electron spectroscopy of h-BN/graphene heterostructure (iii) Optical image of h-BN/graphene heterostructure [34]. Adapted with permission from [34].
Copyright (2018) Nature.
of synergetic effect of different layered materials [38]. Scalable production of MoS2/

black phosphorous heterostructure is obtained by an in situ solvothermal synthesis in
which black phosphorous is obtained by electrochemical exfoliation [39]. Composite
showed a high catalytic activity with h low η10 overpotentials of 126, 237, 258 mV
for hydrogen evolution reaction (HER) in acidic, alkaline, and neutral electrolytes,
respectively [39].
13.3 SUPERCAPACITOR
Environment issues and increasing use of fossil fuel demand to develop alternative
energy resources. Supercapacitors and batteries are such electrochemical alternatives,
which can replace or reduce the use of fossil fuels. First, working of the supercapaci-
tor will be described and then some of the works on 2D composites supercapacitors.
13.3.1 MECHANISM
In conventional capacitors, energy is stored in the form of charges. Capacitors have a
large value of power density but have very less energy density. Batteries on the other
hand have a high value of energy density but low power density. Supercapacitors
provided us an intermediate solution of balanced energy density and power density.
The mechanism of working supercapacitors depends upon the type of supercapacitor.
They are mainly of two types, i.e., electrochemical double-layer capacitor (EDLC)
and pseudocapacitors. In EDLC, charging and discharging occurred because of
absorption and desorption of the ions as in the case of conventional capacitors. But
unlike the conventional capacitors in case of supercapacitors there is double layer
charge deposition phenomenon, which results in high energy density and power den-
sity. A double layer of opposite charges is formed at the interface of electrode/elec-
trolyte. In case of pseudocapacitors, chemical reactions are the main cause for the
storage of energy. Because of abovementioned phenomenon, they are also named as
Faradic and non-Faradic type supercapacitor. Faradic supercapacitors are pseudo-
capacitors and non-Faradic supercapacitors are EDLC [40,41]. A schematic of both
types is shown below in Figure 13.5. Figure 13.5a shows a schematic of electrochemi-
cal double-layered supercapacitor. It can be seen from this schematic (a) that how the
charges are accumulated as double layer and (b) electrochemical reaction are main
cause for energy storage. Figure 13.5c giving a comparison of energy and power den-
sity of batteries and supercapacitors and EDLC supercapacitor are effcient enough in
proving the good energy density and power density at the same time [41].
13.3.2 2D MATERIAL COMPOSITES AS A SUPERCAPACITOR

Different materials like carbon nanotubes, transition metal oxide/hydroxides, 0D
materials, and 2D materials are used as supercapacitor electrode materials. But the
large surface area of 2D material makes them a suitable choice. In case of 2D mate-
rials graphene is used as an electrode material for EDLC supercapacitor as its high
surface area (2,630 m2 g−1) results in large charge adsorption. Other than graphene,
TMDs, MXene, and conducting polymers mainly work on the pseudocapacitance
FIGURE 13.5 (a) Schematic representation of electrochemical double layer supercapacitor,

(b) Pseudocapacitor, and (c) Ragone plot at different time constant [41]. Adapted with permis-
sion from [41]. Copyright (2019) Elsevier.
phenomenon. Phosphorene or black phosphorous is also being explored by research-

ers for its use as a supercapacitor electrode. Composite of abovementioned materials
with metal oxide/hydroxide and ceramic will result in a hybrid-type supercapacitor
in which energy and power densities are because of the contribution of both surface
area and redox reactions. Such composite formation is important because both factors
are important for its commercial applications [42]. Xiang et al. [43] reported in one of
such effort in which reduced graphene oxide/Co3O4 composites are synthesized by in
situ composite formation using hydrothermal synthesis. Morphological studies show
that 20 nm Co3O4 nanoparticles are decorated on rGO sheets. Composites showed
specifc capacitance of 472 F g−1 at a scan rate of 2 mV s−1 with 82.6% retention of the
capacitance at 100 mv−1 increased scanned rate with each step. Superior performance
of the composite is due to the synergetic effect of redox reactions due to Co3O4 and
conductivity of rGO matrix [43]. As discussed above, heterostructure composites
formation can be done by stacking different 2D materials layer. Bissett et al. [44]
synthesized such heterostructure composite, which is capable of giving 11 mF cm−2
at 5 mV s−1. Composites were prepared by dispersing the mixture of exfoliating lay-
ers of MoS2 and graphene in solution of N-methyl-2-pyrrolidone (NMP) dispersed
isopropanol (IPA). Ramakrishnan et al. [45] also published a work on MoS2-rGO
composites for electrode material in Li-ion capacitors. Composite delivered a 52
Wh kg−1 and 60 W kg−1 energy density and power density, respectively. Polymer
composites are also found to be used as an effective supercapacitor electrode. Wang
et al. [46] synthesized MoS2/polyaniline composites, which offered a high specifc
capacitance of 390 F g−1 with 86% of retention after 1,000 cycles. Composite is
synthesized by in situ polymerization of exfoliated sheets of MoS2 with aniline. 3D
ternary composites of molybdenum disulfde/polyaniline/reduced graphene oxide
aerogel are prepared by Sha et al. [47]. Composite formation of mass ratio 1:1 for
MoS2/rGO to PANI showed the highest specifc capacitance of 618 F g−1 at 1.0 A
g−1 with 96% of retention after 2,000 cycles [47]. MXene composite with 1T-MoS2
also showed a high specifc capacitance of 386.7 F g−1 at 1 A g−1. 1T-MoS2/Ti3C2
MXene heterostructures are synthesized using magneto-hydrothermal synthesis.
It is similar to the hydrothermal synthesis method, the only difference is the intro-
duction of 9T magnetic feld, which helps in the formation of the heterostructure
composites. Also, morphology study showed that 1T MoS2 nanosheets are success-
fully grown on Ti3C2 MXene. Electrochemical study cyclic voltammetry and galva-
nostatic charge–discharge results are shown in Figure 13.6. Figure 13.6 also explains
the mechanism of storage in the heterostructure composites and the morphology
image shows the stacked layers of the composite. Figure 13.6 given above showed
the cyclic voltammetry and galvanostatic charge–discharge data for 1T-MoS2, Ti3C2
MXene, 1T-MoS2/Ti3C2 MXene heterostructures composites [48]. Figure 13.6a–d
are the cyclic voltammetry and galvanostatic charge–discharge results of different
samples and the large area under the curve indicates the high specifc capacitance.
Peaks in Figure 13.6a and c are direct consequences of the redox reactions. It is
concluded by the electrochemical study that the high value of specifc capacitance
is because of the three factors that are 1T-MoS2, Ti3C2 MXene, and extra H+ storage
formation in between the two composite layers as shown in Figure 13.6e. Figure 13.6f
is the capacitance retention study that was found to be 96.8% after 20,000 cycles at
50 A g−1, which is very signifcant for its electrode uses. Layer structure is preserved
even after the 20,000 cycles as shown in SEM image of 1T-MoS2/Ti3C2 MXene in
Figure 13.6g [48].
Zhao et al. [49] described the development of metal-matrix composite of gra-
phene, which explained the methods of synthesis and their application in a detailed
manner. 2D material and modifed 2D material like heteroatom doped grapheme
[50], graphene, h-BN, MoS2 [51], carbon-based 2D materials and their derivatives
[52] have been reported for energy storage applications. VSe2/N-doped carbon sphere
composite gave an energy density of 85.41 Wh kg−1 at a power density of 701.99 W
kg−1 [53]. Moghaddam et al. [54] review on TMDs and polymer composites describe
all the aspects related to these composites. Black phosphorous composite is also get-
ting attention due to its exceptional characteristics. Moghaddam et al. [31] synthe-
sized the black phosphorous/polyaniline composite and analyzed its performance for
supercapacitor application. Pseudocapacitor composite was capable of giving 354 F
g−1 at a current density of 0.3 A g−1. Another such composite thin flm of polypyrrole/
black phosphorus is fabricated by Luo et al. [55]. Composite flms have an excel-
lent stability and a high specifc capacitance (497.5 F g−1). So, this discussion can
conclude that 2D material composite can give highly effcient supercapacitors with
enhanced electrochemical properties.
13.4 BATTERIES
Batteries are an electrochemical device, which delivers electric energy at the expense
of chemical energy.
13.4.1 MECHANISM
In battery, redox-reaction is a source for current generation that is at one electrode oxi-
dation takes place and on another reduction. Electron loss at oxidized electrode is being
forced to the pass through outer circuit which can be utilized for some useful work.
234
FIGURE 13.6 Electrochemical performance of 2H-MoS2, 1T-MoS2, Ti3C2 MXene, 2H-MoS2/Ti3C2 MXene, and 1T-MoS2/Ti3C2 MXene electrodes.
(a) and (b) CV and GCD curves of 2H-MoS2, Ti3C2 MXene, and 2H-MoS2/Ti3C2 MXene. (c) and (d) CV and GCD curves 1T-MoS2, Ti3C2 MXene,
and 1T-MoS2/Ti3C2 MXene. (e) Schematic diagram showing the H+ ion storage of 1T-MoS2 or Ti3C2 MXene and extra H+ ion storage in 1T-MoS2/Ti3C2
2D Nanomaterials
MXene heterostructure at charged–discharged state. (f) Capacitance retention after 20,000 cycles for 1T-MoS2/Ti3C2 MXene electrode at 50 A g−1. (g)
SEM images of 1T-MoS2/ Ti3C2 MXene electrode after long-term cycling [48]. Adapted with permission from [48]. Copyright (2020) Wiley.
This process is continuously repeated, which is called charging and discharging of

the battery. For balancing this reaction an ion is also transported from one electrode
to another [56].
13.4.2 2D MATERIAL COMPOSITES AS A BATTERY

2D materials and their composites are also found to be suitable for battery elec-
trodes. High conductivity and structural characteristics associated with these materi-
als results in increased electrochemical performance. Graphene as well as other 2D
materials composites are successfully being used for the electrodes in the battery
and their synergistic effects result in highly effcient electrodes. Li et al. [57] synthe-
sized graphene/BN thin flm and used it as anode in the battery. Composite flm was
fabricated by vacuum fltration method by the dispersion of both GO and BN. Then
vacuum-fltered thin flm was annealed at 300°C for 2 hours in argon atmosphere.
Resulting thin flm was analyzed by cyclic voltammetry, galvanostatic charge–
discharge, and electrochemical impedance spectroscopy. Composite thin flm with
2 wt.% content showed excellent reversibility of 278 mAh g−1 and good retention
on 200 cycles [57]. Metal oxide/graphene composites also offer good battery elec-
trodes. Liang et al. [58] synthesized SnO2/graphene composite and analyzed it as
battery anode. Reported synthesis method is a facile green one-step approach, which
also makes this cost-effcient and environmental friendly as well. Nanocomposite
exhibited a reversible capacity of 690 mAh g−1 with 63% capacity retention after 20
cycles [58]. Heterostructure composite of g-C3N4/graphene has also been used for
the cathode interlayer in Li-sulfur batteries [59]. As in Li-S batteries, performance is
limited by the shuttle effect and the limited intrinsic electrical conductivity of sulfur.
Shuttle effect is the main cause for limiting the performance of sulfur, which causes
the dissolution of intermediate polysulfde, which leads to reversible loss of sulfur.
This is because of the weak interaction between the cathode and dissolved lithium
sulfde thus introducing an interlayer, which increases the interaction between dis-
solved lithium sulfde and interlayer. This type of arrangement can restrain the shuttle
effect. Such an effort is done by Qu et al. [59]. They prepared an interlayer of g-C3N4/
graphene by using a simple stirring and centrifugation of mixture of graphene and
g-C3N4. Schematic Figure 13.7a, showing the arrangement of battery and how it is
helping in restraining the shuttle effect. This interlayer is incorporated in between
sulfur/carbon (S/KB) composites cathode and separator. Figure 13.7b image gave the
morphology and how the S/KB layer is attached with g-C3N4/graphene. It is found
that such arrangement results in strong stacking, which can also be approximated
by overall performance. Figure 13.7c–e are the cyclic voltammetry, galvanostatic
charge–discharge, and electrochemical impedance spectroscopy results. Resulting
cell is capable of giving a high retention capacity and it remains good in the range
from 0.1 to 2 C that is from 1,191.7 to 1,026.2 mAh g−1, respectively, for 1,000 cycles.
This study concludes that there is increase in Li+ diffusion coeffcient, which sig-
nifcantly increases the charge transfer at the electrolyte/electrode interface and
thus reduces the shuttle effect [59]. Chen et al. [60] also developed Fe3O4 nanopar-
ticle/MoS2 nanosheet composites for battery application. Fe3O4 nanoparticle/MoS2
nanosheet composite anode battery has highest delivering capacity of 1,033 and 224
FIGURE 13.7 (a) Schematic of cell confguration, which is incorporated with g-C3N4/GS
cathode interlayer. (b) SEM image of a section of the S/KB@C3N4/GS cathode. (c) CV curves
at a scanning rate of 0.1 mVs−1, (d) galvanostatic charge–discharge study at 0.1 C, and (e) EIS
Nyquist plots for the S/KB@C3N4/GS cathode in the initial fve cycles and the corresponding
equivalent circuit model (inset) [59]. Adapted with permission from [59]. Copyright (2019)
Wiley.
mAh g−1 at current densities of 2,000 and 10,000 mA g−1. A sandwich-like silicon/
Ti3C2Tx MXene composite have a reversible capacity of 1,067.6 mAh g−1 at a current
of 300 mA g−1 as reported by Zhang et al. [61].
Carbon and polymer composites are also being used for battery application like
carbon/g-C3N4 composite is also used as an anode in battery [62]. 254 mAh g−1 is the
reversible capacity offered by carbon/g-C3N4 composite, which have very high reten-
tion capacity that is 99.8% after 14,000 cycles. Kumar et al. [63] discussed the recent
progress of graphene and its composites for Li-ion battery applications. Choi et al.
[64] prepared anode material for battery that is crumpled graphene–molybdenum
oxide composite. Composite showed a discharge capacity of 1,490 mAh g−1 at 2 A g−1
with a retention capacity of 47% after 100 cycles. Sb2O3/MXene (Ti3C2Tx) hybrid
anode materials can give a reversible capacity of 295 mAh g−1 at 2A g−1 [65].
A ternary heterostructure of 2D transition metal chalcogenide-MXene-carbonaceous

nanoribbon composite is used for boosting the sodium and potassium ion storage.
Synergetic effect of all three components of this composite results in increased
sodium (536.3 mAh g−1 @ 0.1 A g−1) and potassium (305.6 mAh g−1 at 1.0 A g−1) ion
storage [66]. There are many reports that gave the evidences that nanocomposite of
2D materials can be used as electrode in the battery.
13.5 SENSOR
Sensor is a device, which responds as a result of some kind of input (mainly chemical
compounds) and these responses are mostly in the form of electric signal.
13.5.1 MECHANISM
2D material and its composite can be a good choice for sensing application because
of their characteristics like high specifc surface area and semiconducting nature.
Sensors can be physical and chemical based on the type of parameters, which are
recorded and analyzed. In physical sensing, any physical parameters like tempera-
ture and pressure are being recorded and in chemical sensing any chemical mol-
ecules interaction is being recorded. There are different parameters in terms of which
we defne the performance of the sensor. Sensor response, sensitivity, selectivity,
response time, recovery time, and lowest limit are some of them. Sensor response
is mostly taken in terms of resistance/current changes as a result of interaction of
the sensor with external materials or parameters. Sensitivity is the response of the
sensor per unit concentration and the selectivity is defned as the type of molecules,
which can interact with sensor. Response time and recovery time are the time in
which a sensor reaches a maximum value of current after being exposed to the sens-
ing material and recovery time is the time in which the sensor reaches at 10% of the
current value from its saturation value. All these parameters are crucial for defning
the overall effciency of a sensor [67]. Different types of sensing can be done by
using 2D materials like H+ ion sensing is important in the areas like food industries,
monitoring waste, organic pollutants, and in chemical laboratories. pH meter works
on the principle of measuring the electric potential difference, 2D material-based
pH meters offer more sensitivity and compatible small-sized designs [68]. Glucose
sensing is vital for monitoring the glucose level in the body. Metal ion sensing is the
most important to monitor increased pollution level and other environmental activity.
13.5.2 2D MATERIAL COMPOSITES AS A SENSOR

Many researchers are devoted for developing the effcient use of 2D material
composites for sensor applications. A recent report on TiO2-C/g-C3N4 composites
showed a successful use of this composite for the sensing of different gases [69].
In this work, heterostructure composites were fabricated by in situ growth method
in which Ti3C2Tx MXene mixed with melamine uniform suspension of this mix-
ture was formed by ultrasonication using water as solvent. Suspended mixture is
dried at 80°C for 12 hours and the powder formed is calcined at 550°C for 4 hours.
FIGURE 13.8 (a) Gas response of T-CN and TC-CN at UV light toward 10 ppm different
VOCs at room temperature. (b) Dynamic response–recovery curve of TC-CN at UV light
toward 10 ppm different VOCs at room temperature [69]. (c) Gas sensing response of different
samples at UV light toward 10 ppm ethanol at room temperature. (d) Gas response of T-CN
and TC-CN at UV light toward ethanol with different concentration at room temperature [69].
Composite sensing response was found to be very good with high sensitivity and
stability. Figure 13.8a and b show the response of the sensor toward different gases
and TC-CN composite has high response and less recovery time as compared to the
T-CN sample. TC-CN composite offers the highest sensitivity toward ethanol and lit-
tle less sensitivity toward other gases. Figure 13.8c compares the response of differ-
ent samples and in which TC-CN composite gives the highest response. Figure 13.8d
shows the response of sensor at different concentrations of alcohol [69]. Therefore, in
conclusion, out of all the samples, TC-CN composite has the best performance [69].
Metal nanoparticles decorated 2D materials are also being used for sensing appli-
cation. Au nanoparticles decorated with a few layers of MoS2 that are used for UV
light-activated NO2 sensing. Work involves a comparison of MoS2 and Au-MOS2
thin flm for NO2 sensing in which Au-MOS2 thin flm showed 10% more sensitivity
toward 2.5 ppm [70]. g-C3N4-WO3 composite materials are synthesized by hydrother-
mal synthesis and analyzed for acetone sensing by Chu et al. [71]. This composite
sensor operating at 310°C temperature has responses of 58.2 and 1.6 for 1,000 ppm
and 0.5 ppm, respectively. Hydrothermally grown GO-ZnO nanorods composite
sheets are capable of sensing SO2 and H2. Sensors have a very good response toward
both SO2 and H2 that is 5.82 and 5.45 at 100 ppm [72]. Zhou et al. [73] reported
Fe2(MoO4)3/MXene nanocomposites for gas sensing application and preparation
method followed for composite formation is single-step hydrothermal method.
Composites have very good stability and fast response and recovery time that were
18s and 24s. Glucose sensing by Graphene/AuNPs/chitosan composites is reported
by Shan et al. [74]. Cathodic current variation is recorded with the variation of glu-
cose concentration from 2.5 to 4.5 mM. Cathode current decreases with the increase
in the glucose concentration. Heterostructure of 2D material has also been used for
sensing, MoSe2-MoO3 heterostructure was used for the nitrite sensing [75]. Sensing
of nitrite ion is important in water quality detection in remote areas so these compos-
ites can be successfully used in those areas. Black phosphorous composites can also
be used for different sensing applications. Black phosphorous and dye composite thin
flms were used for chemical gas sensing and formation of thin flms was carried out
by using Langmuir–Blodgett (LB) technique [76]. Composite thin flms have good
sensitivity toward acid and alkali gases. Biosensing of exosomes by black phosphorus
quantum dots (BPQDs) functionalized MXenes was done by Fang et al. [77]. BPQDs
and MXene both show photothermal effect that makes them suitable as photothermal
immunosensor for bioanalysis. Usually pH sensing is done by glass-based pH sen-
sors, which consume space as well as also have drawback of fragile nature. These
problems can be overcome by replacing these pH sensors with 2D-based composites
materials. Amino-functionalized graphene and polyaniline composite flm have been
used for pH sensing by Xu et al. [78]. This composite works in a wide range of pH
from 1 to 11 and have high sensitivity and fast response. Cysteic acid/graphene oxide
nanocomposites are also reported for pH sensing uses [79]. So, 2D material compos-
ites started to play a signifcant role in sensing area as a result of researcher’s efforts.
13.6 CONCLUSIONS
2D materials like graphene, TMD, black phosphorous, and few more are extensi-
bly being used in various areas of material science. Although pristine 2D materi-
als are effcient enough to be used in different applications, composite formation
of these materials signifcantly increases the performance and also helps to over-
come some limitations. Different types of composites are possible depending upon
the matrix material. Metal-matrix, ceramic-matrix, and polymer composites are the
popular ones among the 2D materials. There are different synthesis methods for
composite formation and sometimes they can be formulated by simple single-step
procedure. Energy storage is an area where 2D materials and their composites have
shown excellent performance because of their properties like high surface area and
high conductivity. Supercapacitor and battery electrodes made of these composites
achieve signifcant results, which are also being used in commercial applications. 2D
material composite-based sensors are also of much importance and researchers are
continuously exploring these areas for better results. So, 2D material and their com-
posites are capable of giving a brighter future to material science and technology.
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14 Recent Developments
in Group II-VI Based
Chalcogenides and Their
Potential Application
in Solar Cells
Saif Ali, Faheem K. Butt, and Junaid Ahmad
University of Education Lahore
Zia Ur Rehman
Yangzhou University
Sami Ullah and Mashal Firdous

University of Education Lahore
Sajid Ur Rehman and Zeeshan Tariq

Minzu University of China
CONTENTS
14.1 Introduction ..................................................................................................246
14.2 Two-Dimensional (2D) Nanomaterials......................................................... 247
14.3 Importance of II-VI Based Chalcogenides ...................................................248
14.4 Synthesis Techniques.................................................................................... 250
14.4.1 Microwave-Assisted Synthesis ......................................................... 250
14.4.2 Hydrothermal Synthesis ................................................................... 251
14.4.3 Electrochemical Synthesis................................................................ 252
14.5 Properties of II-VI based Chalcogenides...................................................... 252
14.6 Applications in Solar Cells ........................................................................... 254
14.6.1 Cadmium-Related Chalcogenides .................................................... 256
14.6.1.1 Cadmium Telluride ............................................................ 256
14.6.1.2 Cadmium Sulfde ............................................................... 256
14.6.1.3 CdTe and CdS Heterojunction ........................................... 256
14.6.1.4 Cadmium Selenide............................................................. 256
DOI: 10.1201/9781003178453-14 245

14.6.2 Zinc-Related Chalcogenides............................................................. 257

14.6.2.1 Zinc Oxide ......................................................................... 257
14.6.2.2 Zinc Sulfde........................................................................ 258
14.6.2.3 Zinc Selenium .................................................................... 258
14.6.2.4 Zinc Tellurium ................................................................... 258
14.7 Future Perspectives....................................................................................... 258
14.8 Conclusion .................................................................................................... 259
Acknowledgment ................................................................................................... 259
References.............................................................................................................. 259
14.1 INTRODUCTION
The II-VI-based compounds have gained much interest from researchers due to their
distinctive properties and applications in numerous felds such as energy storage
and conversion. These compounds show a large limit of bandgaps such that they
can cover the whole solar spectrum. The wide bandgap elements majorly comprise
the chalcogen compounds of Cd and Zn like ZnS, CdTe, and ZnTe. The ZnS has the
widest bandgap value which is 3.4 eV. The elements with smaller bandgap comprise
mercury chalcogenides like HgTe and HgSe. HgTe exhibits the negative bandgap
value which is −3.0 eV. These compounds exhibit such types of applications that
are exhibited by the developed semiconductors like Ge, Si, and some of the ele-
ments from group III-V. Moreover, the range of bandgap becomes continuous with
the addition of ternary II-VI elements like CdHgTe. These types of materials are
potential candidates for various applications such as solar cells, switches, electrolu-
minescent diodes, radiation detectors, lasers, a passivation layer, phosphors, and
infrared detectors [1,2].
Most of the II-VI elements are crystallized both in zincblend and wurtzite mor-
phologies. The repeated and famous characteristic of these frameworks is that every
single atom is surrounded or shared by the four atoms of other material. In zinc-
blend, these frameworks are arranged in cubic assembly while in wurtzite, they are
aligned in the hexagonal assembly. Generally, the elements from group II contain
two electrons in the outermost shell of the atom with s2, and elements from group VI
contain six electrons in the outermost shell with s2p4 confguration. After combin-
ing the elements of group IIA with group VI, electronegativity remains strong due
to which element from group IIA donates its two electrons to the element of group
VI. As a result of this combination, octahedral type morphology obtained similar to
NaCl. This type of bonding is prominent in IIA chalcogenides. Furthermore, when
the elements from group IIB such as Zn, Hg, and Cd are combined with the ele-
ments of group VI, then, the ionization potential exhibits enough high value due to
which these metals do not provide their whole electrons and only donate their free
electrons with their neighbors, which belong to non-metal chalcogenides. As a result
of this combination, tetrahedrally arrange covalent bonds developed due to which
tetrahedrally based wurtzite and zincblende frameworks formed. Data related to
II-VI materials are continuously being produced as a result of research work per-
formed in this feld. Consequently, these data are utilized in the development of new
applications [1–3].
Potential Application in Solar Cells 247
14.2 TWO-DIMENSIONAL (2D) NANOMATERIALS

Dimensional division of the nanomaterials is one of the approaches to categorize the
nanomaterials because the same material can show remarkably different features
by confning it into zero-dimensional (0D), one-dimensional (1D), two-dimensional
(2D), and three-dimensional (3D) crystal framework [4]. Here, we are curious about
2D nanostructured materials (NSMs), therefore, 2D NSMs with their applications
are illustrated in Figure 14.1. 2D NSMs are considered as the slimmest NSMs owing
to their opacity and size on nanoscale or microscale. These NSMs contain a lay-
ered framework having vigorous bonds among the planes and feeble van der Waals
among the layers. In the last few years, 2D NSMs like graphene, metal dichalcogen-
ides, metal carbides/nitrides (MXenes) [5,6], metal oxides, hexagonal boron nitride
(h-BN) [7], and metal halides have grasped much attention owing to their excellent
features and extensive utilization in the feld of electronics, energy storage and con-
version, optoelectronics, sensors, lithium-ion batteries, catalysts, and solar cells [8,9].
The illustrative framework of graphene, h-BN nanosheets, and WSe2 as a dichal-
cogenide has been shown in Figure 14.2. These compounds are assembled in a
honeycomb-like morphology, but the ordering of the nearby atoms in the top and bottom
layers of 2D NSMs is unlike. Every carbon atom in the structure of graphene is present
next to other carbon atom in the top and bottom layers, but in the framework of h-BN
every atom is present in the middle of the benzene ring on the top and bottom layers.
Moreover, every atomic sheet of metal is sandwiched among the two sheets of X [9].
FIGURE 14.1 Different NSMs and applications of 2D NSMs. Adapted with permission
from [8] Copyright (2020) Journal of Materials Chemistry C.
FIGURE 14.2 The framework of (a) graphene, (b) nanosheets of boron nitride (B: blue, N:
pink), and (c) WSe2 (W: blue, Se: yellow). Adapted with permission from [9] Copyright (2019)
IntechOpen.
Transition metal dichalcogenides (TMDCs) have gained the attention of research-

ers in 2010 when the monolayer MoS2 having direct bandgap was discovered and in
2011 fascinating electrical features of multilayered MoS2 were observed [10]. However,
the reliability of the mobility obtained from transistors based on MoS2 was uncertain.
At that time, W and Mo-based dichalcogenides such as WS2, MoTe2, MoS2, WSe2,
MoSe2, and WTe2 were popular. Generally, TMDCs are written by MX2 where M is
a metal or transition metal and X represents chalcogen. More than 30 TMDCs have
been fabricated by utilizing various fabrication techniques [11,12]. The band frame-
work in 2D TMDCs can be tuned by varying the radioactive decay time of excitons
or by ordering the heterolayers in bilayers or multi-layers, but in vertical ordering,
the band arrangement is restricted to bilayer or tri-layer. At room temperature, 2D
TMDCs exhibit electron mobilities of about 200 cm2/Vs having bandgap of 1–2 eV
in the visible spectrum. In electronic gadgets, such type of materials is utilized in the
operation of logic gates having large on/off fraction and small power [8].
14.3 IMPORTANCE OF II-VI BASED CHALCOGENIDES

Chalcogenides nanomaterials are attaining great importance due to their unusual quan-
tum phenomena and important applications. Chalcogenide glasses are already being
used as thin flms in optical data storage. Because of the transmission of light at longer
wavelengths than is possible with silica, chalcogenide fbers have great interest. The
two-dimensional chalcogenides are said to be a helical spin state. Such a different elec-
tronic arrangement provides an ideal platform for the invention of spintronic devices.
There is a wide bandgap in Chalcogenides semiconductors that is fundamental for the
present electronic contraptions and energy applications because of their incredible opti-
cal transparency, controllable carrier fxation, and capable conductivity [13].
Chalcogenides are also benefcial for medical treatments such as laser surgery,
which needs around a 3 μm wavelength. At this wavelength, Lanthanum sulfde fbers
from gallium transmit well, and their non-toxic components and great melting tem-
perature are suitable for minimally invasive surgery. In spectroscopy and sensing
at similar wavelengths, chalcogenide fbers have various atmospheric transmission
windows for important utilization [14]. Furthermore, with the advantage of inorganic
nanoparticles' quantum confnement effect, they can be easily formed into various
shapes, like prisms, wires, spheres, strands, rods, and even longer and more complex
structures, like a tetrapod or hyper-branched. The involvement of light-absorbing
lysine chalcogenides through inorganic receptors can also produce images of the
carrier in charge, which may exceed the absorption contribution of fuorine deriva-
tives. They offer the possibility to select the spectral window of the corresponding
absorption profle with respect to the polymer since it is possible to make absorption
quantum dots (QDs) to cover a wide spectral range [15].
Chalcogenide glasses are technically very important for read-write storage
devices, as they can be quickly (in nanoseconds) interchanged within crystalline and
amorphous phases by applying suitable thermal pulses. Chalcogenide glasses are
attracting great interest with their mid-infrared transparency and highly nonlinear
qualities. Due to their suitable amorphous semiconductor characteristics, chalco-
gens glass materials are applied in various technologies. Surface plasmon resonance
(SPR) is a very versatile and precise technique for quantifying small changes in opto-
electronics parameters. Therefore, optical materials based on chalcogenide glass (or
anodized glass) may be a potential candidate for the manufacturing of SPR sensors
to operate in the near-IR region [16].
In the mid-infrared region, the large optical window of chalcogenide glassy
material allows scanning the whole spectrum area, including biomolecular vibra-
tional patterns. Amorphous chalcogenides are resistant to chemical corrosion,
which is better for their biological compatibility with biological components.
Glass chalcogenides also have a hydrophobic surface quality; they attract non-
polar organic species because they return to the water. As a result, the optical
signal of Devices based on chalcogenide glass has also demonstrated the possibil-
ity of producing low loss waveguides due to the huge refractive index between
the glasses. Chalcogenide glass alloys can also be developed by adding metallic
materials (such as Ag, Cu, Fe, Cd, and Zn) to get an order of magnitude greater
thermal stability [17]. The porosity level of the tilt-controlled flms, when the
substrate is away from the deposition source, produces a controlled difference in
the effective optical constants, making chalcogenide glass a promising material
for chemical sensing [16].
In modern ages, Zinc sulfde has been achieving great attraction due to its
potential importance in various felds such as biological labeling, solar cells, pho-
tocatalysts, photoconductors feld-effect transistors, phosphors, sensors, optical,
electroluminescent materials, and other light-emitting materials. ZnS is an impor-
tant inorganic chalcogenide semiconductor with a broad bandgap extending from
3.5 to 3.7 eV [18].
Cadmium Telluride CdTe is a charming competition and produces a commercial
thin-flm unit of PV solar cells around the world. Thin-flm solar cells of Champion
CdTe have gained conversion capabilities, which is exceeding 16%. A thin flm of
CdTe is about a 10th of the diameter of human hair. The CdTe thin flm absorbs
visible light inside the micron of the material that works as the fundamental pho-
toconversion layer. CdTe is a direct bandgap composite semiconductor, so it is
used as photovoltaic (PV) energy conversion worldly having almost best match
to the solar spectrum. The CdTe, central and transparent conducting oxide flms
(e.g., SnO2 or Cd2SnO4) generate an electrical feld, which is going to convert light
absorbed by CdTe (intrinsic) layer into current and voltage. All of these layers with
metal are deposited on incoming glass and form complete solar panels within a few
hours [19] (Figure 14.3).
FIGURE 14.3 Physical structure of chalcogenide solar cells.
14.4 SYNTHESIS TECHNIQUES

PV solar cells are a hot topic in the energy sector. However, there are still many chal-
lenges to overcome before they can be implemented on a large scale. The effciency
of PV cells is limited by the quality and purity of their materials, which have been
developed over decades through expensive research and development processes. To
make this technology accessible for everyone, we need to fnd cheaper ways to pro-
duce high-quality solar cell materials while maintaining their performance charac-
teristics. Several synthesis techniques including Microwave-assisted method [20,21],
hydrothermal [22], sol–gel [23], thermal decomposition [24], electrochemical [25],
and chemical bath deposition [21,26] are employed among other synthesis tech-
niques. The abovementioned techniques are reported by most of the researchers to
synthesize II-VI chalcogenides in a large quantity and they are non-toxic to the envi-
ronment. These synthesis methods allow us to quickly manufacture these materials
at a low cost with high yields and good quality control parameters. Here, in this sec-
tion, we have discussed some important synthesis techniques for II-VI chalcogenides
that are Microwave-assisted method, hydrothermal, sol–gel, and electrochemical
synthesis. Moreover, we have listed a comparison table for various synthesis methods
to fabricate II-VI chalcogenides.
14.4.1 MICROWAVE-ASSISTED SYNTHESIS

The microwave-assisted method is a methodology increasingly used for the syn-
thesis of 2D nanomaterials. This method is widely used for the preparation of
II-VI-based chalcogenides as it is a very easy, cost-effective, and green synthesis
technique [27]. Guang Zhu et al. reported the microwave-assisted chemical bath
decomposition synthesis technique to produce the CdS/CdSe QDs cosensitized
TiO2 flms. They reported that the performance of the prepared cell was good and
achieved the power conversion effciency (PCE) of 3.06% and current density of
16.1 mA cm−2. They further described that this technique allows rapid and direct
deposition of QDs [21]. Similarly, Guang Zhu et al. in their other work reported
the fabrication of CdSe QDs-sensitized TiO2 flms by using a one-step microwave-
assisted chemical bath deposition method. They used the prepared flms as pho-
toanode for QDs-sensitized solar cells. As a result, they obtained 1.75% PCE and
12.1 mA cm−2 maximum circuit current density.
FIGURE 14.4 (a) J–V characteristics comparison of QDs-sensitized solar cells. (b) Spectra
of incident photon to current conversion effciency. Adapted with permission from [20]
Copyright (2014) Chemical Communications.
Jianheng Luo et al. prepared CdSexTe1−x –CdS QDs and core–shell type II via fac-
ile microwave aqueous method. They described that this is the rapid method to pre-
pare the QDs. The core–shell of CdSexTe1−x –CdS type II were used in QD-sensitized
solar cells that showed a higher PCE of 5.04% [20] (Figure 14.4).
14.4.2 HYDROTHERMAL SYNTHESIS

Hydrothermal synthesis for the preparation of II-VI-based chalcogenides offers sev-
eral advantages over other synthesis techniques such as easy experimental setup,
high yield, low cost, and higher effciency. This technique involved the mixing of
proper agents and precursors into a solvent. This enables a crystalline nanostruc-
ture with an appropriate ratio. Li, Haiyan et al. fabricated the CdS nanoparticles
decorated TiO2 nanobelts via hydrothermal synthesis route. They reported that
solar cells of CdS nanoparticles-decorated with TiO2 nanobelts have 2.52% of PCE.
While they further reported an effciency of 2.84% when they deposited the nano-
belts onto ZnO nanowires [22]. GuangchaoYin et al. successfully embedded CdS
nanorods in CdTe absorbing layers by low cost and electrodeposition method and
facile hydrothermal method. They obtained high-quality 3D heterostructures and
examined their optical, structural, and electrical properties. They reported that the
prepared 3D heterostructures have superior optical absorption properties. In addi-
tion, their studies indicated an 18.5% increase in the heterojunction solar cell energy
conversion effciency [28].
Mehdi Mousavi et al. prepared the CdIn2S4 nanostructures for solar cell applica-
tion by using a facile hydrothermal method. They studied the optical, morphology,
structure, and compositional properties by different characterization techniques. The
prepared nanostructures of CdIn2S4 were used as a barrier layer in dye-sensitized
solar cells; they showed notable enhancement in the effciency of solar cells that
was ~19%. Further, they described that the PCE of the solar cell was affected by the
morphology and structure size [29].
14.4.3 ELECTROCHEMICAL SYNTHESIS

Electrochemical synthesis is a simple and economical method to synthesize
the II-VI-based chalcogenides for large-scale production at low temperatures.
The architecture of nanomaterials can be tailored by this synthesis technique. This
is the most suitable synthesis technique to prepare high-quality heterojunction
solar cells. Chen-Zhong Yao et al. studied the vertical and high-density core–shell
ZnO/CdS nanorods that were prepared by a two-step electrochemical deposition
process. The prepared sample was used in QD-sensitized solar cells and showed
improved performance. They reported 1.07% of PCE with Jsc of 5.43 mA cm−2 [30].
Shinya Higashimoto et al. reported a two-step route of template-free electro-
chemical deposition to prepare CdS nanotubes. They used the combination of
polysulfde (Sx2−/xS2−), CdS NT, and carbon electrode for photo-electrochemical
solar cells that exhibited the high effciency of 80% at 510 nm due to effective light-
harvesting performance. IPCE curve for the prepared CdS flms fabricated for solar
cells is shown in Figure 14.5b [25].
Dongjuan Xi et al. reported the hybrid flms containing CdS nanorods arrays that
were prepared by the electrochemical deposition technique. Due to the cathodic pro-
cess, these nanorods were self-assembled on the gold-coated glass substrates. They
further investigated their properties for solar cells and measured the open-circuit
voltage of 0.84 V and 0.38% of overall PCE [31] (Table 14.1).
14.5 PROPERTIES OF II-VI BASED CHALCOGENIDES

In this section, we will briefy discuss the general properties of II-VI based
Chalcogenides. Crystal structures of these materials are rather complex. Most II-VI
based Chalcogenides crystallize in the wurtzite Zinc Blende and Wurtzite structures.
Normally, these materials are found in Zinc-Blende structure at room temperature
while at higher temperatures these are found in Wurtzite structure. One of the fas-
cinating properties of these materials at atmospheric pressure is that they undergo
a solid–solid phase transition below the melting point. This property enables these
materials to apply in cooling systems now a day. Normally, CdSe and CdS crystallize
in the HCP Wurtzite structure, CdTe and ZnTe in Zinc-Blende structure, whereas ZnS
and ZnSe can exist in both of these structures. Bonding in II-VI-based Chalcogenides
is a mixture of covalent and ionic types because the average number of electrons per
atom is still four. As group-VI atoms are more electronegative than group-II atoms,
so we can see ionicity in these materials. This ionic character varies considerably
over the whole range and increases as the atomic size decreases. Therefore, ZnS
is predominately ionic while the bonding in HgTe is nearly covalent. As we know
that the ionic character has the effect of binding the valence electron rather tightly
to the lattice atoms. Therefore, these materials have a wide direct bandgap. II-VI-
based Chalcogenides with a wide bandgap have higher melting points. When they are
heated to their melting point, the overheating effect occurs due to their high ionicity.
It is diffcult to produce bulk crystals from melt because of the greater vapor pres-
sures at their melting points. The vapor phase, on the other hand, makes it simple
Potential Application in Solar Cells
FIGURE 14.5 (a) Characteristics curve of photocurrent density and voltage for heterostructure solar cells. Based on 3D CdS nanorods/CdTe photo-
electrode. (Adapted with permission from [28] Copyright (2017) Journal of Molecular Liquids.) (b) IPCE curve for the prepared CdS flms fabricated
for solar cells. Adapted with permission from [25] Copyright (2012) Electrochemistry communications.
253
TABLE 14.1
Comparison of Recent Synthesis Techniques and Solar Cell Effciency
Power Conversion
II-VI Chalcogenides Synthesis Methods Effciency (%) Application Ref
CdS/CdSe quantum-dot Microwave-assisted chemical 3.06 QD-sensitized solar [21]
(QD)-cosensitized TiO2 bath deposition (CBD) cells
TNARs/CdS/CdS Hydrothermal, chemical bath 2.66 QD-sensitized solar [32]
deposition (CBD) cells
CdSe CBD 6.8 QD-sensitized solar [33]
cells
CdS/CdSe QDs Organometallic high-temperature 5.32 CdS/CdSe- [34]
injection method sensitized solar
cells
CdS/CdSe QDs Successive ion layer absorption 4.62 CdS/CdSe- [34]
and reaction (SILAR) method sensitized solar
and CBD cells
CdS/CdSe QDs SILAR 3.11 QD-sensitized solar [35]
cells
CdTe-CdS NCs Hot-injection chemical 4.2 QD-sensitized solar [36]
precipitation method cells
CdTe nanocrystal Solution processing 12.3 CdTe nanocrystal [37]
solar cells
ZnO/ZnSe core/shell High temperature arrested 2.2 Liquid junction [38]
nanorods precipitation nanowire solar
cells
Cu-doped ZnTe flm Electrochemical deposition 3.4–7.1 CdTe solar cells [39]
to build bulk crystals and their flms. As a result, it is vital to analyze the physical
and chemical features of flm and bulk crystal formation before introducing them.
The parameters of some of the most common II-VI based Chalcogenides are shown
in Table 14.2 [40–44].
14.6 APPLICATIONS IN SOLAR CELLS

In the era of science and technology, energy demand has been escalating day by
day. The non-renewable resources are decreasing very fast with time. In this aspect,
renewable resources such as hydropower, geothermal power, wind energy, and solar
energy are better options to fulfll the energy requirement. Solar energy is the green
and environment-friendly renewable energy resource available in large amounts in
the universe. Solar cells or PV cells convert sunlight into electrical energy. This tech-
nology is sustainable and increased tremendously in recent years [46]. This remark-
able increment in the usage of solar cells is due to advanced technologies, better
construction materials, and public awareness about the advantages of solar energy. In
this process when sunlight falls on the solar cell material the electrons in the material
come in the conduction band and produce electricity. This phenomenon is called the
TABLE 14.2
Properties of Some II-VI Based Chalcogenides
Material Property ZnS ZnO ZnSe ZnTe CdS CdSe CdTe
Melting point (K) 2038 (WZ, 2248 1797 1513 2023 (WZ, 1623 1370
150 atm) 100 atm) [45]
Energy gap Eg at 300 3.68/3.911 -/3.4 2.71/- 2.394 2.50/2.50 -/1.751 1.475
K (eV) (ZB*/WZ*)
dEg/dT(×10−4eV/K) 4.6/8.5 -/9.5 4.0/- 5.5/- -/5.2 -/4.6 5.4/-
ZB/WZ
Structure ZB/WZ WZ ZB/WZ ZB WZ WZ ZB
Bond length (µm) 2.342 (WZ) 1.977 2.454 [45] 2.636 2.530 [45] 2.630 [45] 2.806 [45]
(WZ) [45]
Lattice constant [45] 0.541 – 0.567 0.610 0.582 0.608 0.648
a0 at 300 K (nm)
ZB nearest-neighbor 0.234 – 0.246 0.264 0.252 0.263 0.281
dist
ZB density at 300 K 4.11 – 5.26 5.65 4.87 5.655 5.86
(g/cm3)
Heat capacity Cp 11.0 9.6 12.4 11.9 13.2 11.8 –
(cal/mol K)
Ionicity (%) 62 62 63 61 69 70 72
Equilibrium pressure 3.7 – 1.0 1.9 3.8 1.0 0.7
at c.m.p. (atm)
Minimum pressure 2.8 7.82 0.53 0.64 2.2 0.4–0.5 0.23
at m.p. (atm)
Specifc heat 0.469 – 0.339 0.16 0.47 0.49 0.21
capacity (J/g K)
Thermal 0.27 0.6 0.19 0.18 0.2 0.09 0.01
conductivity
(W/(cm K))
Young/s modulus 10.8Mpsi – 10.2Mpsi – 45 GPa 5 × 1011 dyne 3.7 × 1011
cm−2 dyne cm−2
m.p., melting point; c.m.p., congruent melting point; ZB, zinc blend; WZ, wurtzite.
PV effect. Many solar cells that are widely used are monocrystalline made with a
single crystal of silicon have an effciency of 26.5% reported but these monocrystal-
line solar cells are expensive [47]. Amorphous silicon solar cells can be fabricated at
low temperatures and deposited on a substrate such as plastics and metal foils. They
degrade when exposed to sunlight and consequently their performance decreases.
Those solar cells made by a thin flm of solar cell (SC) material have an advantage
over the monocrystalline and amorphous silicon crystal. The reason is that polycrys-
talline solar cells have good effciency and build a good electric feld between the
two different SC materials, which is known as a heterojunction. The semiconduc-
tor materials of II-VI group have great potential for the absorption and emission of
light [48]. During the past few years, 2D layered materials have become an attractive
feld of research due to the promising and attractive properties of materials. Among
these most emerging materials, II-VI chalcogenides have gained great potential in
PV applications due to appropriate bandgap and other unique properties [49]. The
detail about some chalcogenides materials is given below.
14.6.1 CADMIUM-RELATED CHALCOGENIDES

14.6.1.1 Cadmium Telluride
Cadmium telluride (CdTe) is a promising and attractive candidate for PV application.
There are many unique properties of this material such as an appropriate bandgap
(1.45 eV) and good optical absorption ability. The thin flm of cadmium telluride
with 2 mm thickness can absorb maximum (100%) incident light [4]. There is another
beneft to use CdTe is that it has many techniques for deposition such as chemical
vapor deposition (CVD), close‐spaced sublimation (CSS), and electrode deposition.
The effciency of CdTe solar cell is 16.5%, which is prepared by the closed space
sublimation. Other strategies are also helpful to attain the high-effciency level, so
this material is very attractive in the feld of solar cells [50].
14.6.1.2 Cadmium Sulfde

The II-VI compounds such as CdS and CdSe have good ability for solar cell appli-
cations. CdS is a promising candidate in wide bandgap materials for PV applica-
tions. The composite of CdTe/CdS has good options to be tuned bandgap between
2.42 eV for CdS to 3.6 eV for ZnS. This combination enhances the wavelength spec-
tral response for visible solar applications [51]. The red emission occurs due to the
recombination of sulfur vacancy at 1.72 eV in CdS [52]. This red emission has been
discussed by Lambe and Klick in the concept of phenomenological model [53] and
in another complementary transition, an emission of 1.1 eV should be produced. The
sum of these two emission energies is 2.82 eV. This value is very near and compa-
rable with the bandgap of CdS, which can be improved with different strategies [54].
14.6.1.3 CdTe and CdS Heterojunction

CdTe and CdS heterojunction is also used for PV cells and showed good performance
for solar energy. This thin layer is helpful to reduce the interfacial defects which are
responsible for better effciency [55]. This layer can be formed with those techniques
which are operating at high temperatures like CVD or CSS. Better performance
is achieved through heat treatment of CsTe/CdS due to the creation of interfacial
layer, recrystallization, and defects passivation [56]. Figure 14.6 about the solar cell
of CdTe and n-CdS composite is given below.
14.6.1.4 Cadmium Selenide

Solar cells based on the CdSe QDs have been described in some publications for PV appli-
cations with organic semiconductor polymer materials. There are some facile and effcient
methods to fabricate the Cadmium Selenide (CdSe) nanomaterials using a single-source
precursor [58]. The mechanism of CdSe to harvest the solar energy in the visible light
FIGURE 14.6 (a) A Schematic layout of a conventional p–n junction CdTe and CdS thin-
flm solar cell. (Adapted with permission from [48] Copyright (2006) Journal of Materials
Chemistry.) (b) Scheme for recombination and electronic transitions-related oxygen vacancy
presented to the bandgap of ZnO. (c) Recombination and electronic-transition scheme for the
sulfur vacancy in the bandgap of ZnS. (d) Recombination and electronic-transition scheme on
the selenium vacancy in the bandgap of ZnSe. Adapted with permission from [57] Copyright
(2013) Journal of crystal growth.
spectrum resembles the CdS and this material is also useful for PV applications. The PL
centered nearly at 1.0eV (1.2mm) is due to the recombination of charge carriers on Se
vacancy [59]. The energy level of Se vacancy can be located at 1.82–1.0 eV=EC −0.82eV
which is very close to CdS. So this material has good ability for solar cells.
14.6.2 ZINC-RELATED CHALCOGENIDES

14.6.2.1 Zinc Oxide
In PV applications, zinc oxide (ZnO) is an attractive and suitable material that can
be used as nanoparticles and as thin flms. Zinc oxide thin flms are useful in solar
cells because it has good conductivity and better transmittance for visible light radi-
ation [60]. Zinc Oxide nanoparticles are also useful to build heterojunction solar
cells. There is another advantage to use ZnO in solar cells is the facile fabrication
of zinc oxide nanoparticles not needed for any further surface modifcation as com-
pared to CdSe to produce solubility in organic solvents [61]. The information-related
electron paramagnetic resonance (EPR) and photoluminescence (PL) quenching
by light as a scheme about recombination are in the bandgap of ZnO via oxygen
vacancy. In this scheme, PL emission arises due to the recombination of a hole from
the valance band and electron caught on the energy level E (VA +). The EPR signal
excitation is produced due to the conversion of VA+2 to VA +1 during the process of an
electron transition. Due to the fast hole-trapping occurs this type of transition starts
p-type photoconductivity for the low intensity of light in all II-VI compounds [57].
This scheme is described in Figure 14.6b.
14.6.2.2 Zinc Sulfde

ZnS is another attractive chalcogenide material for solar cells application. The compos-
ite of the wide bandgap of ZnS 3.6 eV with CdS (2.42 eV) is also helpful for harvesting
the maximum visible light radiation for solar energy. So this composite is also a suit-
able and attractive material for PV applications [51]. In Figure 14.6 during the reaction
VS2+ + e → VS + transition 1 occurs and transfer VS+2 to the EPR center, VS +. In the
second transition come back the EPR center to the natural state following the reaction
VS+ + e → VS0. Due to this transition p-type photoconductivity was produced for the
weak below bandgap [62]. The scheme of this process is shown in Figure 14.6c.
14.6.2.3 Zinc Selenium

ZnSe is another material for PV applications for solar cell applications. Its appropri-
ate bandgap is suitable and helpful to increase its effciency. In Figure 14.6d it is
observed that after the irradiation mid-bandgap was much closer to the Fermi level
between valance and conduction band. Due to this part of Se vacancies were caught
electrons and transformed into the EPR center, VSe+. Similarly in the ZnS, ZnO, the
photo-EPR center measurements play an important role and released quenching of
EPR light. Shirakawa and Kukimoto and by Kishida et al. in Japan took measure-
ments about the photosensitive band on ZnSe and this quenching spectra resembled
their measurements [63,64]. In this scheme, the electronic transition coincided with
anion vacancy and was constructed with permission as shown in Figure 14.6d.
14.6.2.4 Zinc Tellurium

Chemically Tellurium resembles selenium and sulfur and all materials belong to the
class of chalcogens elements. The data about the absorption of light, recombination
of photogenerated charge carriers, and EPR are very less related to the Te vacancies
in the ZnTe composite. The energy level in this material associated with vacancy
about Te, VTe2+/+ was measured at the position level of EV +0.7 eV [65]. Due to the
short data on an energy level, it is very diffcult to fnd out the centers which are
the reasons for PL peaks [66]. So we supposed the recombination scheme for ZnTe
vacancy is similar to ZnO, ZnS, and ZnSe.
14.7 FUTURE PERSPECTIVES

Research studies are more and more directed to the rapid applications of II-VI-based
chalcogenides. These materials are achieving much attraction because of their amaz-
ing properties. 2D-layered semiconducting materials such as ZnX and CdX materi-
als have long been of enormous interest for a broad range of uses, such as transistor,
PV devices, heterojunction diodes, and photoconductors. 2D ZnX, CdX due to their

bandgap, and high visual absorption coeffcient are widely using solar cells that can
store 100% of solar radiation. The effciency of these materials is very high so low-
cost, scalable solar cells energy can be produced. These trends will accelerate the
development of the department, which is still rich in remarkable discoveries.
14.8 CONCLUSION
2D nanomaterials have gained signifcant attention from the scientist due to their
high stability and reliability, applicability onto fexible substrates, aesthetical appear-
ance, monolithic deposition, and superior temperature coeffcient. Similarly, 2D
chalcogenides nanomaterials are now widely used in solar cells due to their supe-
rior properties. They have enhanced the effciency of solar cells. The II-VI-based
chalcogenides nanomaterials are commonly used to enhance the effciency, current
density, and performance of solar cells. In this chapter, we have reviewed II-IV-
based chalcogenides and their applications in different types of solar cells. Moreover,
in-depth comparisons of various low-cost, scalable, economical, and easy synthesis
techniques and types of various II-VI chalcogenides-based nanomaterials have been
described in this chapter.
ACKNOWLEDGMENT
F. K. Butt acknowledges the funding support from HEC through grant number 7435/
Punjab/NRPU/R&D/HEC/2017.
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15 Photovoltaic Application
of Graphene Oxide and
Reduced Graphene Oxide
Perspectives on Material
Characteristics and
Device Performance
Tabitha A. Amollo
Egerton University
Vincent O. Nyamori
University of KwaZulu-Natal
CONTENTS
15.1 Introduction .................................................................................................. 263
15.2 Overview of Organic Photovoltaics Operation............................................. 265
15.2.1 Polymer Solar Cells .......................................................................... 265
15.2.2 Dye-sensitized Solar Cells................................................................266
15.3 Graphene Oxide and Reduced Graphene Oxide........................................... 267
15.3.1 Application of Graphene Oxide, Reduced Graphene Oxide
and Their Nanocomposite in Polymer Solar Cells ........................... 268
15.3.2 Application of Graphene Oxide, Reduced Graphene Oxide
and Their Nanocomposite in Dye-sensitized Solar Cells ................. 273
15.4 Conclusion .................................................................................................... 275
References.............................................................................................................. 276
15.1 INTRODUCTION
The 21st century has seen exponential growth in demand for energy owing to the
growing world population and day-to-day technological advancements. Thus, there
is a need for a reliable and sustainable energy source for domestic and industrial use.
Also, the adverse climate change experienced in the world today is largely occasioned
by the emission of greenhouse gases. The burning of fossil fuels, as in automobiles
DOI: 10.1201/9781003178453-15 263

and industries, is a major contributor to the emission of such gases. Hence, there is
a need not only for a reliable and sustainable but also clean energy resource. Solar
energy comes in handy as it is a clean, reliable and sustainable source that is abun-
dantly available worldwide. The effective conversion of solar energy to electricity
requires high-performance solar cells devices.
Photovoltaic technology has evolved over the past decades giving rise to what’s
commonly referred to as the ‘generations’ of solar cells. To date, there have been
four phases of photovoltaic technological evolution. The silicon-based solar cells
comprise the frst-generation solar cells. These have been in the market for over
the past half-century. Even though silicon-based solar cells exhibit high power
conversion effciencies (PCEs), their fabrication is complex and costly, making
them non-cost-effective to the global population. Besides, their rigidity limits their
applications. The second-generation solar cells consist of thin-flm technology that
makes use of inorganic compounds such as amorphous silicon (a-Si:H), gallium
arsenide (GaAs) and cadmium telluride (CdTe). These approaches are associated
with high cost of production; for example, the thin flm preparation necessitates
the use of vacuum vapor deposition. The solution-processable thin-flm solar cells,
including polymer solar cells (PSCs), dye-sensitized solar cells (DSSCs), quantum
dot solar cells and multijunction solar cells, form the third-generation solar cells.
These are advantageous in terms of production and materials cost, environmental
safety, fexibility and lightweight property. Perovskite solar cells (PVSCs), which
form the fourth-generation solar cells, were introduced to overcome the challenges
experienced in the synthesis of dyes for DSSCs. The fourth-generation solar cells
also include types of PSCs in which the active layer comprises a polymer/nanopar-
ticle composite. This chapter focuses on organic photovoltaics (OPV), that is, the
PSCs and DSSCs.
Functional materials are a prerequisite to high-performance solar cells. As the
photovoltaic technologies evolved with time, equally have the materials developed
for the solar cells advanced, from crystalline silicon through the inorganic com-
pounds to the polymers, small molecule compounds, dyes and perovskites. Thus, the
scientifc research community is focused on developing cutting-edge energy materi-
als for photovoltaic application. Among the functional nanomaterials under intense
research is graphene. Graphene is the frst truly 2D nanomaterial composed of a
monolayer of sp2-hybridized carbon atoms. It is characterized by outstanding prop-
erties such as high carrier mobility, optical transparency, mechanical strength, fex-
ibility and thermal conductivity. Because of these unique properties, graphene has
been utilized in various categories of solar cells, mainly PSCs, DSSCs and PVSCs.
Good results have been reported for such studies, and yet more studies on the same
are ongoing.
Nevertheless, research reports have indicated challenges in using pristine gra-
phene in the solution-based processing of solar cells owing to its hydrophobic nature.
For this reason, graphene derivatives have been/are being developed for application
in solar cells. This chapter focuses on the application of graphene derivatives in PSCs
and DSSCs. The nanomaterials under focus are graphene oxide (GO), reduced gra-
phene oxide (rGO) and their nanocomposites.
Photovoltaic Application of GO and rGO 265
15.2 OVERVIEW OF ORGANIC PHOTOVOLTAICS OPERATION

OPV is a class of solar cells comprising the PSCs, DSSCs and PVSCs. These have
the advantage of solution-based-processability, implying the capability of large-scale
production. Under illumination, the absorber material in OPV generates an exciton
that diffuses and dissociates to holes and electrons at the interface. This is followed
by charge transfer to the electrodes (outward circuitry/load). Thus, the generation
of charge carriers, diffusion and separation are the determinant factors of the PCE.
These processes are mainly governed by the optoelectronic properties of the materi-
als of the solar cell. Device engineering, morphological characteristics of the formed
thin flms and fabrication conditions are other factors that infuence OPV perfor-
mance. Generally, the photovoltaic performance of solar cells is characterized by the
open-circuit voltage (Voc), short-circuit current density (Jsc), fll factor (FF) and the
ultimate PCE (˜ ).
15.2.1 POLYMER SOLAR CELLS

PSCs can be fabricated in the planar or bulk heterojunction (BHJ) device structures.
The latter structure is more commonly used as it enables longer exciton diffusion
length. The planar structure has the donor and acceptor material intimately contacted
together, while in the BHJ structure, the donor and acceptor materials are intermixed
to form a blend. The typical BHJ structure is formed by the anode (transparent con-
ductive electrode (TCO))/hole transport layer (HTL)/active layer/electron transport
layer (ETL)/cathode, as shown in Figure 15.1a. The photoactive medium of the proto-
type PSC consists of poly-3-hexylthiophene (P3HT) and (6-6) phenyl-C61-butyric acid
methyl ester (PCBM) as the donor polymer and the fullerene acceptor, respectively.
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and LiF/Ca
forms the HTL and the ETL, respectively, while the anode is usually of indium tin
oxide (ITO) and the cathode is of Al. The operation of the PSCs is explained in
Section 15.2. The active layer may consist of a polymer donor and fullerene acceptor
materials, a polymer donor and small molecule electron acceptor (SMA) materials
or a polymer donor and polymer acceptor materials. The interfacial layers, HTL and
ETL, create an ohmic contact between the active layer and the electrodes and pro-
mote the injection of charge carriers.
Though PEDOT:PSS ensures effective transfer of holes to the anode, its acidic
and hydrophilic nature causes interface instability thus, leads to device degradation.
Similarly, the low work function metals used in the ETL like Ca and Li are eas-
ily oxidized, causing an increase in series resistance at the interface thus, leads to
device degradation [1]. Though characterized by high carrier mobility, the fullerene
acceptors suffer from morphological instability, low light-harvesting capability, and
diffculty in bandgap engineering [2]. Also associated with the fullerenes is photon
energy loss through recombination processes occasioned by the electron disorder and
low dielectric constant of the materials [3]. Because of these factors, fullerene-based
PSCs manifest low Voc and Jsc. Non-fullerenes, which include polymeric and SMAs,
have been developed to overcome the challenges of fullerenes. These are designed
FIGURE 15.1 PSCs of (a) conventional and (b) inverted BHJ device structure.
in such a way as to offer complementary optical absorption to the donor materials.

Also, the non-fullerene acceptors have the advantage of tunable energy levels [4] and
low energy loss [5]; thus, high Voc values are achievable with this class of materials.
Nonetheless, the non-fullerenes are associated with lower carrier mobilities com-
pared to their fullerene counterparts.
PSCs can also be fabricated in the inverted structure of TCO/ETL/active layer/
HTL/cathode, as shown in Figure 15.1b. The inverted structure was enabled by the
tunability of the work function of ITO to form a low work function cathode [6]. In
the inverted structure, a high work function transition metal oxide like molybdenum
oxide and vanadium oxide or PEDOT:PSS form the HTL, while a low work func-
tion compound forms the ETL. The anode comprises a high work function metal
like Au or Ag. The inverted confguration is advantageous in terms of device stabil-
ity [7], vertical phase separation in the active layer [8] and provides provision for
design fexibility for tandem solar cells. Generally, good photovoltaic performance
has been recorded for the PSCs, with those devices utilizing non-fullerene acceptors
outperforming their fullerene-based counterparts [9]. Nevertheless, the PSCs have
limitations of low carrier mobility and non-optimal optical absorption. Research on
material development for PSCs is still ongoing with a view of optimizing not only the
optical and electronic properties of the donor and acceptor materials but also interfa-
cial layer materials for effective charge transfer. To this end, graphene nanomaterials
are under intense investigation.
15.2.2 DYE-SENSITIZED SOLAR CELLS

DSSCs are fabricated in the TCO/counter electrode (CE)/electrolyte/dye/photo-
anode/TCO structure, as shown in Figure 15.2. The operation of DSSCs begins with
the absorption of incident light by the dye promoting an electron from its highest
occupied molecular orbital (HOMO) to its lowest unoccupied molecular orbital. This
is followed by the injection of the electrons to the photoanode by the dye for further
diffusion to the cathode (external circuitry). The electrons then return to the CE and
regenerate the electrolyte which had regenerated the oxidized dye. In typical DSSCs,
fuorine doped-tin oxide (FTO) or ITO forms the TCO, titania (TiO2) forms the pho-
toanode, platinum nanoparticles forms the CE. The dyes used in DSSCs are based
on ruthenium, while the electrolytes are based on redox pairs like those of cobalt or
FIGURE 15.2 DSSCs device structure.
iodide/triiodide. The photoanode facilitates dye adsorption and charge transfer while
the CE serves as a catalyst for the reduction reaction of the redox pairs in the electro-
lyte. Titania is mostly used as the photoanode because of its favorable optoelectronic
properties viz. wide energy bandgap of 3.2 eV and optical absorption at wavelengths
only below 388 nm, thermal stability, non-toxicity and chemical inertness [10]. The
major challenge with the DSSCs is the poor stability of the dyes and the electrolytes.
15.3 GRAPHENE OXIDE AND REDUCED GRAPHENE OXIDE

GO is an oxygen-functionalized derivative of graphene. It consists of oxygen func-
tional groups on the graphene backbone viz. the epoxy and hydroxyl groups on the
basal planes and the carboxylic groups at the edges. The hybridization system of these
oxygen functional groups differs in that the epoxy and hydroxylic groups’ atoms are
sp3-hybridized while those of the carboxylic groups are sp2-hybridized. The result
of this mixed hybridization system is a disruption of the sp2 conjugation network of
the graphene lattice. For this reason, GO exhibits insulating behavior. Nevertheless,
charge transfer does occur in GO via the hopping mechanism within the localized
sp2 sites. The polar oxygen functional groups on GO make it hydrophilic; thus, it’s
compatible with solution-based device processing. Homogenous solutions of GO in
water or organic solvents can be obtained by stirring or sonication. The common
synthesis route for GO involves the exfoliation of graphite fakes/powder using strong
oxidizing agents such as potassium permanganate. This was frst demonstrated in
1859 by Brodie [11], but the synthesis protocol has developed over time. Today, the
commonly used method is the modifed Hummers method, which was frst demon-
strated in 1958 [12].
rGO is obtained from GO via chemical or thermal reduction. The reduction
treatment is aimed at reducing the oxygen functional groups. This is a means of
restitution of the disrupted sp2 conjugation network of graphene thus, restoring the
electrical conductivity behavior. Chemical reduction of graphene involves reducing
agents such as hydrazine, sodium borohydride and hydroquinone [13]. On the other
hand, thermal reduction involves thermal annealing of the GO samples under the
fow of a reducing gas like hydrogen or nitrogen. Typically, the GO sample, in a
crucible, is placed in a quartz furnace and heated at temperatures as low as 150°C to
as high temperatures as 2,000°C. In this procedure, the quality of the rGO samples
FIGURE 15.3 TEM images of (a) Hydrazine hydrate reduced rGO and (b) thermally
reduced rGO at 500°C.
produced is dependent on the annealing temperature. For example, thermal reduction

at lower temperatures yields rGO with lots of defects, but as the annealing tempera-
ture increases, a reduction in the number of defects is observed [14]. Also, although
both the chemical and thermal reduction routes yield rGO, the quality of the samples
produced differ. As exemplifed in Figure 15.3, the hydrazine hydrate reduced rGO
manifests a more wrinkled structure (with more folds) than the thermally reduced
rGO. The sample quality is key to the performance of devices based on these materi-
als; thus, one would need to optimize not only the synthesis methodology but also
their corresponding conditions.
15.3.1 APPLICATION OF GRAPHENE OXIDE, REDUCED GRAPHENE OXIDE

AND THEIR NANOCOMPOSITE IN POLYMER SOLAR CELLS
Both GO, rGO and their nanocomposites have been utilized in the interfacial and
active layers of PSCs. In both cases, the graphene materials infuence the perfor-
mance of the devices, albeit via different mechanisms. Recently, we reported the use
of graphene nanomaterials, namely GO, rGO and reduced graphene oxide germa-
nium dioxide (rGO-GeO2) in the photoactive medium of PSCs. Similarly, we have
employed GO and reduced graphene oxide germanium quantum dots (rGO-Ge) in
the HTL of PSCs of the structure glass/ITO/PEDOT:PSS/active layer/LiF/Al. The
active layer of the PSCs consisted of P3HT:PCBM. The optimum concentrations for
GO, rGO and rGO-GeO2 in the active layer were 10, 3 and 3 wt.%, respectively, while
for the GO and rGO-Ge in the HTL, the optimum concentration was 0.125 wt.%.
Reference devices were also fabricated for all the experiment sets. For all the fab-
ricated devices, the use of the graphene nanomaterials improved their photovoltaic
performance, albeit via different mechanisms. The electrical properties of these
devices are listed in Table 15.1. GO in the active layer improved the device’s PCE by
120% [15]. This resulted from improved Jsc occasioned by the high optical absorp-
tion of the GO modifed active layer device. The high Jsc of 18.2 mA cm−2 indicated
high photogeneration of charge carriers and effective charge transport in the device,
which corroborated the enhanced carrier mobility by two orders of magnitude.
TABLE 15.1
Electrical Parameters of BHJ Solar Cells Modifed with Graphene
Nanomaterials in the Active Layer and HTL
Voc Jsc (mA FF PCE Improved PCE
HTL Active Layer (volts) cm−2) (%) (%) index (%) Ref
PEDOT:PSS P3HT:PCBM:GO 0.57 18.2 43 4.4 120 [15]
PEDOT:PSS P3HT:PCBM :rGO 0.52 10.0 38 2.0 25 [17]
PEDOT:PSS P3HT:PCBM:rGO-GeO2 0.44 17.0 31 2.3 53 [17]
PEDOT:PSS-GO P3HT:PCBM 0.53 14.0 38 2.8 40 [15]
PEDOT:PSS/rGO-Ge P3HT:PCBM 0.51 10.3 46 2.4 50 [16]
The FF of the device was comparable to the reference device, while there was a slight
improvement in the Voc. The active layer flm was of smooth morphology following
the high crystallinity of the GO sample. This aided the charge carriers separation
process. An improved PCE of 40% was achieved in devices with GO in the HTL.
This resulted from improved Jsc. Also, the carrier mobilities improved by two orders
of magnitude. The GO material served to lower the injection barrier at the interface
thus, favoring extraction of holes. Also, given the insulating behavior of GO, it aids
in selective blocking of electrons at the interface, thereby reducing recombination
processes. GO inclusion in both the active layer and HTL resulted in the formation of
interconnected pathways for charge transport. The device with rGO-Ge in the HTL
manifested improved PCE by 50%, arising from improved Jsc and FF [16]. This was
achieved even though the HTL flm was characterized by agglomerates, which are
potential sites for current leakages. The rGO-Ge nanocomposite used was of good
electrical conductivity thus, provided more percolation pathways in the HTL. This
served to reduce non-geminate charge recombination. Also, the Ge quantum dots of
high electron affnity served to aid selective electron blocking. Thus, the inherent
properties of the HTL materials served to improve the photovoltaic performance of
the devices outdoing the detrimental effects of unfavorable morphology. rGO-GeO2
nanocomposite and rGO employed in the photoactive medium of PSCs resulted in
improved PCE by 53% and 25%, respectively [17]. The rGO-GeO2 nanocomposite
in the active layer resulted in remarkable improvement in Jsc to 17 mA cm−2, though
with lower Voc and FF values. The charge carrier mobility in these devices improved
by order of magnitude. The high electron affnity of Ge resulted in a high built-in
potential difference between the donor and acceptor phases causing effective exciton
dissociation. This served to limit geminate charge carriers recombination. The lower
Voc and FF were due to increased non-geminate charge recombination occasioned
by the rough morphology of the active layer flm. Nevertheless, the effective charge
separation in the devices yielded a remarkable improvement in the Jsc. An increase in
PCE by 25% was achieved by employing rGO in the active layer of PSCs. In terms of
Voc and FF, the rGO modifed devices performed comparably to the reference device.
But there was a slight improvement in the Jsc which resulted in the improvement of
the PCE. Also, the charge carrier mobility was improved by two orders of magni-
tude, implying more percolation pathways upon inclusion of rGO. For all the devices
fabricated with the graphene nanomaterials either in the HTL or active layer, there
was observed improvement in charge carrier mobility which yielded an improved Jsc.
GO was utilized as the HTL material for poly [N-9′-heptadecanyl-2, 7-carbazole-
alt-5,5-(4′, 7′-di-2-thienyl-2′, 1′, 3′benzothiadiazole)] PCDTBT:PC71BM based solar
cells [18]. At an optimum GO concentration of 1 mg/ml, a Voc, Jsc, FF and PCE of
0.8 V, 8.14 mA cm−2, 42% and 2.73%, respectively, were achieved. The work demon-
strated the effect of material concentration and thickness of the HTL. At a higher
concentration of GO and consequently the thickness, the device performance dete-
riorated with lower Jsc and high series resistance being manifested.
The effect of oxidation level of GO for application as HTL in PSCs was investi-
gated by Wu et al. [19]. Table 15.2 shows the electrical parameters of P3HT:PCBM-
based PSCs with GO at different oxidation levels as the HTL. The Voc, FF and PCE
increased with an increase in the oxidation level. The increase in Voc (0.34–0.56 V)
with increasing oxidation level (50%–400%) was attributed to an increased work
function. At the optimum oxidation level (400%), better dispersion and smooth mor-
phology of GO were observed. The attained work function (5.1 eV) at the optimum
oxidation level matches that of P3HT (5.2 eV), implying a lowering of the Schottky
barrier at the interface. Thus, it yielded an ohmic contact for charge extraction.
However, the photovoltaic performance of the device with GO oxidation level beyond
the optimum dropped due to poor electrical conductivity. Nevertheless, P3HT:PCBM-
based devices with GO HTLs at optimum oxidation level performed better due to
increased dispersion (yielding better flm morphology) and work function (yielding
an ohmic contact at the interface). This observation echoes the interplay of the vari-
ous factors that affect the performance of PSCs like material properties, energy level
alignment at the interface and flm morphology. This study showed that the optoelec-
tronic properties and dispersibility of GO could be optimized by reasonable control
of the oxidation level.
Singly applied (spin-coated) GO/PEDOT:PSS HTL yielded an improved per-
formance in P3HT:PCBM solar cells than either GO or PEDOT:PSS only HTL
devices [20]. While the Voc and FF of the devices were comparable, the double-
layered HTL device attained a PCE of 4.83% with Jsc of 15.42 mA cm−2 while the
GO and PEDOT:PSS devices attained PCEs of 3.16% with Jsc of 11.18 mA cm−2
TABLE 15.2
Electrical Parameters of P3HT:PCBM-Based PSCs with GO at
Different Oxidation Levels as the HTL
HTL Material Voc (volts) Jsc (mA cm−2) FF (%) PCE (%)
PEDOT:PSS 0.60 8.22 60 3.2
GO(50 wt.% KMnO4) 0.34 7.93 33 1.1
GO(100 wt.%KMnO4) 0.41 7.69 52 2.0
GO(400 wt.%KMnO4) 0.56 7.71 64 3.0
GO(600 wt.%KMnO4) 0.54 7.67 62 2.7
Adapted with permission from [19]. Copyright (2015) Royal Society of Chemistry.
and 4.00% with Jsc of 13.38 mA cm−2, respectively. Also, the GO/PEDOT:PSS HTL
device exhibited superior environmental stability. The performance gains in these
devices were attributed to the occurrence of molecular-level interaction at the GO–
PEDOT:PSS interface. Such an interaction would yield a linking bridge for charge
transport, enabling the transport of holes from the donor phase of the active layer to
the anode, leading to superior photovoltaic performance. Also, the strong molecular
interaction acted as a barrier to prevent absorption of water molecules and impede
the diffusion of molecules between the active layer and the anode thus, improving
the device’s stability.
Sulfonated reduced graphene oxide (S-rGO) obtained by treating GO with con-
centrated sulfuric acid was used as HTL in inverted P3HT:PCBM solar cells [21].
The S-rGO showed tunability of optical bandgap and electrical conductivity with the
level of sulfonation and reduction of GO. The sample, S-rGO1, which was the most
reduced and least sulfonated, exhibited a C/O ratio of 2.59 and electrical conductiv-
ity of 1.4 S cm−1. The other samples, S-rGO2 and S-rGO3, manifested C/O ratios of
1.10 and 0.73 and electrical conductivities of 1.1 and 0.73 S cm−1, respectively. The
optimized S-rGO HTL device exhibited comparable performance (a PCE of 2.80%)
to the reference PEDOT:PSS HTL device (PCE of 2.75%). This was fabricated with
S-rGO2 as the HTL, while S-rGO1, the most reduced sample, yielded an inferior
performance with a PCE of 1.54%. It should be noted here that the S-rGO1 sample,
which was the most reduced and exhibited the highest electrical conductivity yielded
an inferior photovoltaic performance; this underscores the fact that various factors
besides the material properties infuence the performance level of PSCs.
A nanocomposite of rGO/Pt nanoparticles (Pt NPs) synthesized through in situ
crystallization was employed in the HTL of a P3HT:PC71BM PSC [22]. They used
ethylene glycol (EG), sodium citrate (SC) and ascorbic acid (AA) as the reducing
agents in the crystallization process. With EG as the reducing agent, rGO/Pt NPs
composite with the most reduced GO and Pt ions and the highest content of Pt NPs
uniformly distributed on the rGO nanosheets were produced. Consequently, this
nanocomposite exhibited the highest electrical conductivity and the lowest HOMO
level to match that of P3HT. PSCs with EG rGO/Pt NPs as the HTL exhibited the
best photovoltaic performance with a PCE of 3.6%. This was a slight improvement
compared to PEDOT:PSS HTL device with a PCE of 3.68%. Whereas, Voc and FF
were comparable, the EG rGO/Pt NPs and PEDOT:PSS HTL devices yielded a Jsc
of 11.01 and 10.02 mA cm−2, respectively. The improved performance was attributed
to better energy level alignment at the HTL active layer interface.
Another study investigated the effect of the size of GO nanosheets on the pho-
tovoltaic performance of BDT-thieno[3,4-b]thiophene (PTB7):PC71BM-based PSCs
[23]. GO nanosheets of small size (SGO), medium size (MGO) and large size (LGO)
prepared by varying the sonication time from 3, 6 and 10 minutes, respectively, were
employed in the active layer. The GO nanosheets’ sizes ranged from hundreds of
nanometers to micrometers. MGOs sized at hundreds of nanometers yielded the best
performance with a PCE of 9.21% at FF of 69.4% and a PCE of 8.27% at FF of
70.5% for inverted and conventional device structures, respectively. These devices’
photovoltaic performance was superior to the reference devices without GO, with
an increase of 16% and 23% in the inverted and conventional device structures,
respectively. The LGO manifested poor dispersion capability leading to aggregated

morphology of the active layer flm. The space charge limited current mobility was
highest in the MGO-modifed devices. Consequently, the high charge transport in
these devices reduced non-geminate recombination leading to the high FF values.
A solution-processed rGO (FGr) functionalized by introducing the vinyl group
and Si-O-Si groups through vinyl triethoxysilane on graphene surface was used as
ETL in PTB7:PC71BM and P3HT:PC71BM-based PSCs [24]. The J–V characteristics
of the devices are shown in Figure 15.4. A PCE of 9.47% and 4.05% was achieved
in the PTB7:PC71BM and P3HT:PC71BM FGr ETL devices, respectively. This was
an improvement from 8.94% (PTB7:PC71BM) and 3.52% (P3HT:PC71BM) in the
PFN ETL devices. The FGr ETL devices exhibited remarkable stability, with the
PCE dropping only by 7.4% after 61 days of storage in a nitrogen glove box. The
same group tested rGO ETL devices which yielded a PCE of 8.96% and 3.74% for
PTB7:PC71BM and P3HT:PC71BM, respectively. The better electron extraction capa-
bilities of the FGr ETL were attributed to the formation of a homogenous ETL layer
resulting from the high dispersion of FGr in the organic solvent. Thus, this work
echoes the infuence of morphological characteristics of not only the active layer but
also the interfacial layers on the photovoltaic performance of PSCs.
TiOx/rGO was employed as ETL in inverted P3HT:PC61BM PSCs [25]. The devices
registered a Voc, Jsc, FF and PCE of 0.66 V, 8.07 mA cm−2, 51% and 2.7%, respec-
tively. This was an improved performance in comparison to the TiOx device, which
recorded a Voc, Jsc, FF and PCE of 0.62 V, 8.42 mA cm−2, 48% and 2.5%, respectively.
The improved Voc and PCE indicated that rGO in the ETL promotes electron extrac-
tion from the active layer to the cathode. Also, the devices with TiOx/rGO as ETL
exhibited good stability, with the PCE reducing by only 27% after 90 days of storage
in ambient conditions. Another study reported using rGO-anatase titania nanocom-
posite in the HTL and the active layer of P3HT:PC61BM PSCs [26]. The device with
the nanocomposite in the HTL yielded a Voc, Jsc, FF and PCE of 0.51 V, 6.56 mA cm−2,
28% and 0.93%, respectively, while the nanocomposite-modifed active layer device
realized a Voc, Jsc, FF and PCE of 0.55 V, 13.59 mA cm−2, 43% and 3.22%, respectively.
FIGURE 15.4 Current–voltage characteristics of PSCs with FGr, rGO and PFN as the ETL
materials. Adapted with permission from [24]. Copyright (2018) Elsevier.
The reference devices with PEDOT:PSS as HTL and P3HT:PC61BM as active layer
registered a Voc, Jsc, FF and PCE of 0.51 V, 6.04 mA cm−2, 37% and 1.1%, respectively.
The improved photovoltaic performance of the nanocomposite active layer modifed
devices resulted from improved photon harvesting occasioned by the presence of the
nanocomposite. This yielded an enhanced Jsc and FF.
15.3.2 APPLICATION OF GRAPHENE OXIDE, REDUCED GRAPHENE OXIDE

AND THEIR NANOCOMPOSITE IN DYE-SENSITIZED SOLAR CELLS
The common application of GO, rGO and their nanocomposite in DSSCs include a
transparent electrode, CE material and a photoanode additive. Graphene is a suitable
replacement for the Pt CE material due to its high catalytic activity, specifc surface
area and chemical stability. The catalytic activity is further improved in GO because
of the presence of the oxygen functional groups. Graphene comes in handy as a pho-
toanode additive, as it facilitates electron transfer from the conduction band of TiO2
to the cathode via the formation of charge percolation pathways and favorable energy
level alignment. For effective electron transfer, the TiO2 species should be uniformly
and densely populated on the graphene nanosheets. Zhao et al. [27] reported the
photovoltaic performance of DSSCs fabricated with rGO produced by in situ thermal
reduction of rGO as CE. GO was frst adsorbed on the FTO substrate to form a flm.
rGO flm was then formed by thermal annealing of the GO flm in a nitrogen atmo-
sphere. For comparison, rGO flm was also directly adsorbed on the substrate. The
rGO CE formed by in situ annealing was observed to be more uniform and adhered
strongly to the substrate compared to the directly adsorbed rGO CE. Consequently,
the devices with the in situ annealed rGO CE yielded a better performance with
a Voc, Jsc, FF and PCE of 0.68 V, 12.93 mA cm−2, 73% and 6.35%, while directly
adsorbed rGO CE device recorded a Voc, Jsc, FF and PCE of 0.60 V, 10.34 mA cm−2,
19% and 1.20%. The poor performance of the directly adsorbed rGO CE device
was due to the aggregation of the rGO sheets and the extremely poor contact with
the FTO substrate. On the other hand, the good performance of the in situ rGO CE
device was attributed to a smooth flm, evidenced by a high FF and strong adhesion
to the substrate. The reference Pt CE device yielded a Voc, Jsc, FF and PCE of 0.74 V,
13.83 mA cm−2, 74% and 7.53%, respectively. This study underscores the infuence of
flm preparation techniques on the photovoltaic performance of solar cells.
rGO-coated polyaniline (PANi/rGO) nanocomposite prepared via in situ polym-
erization was used as the CE in DSSCs [28]. Figure 15.5 shows the current–voltage
characteristics of the devices fabricated with the nanocomposite as CE. The nano-
composite CE device yielded a PCE of 3.98%, which was a better performance in
comparison to PANi and rGO CE devices with a PCE of 1.83% and 1.07%, respec-
tively. The better PCE achieved by the nanocomposite CE device resulted from better
Jsc and FF being 12.58 mA cm−2 and 55%, respectively. The Jsc and FF of the PANi
CE device were 11.03 mA cm-2 and 47%, while those of the rGO CE device were
9.41 mA cm−2 and 36%, respectively. The nanocomposite offered a larger surface
area for better catalytic activity, resulting in the high Jsc and FF. The rGO CE per-
formed poorly because of surface defects, which adversely affected the electrical
conductivity and catalytic activity. Nonetheless, the Pt CE device performed better
FIGURE 15.5 Current–voltage characteristics of DSSCs with rGO, PANi, PANi/rGO and
reference Pt CEs. Adapted with permission from [28]. Copyright (2020) Copyright The
Authors, some rights reserved; exclusive licensee [Elsevier]. Distributed under a Creative
Commons Attribution License 4.0 (CC BY) https://creativecommons.org/licenses/by/4.0/.
than the nanocomposite one with a Jsc, FF and PCE of 13.11 mA cm−2, 63% and
4.75%, respectively. This was attributed to the superior electrical conductivity of Pt
CE, yielding the highest Jsc and FF.
Sudhakar et al. [29] utilized PEDOT:PSS/rGO nanocomposite prepared by sim-
ple sonication as the CE in DSSCs. The device’s electrical performance is shown
in Table 15.3. DSSCs with PEDOT:PSS/rGO as CE recorded a comparable perfor-
mance to that of Pt. The good performance was attributed to good catalytic activity
and electrical conductivity of the nanocomposite CE, as well as good adherence of
the nanocomposite to the substrate. Additionally, the nanocomposite improved the
stability of the device, with insignifcant changes being observed upon irradiation of
the device with the light of different intensities.
rGO-TiO2 composite nanofbers with rGO at various concentrations were utilized
as a photoanode additive in DSSCs [30]. Table 15.4 shows the electrical parameters
of the fabricated devices. The enhanced performance at 2 mg rGO-TiO2 loading was
TABLE 15.3
Electrical Parameters of DSSCs with of PEDOT:PSS/rGO
Nanocomposite as the CE
Pt 0.75 17.3 74 9.64
rGO 0.73 12.9 71 6.70
PEDOT:PSS 0.76 11.2 72 6.10
PEDOT:PSS/rGO 0.78 16.1 76 9.57
Adapted with permission from [29]. Copyright (2020) ACS Publications.

TABLE 15.4
Electrical Parameters of DSSCs with Photoanode of rGO-TiO2
Composite Nanofbers
TiO2 0.67 9.73 59 3.83
2 mg rGO-TiO2 0.65 10.82 59 4.10
4 mg rGO-TiO2 0.65 10.92 62 4.43
6 mg rGO-TiO2 0.66 9.64 62 3.93
attributed mainly to effective electron transfer in the devices. The reduced diam-
eter of the nanofbers in this sample resulted in increased surface area. The best
performance of the 4 mg rGO-TiO2 photoanode was attributed to improved electron
transport and dye adsorption. Further increase in the amount of GO in the composite
resulted in a drop in performance. This was attributed to a decreased dye adsorption
with increased diameter TiO2. Also, the GO would compete for solar absorption with
the dye. Overall, the devices with rGO-TiO2 photoanode performed better than the
pristine TiO2 photoanode device.
rGO prepared by microwave exfoliation method was utilized as a photoanode
additive and as a transparent layer deposited prior to TiO2 photoanode in DSSCs with
quasi-solid polymer electrolyte [31]. The devices with rGO as a photoanode additive
performed poorly, recording a lower PCE c. 0.2% than that of the reference device c.
0.22%. The rGO sample was of high crystallinity, which hampered interaction with
TiO2 in the photoanode. This poor interaction impeded electron transfer, which led to
poor results. The device with rGO as a transparent electrode yielded an improvement
in PCE c. 0.58%. The highly crystalline rGO as a working electrode enabled better
electron transfer leading to improved performance. Also, the better performance was
attributed to a large surface area for dye adsorption and consequently an increased
light harvesting. This corroborated with the better Jsc in this device. It is usually
the case that highly crystalline samples are desirable for application in functional
devices like solar cells. This study, however, shows that molecular-level interaction is
not favored by highly crystalline samples.
15.4 CONCLUSION
In summary, this chapter examined the application of GO, rGO and their nanocom-
posite (graphene nanomaterials) in the interfacial and photoactive layers of PSCs,
as well as the CE and photoanode additive of DSSCs. In all cases, the graphene
nanomaterials improved the devices’ performance, albeit via different mechanisms.
As the interfacial layer material, the graphene nanomaterials promote charge car-
rier extraction from the active layer to the respective electrodes. However, high con-
centrations of the graphene nanomaterial in the ETL impair optical transmittance
leading to decreased light absorption in the device. In the active layer, the graphene
nanomaterials improve light harvesting and charge transport. In both cases, the inclu-
sion of the graphene nanomaterials results in improved environmental stability of the
devices. Besides the good catalytic activity of the graphene nanomaterials, their use
as a CE in DSSCs affects a larger surface area for increased catalytic activity. As a
photoanode additive, the graphene nanomaterials improved the electron transport
and affect a large surface area for dye adsorption. Nonetheless, a high concentration
of graphene nanomaterials competes with the dye in light harvesting thus, impairs
device performance. Generally, the graphene nanomaterials create percolation path-
ways for charge transfer thus, improves charge carrier transport in the devices; this,
in turn, reduces charge recombination effects.
Material properties and preparation process/technique are determinants to the
performance of OSCs. Both GO and rGO are hydrophilic, which makes them com-
patible with solution-based device processing. Even though the oxygen functional
groups in GO effects insulating behavior, charge transport occurs via the hopping
mechanism. Thus, GO facilitates effective charge transport in OSCs. The oxidation
level of GO infuences the performance of the device. A higher oxidation level is
desirable for the formation of smooth flms and better interfacial energy alignment
because of increased dispersibility and work function, respectively. The dispers-
ibility of GO and rGO-based nanomaterials is affected by the sample sizes. Small-
sized samples exhibit higher dispersibility and hence, form better flm morphology.
The patterning of the devices and the thin flm preparation technique also infuence
the photovoltaic performance. For example, a HTL of GO layer applied prior to
PEDOT:PSS performs better than either GO or PEDOT:PSS HTLs because of bet-
ter molecular-level interaction, improving charge transport. Similarly, a thin flm
of rGO formed by in situ thermal annealing on the substrates performs better than
rGO that’s directly adsorbed on the substrate because of better flm morphology.
The level of reduction of rGO infuences the devices’ performance. The reduc-
tion level is dependent not only on the control of the reduction process but also on
the reducing agent used. rGO sample with a low C/O ratio exhibits better electri-
cal conductivity, which translates to better photovoltaic performance. However, at
a high level of reduction of the oxygen moieties, the sample becomes hydropho-
bic, which leads to the formation of agglomerates on the flms. In all cases, the
optimum concentration of the graphene nanomaterials is key to high-performance
devices. High concentration leads to the formation of thicker flms, which yield
poor performance.
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16 Revolutionizing the
Field of Solar Cells by
Utilization of Nanoscale
Metal Oxide/Hydroxide
Based 2D Materials
Shaan Bibi Jaffri and Khuram Shahzad Ahmad
Fatima Jinnah Women University
CONTENTS
16.1 Introduction .................................................................................................. 279
16.2 Advancements in the Doped Electron Transport Layers (ETLs) ................. 282
16.2.1 Doped TiO2 ETL............................................................................... 282
16.2.2 Doped SrSnO3 ETL .......................................................................... 285
16.2.3 Doped ZnO ETL............................................................................... 285
16.3 Conclusions and Prospects ........................................................................... 287
References.............................................................................................................. 288
16.1 INTRODUCTION
For the sustainable future of humanity, the quest for pursuit of inexhaustible energy
needs to be addressed fully in addition to the resolution of other environmental issues,
i.e., climatic change, negative impacts associated with the mining of fossil fuels,
impoverishment of resources, global scale energy scarcity. Consumption of energy at
the global scale is anticipated to augment in a twice manner by 2050, in comparison
to the global energy consumption rate of 13.5 terawatt (TW) in 2001, due to swiftly
cumulative ecospheric populace and monetary expansions. Amplifed energy demand
at global scale points the need for the exploration of substitution of the fossil fuels with
carbon-free and inexhaustible energy sources. Solar energy accounts for the most plen-
teous renewable resource among all energy resources. Generation of the solar energy
can be done by conversion of solar aurora into thermal or electrical energy by employ-
ment of different photovoltaic (PV) contraptions. There is a global scale installation
of a huge number of gigawatts of the renewable energy technologies in form of wind
turbines, hydropower production tech savvy, and solar PV segments in addition to the
DOI: 10.1201/9781003178453-16 279

geothermal and tidal energy [1]. Remarkable features associated with the renewable
energy technologies signifes the domination of future by the one-thirds of the energy
generation from PV technologies based on the solar energy [2]. Nevertheless, the limi-
tation of different kinds of renewable energy sources by means of the geographical and
ecological factors makes them diffcult for energy harvesting on a global scale. Hence,
the suitability of the solar energy due to its green nature is expressed by lesser limita-
tion of solar energy by the terrain and environmental factors [3].
Exploitation of solar energy is preferable over other renewable energy resources
since it is clean, unobtrusive, infnite, sustained, and unswerving. Such advantageous
features marks the successful candidacy of the solar energy for fulflling the ever
growing electrical energy demand at global scale due to the population boom and
enlargement of infrastructure. The attractiveness associated with the solar energy
for fulflling the global energy demands is due to its sustainability and affordability.
Therefore, solar PV technologies are the most dominant technologies and growing at
an annual rate of 60% as per estimations done between the years 2000 and 2016. In
the present era, despite heavy pressure on the fossil fuels, the production of total elec-
tricity is insuffcient to satisfy the global energy requirements. In the current age, the
derivation of energy from fossil fuels is known for its fniteness and thus, becoming
defcient. Even the utilization of the presently available energy sources obtained from
fossil fuels is giving rise to a wide range of environmentally deteriorative phenom-
enon, e.g., global warming. Such events are increasing with the passage of time [4].
Therefore, human intellect and logic must be used for achieving the goals of sustain-
able development in presence of such challenges. In this regard, solar energy, among
all other renewable energy resources has a very good future prospect in derivation of
the electrical energy in a sustainable mode [5].
Abundantly available solar energy can be scaled up for meeting world energy
demands [6] since earth receives 173,000 terawatts of solar energy on continuous
basis. By utilization of only 0.02% of this solar energy, solar cells carry out the
direct conversion of the solar to electrical energy. The research in this regard is ever
increasing and emerging with passage of the time and through rigorous efforts, an
enhancement in the effciency has been achieved [7–10]. Considering the augmenting
effciency of the perovskite solar cellc (PSCs), at present the silicon crystal cells and
PSCs are comparable [11].
PSCs have been named so because they have a crystal structure specialized in
light absorption, mimicking the structure of the mineral CaTiO3. Presently, num-
ber of synthesized compounds with ABX3 stoichiometric characteristics have been
investigated for their light absorptive behavior, where A and B expressed the cat-
ionic species and X represents the anionic species [12]. The crystalline structural
form of the ABX3 perovskite usually consists of an angle sharing [BX6] octahedra
with the cationic A type species and occupies 12-fold synchronization location,
which is being formed at the central position of cube of eight in such octahedra.
Such crystalline geometry is ideal one and is a rare one because the naturally
existing mineral perovskite form is also known for slight distortion. Oxides-based
perovskites are the most studied ones. Perovskite group of compounds is quite
famous for their fexibility in the accommodation of a great number rather all ele-
ments existing in the periodic system.
Revolutionizing the Field of Solar Cells 281
Zhou and co-workers [13] have for the frst time developed such colossal super-
alkali perovskite, e.g., Li3O, Li2F, and H5O2. The developed super-alkali perovskites
were studied via density functional theory (DFT) and molecular dynamics simulation.
DFT and simulation results were indicative of the unstable dynamics functionality of
the super-alkali perovskites inclusive of metallic atoms at ambient temperature and
pressure. Conversely, considerably stabilized dynamics functionality was obtained
for cubic H5O2MBr3 (M = Ge, Sn, Pb) and H5O2PbI3 having super-alkali perovskites-
based composition. In addition to favorable dynamics, the modifed super-alkali
perovskites also exhibited remarkable tolerance factors, generation energies that
were negative, bandgaps that can be easily tailored, smaller effcacious hole sizes
and electronic masses. Considering the bandgap issue of CH3NH3PbI3 perovskite
material, i.e., 1.55 eV and it exceeds the most favorable range of 1.1–1.4 eV in terms
of the single junction PSCs, another DFT-based study has been conducted by Zhou
and co-workers [14]. Organized DFT-based investigation included the cubic (Li3O)
M(BH4)3−xBrx (M ¼ Ge, Sn and Pb; x ¼ 0–3) perovskites for bandgap suitability and
electronic structures tailoring employing frst principle calculations. An auspicious
PCE of 23.12% was indicated by DFT studies for cubic (Li3O)Ge(BH4)Br2 and (Li3O)
Pb(BH4)2Br perovskites with other favorable features [14] as obtained in case of cubic
H5O2MBr3 (M = Ge, Sn, Pb) and H5O2PbI3 super-alkali perovskites [13]. The func-
tionality of perovskites for obtaining high-quality PSCs has also been altered in an
effcient way through utilization of different additives, e.g., 2-aminoethanesulfon-
amide hydrochloride. Upon doping-based modifcation, the perovskite thin flms
expressed an overall performance improvement, which can be attributed to the better
morphological and crystalline characteristics in addition to trap states considerably
reduced in addition to reduced hysterical response [15].
For any PSC device to work in an effcient manner, there should be a perfect syn-
chronicity between the band alignment of the constituents including hole transport
layer (HTL), electron transport layer (ETL), and active absorber perovskite layer. The
role of HTL in an effcacious extraction of holes and transferal cannot be overlooked.
The most frequently used HTL is poly (3,4-ethylenedioxythiphene):poly(styrenesulf
onate) (PEDOT:PSS) [16,17]. Among various strategies adopted for improvement of
the PSCs, utilization of diverse ETLs has been highly emphasized. For instance, in a
recent work by Yang et al. [18], a novel inorganic CsPbIBr2-based PSC was fabricated
employing In2S3 ETL, which was processed at a low temperature of 70°C. The modi-
fed device exceeded in gaining a PCE of 5.59% with a profound reduction in the hys-
teresis extent. This work signifed the metallic sulfdes of transition group to be future
candidates for ETLs in PSCs. In addition to experimentation with different materials
for use as ETLs in PSCs, ETLs have been modifed by means of doping with effec-
tive materials to enhance their functionality and thus positively impact the overall
effciency of the PV device. PSCs have been especially emphasized considering the
future candidacy of PSCs in competing with the silicon solar cells. Furthermore, this
chapter also provides a detailed account of the compositional aspects of the presently
employed ETLs. Thorough comprehension of the advancements done in the doping
of the ETLs provides a layout for the better selection of doping materials for ETLs
for obtaining PSCs with commendable effciencies and stability so that they can be
commercialized and used for beneft derivation in the real life [19–22].
16.2 ADVANCEMENTS IN THE DOPED ELECTRON

TRANSPORT LAYERS (ETLs)
Commercial-scale functionality of the PSCs depends upon all the components either
in mesoscopic or planar confguration. In this regard, PV performance is predomi-
nantly controlled by the electronic transferal characteristics of the perovskite active
absorber layer. PSCs are based on CH3NH3PbI3 function in a better manner if devel-
oped in the mesoscopic fashion, while PSCs having CH3NH3PbI3−xCl x express bet-
ter functionality in the planar mode in terms of the various modes of the electronic
diffusion in both cases [23–27]. However, the presence of ETL is mandatory in both
types of confgurations. Most frequently used ETLs must be specialized in over-
coming different issues, e.g., oxygen vacant sites assuming the role of trap sites. For
addressing the issues associated with the functionality of different ETLs, doping
strategy has been adopted. Most recent advances done in doping of different ETLs
has been comprehensively elucidated in the following section:
16.2.1 DOPED TIO2 ETL

Jeon et al. succeeded in achieving good quality PSC comprising of the mixed halide
and cationic formulation of (FAPbI3)0.85(MAPbBr3)0.15 composition with a certifed
PCE of 17.9% [27]. Such PSC device consisted of the record solar cell confguration
with mesoporous TiO2 ETL, permeated by perovskite precursor solution in the liquid
form leading to the formation of the perovskite flm in solidifed form following the
annealing step. Most of the optoelectronic applications, e.g., electrodes having higher
surface area make use of mesoporous TiO2 [28]. Particularly, it has been used in the
dye-sensitized solar cells (DSSCs) for collection and transportation of the electrons
that are photo-injected from sensitizer with surface-adsorbed features. Substitutional
dopants utilization has been done for the improvement of such cells making use of
the mesoporous TiO2 ETL. For achieving an alleviation in the conduction band edge
of the mesoporous TiO2 ETL, lithium intercalation has been profoundly done for the
facilitation of the electronic injection and transportation inside TiO2 ETL [29].
Lithium salts have been utilized for the n-doping of the mesoporous TiO2 ETL
by means of the easier treatment of the device flms. Modifcation of mesoporous
TiO2 ETL by Li+ doping exhibited auspicious electrical characteristics, by causing
assuagement of the trap states and thus subsequently ensuring the rapid electronic
transferal. Scrupulous comparison of the Li+ doped ETL devices and undoped
devices exhibited remarkably conspicuous performances for the modifed TiO2 ETL
PSC comprising of the CH3NH3PbI3 light harvester in addition to the improvement
in the PCE from 17% to over 19% with insignifcant hysterical performance < 0.3%.
Results in this regard expressed a signifcant difference of the backward and the
forward scans in case of the pristine device in comparison to the device having
Li+-doped TiO2 ETL. Doping mechanism and chemistry present a commendable
approach for the modifcation of the electronic band morphologies and surfcial
states of the substances. In comparison to the DSSCs based on the liquid electro-
lyte, the effect of ETL doping in PSC has not been as much explored till 2010,
except fewer reports expressing the signifcant role of the doping with aliovalent
substitutions using Y3+, Nb5+, or Ta5+ doping into TiO2 ETL elucidating the effec-
tiveness of these dopants in enhancing TiO2 ETL electrical properties. Among these
aliovalent substitutions, Nb5+ has been considered as one of the suitable n-type dop-
ant for the enhancement in the charge assortment characteristics. In case of DSSCs,
different PV researchers investigated their infuence for generation of Nb:TiO2
(NTO) compact layer and mesoporous layer comprising of the NTO nanoparticles
(NPs). Nevertheless, previous investigations based on NTO NPs have not isolated
the pristine effect of Nb doping on PV characteristics since NTO NPs expressed
various sizes or diverse phases at different levels of Nb5+.
Results for Nb:TiO2 ETL expressed the lighter Nb doping, i.e., 0.5% and 1.0%
enhancing the optical bandgap. Doping in greater amounts, i.e., 5.0% lead to the sub-
sequent reduction in the optical bandgaps. There was a profound similarity between
the fermi levels of the conduction band in case of both light Nb doping and undoped
TiO2. However, fermi level was assuaged to ~0.3 eV for heavier doping of the Nb
into TiO2. Furthermore appreciable PCEs were obtained for lightly doped TiO2 with
Nb with 10% PCE > undoped TiO2 (12.2%–13.4%), and 52% > heavily doped TiO2
(8.8%–13.4%). Such commendable PCEs of the modifed PSC are attributable to
the faster electronic injection/transferral and well-kept-up electronic lifespan [30].
Doping enhances the conductivity of the host ETL by not only transforming the
electronic mobility pattern but also the amount of electronic concentration being
supplied to TiO2 photo-anode is increased. Furthermore, the locations of conduction
bands are altered leading to the passivation of the surfcial defects and impacting
host morphologies. Apart from PSCs, Nb-doped TiO2 fnds employment in different
applications. In case of Nb doping, often the simplifed doping effects can be seen in
case of the utilization of the TiO2 flms as scaffolds.
In a recent investigation by Liu et al. [31], facile route using solution processing at low
temperature was adopted for doping Zn into TiO2 crystal lattice. Zn doping into TiO2
ETL expressed an alleviated trap states density and improved conductivity in compari-
son to the pristine flms without any doping. Results were also indicative of the uplifting
of the TiO2’s fermi level causing an improvement in the carrier detachment and convey-
ance. PSC device modifed with Zn-doped TiO2 ETL and having a perovskite composi-
tion of the CH3NH3PbI3 attained PCE of 17.6%, which is almost 27.5% higher than the
archetypal device without Zn doping, i.e., 13.8%. Ag doping into TiO2 ETL is associ-
ated with the reduction in the bandgap in a correlative manner as the concentration of
Ag is increased there will be further alleviation in the bandgap. Furthermore, it is also
associated with the enlargement of the Jsc due to an enhanced electrical conductivity.
Nevertheless, there is also an issue of the suffering of planar structured PSC from severe
J–V hysterical behavior and thus, results in the misjudgment of the PV functionality.
In another recent investigation, Ag doping was done in TiO2 making up meso-Ag:TiO2
ETL, results expressed that an enhanced PCE of 17.7% was achieved by optimization of
the different parameters of the modifed PSC in addition to the alignment of the energy
bands between active absorber perovskite layer and meso-Ag:TiO2 ETL.
TiO2 ETL morphology, surfcial trap sites, and lattice structure have often been
modifed via doping. Doping impacts the electrical characteristics of the host mate-
rial. Recently, Al and Mg doping was done in TiO2 with CH3NH3PbI3 as an active
perovskite absorber layer in mesoscopic confguration. Al- and Mg-doped TiO2
ETL containing PSC exhibited 22% higher in comparison to the control device
without Al- and Mg-modifed device. Results were indicative of the superior nature
of Al doping in enhancing the Voc, Jsc, and FF in an effective manner, while Mg dop-
ing only enhanced the Voc to some extent. The augmented generation of electron–
hole pair is due to an alleviation of the bandgap of doped TiO2. This phenomenon
leads to the injection of even more electrons from the active absorber perovskite
into the ETL. Mg has been used for modifcation of the physical and optoelec-
tronic characteristics of TiO2. Mg doping in TiO2 ETL is associated with facilita-
tion of the charge transportation and suppression of the charge carrier concurrence
between the TiO2 ETL and active perovskite absorber layer. Mg-doped TiO2 ETL
modifed PSC device obtained a PCE 15.73%, which is commendable in terms of
the effciency obtained for carbon-based planar PSCs. The augmentation in PCE is
due to rapid extraction of the charges, enhanced electrical conductivity, and kerbed
charge concurrence of the Mg-doped TiO2 ETL. Furthermore, the procedural steps
were conducted maintaining temperature of 100°C, paving a way for the develop-
ment of the cost-effective and remarkably stable PSCs possessing compatibility
with supple substrates. Elemental doping is associated with the dual functional-
ity of enhancing the conductivity, carrier transferral, and also tailors the energy
band morphology subsequently giving rise to the improved quality of the ETL
quality. Recently, Ni was used as a dopant for development of the Ni-doped rutile
TiO2 ETL having higher crystallinity index and HTL was composed of the copper
phthalocyanine (CuPc) in a heterojunction PSC device having carbon composition
in planar confguration. There is an upward shifting of the fermi level of ETL due
to Ni doping and augmentation in the charge transferral of the ETL, subsequently
enhancing the charge conveyance and extraction. PSC modifed with Ni-doped
rutile TiO2 ETL achieved a PCE of 17.46% with 0.01 M Ni doping, which is so
far highest effciency reported for carbon-based PSCs. In addition to an enhanced
PCE, Ni-doped rutile TiO2 ETL containing PSC with CuPc HTL exhibited an out-
standing stability with negligible deterioration in the PCE even after storage in
ambient air for 1,200 hours.
Specifcally, doping can perform specialized functions of carrier concentra-
tion increment, e.g., Nb5+, or mobility improvement, e.g., Sn4+ or the reduction in
the surfcial defect trap states can also be achieved, e.g., Al3+ or Zr4+. Otherwise,
there is also a great room for the TiO2 surfcial modifcation by means of using
functional molecules or ionic species in form of a monolayer for trap states reduc-
tion. Sn doping for TiO2 ETL has been reported but it is marked by requirement of
higher temperature for processing at 450°C, which is in turn associated with the
prevention of the doped TiO2 ETL employment in PSCs that are manufactured at
a lower temperature. Hence development of an effcacious method for doping TiO2
ETL below 100°C is required for commercialization of the PSCs at industrial scale.
Recently, PSC was developed by the successful deposition of the Sn-doped TiO2
flms at lower temperature as an ETL. In comparison to the archetypal TiO2 ETL,
Sn-doped TiO2 ETL exhibited higher effciency for the transferal and extraction of
the photo-generated electron, elucidating an alleviated trap-state density and aug-
mented conductivity. Sn-doped TiO2 ETL containing PSC yielded a PCE of 17.2%
exceeding the pristine device up to 29.3%.
16.2.2 DOPED SRSNO3 ETL

Perovskite device functionality has been considerably improved by means of a
myriad of approaches, e.g., meticulous choice of ETL and HTL, crystalline growth
control of the perovskite flm, interfacial engineering, and device confgurational
device. Nevertheless, the dependence of the higher functionality PSC is dependent
upon the mesoscopic TiO2 ETL [32], which needs an augmented sintering tempera-
ture >450°C, presenting a conspicuous drawback for the commercialization of the
economically viable PSCs. Hence, PV community has been putting efforts on the
elimination of the ETLs processed at higher temperature inside PSCs, for inducing a
greater level of simplicity in the planar PSC. Generally, PSCs with the planar hetero-
junction confguration are developed with two types of structure, i.e., inverted (p-i-n)
assemblage or conventional (n-i-p) assemblage, on the basis of the charge restric-
tive contact. Thus, for the purpose of charge carrier transportation and extraction,
the development of planar PSC with higher effciency with ETLs and HTLs hav-
ing low-temperature processing is highly desirable. Recently, TiO2 ETL has been
replaced successfully with SrSnO3 ETL, having good conductivity and low-tempera-
ture processing. SrSnO3 possessing ABO3 perovskite structure having orthorhombic
geometry is employed in a myriad of applications, e.g., transparent conducting oxide
(TCO) [33], batteries having Li+ ion, or DSSCs. In spite of the favorable features of
the SrSnO3 in terms of wider bandgap, higher conductivity, and remarkable charge
carrier maneuverability, PSC devices are yet far away from commercialization at the
industrial scale. Furthermore, there is also a need for the effcient way of the synthe-
sis inclusive of the traditional solid-state procedures since the conventional synthetic
modes require higher temperature and very extensive reaction timings.
In a recent investigation by Guo et al. [34], SrSnO3 perovskite nanoparticles were
fabricated by a low-temperature process in colloidal form and are used as an ETL.
Furthermore, the modifcation of PSC containing SrSnO3 ETL was carried by dop-
ing with yttrium, which possessed remarkable electronic conductivity, rapid electronic
transferal, perfect band alignment between ETL and active absorber layer in compari-
son to the controlled device having undoped SrSnO3 ETL in seamless conformity with
the theoretical calculations. As a result, such factors boosted the PV functionality of the
overall champion device exhibiting an average effciency of 17.8% and PCE of 19% with
negligible alleviation in the J–V hysterical features and an extensive period stability.
16.2.3 DOPED ZNO ETL

PSCs have also been developed with composite ETLs comprising ZnO or TiO2 and
polymeric substances by means of formation of mixture prior to deposition. However,
some investigations report the utilization of composite ETLs as a replacement for
bilayer ETLs in polymeric ETLs. For instance, polymeric solar cells comprise of the
amalgamated ETL based up on polyethylene oxide (PEO), poly(ethylene glycol), and
polyethylenimine (PEI), with ZnO flms. Such ETLs are known for causing an alle-
viation in the bulk traps inside semiconducting oxide flm, which is in return associ-
ated with the reduction in the probability of trap-propped interfacial concurrence of
charges, improving overall device functionality [35]. Nevertheless, such composite
ETLs having polymer constituent have not been utilized in PSCs. Utilization of ZnO
as an ETL is marked by processing at low temperature and higher electronic mobil-
ity. Furthermore, a considerable reduction in the trap states density has been achieved
by Rehman et al. [36], aimed at obtaining stabilized PCE so that the scaling up of
such doped ETLs containing PSCs can be made possible [36]. Further researches in
this regard are also supportive of the B:ZnO to be an effcient photo-anode for pos-
sessing improved electronic transferal properties leading to higher effciencies by the
dint of comparatively larger surfcial area and good potential for light harvesting in
comparison to single layers comprising of only ZnO.
Indium (In) has been considered as a suitable dopant for ZnO ETL due to reduced
reactivity and remarkably resistive in terms of oxidative environment in comparison
to Al or Ga. Furthermore, In doping is also known for causing an augmentation in
the carrier amount of the ZnO and thus resulting in a superior level conductivity.
In-doped ZnO having nano-fbrous morphology has also been utilized as ETL mate-
rial developed by means of electrospinning route in PSCs. In-doped ZnO modifed
device achieved PCE of 17.18% with non-existent hysterical behavior due to an out-
standing porosity and crystallinity.
ZnO is used as an alternative ETL to TiO2 in PSCs. In this case, ZnO has been
used as an archetypal material in addition to its modifed forms obtained by extrinsic
doping with different elements, e.g., Al, In, Li, Ga, Mg, W, or Cu. Among differ-
ent elements, gallium (Ga) has been preferred over other dopants due to its three
valence electrons, furthermore, there is a close proximity between the ionic radius
of Ga3+(0.062 nm) and Zn2+ (0.074 nm), and also the estimated covalent bond lengths
are 1.92 Å and 1.97 Å for Ga-O and Zn-O, respectively. Such characteristics are sug-
gestive of the minimal distortion of the ZnO wurtzite structure even after incorpora-
tion of the highest concentration of Ga3+ in ZnO in comparison to In-doped ZnO or
Al-doped ZnO. ETL materials utilized in PSC devices, the potential of electronic
extraction is usually determined by conductivity and surface work function (WF). If
there is a perfect matching between the WF of the used ETL and electronic affnity
of the perovskite absorber layer, then there is a considerable reduction in the Schottky
barrier and formation of the Ohmic contact for facilitation of the electronic extraction
and assemblage. There is a profound adjustability associated with the surface WF of
ZnO, which is estimated by the polarization extent, morphological features, doping
concentration, and surfcial defects. The majority of the ETLs processing relying
upon elevated temperatures processability makes them commercially unattractive.
Recently, excimer laser annealing (ELA) was employed for treating Ga-doped ZnO
ETL at ambient temperature. ELA treatment gave rise to the enhanced optically
transparent features and electrical conductivity, subsequently improving the light
absorptive aspects, electronic injection, and depression of the charge concurrence.
In a recent investigation by Chen et al. [37], PSC containing Ga-doped ZnO ETL
succeeded in obtaining a PCE of 21.132% with good surfcial WF of 3.9 eV, reducing
the interlayer connexion barrier and optimization of energy levels alignment [37].
Utilization of the doped ZnO is associated with the shifting of the Fermi level
toward conduction band, which signifes a greater favorability in conductivity
enhancement and WF reduction. Al doping increasing charge mobility and band
energy matching can be attributed to the reaction occurring between ZnO having
basic nature and protonic specie present on CH3NH3+. Using pristine ZnO as an
ETL in PSC expressed lower cell effciencies but ZnO nanorods doped with alumi-
num (Al) expressed profound alleviation in the charge recombination at the inter-
face between active absorber perovskite layer and Al:ZnO ETL. Similar enhanced
PCE of 8.5%–10.7% was reported by Dong et al. [38] for PSC having nanorod (NR)/
Al:ZnO/CH3NH3PbI3/SpiroOMeTAD/Au/ZnO architecture indicative of the role
of Al doping in reducing the charge recombination. Such an auspiciousness of Al
can be ascribed to its remarkable ionic radii and optical transmission functionality,
which enhanced charge carriers and electronic movement in a quantitative manner,
subsequently increasing conductivity of the device. Al doping in ZnO has also been
tested for inverted PSCs over ambient conditions for preparation of a novel Al:ZnO
ETL via radio-frequency magnetron sputtering. The deposition of this layer was done
between organic PTB7 and PC71BM mixture active layer and the TCO based on
indium tin oxide (ITO) electrode. Through this approach, Lee et al. [39] succeeded
in obtaining higher PCEs of 7.87% in comparison to the pristine PSCs yielding up to
4.19% only [39]. Another interesting feature associated with Al: ZnO-based PSCs is
the observation of the stability potential of such devices showing 75% of their origi-
nal functionality being conserved even after an aging of 1,000 hours.
Although, utilization of solution processed ZnO ETLs signifes easier and eco-
nomically facile mode. Nevertheless, the fact that ZnO possesses comparatively open
structure with closely packed lattice hexagonal crystallites. In such geometry, native
Zn atoms express occupancy of only half of the tetrahedral locations, while the tetra-
hedral sites remain vacant. These vacant locations behave as defect states, which can
be lying very deep as 0.2 eV within ZnO bandgap Therefore, PSCs having pristine
ZnO as ETL is often observed to cause the jumping of the photo-generated electronic
species from the conduction band of the perovskite material to such trap sites, even
before fnal extraction by the electrode material. Such jumping mechanism leads to
the trap-facilitated charge carriers recombination at the interfacial region express-
ing a serious drawback for ZnO ETL. Thus, such mechanistic issues are overcome
by using doping mechanism. Lithium (Li)-doped ZnO used in PSCs having triple
cationic composition, i.e., MA0.57FA0.38Rb0.05PbI3. An interstitial doping-based phe-
nomenon using Li:ZnO as an ETL having Li intercalated in the ZnO lattice caused
the passivation of inherent ZnO defects by downshifting the fermi levels [40]. In
addition to different dopants, iodine (I) has also been employed in PSCs fabricated
via spin coating using ZnO:I nanopillar in planar architecture. By means of I dop-
ing, the crystalline growth of one-dimensional (1D) ZnO was detected along [0001]
plane signifying hexagonal crystalline pattern being suppressed. Such a modifed
PSC succeeded in attaining 18.24% PCE for ZnO:I nanopillars having CH3NH3PbI3
as active absorber layer [41]. Effciency in increment in the PSCs was also obtained
for nitrogen-doped ZnO and Erbium-doped ZnO ETLs.
16.3 CONCLUSIONS AND PROSPECTS

Sustainable development goal 7, i.e., clean and affordable energy can be realized via
adoption of green chemistry for development of energy devices, which are not only eff-
cient but also benefts a larger population consolidating the concept of environmental
sustainability. With a modifying human life style being demanding of greater utilization
of power, the fnite fossilized resources are being exploited in an unregulated manner.
This type of consumptive pattern is not only weakening the concept of sustainability
where we are depriving our generations from benefts we enjoyed from nature, but we
are also damaging our current resources. Switching to sustainable materials via engi-
neering can prove to be a savior. Perovskite solar cells are deemed as next-generation
PV technology by the dint of their solution processability, lower costs, and remarkable
photo-responses. Today, a large number of investigations reporting different features,
designing, functionality, stability, etc. of perovskites are being published and an effort
is being done to resolve the obstacles faced by the PV researchers when it comes to
the industrial modulation of these cells. Top ranking PV commercial companies have
even tried to turn this dream into reality, e.g., Saule Technologies, Solaronix, Toshiba,
Oxford PV, and Slliance. However, the lab-based work requires further upgradation for
such commercial companies to make effcient contraptions and make them available to
general public at affordable costs. The future researchers working on the performance
enhancement of the perovskite solar cells in terms of doping must investigate the neo-
teric modes for the optimized development of the modifed perovskite solar cell devices
so that the dream of making perovskite solar cells as a replacement to costly silicon-
based PV devices can be realized on a practical scale. The revolutionary characteristics
of the perovskite solar cells-based devices are associated with the transfguration of
human lives on a global scale for production of cheap energy.
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17 2D Materials for
Flexible Photo Detector
Applications
Aruna Pattipati and Joseph Chennemkeril Mathew
Dayananda Sagar College of Engineering
CONTENTS
17.1 Introduction .................................................................................................. 291
17.2 Photodetectors .............................................................................................. 292
17.3 Materials Used in Photodetectors................................................................. 292
17.4 Photodetectors for Different Wavelengths.................................................... 296
17.5 Conclusion .................................................................................................... 297
References.............................................................................................................. 298
17.1 INTRODUCTION
Over the past few years, two-dimensional (2D) photodetectors have gained a lot of
importance and are widely studied due to their features such as fast response, high
responsivity and spectrum specifcity [1]. Photodetectors (PDs) based on 2D materi-
als have greater prospects due to their fexible tuning, lack of dangling bonds, high
mobility and so on. These PDs can detect a wide range of wavelengths from visible
light to terahertz band. 2D materials have excellent optoelectronic properties due
to their ultrafast charge transport and tunable photon absorption. These materials
include semimetal Graphene, semiconductor black phosphorus (BP) and transition
metal dichalcogenides (TMDCs) and so on.
Organic materials have advantages like low fabrication cost, high fexibility and
large area scalability. 2D materials have features like high carrier mobility and tun-
able optical absorption. These 2D materials-based PDs have unique advantages like
fast and high responsivity and spectrum specifcity [2,3]. To tune the photoelectric
properties of 2D materials, organic materials can be attached to the surface either by
solution or epitaxial growth.
In 2D materials, atoms are connected by covalent bonds and the layers are con-
nected by Van der Waals bonds. Quantum confnement effect in the out-of-plane
direction in 2D materials makes them exhibit excellent electronic and optoelectronic
properties. High mobility and in-plane thermal conductivity of Graphene [4], strong
interaction of TMDCs with light [5], anisotropy and direct bandgap of BP make
them suitable candidates for wide band detectors [6]. 2D materials have applications
DOI: 10.1201/9781003178453-17 291

FIGURE 17.1 Characteristics of two-dimensional materials.
in emerging felds of optoelectronics such as sensing, motion detectors, digital imag-

ing, spintronics, low power electronics, photonics, plasmonics and super capacitors.
Characteristics of 2D materials are shown in Figure 17.1.
17.2 PHOTODETECTORS
PDs are devices, which can detect light and have a variety of applications such as
optical communication, environmental monitoring, military and biomedical applica-
tions. Utilizing the property of absorption tunability and high carrier mobility of 2D
materials and combining those with organic materials to form thin-flm heterojunc-
tions with high and fast responsivity with a wide spectra region PDs. Organic PDs
have usage in biomedical science, education, environmental monitoring, optical com-
munication, computer vision and sensory imaging [7]. Although silicon and other
traditional materials-based PDs are being used, they have limitations in operational
wavelengths as well as responsivity and speed. Ease of preparation and integration of
2D materials with other materials along with their high mobility and strong interac-
tion with light makes them achieve high sensitivity and responsivity. Hence a lot of
research on these types of materials is going on in this line.
Contrary to conventional optoelectronic devices, fexible optoelectronic devices
are fabricated on fexible substrates, which revolutionized their applications. Flexible
optoelectronic devices are compact and mechanically fexible as they can be bent,
twisted or even rolled, which makes them fnd various applications in bioelectronics
for wearable and implantable devices, which is not possible with conventional devices.
17.3 MATERIALS USED IN PHOTODETECTORS

In this chapter few 2D materials useful for PDs in the various wavelength regions are
discussed. Graphene has extraordinary optical, electrical, magnetic and mechanical
properties due to which it is a widely studied 2D material. It is an allotrope of carbon,
which was discovered in 2004. It consists of a fat monolayer of sp2 bonded carbon
atoms. Graphene is a 2D sp2 bonded carbon sheet with a high theoretical surface
area of around 2,630 m2g−1 arranged in a hexagonal honeycomb lattice [8]. It has
Flexible Photo Detector Applications 293
a high electrical conductivity with a carrier mobility of 15,000 cm2 V−1 s−1 at room
temperature. 2D lattice in Graphene suppresses the back scattering of charge carriers
and hence the effective mass of Graphene is almost zero. Graphene has zero bandgap
and hence it will be in ON state which makes it useful in analog devices like sen-
sors rather than digital devices. It has a wide absorption band, short carrier lifetime
and high carrier mobility as mentioned earlier. Graphene has an excellent mechani-
cal fexibility, strong atomic bonding and outstanding young modulus and hence a
promising candidate for fexible electronics. It also has good optical properties and
it is being studied to be used as a conductor for transparent and fexible devices as it
has a transmittance of around 97%, which can also replace Indium Tin Oxide (ITO).
Lack of bandgap didn’t pose any limitation for Graphene to be used in applications
like heat spreaders, transparent conductive flms, acoustic speakers and mechanical
actuators. It offers the fastest charge transport, stiffness and thermal conductivity [9].
Graphene PDs are used in ultra-wideband range (300nm ∼ 6μm) although these devices
have problems like low responsivity, low external quantum effciency and absence of
spectral selectivity due to weak light absorption and quick recombination of carriers.
Graphene is used in devices like wearable sensing devices and for the detection of
oral bacteria-based sensors are examples for fexible biocompatibility and compact-
ness [10]. Graphene is also used in devices like tattoo sensors, electrocardiograms
(ECGs), electromyograms (EMGs) and electroencephalograms. Functionalization of
Graphene with biomolecules enables targeted detection of specifc cancer cells [11].
Graphene changes its electrical characteristics due to environmental stimuli and this
characteristic is utilized in the development of Graphene-based fexible sensor sys-
tems. As Graphene is highly stable, this is used as electrodes/channels in sensors
and energy storage devices such as super capacitors and batteries [12]. Graphene
can be produced on a large area by a simple chemical vapor deposition technique.
Unique advantages of Graphene make it useful in PD applications especially in the
far-infrared and terahertz regions.
TMDCs are extensively studied for use in fexible devices after Graphene.
TMDCs can be fabricated as a monolayer and this family can exhibit various electri-
cal properties like metallic, half metallic and semiconducting making them useful
in various types of devices. Semiconducting TMDCs have bandgaps of 1–2 eV and
among TMDCs, Tungsten disulfde (WS2) has a high optical absorption coeffcient
and a large exciton binding energies of 700–800 meV making it a better alternative
to Graphene. These materials can be easily coated on fexible substrates for wear-
able devices. Utilizing semiconducting properties of TMDCs, Lim et al. fabricated
a TMDC-based MoS2 PD [13], which maintained their characteristics even with
105 bending cycles. Gas sensors were also reported with MoS2 channel and reduced
Graphene oxide electrodes [14]. TMDCs have a layered structure of either a single or
a few layers. The general formula for TMDCs is MX2 (M=Mo/W/Re and X= S/Se/
Te) like Molybdenum disulfde (MoS2), Tungsten disulfde (WS2) and Molybdenum
diselenide (MoSe2).With various combinations of chalcogenides and metals, there
are around 40 TMDCs and these have a variety of properties such as charge density
wave, semimetal and superconductivity [15,16]. The direct bandgap of a monolayer
MoS2 changes from 1.8 eV to indirect bandgap of 1.2 eV when the number of rel-
evant layers increases [17]. Due to its symmetry in the electronic state, topological
semimetals like Platinum diselenide (PtSe2), Palladium ditelluride (PdTe2) and

Platinum ditelluride (PtTe2) have unique carrier properties and can remarkably per-
form in broadband PDs [18]. Due to these properties, they are used in tunable exciton
devices and spin valley lasers [19] with a disadvantage of being indirect bandgap
materials having low mobility [20].
Due to the limitations of Graphene and TMDCs, BP and other group V elements
layered materials are also considered as potential 2D materials for their usage in opto-
electronic applications due to their high mobility and adjustable bandgap [21]. The
bandgap of BP changes with the number of atomic layers and can be directly coupled
with light. It has a strong optical conductivity in the visible to mid-infrared range; it is
a promising candidate for PD applications in this range [22]. However, its application
is limited due to its poor stability when exposed to water, light and oxygen [23].
Black arsenic (BA) has a single layered puckered structure resembling BP making it
to have anisotropy and is more pronounced than that of BP [24]. Preparation and appli-
cation of large area ultra-thin flm samples is possible as BA is more stable than BP.
In recent years, a new semiconducting 2D material, Antimonene is also used
for fexible PDs with a hybrid structure showing a good response and on/off ratio.
Compared to other 2D materials, Antimonene has a short layer distance and small
binding energy suitable for exfoliation and surface modifcation methods. Though
bulk antimony exhibits metal electrical transport characteristics, 2D layered anti-
mony exhibits indirect bandgap semiconducting properties [25]. Owing to these
characteristics, its usage is limited in the development of optoelectronic devices.
These 2D layered semiconducting materials, arsenic and antimony, have high carrier
concentration and mobility making them widely studied materials for their usage in
transistors, quantum spin devices and other optoelectronic devices. At present, stud-
ies on these materials are limited and need to be developed.
Extensive research is going on organic–inorganic perovskite 2D nanoplatelet or
nanosheets (NSs) due to their large lateral size, narrow band absorption, long diffu-
sion length, excellent charge transport properties and long carrier lifetime making
them excellent candidates for photovoltaic and optoelectronic applications [26,27].
Organic–inorganic halide perovskites have gained more attention than their inor-
ganic counterparts as they have advantages like easy solution processing at room
temperature, good stability and excellent optoelectronic properties [28]. By control-
ling the thickness of the 2D NSs, bandgap tuning can be achieved in this material. A
white light converter was fabricated using the composition CH3NH3PbBrI2 NSs on
a blue LED chip. Parveen et al. [29] reported a 2D perovskite PD with a stable and
very fast rise/fall time (24 μs/103 μs) along with high responsivity and detectivity of
~1.93 A/W and 1.04 × 1012 Jones, respectively. As reported, storage, operational and
temperature-dependent stability studies reveal high stability of the 2D perovskite
NSs under the ambient condition with high humidity.
Recently buckled Graphene analogues (Xenes) have created interest among research-
ers and are being studied theoretically for their usage in fexible nanoelectronics [30].
MXenes are a new type of 2D material composed of elements Mn+1XnTx elements where
M is a transition metal element, X is Carbides or Nitrides and T is a group or modifcation
on the surface of the 2D material and n takes the value in the range 1–3. MXenes have
the advantages like good optical transmittance, fast charge transfer, tunable bandgap,
more active sites, ease of modifcation and low cost of fabrication [31]. Currently most
of the MXenes exhibit metal-like properties with small bandgaps [32] and provide a
platform for photon electron coupling on the surface. Hence they are widely used in
biological, chemical and optical sensors [32]. Room temperature solid-state properties
of selected 2D crystalline materials are mentioned in a previous report [9].
Polymer PDs have gained a lot of importance in recent years due to their ease of
fabrication on fexible substrates at low cost. Many of the polymer PDs are based
on bulk-heterojunction structure [33,34] with donor–acceptor (D-A) blended active
layers. To overcome the weak absorption of fullerenes and hard-to-modify bandgap,
non-fullerene acceptor-based PDs are being studied in recent times [35]. Organic
semiconductors have excitation energy in the range 0.3–1 eV, which is higher than
that of inorganic materials [36] and hence these have effcient exciton dissociation
[37], which in turn improves the device effciency of a PD. Planar heterojunction
(PHJ) devices, due to their layered structure have several advantages like high car-
rier mobility, ease in fabrication and reproducibility [38]. PHJ structure refers to the
contact surface of two materials in the D-A plane. To enhance the contact area of
D-A, which increases the exciton dissociation, the PHJ concept was proposed in the
polymer fullerene system [39].
The performance of heterojunctions of single-layer organic small molecules and
polymers is inferior due to the weak interaction between the interfaces. To over-
come this, 2D materials are incorporated into bulk/multilayer heterojunctions [40].
For obtaining the best charge separation effciency, the thickness of the multilayer
should be less than the exciton diffusion length. Weak electrons in 2D materials
interact with photons and hence enhance photocurrent response [41]. 2D materials
and organic interface play an important role in the performance of the device. To
enhance the photo trapping effect, which increases the light absorption of 2D materi-
als, plasmonic effect is also utilized [42].
Effciency of the gold nanoparticles (AuNPs) doped P3HT device was enhanced
due to the charge transfer between P3HT and AuNPs as reported earlier [43]. The
layers on ITO-coated glass substrate consisted of thin flms of PEDOT: PSS, P3HT
with Au nanoparticles and Al metal contact on which the photosensing studies were
carried out. Photoresponse curve of the device is shown in Figure 17.2.
Following are things to be considered to have a good responsivity of a PD: (a)
building an effective electric feld in the photoactive layer, (b) to select a material
to trap the charge carriers and (c) to prolong the trapping time within the photoac-
tive layer.
The effect of doping concentration of AuNPs on various properties of the device
was reported and is shown in Table 17.1 as reported earlier [43]. The layers on ITO-
coated glass substrate consist of thin flms of PEDOT: PSS, P3HT with Au nanopar-
ticles and Al metal contact on which the photosensing studies were carried out and
the photosensing parameters were determined as shown in Table 17.1.
In recent times, researchers are using 2D materials to trap the carriers using a
hybrid structure strategy [44]. According to a recent report, a variety of ‘all 2D’ het-
erostructure PDs were studied [45]. Plastic PDs utilizing the low bandgap polymers
were also studied for fast response and high sensitivity [46]. Polymer organic PDs lead
the way for 2D-based optoelectronic devices. As per previous reports of Aruna et al.
FIGURE 17.2 Photosensing of ITO/PEDOT: PSS/P3HT: AuNPs (170 nm)/Al devices for
different concentrations of AuNPs. Inset: Photoresponse Curve for different AuNPs concen-
trations. Adapted with permission from [43]. Copyright (2021) Elsevier Publishers.
TABLE 17.1
Optical and Photosensing Parameters of the ITO/PEDOT: PSS/P3HT: AuNPs
(170 nm)/Al Devices
Concentration of Dark Photo
AuNPs in P3HT Bandgap On/off Ratio Current Current Responsivity Photoresponse
Thin Films (%) (eV) (Resistance) Idark (nA) Ilight (nA) (μA/W) ΔIresp = Ilight/Idark
0 2.10 100 0.28 28.5 7.1 101
0.1 1.75 571 0.25 142.9 35.7 571
0.2 1.90 50 1 50 12.2 50
0.3 1.95 40 1.6 66 16.1 41
Adapted with permission from [43]. Copyright (2021) Elsevier Publishers.
[47], the photoresponse with respect to different wavelengths is shown in Figure 17.3
indicating the variation of the responsivity with respect to the wavelength used. The
layers on ITO-coated glass substrate consist of thin flms of C60-doped P3HT and Al
metal contact on which the photoresponse studies in light and dark were carried out.
17.4 PHOTODETECTORS FOR DIFFERENT WAVELENGTHS

PDs in the visible wavelength region (400–750 nm), near-infrared region (750 nm–
1.1 μm) and short wave infrared region (1–3 μm) have applications in the felds like
biomedical imaging, night vision thermal imaging and communication [48,49].
Mueller et al. studied Graphene-based PD, which adopted a metal Graphene metal
structure and achieved a responsivity of 6.1 mAW−1 at a wavelength of 1.55 μm [50].
FIGURE 17.3 Photoresponse characteristics of P3HT:C60 device. Adapted with permission

from [47]. Copyright (2018) Elsevier Publishers.
Yin et al. studied TMDCs-based single-layer MoS2 phototransistors and it showed

a better optical response compared to Graphene-based devices [51]. Huang et al.
demonstrated a high-performance PD based on BP in the wavelength region 400–
900 nm [52]. Tan et al. demonstrated a tunable black phosphor carbide infrared pho-
totransistor with a wavelength of 2,004 nm and it showed a responsivity of 2,163
AW−1 [53]. PDs in the mid-infrared region (3–30 μm) have applications in the felds of
free space communication, environmental monitoring and biomedicine [54,55]. Liu
et al. reported a broadband PD with two Graphene layers sandwiching a thin tunnel
barrier and the responsivity of this detector was more than 1 A W−1 at 3.2 μm [56].
BP has a moderate bandgap and has a high mobility and low dark current and can
be integrated with traditional materials like Silicon. Guo et al. reported a PD based
on BP with photoresponsivity up to 82 A W−1 at 3.39 μm [57]. BA phosphorus is an
alloy of BP and arsenic atoms and is similar to BP and has a narrow bandgap and is
semiconducting in nature [58]. Amani et al. reported a photoconductor based on BA
phosphorus in the wavelength region 3.9–4.6 μm [59]. Utilizing the excellent opto-
electronic properties of 2D materials, they can be used in PDs, which can detect light
in the terahertz region (30 μm–3 mm). Zak et al. reported a THz PD based on split-
bow-tie antenna integrated with Graphene feld effect transistor [60].
17.5 CONCLUSION
2D materials have great potential for incorporating in devices while fabricating PDs
for excellent effciency. With continuous emergence of 2D materials, their excellent
properties have been utilized in the area of PDs. Still there are a few challenges faced
by the scientifc community, one of which is the production of these 2D materials in a
large area as most of the high-quality 2D materials are obtained by micro-mechanical
exfoliation. Another challenge is that the contact barrier between 2D material
and the electrode is relatively high because of which the stability of the device is
poor. By overcoming these limitations, one can achieve PDs with high effciency.
Flexible PDs based on 2D materials will have remarkable progress and great pros-
pects in near future.
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18 2D Nanomaterials
for Electrocatalytic
Hydrogen Production
Arun Prasad Murthy and Nihila Rahamathulla
CONTENTS
18.1 Introduction .................................................................................................. 303
18.2 2D Nanostructures as HER Electrocatalysts ................................................307
18.2.1 Holey Pt Nanosheets on NiFe-Hydroxide Laminates.....................307
18.2.2 Two-Dimensional Transition Metal Dichalcogenides ....................308
18.2.3 MoS2 Quantum Dots on Graphitic Carbon Nitride ........................308
18.2.4 2D Metal-Organic Frameworks......................................................308
18.2.4.1 2D Porous NiCoSe Nanosheet Arrays on Ni Foam .........308
18.2.4.2 2D CoNi Bimetallic MOF................................................309
18.2.4.3 NiFe(dobpdc)-MOF with an Extended Organic Linker...309
18.2.4.4 2D Layered CuS-C........................................................... 310
18.2.5 Wrinkled Rh2P Nanosheets ............................................................ 310
18.2.6 Graphene Hybrid Systems .............................................................. 310
18.2.6.1 Metal-Doped Graphene ................................................... 311
18.2.6.2 Metal Sulfde or Metal Selenide−Graphene Hybrids ...... 311
18.2.6.3 Metal Phosphides or Metal Carbides–Graphene Hybrids ... 311
18.2.6.4 Bimetallic Phosphides on Reduced Graphene................. 311
18.2.7 CoP Nanosheet Aerogel.................................................................. 312
18.2.8 Ruthenium-Doped Bimetallic Phosphide on Ni Foam................... 312
18.2.9 Porous W-Doped CoP Nanofake Arrays ....................................... 315
18.2.10 Single Atom on the 2D Matrix........................................................ 316
18.3 Concluding Remarks .................................................................................... 317
References.............................................................................................................. 318
18.1 INTRODUCTION
Nanotechnology has made revolutionary developments in the advancement of industrial
processes, materials, and applications by completely exploiting the unique surface phe-
nomena that matter exhibits when reduced to their nanoscale. Surprisingly, nanomate-
rials exhibit entirely different properties from their bulk materials. Nanomaterials are
classifed based on their nanoscopic dimensions as zero-dimensional (0D) nanomaterials
DOI: 10.1201/9781003178453-18 303

(nanoparticles), one-dimensional nanomaterials (1D) (nanotubes, nanorods, and nano-

wires), two-dimensional nanomaterials (2D), and so on.
2D nanomaterials are ultrathin (less than 5 nm) nanosheets consisting of one or
few atomic layers. In 2004, 2D single-atom-thick graphene crystallites, the frst 2D
nanomaterial was isolated from bulk graphite by Prof Andre Geim and Prof Kostya
Novoselov [1]. Since then, 2D nanomaterials such as transition metal dichalcogen-
ides (TMDCs), transition metal oxides, carbides, nitrides, carbonitrides (MXenes),
2D metal-organic frameworks (2D-MOF), and 2D polymers have been extensively
explored by the researchers. Different structures of 2D nanomaterials are shown
in Figure 18.1. The 2D nanomaterials have numerous applications in the felds of
nanoelectronics, catalysis, biomedical, bioimaging, photothermal therapy, separation,
transistors, sensors, and energy storage due to their atomic thickness, electron confne-
ment in two dimensions, sheet-like structure, fexibility as well as high anisotropic,
optical, mechanical, thermal, and physicochemical properties. 2D nanomaterials exist
in many crystalline forms and therefore they exhibit electric conductivity properties
ranging from insulators to super metallic conductors. The structural and conductive
properties of 2D nanomaterials have drawn signifcant research attention to catalytic
applications such as electrocatalysis. The presence of dopants or defects in 2D nano-
materials can tune the energy bandgap to obtain desired electric conductivity [2].
In addition, the high surface-to-volume ratio with abundant catalytically active sites
exposed on the surface renders 2D metal nanomaterials to be employed as electrocat-
alysts in water splitting, fuel cells, metal−air batteries, CO2 reduction, etc., and have
proved to be of having great potential in replacing the commercial electrocatalysts.
This chapter discusses in detail the importance of 2D nanomaterials employed as
electrocatalysts in water splitting, specifcally in hydrogen evolution reaction (HER).
The global energy crisis is expected to increase with the burgeoning global pop-
ulation in addition to climate change due to increased CO2 emissions from fossil
FIGURE 18.1 Structures of different 2D nanomaterials such as graphene, transition metal

oxides, layered double hydroxide (LDH), gC3N4, hBN, TMDs, and black phosphorous.
Adapted with permission from ref [2]. Copyright (2020) Elsevier B.V.
Electrocatalytic Hydrogen Production 305
fuel combustion [3–5]. This has led to ever-increasing demands for sustainable and
carbon-free clean energy sources. However, renewable energy sources necessitate
highly effcient technologies to capture, convert, and store as they are intermittent
in nature. Solar energy is the supreme source of renewable energy source though
intermittent in nature. Hydrogen is considered to be the future energy carrier. Solar-
driven electrocatalytic water splitting is a promising method for the conversion of
solar energy into chemical energy and its further storage, for example, as fuel hydro-
gen. At present, however, hydrogen is produced mainly from steam reforming of coal,
petroleum, and natural gas, which still leads to the global CO2 emission [6,7]. Another
propitious method for clean hydrogen production is electrocatalytic water splitting.
Water electrolysis consists of two half reactions: hydrogen and oxygen evolution reac-
tions that require a thermodynamic potential of 1.23 V at 25°C to produce hydrogen
at the cathode and oxygen at the anode [3]. The oxygen produced can be utilized for
industrial or medical use and the signifcance of the later use can be understood in this
pandemic period while the hydrogen can be stored as a fuel. This high pure hydrogen
when utilized as fuel to generate energy, it has the potential for near-zero greenhouse
gas emission as the by product is only water vapor and warm air. Hydrogen possesses
high energy density per unit mass, low toxicity, and the ability to transport it safely
qualifes hydrogen to be the near future’s sustainable energy source [8–10].
Mechanism of HER consists of combination of elementary steps such as Volmer
step and either Heyrovsky step or the Tafel recombination step as given below [12,13].
a. Volmer step: Initial discharge of proton or
In acidic media:H 3 O+ + e − ° H ads + H 2O (18.1)
In basic media: H2O + e −  H ads + OH − (18.2)
b. Heyrovsky or Tafel step: Hydrogen formation
In acidic media:H ads + H 3O + + e − ˝ H 2 + H2O ( Heyrovsky stepor desorption step )

(18.3)
In basic media: H ads + H 2O + e −  H 2 + OH − (18.4)
Or
H ads + H ads ˝ H 2 ( Tafel stepor recombination step ) (18.5)
Therefore, two possible mechanisms are Volmer–Tafel and Volmer–Heyrovsky based

on the elementary steps. Different pathways of HER reaction in acidic and basic medium
are illustrated in Figure 18.2. All these steps require an effcient electrocatalyst with
highly active adsorption sites. An important contrivance in determining the mecha-
nism and rate-determining step (RDS) is the Tafel equation η = b log (j) + a where η is
the overpotential, b is the Tafel slope, and a is the Tafel constant [14]. When the Tafel
slope reaches 120 mV dec−1, the RDS becomes a Volmer reaction, a desorption reaction
at 40 mV dec−1, and a Tafel reaction at 30 mV dec−1 [3]. A lower Tafel slope is always
306
FIGURE 18.2 Different pathways for HER: (a) in acidic media and (b) in basic media. Adapted with permission from ref [11]. Copyright (2020)
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
2D Nanomaterials
preferred for an electrocatalyst since greater catalytic current can be attained at mod-
erately lower overpotentials. The kinetic barrier for water electrolysis, however, neces-
sitates a greater potential overpotential (η) than the thermodynamic potential (1.23 V)
to overcome the kinetic barrier. Overpotential is another important parameter to evalu-
ate the HER activity of the electrocatalysts. Generally, the overpotential required to
attain a current density of 10 mA cm−2 (η10) is used to compare the HER activities
among different electrocatalysts. Under equilibrium conditions, the exchange current
density (j0) is an account of the intrinsic charge transfer [15]. A higher exchange cur-
rent density indicates lower charge transfer resistance (Rct) and therefore, a lower reac-
tion barrier. In brief, a lower Tafel slope, overpotential, and Rct result in faster reaction
kinetics and enhanced HER performance. Noble metals like Pt and Pt-based materials
are the best-known electrocatalysts for the HER with negligible overpotential even
at high reaction rates. But, its utilization for large-scale use is limited due to its high
cost and limited abundance. Non-noble electrocatalysts with low cost, abundance, high
activity, lower overpotential, and long-term stability have been under investigation in
recent past years. In this context, due to the distinctive physical and chemical properties
derived from their structural and electronic features of 2D ultrathin materials with a
single- or few-layered thickness, they have been explored as HER electrocatalysts [16].
Especially, when the bulk materials are reduced to 2D nanosheets, their reduced thick-
ness results in enhanced HER activity. The superiority of ultrathin 2D nanomaterials
as electrocatalysts arises as they have more exposure to active sites by decreasing the
energy barrier, which is achieved by introducing defects in the basal plane or by doping
with conductive heteroatoms. Thus, 2D electrocatalysts with their unique anisotropic
properties open a new path for enhanced HER performance.
18.2 2D NANOSTRUCTURES AS HER ELECTROCATALYSTS

18.2.1 HOLEY PT NANOSHEETS ON NIFE-HYDROXIDE LAMINATES
The most active and benchmark electrocatalyst for HER is well-known Pt. However,
many researchers have been ardently investigating the reaction mechanisms and
innovating the designs for effcient Pt-based electrocatalysts due to their limited per-
formance in alkaline solutions. Jang et al. [17] fabricated a 2D−2D interfacially inte-
grated nanoplatform of nanoporous 2D-Pt on NiFe-LDH (layered double hydroxide)
nanosheets and employed it as an effective electrocatalyst for HER. The electrocata-
lyst synergistically hastened the water dissociation with maximum Pt-atomic utili-
zation effciency, furnishing 6.1 times higher Pt mass activity than the commercial
20 wt.% Pt/C and exhibited HER operational stability for about 50 hours. A high
HER activity was exhibited by the electrocatalyst with a Tafel slope of 32.3 mV dec−1.
It exhibited η100 of 61 mV, which was remarkably lower than the commercial 20 wt.%
Pt/C catalyst (η100 = 342 mV). The in situ-generated hybrids of the electrocatalyst
showed 2.57 times higher electrochemically active surface area (ECSA) than that of
the physically mixed electrocatalyst (LDH + 2D-Pt), suggesting that the synthesized
hybrids possessed a higher number of active sites when compared to (LDH + 2D-Pt).
The authors attributed the high HER activity of the electrocatalyst to the structural
lamellar design with 2D−2D interfacial 2D-Pt layers clamped on NiFe-LDH sheets.
18.2.2 TWO-DIMENSIONAL TRANSITION METAL DICHALCOGENIDES

2D transition metal dichalcogenides (2D TMDC) have been a promising electrocata-
lyst for HER. The 2D layered structure of TMDC nanosheets offers a number of
reaction sites and has less in-plane resistivity through the basal plane, facilitating
easier electron transport. For enhanced HER performance, Chen et al. [18] employed
a monolayer of MoTe2 as a representative for activation of the basal plane of 2D
TMDCs. The structural stabilities and energetics of possible 2H/1T′ phase boundary
confgurations were examined by comprehensive frst-principle calculations. Te, Mo,
and hollow sites were identifed as energetically stable phase boundaries and potential
catalytic centers for HER by employing basal plane activation, resulting in increased
HER activity over the pristine basal lattice. In specifc, the hollow sites, a new group
of sites generated by phase boundaries exhibited a Gibbs free energy (∆G�) near the
thermoneutral value, similar to that of Pt for hydrogen adsorption. The mechanisms
of hydrogen adsorption at phase boundaries were analyzed, which were attributed to
their distinct electronic structure and local hydrogen adsorption geometries.
18.2.3 MOS2 QUANTUM DOTS ON GRAPHITIC CARBON NITRIDE

Graphitic carbon nitride (g-C3N4) is an important metal-free-carbon-based semicon-
ductor electrocatalyst for HER due to its electronic structure, nitrogen content, and
stability. However, to enhance the catalytic activity of pristine g-C3N4, Liu et al. [19]
decorated it with MoS2 quantum dots. MoS2 having a similar structure to that of
g-C3N4 promoted the formation of the 2D hybrid nanosheets with a p-n heterojunc-
tion interface. Unsaturated Mo and S atoms at the edges also served a greater num-
ber of catalytic active sites. Electrochemical studies were conducted by a standard
three-electrode system in an acidic medium. Clearly, with the introduction of MoS2
quantum dots on g-C3N4, lowering of activation barriers, decrease in onset potential
and enhanced HER activity were observed.
18.2.4 2D METAL-ORGANIC FRAMEWORKS

2D-MOF nanosheets, integrating the advantages of 2D material and MOF have been
spurring research attention in catalysis application on account of its ultrathin thick-
ness, high surface-to-volume atom ratios, tunability, and large surface area. MOF
contains metal ions and organic ligands via coordination bonds. MOF-derived mate-
rials have been used in electrocatalytic HER in alkaline media on account of their
high conductivity and better electrochemical properties.
18.2.4.1 2D Porous NiCoSe Nanosheet Arrays on Ni Foam

Zhou et al. [20] developed in situ growth of porous NiCoSe nanosheet arrays based
on 2D MOFs on Ni foam (NiCoSe-NF) and employed them as an effective HER elec-
trocatalyst. The characteristic porous 2D framework of the electrocatalyst provided
high surface area for HER, facile electrolyte penetration, high conductivity, and
enhanced release of gaseous products. The 2D porous NiCoSe nanosheet arrays on
Ni foam were synthesized using ZIF-67 as a precursor, which was further subjected
to react with x mmol of Se powder (x = 2, 4, 6, 8,) to fabricate different compositions

of NiCoSe-NF. The HER activity was evaluated using a three-electrode system in
an alkaline medium. For comparison, the commercial Pt/C loaded on the Ni foam,
bare Ni foam, NiCo LDH-NF were also analyzed under the same conditions. NiCoSe
(8 mmol) had a Tafel slope of 82.3 mV dec−1, which was found to be less than those of
NF (153.4 mV dec−1), NiCo LDH (128.3 mV dec−1), NiCoSe (2 mmol) (130.9 mV dec−1),
NiCoSe (4 mmol) (130.3 mV dec−1), and NiCoSe (6 mmol) (107.4 mV dec−1). The η10
of NiCoSe (8 mmol) was 170 mV, which was lower than those of other compositions
as well as NiCo LDH (229 mV). Rct was evaluated using electrochemical impedance
spectroscopy (EIS) analysis. The NiCoSe (8 mmol) nanosheets also exhibited the
smallest Rct of 2.614 Ω, facilitating the highest electron transferability among the
investigated electrocatalysts. Superior oxygen evolution reaction (OER) performance
was also exhibited by NiCoSe (2 mmol) with lower Tafel slope (92 mV dec−1) and Rct
values (2.325 Ω). A system of two-electrode cell was constructed by the authors to
study the water electrolysis in 1 M KOH solution in which NiCoSe samples served as
both cathode and anode. The electrocatalyst with high electrochemical surface area,
mesoporous structure, and synergic effect between Ni foam and NiCoSe nanosheet
arrays served not only as a HER electrocatalyst but also as an unprecedented bifunc-
tional electrocatalyst in overall water splitting.
18.2.4.2 2D CoNi Bimetallic MOF

2D CoNi-MOF nanoplate array grown on the Cu foil having direct exposure of metal
nodes present in the porous structure was investigated as a promising HER electrocat-
alyst of MOF group. Liu et al. [21] synthesized the bimetallic CoNi-MOF (1:1,Co:Ni)
and also annealing 1:1 CoNi-MOF through annealing with NH3 forming Ni nitride
composites on amorphous carbon (CoNiN-C). Electrochemical studies were con-
ducted for both OER and HER activities in 1 M KOH. The CoNiN-C required η10
of 120 mV, which was lower than that of 1:1 CoNi-MOF (376 mV). The lower higher
charge transfer resistance of CoNiN-C (4.62 Ω) than 1:1 CoNi-MOF (102.4 Ω) sug-
gests that CoNiN-C has better HER activity than 1:1 CoNi-MOF. Stability tests also
demonstrated the better durability of CoNiN-C as a remarkable water-splitting elec-
trocatalyst. On account of better OER and HER activities, CoNiN-C was employed as
cathode CoNiN-C and CoNi(1:1)-MOF as anode for overall water splitting. Faradaic
effciency of 99.0% was achieved for H2 production on CoNiN-C similarly 98.9%
was obtained for O2 production on CoNi(1:1)-MOF [21].
18.2.4.3 NiFe(dobpdc)-MOF with an Extended Organic Linker

Various analogues of M2(dobpdc) (where M-metal and dobpdc4− -4,4´-dioxido-
biphenyl-3,3´ - dicarboxylate) have been widely used for HER electrocatalysis.
Qi et al. [22] fabricated NiFe(dobpdc) as an electrocatalyst for overall water split-
ting and carried out various electrochemical studies. NiFe(dobpdc) has a yarn-ball-
like structure and the extended organic linker (dobpdc) can increase the Brunauer,
Emmett and Teller (BET) surface area, which in turn can enhance the interaction
between NiFe(dobpdc) electrocatalyst and water. The HER activity was evaluated
using a three-electrode system in an alkaline medium. NiFe(dobpdc) required η10
of 233 mV and η100 of 170 mV. The Tafel slopes of NiFe(dobpdc) was 69 mV dec−1,
which was smaller than those of Fe2(dobpdc) and Ni2(dobpdc). Notable OER activity
was also shown by NiFe(dobpdc) encouraging the setup of a two-electrode system in
1.0 M KOH for overall water splitting.
18.2.4.4 2D Layered CuS-C

Rong et al. [23] synthesized 2D layered CuS-C as a Cu-based MOF (Cu-BDC
nanosheets) via sulfdation of Cu-BDC nanosheets. HER electrocatalytic investiga-
tion of layered CuS-C, bulk CuS-C, and Cu-C was examined in acidic medium by
linear sweep voltammetry (LSV). The Tafel slope of layered CuS-C was found to
be 44 mV dec−1, which was lower than those of bulk CuS (91 mV dec−1) and Cu-C
(102 mV dec−1). In contrast, layered Cu-C exhibited a much smaller onset potential of
128 mV to attain η10 than bulk CuS (370 mV). A charge transfer resistance (Rct) of 55
Ω was exhibited by CuS-C, which was lower than those of bulk CuS-C (147 Ω) and
Cu-C (272 Ω). Layered CuS-C gave excellent stability and exhibited negligible decay
even after 1,000 potential cycles and also HER current was retained to 96.5% of the
initial value which marks its excellent stability.
18.2.5 WRINKLED RH2P NANOSHEETS

Metal phosphides and sulfdes supported on carbon are Pt-free electrocatalysts that
have drawn attention for HER electrocatalytic activity. Wang et al. [24] fabricated
a new category of wrinkled Rh2P ultrathin nanosheets as an universal-pH-effcient
HER electrocatalyst. Wrinkled Rh2P and Rh nanosheets were supported on carbon,
which was denoted as w-Rh2P/C and Rh/C, respectively. Electrochemical studies of
these electrocatalysts were conducted in alkaline (0.1 M KOH), acidic (0.1 M HClO4),
and neutral (0.5 M phosphate-buffered saline (PBS) solution) media. In alkaline
medium, w-Rh2P/C exhibited η10 of 18.3 mV, which is lower than 68.9 mV of Rh/C.
The Tafel slopes obtained for w-Rh2P/C and Rh/C were 61.5 and 113.0 mV dec−1,
respectively. Under similar conditions, commercially available Pt/C exhibited η10 of
58.4 mV and the Tafel slope of 87.4 mV dec−1. The HER electrocatalytic properties
exhibited by w-Rh2P/C were found to be superior to commercially available (20%)
Pt/C. In acidic medium, w-Rh2P/C required overpotential of 15.8 mV (η10) lower
than those of Rh/C (41.6 mV) and commercial Pt/C (22.1 mV). The Tafel slope of
w-Rh2P/C was 29.9 mV dec−1, which was similar to Pt/C 29.6 mV dec−1 and lower
than that of Rh/C (37.4 mV dec−1). Further, HER activity was evaluated in PBS solu-
tion (pH 7), which resulted in η10 of 21.9 mV and a Tafel slope of 78.4 mV dec−1.
The HER performance of w-Rh2P/C was better than those of Rh/C and commercial
Pt/C in neutral medium. Wrinkled Rh2P exhibited η10 of 18.3 mV and Tafel slope of
61.5 mV dec−1, which was better than commercial Pt/C used widely as a benchmark
electrocatalyst for HER in alkaline medium.
18.2.6 GRAPHENE HYBRID SYSTEMS

Graphene is a monolayered carbon with honeycomb structure that has been widely
employed as an electrocatalyst or as support for electrocatalytic water splitting.
Researches on graphene suggest that graphene hybrid by doping it with various
heteroatoms and compounds enhance the electrochemical properties of graphene.

Chemical doping on graphene signifcantly increases the electronic structural prop-
erties of active sites leading to enhanced electric conductivity and stability under
drastic reaction conditions. Li et al. [25] investigated HER and OER properties of
certain graphene hybrids to fabricate highly active electrocatalysts for overall water
splitting. Nitrogen, Phosphorous, or Sulfur (N, P, or S)-doped graphene potentially
improved HER performance compared to intrinsic graphene. N/P binary-doped gra-
phene exhibited ▵GH* of 0.53 eV, which was smaller than that of N-doped graphene
(▵GH* = 0.81 eV) and the smallest ▵GH* of 0.23 eV was obtained for N/S binary-
doped graphene.
18.2.6.1 Metal-Doped Graphene

Li et al. [25] investigated atomic Co on N-graphene (Co/N-graphene) for the HER
activity of metal-doped graphene. Co/N-graphene exhibited an onset potential and
η10 of 30 and 147 mV, respectively. Tafel slope obtained was 82 mV dec−1. Further,
the electrocatalyst showed excellent stability for about 10 hours in 0.5 M H2SO4 in a
stability test. Ni-doped graphene also manifested excellent electrocatalytic activity
for HER with a Tafel slope of 45 mV dec−1 and stability of 5 hours in 0.5 M H2SO4.
18.2.6.2 Metal Sulfde or Metal Selenide−Graphene Hybrids

Li et al. [25] synthesized MoS2 on reduced graphene (MoS2/rGO) hybrids by solvo-
thermal method and its electrochemical measurements were conducted in an acidic
medium. MoS2/rGO decreased the aggregation of MoS2 during HER and provided
abundant active sites at edges for HER. MoS2/rGO showed a Tafel slope of 41 mV
dec−1 and maintained the catalytic activity for about 1,000 potential cycles in a stabil-
ity test. MoSe2 on layered graphene also manifested high HER activity than intrin-
sic graphene. Presence of synergetic effect on MoSe2/graphene hybrids bestowed an
onset potential of 125 mV and a Tafel slope of 67 mV dec−1. Excellent stability was
also maintained, which was evaluated by a measuring current density over 6,000
seconds in 0.5 M H2SO4.
18.2.6.3 Metal Phosphides or Metal Carbides–Graphene Hybrids

Transition metal phosphides (TMPs) and carbides on graphene have made extensive
advances in HER studies. Li et al. [25] synthesized porous CoP/graphene hybrids and
subjected to electrochemical analysis in alkaline media (1.0 M KOH). The electro-
catalyst exhibited a smaller Tafel slope of 38 mV dec−1 than that of bare CoP (60 mV
dec−1) and a stable catalytic current density for nearly 20 hours. Iron phosphides on
graphene exhibited a remarkable HER activity with an onset potential of 30 mV, Tafel
slope of 50 mV dec−1, and η10 of 123 mV. The synergistic effects between metal phos-
phides and graphene resulted in improved electrical conductivity with and abundant
exposure of active sites.
18.2.6.4 Bimetallic Phosphides on Reduced Graphene

Li et al. [25] synthesized cobalt-doped nickel phosphides on reduced graphene oxide
(NiCoP/rGO) and employed as a bifunctional hybrid catalyst for the overall water
splitting in all pH ranges. Tafel slopes of NiCoP/rGO hybrids were 91.0 mV dec−1
in 1.0 M PBS buffer (neutral medium) and 124.1 mV dec−1 in 1.0 M KOH. However,
the electrocatalyst showed excellent HER activity in 0.5 M H2SO4 with Tafel slope
of 45.2 mV dec−1 and η 20 of 55 mV. High catalytic stability over 18 hours was also
exhibited by the electrocatalyst. On account of the bifunctional catalytic properties
exhibited by NiCoP/rGO hybrids for both OER and HER, a two-electrode system of
NiCoP/rGO||NiCoP/rGO in 1.0 M KOH was constructed, which showed η10 of 1.59 V
for more than 75 hours with ~100% Faradic effciency. Even though graphene-based
electrocatalysts are widely studied for improving overall water splitting, and it is still
challenging for large-scale practical applications.
18.2.7 COP NANOSHEET AEROGEL

TMPs are one of the highly active classes of HER electrocatalysts. CoP nanostruc-
tures, as an example of TMPs were subjected to distinct morphologies to obtain
better HER catalytic activity. Li et al. [26] synthesized 2D ultrathin CoP Nanosheets
on aerogel by ice-templating method as illustrated in Figure 18.3 and demonstrated
enhanced HER performance at all pH ranges. The porous structure of aerogel and
lower thickness of CoP (<1.5 nm) augmented higher mass transfer and also prevented
agglomeration of CoP nanosheets. The HER performance was evaluated using a
three-electrode system in all pH ranges. The Tafel slope and η10 values of CoP aero-
gels were 67 mV dec−1 and 113, respectively, in 0.5 M H2SO4. The HER properties
of CoP aerogels were exceptional when compared to previously reported Co-based
electrocatalysts. The authors investigated HER activities of the electrocatalyst in 1 M
KOH and 1 M PBS. The electrocatalyst exhibited Tafel slopes of 72 and 81 mV dec−1
in the 1 M KOH and PBS media, respectively. Compared to 0.5 M H2SO4 electrolyte,
CoP aerogels exhibited higher η10 in 1 M KOH (154 mV) and 1 M PBS (161 mV).
ECSA studies were carried out through double-layer capacitance (Cdl) measurements.
CoP aerogels showed Cdl values of 19.16 mF cm−2 in 0.5 M H2SO4 and 7.66 mF cm−2
in 1 M KOH. The electrocatalyst also showed remarkable stability in all pH range
with negligible deactivation during the catalytic cycles.
18.2.8 RUTHENIUM-DOPED BIMETALLIC PHOSPHIDE ON NI FOAM

Heteroatom-doped electrocatalysts have proved to lower the activation energy
resulting in accelerated reaction kinetics enhancing HER performance. Metal-
hydrogen bond strength and water-dissociation properties of Ru are similar to
those of Pt. Lin et al. [27] fabricated HER electrocatalyst by doping trace amount
(0.6 wt.%) of Ru-bimetallic phosphide on Ni foam (Ru-NiFeP/NF). It was derived
from 2D MIL-53(NiFe) MOF nanosheets and synthesized via hydrothermal pro-
cess followed by phosphorization. The schematic representation of synthesis of
Ru-NiFeP/NF is illustrated in Figure 18.4. HER and OER electrochemical studies
of Ru-doped NiFeP/NF were conducted in acidic (0.5 M H2SO4), alkaline (1 M
KOH), and neutral (PBS) media. For comparison, the electrochemical studies of
NiFeP/NF and Pt/C/NF electrocatalysts were conducted under similar conditions.
Ru-NiFeP/NF demonstrated enhanced HER activity in acidic medium with η10
of 29.3 mV while that of NiFeP/NF was 146.6 mV. It may be noted that η100 of
Electrocatalytic Hydrogen Production
FIGURE 18.3 Schematic representation of preparation of CoP aerogel nanosheets. Adapted with permission from ref [25]. (a) SA+Co dispersion.
(b) After liquied freezing. (c) After freeze drying. (d) Nanosheets and microstructure. Copyright (2018) WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim.
313
314
FIGURE 18.4 Schematic representation of synthesis of Ru-NiFeP/NF nanosheets. Adapted with permission from ref [26]. Copyright (2020) Elsevier B.V.
2D Nanomaterials
Ru-NiFeP/NF (88.2 mV) was lower than that of Pt/C/NF (136.2 mV). The Tafel
slope of Ru-NiFeP/NF was found to be 55.7 mV dec−1. When compared with other
electrocatalysts studied by the authors, Ru-NiFeP/NF possessed smaller Rct indicat-
ing faster electron transfer. In neutral medium, η10 of Ru-NiFeP/NF was 105.1 mV,
which was lower than that of NiFeP/NF (218.1 mV). The Tafel slope of Ru-NiFeP/
NF in the same medium was 82.7 mV dec−1, but was greater than that of Pt/C/NF
(53.7 mV dec−1). Ru-NiFeP/NF exhibited η100 of 139.5 mV, which was lower than
that of Pt/C/NF (153.4 mV) in alkaline medium. Ru-NiFeP/NF showed excellent
long-term stability with no apparent in its initial activity. The above studies indi-
cated that Ru-NiFeP/NF was superior to previously reported HER electrocatalysts
such as Ru-MoO2, Ru-MoS2/CC, and NiCo2Px nanowires in a wide pH range.
18.2.9 POROUS W-DOPED COP NANOFLAKE ARRAYS

TMPs have been used extensively as effcient HER electrocatalysts due to their remark-
able intrinsic properties and prolonged stability. Doping TMPs with heteroatom can
modulate their electronic structures and facilitate their electronic conductivity, which
can signifcantly enhance their HER performance in a wide pH range. TMPs-based
electrocatalysts exist in powder form having complex preparation methods involving
polymeric binders. These polymeric binders can block the catalytic active sites and
result in poor catalytic activity. In this context, an effcient synthesis route with hier-
archical nanoarrays grown on conducting substrate was designed by Wang et al. [28].
The authors synthesized W-doped CoP nanofake arrays on carbon cloth (W-CoP/
CC) and employed it as a superior HER electrocatalyst in a wide pH range. Schematic
representation of synthesis of W-CoP NAs/CC is illustrated in Figure 18.5. W-CoP/
CC HER performance was evaluated in acidic, alkaline, and neutral media. For
FIGURE 18.5 Schematic representation of synthesis of W-CoP NAs/CC. Adapted with

permission from ref [27]. Copyright (2019) WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim.
comparison, the HER performance of Pt/C/CC, CoP/CC, and Co3O4/CC electrocata-

lysts was also studied under similar conditions. In 0.5 M H2SO4, W-CoP/CC exhibited
an onset potential of 31 mV and the η10 was 89 mV, which was lower than that of CoP/
CC (123 mV), but greater than that of Pt/C/CC (35 mV). The Tafel slopes of W-CoP/
CC, Pt/C/CC, and CoP /CC were 58, 32, and 97 mV dec−1, respectively. In 1.0 M KOH,
η10 of W-CoP/CC was 94 mV, which was lower than those of Co/CC (129 mV) and
Co3O4/CC (305 mV). The Tafel slope of W-CoP/CC (63 mV dec−1) was also lower than
those of CoP/CC (74 mV dec−1) and Co3O4/CC (128 mV dec−1). Among the above three
electrocatalysts, W-CoP/CC exhibited the best catalytic activity in alkaline medium.
In 1.0 M PBS, the onset potentials of W-CoP/CC, CoP NAs/CC, and Co3O4/CC were
51, 79, and 313 mV and the η10 values were 102, 132, and 397, respectively. Also,
the Tafel slope of W-CoP/CC (87 mV dec−1) was lower than those of CoP/CC (98 mV
dec−1) and Co3O4 /CC (117 mV dec−1). W-CoP/CC exhibited about 100% Faradaic eff-
ciency and also high stability with no appreciable degradation in activity for about
36 hours in all three media. The excellent electrocatalytic performance of W-CoP/
CC could be attributed to the hierarchically porous nanofake array confguration and
heteroatom doping with W, resulting in highly exposed active sites facilitating the dif-
fusion of H2 produced and effciently enhancing the HER performance.
18.2.10 SINGLE ATOM ON THE 2D MATRIX

It is well-known that noble metals-based electrocatalysts are the most effcient
electrocatalysts for HER but their scarcity and high cost limit their utilization for
large-scale hydrogen production. An alternative way is to reduce the size of noble
metals-based electrocatalysts to single-atom catalysts (SACs) [29]. SACs act as a
link between heterogenous and homogenous catalysis. Examples of SAC present in
nature are Mg in chlorophyll entailed in photosynthesis and other metals present in
enzymes that carry out biocatalysis. Reducing the size of catalysts to SACs results
in an enhanced electronic and atomic structure with a greater number of exposed
surface atoms thereby enhancing catalytic performance. But, reducing the size may
lead to aggregation and the particle set off instability. Therefore, stable SACs need to
be synthesized effciently using solid support with a larger surface area, for example,
2D matrix of N-doped graphene, LDH, graphdiyne, 2D MOFs, and transition metal
dichalcogenides (TMDs). These SAC hybrids are highly stabilized by the covalent
interaction present between 2D-matrix and single atoms. These interactions will con-
struct a new electronic state, which leads to a new set of active sites and maximize
atom utilization effciency thereby enhancing catalytic performance to a large extent.
Yu et al. [30] supported zero-valent palladium atoms on graphdiyne nanosheets
(GDY-Pd0) at a mass loading of 0.2%. GDY-Pd0 HER studies were conducted in
0.5 M H2SO4. For comparison, pristine GDY, Pd nanoparticles decorated on GDY
(Pd NP/GDY), and commercial Pt/C (20 wt.%) were also studied by the authors under
similar conditions. GDY-Pd0 exhibited excellent HER activity with η10 of 55 mV,
which was lower than those of commercial Pt/C (62 mV), Pd NP/GDY (115 mV), and
pure GDY (481 mV). The mass activity of GDY-Pd0 was 26.9 times higher than that
of Pt/C. The Tafel slope of GDY-Pd0 was (47 mV dec−1) lower than those of Pd NP/
GDY (139 mV dec−1) and GDY (212 mV dec−1). Rct of GDY-Pd0 3.37 Ω was very much
lower than that of the pristine GDY (30.97 Ω) indicating faster electronic transfer.
Thus, zero-valent palladium atoms on 2D graphdiyne nanosheets fabricated by the
authors delivered exceptional HER performance compared to Pd NP/GDY and com-
mercial Pt/C (20 wt.%).
18.3 CONCLUDING REMARKS

In water electrolysis, HER has both of practical and fundamental importance and has
gained captivating utilization as hydrogen fuel in the future hub of renewable energy.
HER is acknowledged as one of the paramount technologies for hydrogen production
as a greener method of production of hydrogen. Materials based on noble metal like Pt
are the best-known electrocatalysts for HER. Due to the scarcity and high cost of pre-
cious metal compounds, the large-scale HER production still remains a challenge. In
this chapter, we have briefy discussed the recent signifcant role of 2D nanomaterials
that are employed as an alternative to Pt-based electrocatalysts for HER facilitating the
electrocatalytic reduction of water to molecular hydrogen. The electrochemical prop-
erties of various 2D nanomaterials have been demonstrated and proved to be of great
potent for HER performance in a wide pH range. Due to their unique physicochemical
properties derived from atomically thin dimensions, 2D nanomaterials have been at
the forefront of research in recent years. 2D electrocatalysts comprise of 2D MOFs,
phosphorene, TMDs, transition metal chalcogenides (TMCs), graphene, graphydine,
hybrids of 2D SACs, and so on, which have shown remarkable HER performance,
wherein some of them have proved to be even better than commercial Pt/C. Extensive
studies on altering compositions, morphological structure, and other properties of
electrocatalysts are still in progress to maximize the HER performance. In recent
years, a wide-ranging family of 2D nanomaterials have been fabricated in the feld of
electrochemistry. This has prompted intense and diverse research projects comprising
both fundamental studies and technology applications [3]. In this context, the suc-
cessful application of 2D nanomaterial electrocatalyst for HER can be attributed to
its exceptional functional capabilities. 2D hybrid electrocatalysts are well-known for
exhibiting enhanced HER activity. For the next-generation renewable energy systems,
large-scale hydrogen production and development are of great signifcance.
Electrocatalysts with 2D layered structures with the beneft of release of stress can
buffer the shock of electrolyte convection, hydrogen bubble rupture, and evolution,
assuring prolonged stability [31]. 2D electrocatalysts with rich porosity enhance the
infltration of electrolyte and facile evolution of hydrogen at the high catalytic current.
Graphene, Phosphorene, etc. have been subjected to doping with heteroatoms, which
has led to the modulation of the electronic structure induced by interfacial charge and
thereby they have exhibited enhanced HER performance. Electrocatalysts with 2D
nanosheet structure have unique characteristics like high morphological anisotropy,
larger electrochemical surface area with a large number of surface-active sites, meso-
porous structure, open ion diffusion channels, synergic effect, along with distinctive
electronic structures. While, 2D-MOF nanosheets have integrated the advantages of
both 2D material and MOF, which are coordination of metal ions and organic ligands
possess several advantages on account of their ultrathin thickness, high surface-to-
volume atom ratios, and large surface area [32]. Another class of HER electrocatalysts
is TMDC nanosheets, which have less in-plane resistivity throughout the basal plane
[11] and relatively high mobility of the charge carriers, which in turn facilitate easier
electron transport. MXenes have emerged recently as a new class of 2D nanomateri-
als with conductivity similar to that of metals or semiconductors and also possess
similar physical properties like that of graphene. However, the 2D surface morphol-
ogy with distinct electronic properties needs to be fully investigated and compre-
hended for progressive HER performance. Further exploration of 2D nanomaterials
as electrocatalysts requires rational design and synthetic methods for optimal HER
performance. It is highly signifcant to further understand their structural and electro-
chemical properties. In addition, creating effective hybrids of 2D nanomaterial-based
structures will furnish more avenues for broader range of electrolytic water splitting.
Hence, the signifcance of in-depth studies on electrocatalytic properties of 2D nano-
materials, especially for HER, can be understood.
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19 Application of Graphene
Family Materials for
High-Performance
Batteries and Fuel Cells
Chen Shen and S. Olutunde Oyadiji
The University of Manchester
CONTENTS
19.1 Introduction .................................................................................................. 321
19.2 Graphene and Graphene-Based Materials.................................................... 322
19.2.1 Classifcation and Fabrication........................................................... 322
19.2.2 Properties.......................................................................................... 324
19.2.3 Characterization Techniques ............................................................ 325
19.2.4 General Applications of Graphene ................................................... 325
19.3 Application of Graphene and Graphene-Based Materials in Batteries
and Fuel Cells ............................................................................................... 326
19.3.1 Introduction ...................................................................................... 326
19.3.2 Structures, Basic Mechanisms, and Key Parameters of
Cells/Batteries................................................................................... 326
19.3.3 The Application of Graphene/Graphene Family Materials on
Batteries ............................................................................................ 328
19.3.3.1 Graphene/Graphene Family Materials in Lithium-ion
Batteries ............................................................................. 328
19.3.3.2 Graphene/Graphene Family Materials on Fuel Cells ........ 333
19.3.4 Discussion......................................................................................... 337
19.4 Summary and Prospective............................................................................ 338
References.............................................................................................................. 339
19.1 INTRODUCTION
Graphene is an allotrope of carbon, whose micro-structure is a repeating hexago-
nal pattern based on benzene ring and only has one layer of carbon atoms. Due to
this special micro-structure, it is treated as one of the representative 2D materials.
Once the word ‘graphene’ captures people’s imagination, the discussion of this mate-
rial never fades away within both professionals and ordinary people. In the public’s
view, graphene is an epic material. After all, ordinary people’s understanding of
DOI: 10.1201/9781003178453-19 321

graphene mainly comes from the Nobel Physics Prize awarded to the co-discoverers
of graphene in 2010, and the news about graphene industrial parks been built around
the world. Besides, the public’s perception is also infuenced by advertisements on
TV and websites, which claim their advanced products apply the latest graphene
technology.
On the contrary, in the researchers’ opinions, graphene is not as ‘wonderful’ as
claimed in the current consumer product advertisements. Indeed, graphene has out-
standing physical properties and stable chemical properties to some extent. However,
these properties are only theoretical values, which are realizable only at a small-
scale micro-level, and that are not likely to be directly applied in real life. Also, it
is not simple to fabricate a fawless and high-quality graphene piece, which further
increases the diffculties of its application. In the researcher’s view, the majority of
commercial graphene products in the market are just a ‘stunt’. Researchers tend to
believe that these products are just conventional products marked with higher retail
prices, which only use this fancy word to attract customers’ attention, especially for
a consumer who does not have a strong background in science.
Among all commercial graphene products, graphene-based electronics, including
power suppliers, capacitors, and electrodes, are, perhaps, the products with the most
voluminous commercial applications, with batteries attracting the most attention. In
the smartphone industry, manufactures are expecting a type of battery with higher
capacity, faster-charging velocity, and thinner thickness to make their product out-
standing. In the electric vehicle industry, a type of battery with a high capacity, long
lifetime, and the reliable output voltage is needed to dominate the power supply feld
in this new feld.
In this chapter, the application of graphene and graphene-based material in the bat-
tery and fuel cell industries is introduced. Section 19.2 covers the basic characteristics
of graphene. How graphene will beneft the performance of batteries and fuel cells
are introduced in Section 19.3, especially lithium-ion batteries (LIBs) and fuel cells.
19.2 GRAPHENE AND GRAPHENE-BASED MATERIALS

19.2.1 CLASSIFICATION AND FABRICATION
Graphene consists of carbon, in its thickness direction it only contains one layer
of atoms. Therefore, graphene can be treated as a two-dimensional material. The
research on this material can be traced back to the 1960s. In 2004, Andre Geim and
Konstantin Novoselov from the University of Manchester, using ductile tape, suc-
cessfully peeled graphene fakes from highly oriented pyrolytic graphite and were
awarded the Nobel Physics Prize in 2010. Graphene’s essential microstructure is a
sp2 C-C bond under a hexagonal benzene-ring shape (honeycomb structure, shown in
Figure 19.1). Theoretically, graphene should be single-layered. Nevertheless, because
of the fabrication diffculty, a local multi-layer or acceptable range of doped elements
(commonly hydrogen or oxygen) is allowed. In practice, the word ‘graphene’ is often
wrongly used to refer to different materials that can be classifed as belonging to the
graphene-based material family. It is correctly used to refer to pristine graphene (pure
graphene, it has the best quality). However, it is wrongly used to refer to graphene
Application of Graphene Family Materials 323
FIGURE 19.1 Microstructure of graphene.
oxide (the oxidation of graphene, it contains a large amount of oxygen atoms) or

reduced graphene oxide (rGO; the product obtained after removing the majority of
oxygen atoms from graphene oxide, it contains a small amount of oxygen).
The methods of fabricating graphene can be classifed as direct methods and indi-
rect methods. Direct methods include physical approaches (e.g., mechanical peeling
and ultrasonic peeling from graphite) and chemical approaches (e.g., chemical vapor
deposition and SiC epitaxial growth), which are used to fabricate continuous pris-
tine graphene sheets directly and typically require a relatively complicated opera-
tion. The product is expected to be of high quality. Indirect methods produce rGO
from graphene oxide, which can be fabricated following the Hummer’s method or
can be directly purchased from the market. By removing the majority of the oxygen
atoms from graphene oxide, rGO can be obtained. Commonly used indirect meth-
ods include photo induction (UV, laser, etc.), chemical induction (hydrazine, sodium
ascorbate, etc.), and thermal induction (annealing, temperature bath, etc.). The fab-
rication process of rGO is relatively simpler to be performed though the quality of
the product is not easy to be fully controlled. The best quality rGO has properties
that are very similar to those of pristine graphene. Indirect methods are popular
within research establishments as they can be used as a replacement for expensive
pristine graphene. The majority of ‘graphene’ produced by researchers themselves
and reported in journal articles refers to ‘reduced graphene oxide’.
Besides, based on the thickness, graphene can be classifed as one-layer graphene,
bilayer graphene, and few-layer (3–9 layer) graphene. Graphene with more than 10
layers of carbon atoms is classifed as graphite. A more general name of graphene
with multi-layer is graphene nano-platelet (GNP), which refers to the mixture of gra-
phene whose thickness varies from 3 to 100 nm. GNP is a popular material to be
used in industrial products, especially for products that do not require the continuity
of graphene. High-quality graphene with only one layer of atoms is also defned as
graphene nano-sheet (GN).
Apart from the thickness and quality, for GN, especially for the sheets smaller
than 50 nm, based on its boundary morphology, it can be further classifed as zig-zag
direction and armchair direction. As shown in Figure 19.1, a zig-zag edge is similar
to the tetracene structure while the armchair edge is close to chrysene. It should be
noted that the differences in boundary directions will not have signifcant infuences
on the properties of graphene; it will only slightly affect the electronic properties at
the edge [1].
19.2.2 PROPERTIES
Table 19.1 lists the properties of graphene. As a form of carbon, graphene is hydro-
phobic. Thus, its dissolvability is low but can form stable dispersion in polarized liq-
uids. Typically, graphene is black, no matter whether it is in solid form or dispersion
form. For relatively low concentration dispersion, sometimes it can be light brown.
Its chemical properties are stable so it cannot simply react with other materials under
normal conditions. Graphene has a low electric resistance rate (200 Ω m−1) and high
intrinsic mobility (200,000 cm2 V−1∙s), which makes it ideal for battery and super-
capacitors. The high melting temperature (4,510 K) and high thermal conductivity
(5,000 W mK−1) also make it suitable to be applied in the thermal feld. Overall,
graphene has outstanding physical properties.
The mechanical properties of graphene have made graphene to be well known.
The widely accepted values are 1 TPa for its Young’s modulus and 130 GPa for ulti-
mate tensile stress. These two values are very high. Comparatively, Young’s modu-
lus of graphene can reach around fve times and the ultimate tensile stress is more
than three times the corresponding properties of steel. However, it should be noticed
that these values are just theoretical values at the micro-level. The samples used for
mechanical tests are fawless micro-fakes. They were tested via the nano-indentation
method under an atomic force microscope (AFM) by Lee et al. [2]. The methods
used to derive these values are not the same as those used at the macro-level, and
the macro-level derived values are not the same as those derived by other methods
that we are familiar with. Researchers also performed macro-level mechanical tests
on graphene sheets though the results are relatively low in value. Apart from the
methodologies to obtain the values, another reason for this difference is the diffculty
in controlling the quality of the macro-sized graphene. It usually contains a large
quantity of micro-cracks and local overlap, which will signifcantly infuence the
TABLE 19.1
Properties of Graphene [1]
Properties Value
Color Black
Specifc surface area 2,630 m2 g−1
Intrinsic mobility 200,000 cm 2 V −1 ˜ s
Theoretical young’s modulus 1 TPa
Theoretical tensile strength 130 GPa
Thermal conductivity Around 5,000 W mK−1
Electric resistance rate 200 Ω m −1
Optical transmittance 97.7%
Melting temperature 4,510 K
Dissolvability Hydrophobic
Chemical stability Prominent
mechanical properties obtained via a traditional tensile test. There is still an argu-
ment about the effective values of the mechanical properties of graphene.
19.2.3 CHARACTERIZATION TECHNIQUES

As introduced in Section 2.1, the majority of ‘graphene’ mentioned in journal arti-
cles, as a matter of fact, is ‘reduced graphene oxide’. The morphology of these two
materials is similar under macro views. Besides, the quality of rGO, including the
quantity of micro-cracks, oxygen and hydrogen contents, the local overlapping (thick-
ness) as well as the reduction level cannot be determined accurately using bare eyes.
Therefore, special characterization equipment and techniques are required. Based
on the expected outcomes, the characterization methods to qualify graphene can be
divided into two groups, for morphology and contents. Typically, morphology obser-
vation equipment that is used includes electronic microscope, transmission electron
microscope, scanning electron microscope, scanning tunneling microscope (STM),
and AFM. The equipment can magnify the observation area 103–109 times to observe
the morphology. Specifcally, AFM and STM can be used to output detailed 3D
images and thickness profles to further characterize the morphology of graphene. To
verify and analyze the content of the sample, X-ray diffraction (XRD), Fourier trans-
forms infrared spectrum (FT-IR), and Raman test are typically used, with Raman
test and XRD being used to verify the material type. The working principle of the
Raman test is based on observation of the location and intensity of the characteristic
band on the refection spectrum. As for XRD, it relies on the location and intensity of
the Eigen peak on the X-ray spectra. FT-IR is used to fnd out the content of the mate-
rial. The functional groups within the sample can be verifed through the refected
infrared light spectrum. The techniques mentioned above are the most commonly
used approaches to characterize graphene/rGO. The quality of graphene/rGO should
be verifed before application.
19.2.4 GENERAL APPLICATIONS OF GRAPHENE

With various outstanding properties, graphene can be applied in various areas. With
good electric conductivity, graphene can be used to synthesize electric conductive
composite and low resistant lead wire. Its high thermal conductivity had already been
applied by smartphone factories as a rapid cooling coating. Besides, the high Young’s
modulus and ultimate tensile stress of G/rGO enables it to be used as micro fllers
to enhance the mechanical properties of composites. Apart from these, graphene
has been successfully used to fabricate a seawater flter, which can directly transfer
seawater into drinking water and provides a relatively cheap method for water desali-
nation. However, limited by the cost of high-quality samples, graphene is more likely
to be applied in military, medical and advanced material felds where performance
is the frst consideration rather than price. Currently, it is not realistic to use this
material in our daily life [1]. The application of graphene in batteries and fuel cells is
introduced in detail in the next section.
19.3 APPLICATION OF GRAPHENE AND GRAPHENE-

BASED MATERIALS IN BATTERIES AND FUEL CELLS
19.3.1 INTRODUCTION
In this section, apart from the use of graphene-based material in batteries and fuel
cells, details about their history, mechanism, and key parameters are also included. To
start with, the defnitions of cell, battery, and fuel cell are provided. Cells and batteries
are both used to supply power to electrical appliances, from small electric watches to
large electric automobiles. A cell is the basic electrochemical/galvanic unit to store
and transform the chemical power stored in the electrode or fuel, while a battery refers
to the device, which consists of piles of cell units for longer output. The storage bat-
tery is most commonly seen in our daily life. A storage battery stores electrochemical
energy in its electrodes, which will be transformed into electrical energy when exter-
nal connections are made to the battery. The modern battery1 was developed over the
past two centuries. It was frst invented by the Italian physicist Alessandro Volta in
1800 with Cu and Zn units, and it can output stable electricity for an acceptable length
of time. In the following century, batteries including Zn-Cu, Zn-acid, iron-carbon,
lead-acid, Zn-Mn, Zn-carbon, and Ni-Cd batteries were gradually invented.
On the other hand, a fuel cell is an electrochemical cell that converts the chemi-
cal energy of a fuel (hydrogen, diesel, ethanol, etc.) and an oxidizing agent (often
oxygen) into electricity through a pair of redox reactions. The concept of the fuel
cell was frst proposed in the 1830s and frst developed in 1932 by the English engi-
neer Francis Thomas Bacon. Due to the ‘green’ product (water), a H-O fuel cell is
expected to play a signifcant role in the next energy revolution. Fuel cells are similar
to batteries but require a continuous source of fuel. They will continue to produce
electricity as long as fuel is available [3].
19.3.2 STRUCTURES, BASIC MECHANISMS, AND KEY

PARAMETERS OF CELLS/BATTERIES
No matter the type, mechanism, and appearance of the cell/battery, it contains three
essential components: anode, cathode, and electrolyte. For a battery, the anode
(marked as ‘−’) is the electrode where electrons are lost (shown conventionally as
the electrode into which current fows at the macro level). This occurs whilst the
battery is in its discharging mode. Typically, the anode material is more active and
is oxidized whilst the battery is functioning. On the contrary, reduction happens on
the cathode (marked as ‘+’), where the cathode material receives the electrons from
the anode. It is generally shown as the end where current fows out. The electrolyte
creates an atmosphere to assist the movement of ions. The output voltage of the entire
cell equals the differences of the half-cell reduction potential between the cathode
and anode. Technically, the more amount of anode material, the longer a battery can
operate.
1 To avoid confusion, the ‘cell’ and ‘battery’ in the usage of the terms ‘fuel cell’ and ‘storage battery’
(hereinafter abbreviated as battery unless otherwise specifed) in the following sections are indepen-
dent of the ‘quantity of basic elements or galvanic cells’.
To describe the properties of a cell/battery, three of the most commonly used

parameters are: capacity, energy, and voltage. Capacity denotes the electric energy
stored within the device. The value is described in Ampere-hour (A∙h), where 1 A∙h
equals to the quantity of electric charge in a 1 Ampere steady current fow for 1 hour.
Energy is described in W∙h and denotes the value of power, which can be output
under specifc environmental conditions. Voltage represents the value of output volt-
age while the device is functioning. Theoretically, energy should equal to the voltage
multiplied by capacity. The information about other parameters, which can be used
to assess the quality of a battery is listed in Table 19.2.
Among storage batteries, LIB, which is widely applied in electric devices, needs to
be highlighted. It has a long lifetime, thin dimensions, high capacity, and can output
stable power. The LIB should be distinguished from lithium battery, whose electrodes
are lithium and are highly active. It is risky while functioning and in storage, therefore
it is not widely applied in our daily life. The electrode material for LIB is a compound
of lithium, which is relatively stable and safe to be used. The LIB reaction is revers-
ible and achieved by the repeatable intercalate/deintercalate process of lithium-ion.
While discharging, the lithium-ion will be oxidized at the anode and will be reduced
while charging. The co-inventors of LIB were awarded the Nobel Prize in Chemistry
in 2019. Nowadays, different kinds of cells/batteries can be found everywhere.
TABLE 19.2
Parameters of Battery
Parameter Unit Meaning
Rated capacity A∙h Value of energy battery can store under test condition
Rated energy W∙h Value of energy battery can output under test
condition, equals to the rated voltage × rated capacity
Rated voltage V Magnitude of voltage while battery is functioning
Energy density W∙h/L Value of energy per unit volume contained
Power density W/L Value of maximum power per unit volume contained
Specifc power W/kg Value of maximum power per unit mass contained
Specifc capacity A∙h/g (mAh/g) Value of energy unit electrode material contains
Specifc energy W∙h/g (mWh/g) Value of energy unit electrode material can output,
equals to the output voltage × specifc capacity
C-rate/E-rate % Discharging rate of current/power against the capacity
of battery
Lifetime - Quantity of cycle a battery can reach before its
capacity is reduced to a given value
Internal resistance Ω Value of resistance of the battery
Self-discharge % Loss of capacity during long-term storage
State of charge (SOC) % Current battery capacity as a percentage of maximum
capacity
Depth of discharge (DOD) % Ratio of output capacity to rated capacity while
working
State of charge (SOD) % Ratio of remaining energy to rated capacity while
functioning
The convenience and fexibility they provide have signifcant benefts to people’s
life and the development of science. Currently, limited by its stability and output
effciency, the commercialization of H-O fuel cells is not yet 100% mature. LIB has
a very high market share. Battery factories are investigating heavily in this feld and
expecting the next generation of batteries to appear soon. The effort scientists are
making to optimize these two types of energy suppliers through graphene, which
will be introduced in the next section.
19.3.3 THE APPLICATION OF GRAPHENE/GRAPHENE

FAMILY MATERIALS ON BATTERIES
19.3.3.1 Graphene/Graphene Family Materials in Lithium-ion Batteries
19.3.3.1.1 Working Principle of Lithium-ion Batteries
As briefy introduced in the previous sections, LIB is the most commonly used bat-
tery to power mobile devices and small electric devices in daily applications. Early
forms of LIB’ cathode materials include Li-TiS2, Li-MoS2, and LixMnO2. Currently,
the most popular LIB electrode materials are LiCoO2-graphite. The working sche-
matics of LIB are shown in Figure 19.2. The left-to-right process is the discharging
process while the right-to-left direction is the charging process. In the discharging
process, Li-ions leave the anode and move to the cathode where they are reduced.
This translates generally to an external electron fow from the graphite anode to the
LiCoO2 cathode whereas the current fows from the cathode to the anode. While
FIGURE 19.2 The charging/discharging process of Li-ion battery.

discharging, the reduction potential for the cathode is 1 V. The cathode half-reaction
can be written as:
CoO 2 + Li + + e − = LiCoO 2
As for the anode, the half-reaction is:
LiC6 = Li+ + C6 + e −
The reduction potential is around −3V. Therefore, the theoretical cell voltage for this
type of LIB is around 4 V, which is suitable to be used for charging. More statistics
about the reduction potential can be found in references [4–6]. The full reaction at
the electrodes can be written as:
CoO 2 + LiC6  LiCoO 2 + C6
Apart from the theoretical output voltage, the theoretical value of battery capacity is
an important parameter as well. It can be calculated using:
F
QTheoretical = n °
M
In which, n is the quantity of electron transferred within the reaction. F is the Faraday
constant, represents the value of charges per mole of electron carries. This value
equals to the product of the Avogadro constant NA (6.02 × 1023/mol) and the elemen-
tary charge (1.6 × 10 −19 C), which is 96,500 C mol−1. M is the molecular weight of the
active material, typically described under g mol−1. The value of capacity is described
in C mol−1. To transfer the value into commonly used mAh g−1, the value needs to be
multiplied by 1/3.6 (1,000 mAh/3,600 s).
As an example, the theoretical value for LiCoO2-graphite battery’s capacity is
given by:
F 96,500 1
QTheoretical = n ° = 1× × ˝ 372 mAh g−1
M 72 3.6
in which, n = 1 due to one electron transferred during the reaction, M = 72 is the
molecular weight of C6.
The theoretical capacity value can only be obtained when the deintercalate
coeffcient of Li-ion equals to 1. In real life, the real deintercalate coeffcient of
the battery needs to be multiplied with the theoretical value to obtain the practi-
cal capacity. If other parameters such as the environmental factors and the loss of
cathode material are taken into account, the more accurate method to acquire the
practical capacity of the battery is to integrate the discharging current curve over
time, written as:
t
˜
Q = I (° ) d°
0
in which, t: Total discharging time, I(τ): The value of electric current, τ: Time.
Moreover, as shown in Figure 19.2, a passivation flm or solid electrolyte interface
(SEI) will be slowly generated at the interface between the liquid electrolyte and
solid phase. It covers the anode during the frst charging process of the battery. This
layer is permselectable for Li-ion and can avoid the unwanted reaction between inter-
mediate products. The SEI flm can act as a protective flm to extend the lifetime of
the anode, whose thickness is typically 100–150 nm. As for the cathode, a passivation
layer can be observed at the interface between the electrode and the electrolyte as
well, though it is signifcantly thinner than the SEI at the anode (usually 1–2 nm), and
it does not function the same way as the SEI. Besides, a physical separator is required
between the anode and the cathode to prevent unwanted shortcuts caused by the con-
tact of the two electrodes. As the separator is immersed into the electrolyte, it should
be made from a material that has good corrosion resistance under an organic envi-
ronment. Thus, the most commonly used materials to make a separator are polymer
flm/polymer composite flms (polypropylene (PP), tetrafuoroethylene (TFE), poly-
vinyl chloride (PVC), polyethylene (PE), etc.). In recent years, advanced materials
including nylon, glass, ceramic, non-woven fbers, and polyester are gradually being
applied. This is because uniformly distributed microporosity is also required on the
separator to ensure low internal resistance and good permeability of electrons and
Li-ions. Moreover, the separator is supposed to have reliable mechanical properties,
thermal stability including low heat shrink rate, good wettability by the electrolyte,
and smooth and fat surface.
Furthermore, for the electrode reaction under real circumstances, due to the
uncontrollable factors such as reaction level, environmental condition, over-
charging, over-discharging, defect on the cell, unexpected impurity, the output
voltage/current, and lifetime will be infuenced. For instance, if over-charged/dis-
charged, the reaction products on the electrodes will be peroxided and irreversible,
which will infuence the lifetime of the electrodes. Over-charging/discharging will
also potentially cause damage to the SEI. The electrolyte will then directly contact
with electrodes and result in the swelling of the battery. If Li-ion functions under
low temperature continuously, the viscosity of the electrolyte will be signifcantly
increased, which will directly infuence the activity of the Li-ion at the cathode
and its ability to pass through the SEI. This will result generally in a short working
time of LIB in cold weather/climate (winter). Nowadays, commercial LIB usually
comes with a protective circuit to prevent negative infuences from unexpected
factors.
19.3.3.1.2 Approaches to Improve the Performance of

Lithium-ion Batteries
Capacity is one of the most important parameters to describe the performance of a
battery. However, for commercial batteries in real applications, especially for mobile
phones, considering the limitation of the dimensions, the output stability, recharge-
able stability, and energy density are the priorities. After all, for public customers, a
cheap and reliable battery is always a better option than a heavy and giant single-use
battery. To optimize the performance of LIB, the commonly used methods are listed
below. The methods can be easily operated though they are complicated to apply.
1. Structure: Optimize the dimension of the battery to increase the ratio of

the active material. It can be achieved by modifying the outer dimensions,
or by optimizing the barrier and interface design within the battery to save
internal space. Besides, ion transferability can also be improved by drilling
micro-holes on the barrier and interface.
2. Electrolyte: Theoretically, the electrolyte is inconsumable during the bat-
tery reaction. It only acts as an agent to assist the transportation of Li+.
Therefore, by improving the conductivity of the electrolyte, the quantity
of electrolyte can be reduced to save more space for the active materials. It
can be achieved by changing the electrolyte materials, or by adding conduc-
tive materials to improve the existing electrolyte’s electrical conductivity.
Moreover, the performance of batteries can also be improved by the optimi-
zation of SEI, which can directly be achieved by adding conductive materi-
als within the electrolyte. This approach will increase the electron transfer
rate and result in the improvement of the battery properties.
3. Electrode: The chemical reactions in a battery are determined by the mate-
rials of the electrode. Therefore, using advanced electrode materials can
optimize the reaction mechanism to ensure more electron transportation
and a stable reaction process. So far, for LIB, it is unreal to fnd a new
method and entirely replace the existing mechanism. It is preferred to opti-
mize the electrodes by doping them with active addictive materials. For the
anode, the doping material should ensure that the electrode has a greater
ability to accumulate Li+ (it can also be achieved by increasing the inter-
layer spacing of graphite). As for the cathode, the level of reaction can be
improved by doping the electrode to increase the level of reactivity, which,
in turn, will lead to higher output of electricity. Apart from doping, the same
effect can also be achieved by surface coating or surface cladding of the
electrodes using carbon or metallic materials. The coating should simplify
the transportation process of Li+ and increase the quantity of exchanged
ions in unit time. The properties of the electrodes can also be optimized
by physical treatment. By refning the particle of the electrodes or by nano-
crystallization, the path for the transportation of Li+ ions will be optimized
via the reduction of the diffusion distance. Increasing the micro-porosity of
the electrodes will also enhance the performance of the batteries. However,
instead of using advanced electrode materials with higher porosity, the
common electrode materials can be used by subjecting them to surface
treatment including fuorination and oxidization.
19.3.3.1.3 Approaches to Improve the Performance of Lithium-

ion Batteries using Graphene Family Materials
Based on the methods introduced in the previous section, the following approach can
be applied to improve the key properties of LIB by using graphene.
Using Graphene on Anode: In a LIB, graphite electrodes typically act as

the anode, which collects the Li+ ions from the cathode while it is charg-
ing. Compared with a graphite electrode, the use of graphene as anode will
change the reaction products at the anode, which will result in a differ-
ent value of the output voltage and potentially higher values of theoretical
capacity. This is due to the ability of a multi-layer graphene sheet to accom-
modate more Li+. It is pointed out by Kaskhedikar and Maier in 2008, that
the interlayer spacing of graphite anode is 3.35 Å while it can be observed for
a multi-layer graphene anode that the layer-by-layer spacing is close to 4 Å,
which provides more space for the Li+ to store. Besides, compared with
graphite, Li+ can be adsorbed on both sides of graphene, which further
increases the Li+ content. Ideally, a product such as LiC3 will be generated
instead of LiC6, which will double the capacity to around 740 mAh g−1 [7].
Moreover, in real life, graphene anode is mainly fabricated by rGO, whose
microstructure typically contains lots of defects and impurities. The defects
within the microstructure will result in a reduction of electrical conductiv-
ity. Nevertheless, it will beneft the accommodation of Li+ to some extent
and further improve the capacity.
According to statistics compiled by Al Hassan et al. (2019), with defects
within the microstructure, the capacity of the battery can be increased from
800 to 2,000 mAh g−1. On the other hand, it should be noted that the defect
within the anode is uncontrollable. Furthermore, although the capacity of the
frst charging/discharging cycle is being signifcantly increased, the capac-
ity drops clearly after 50–100 cycles. Besides, compared with a graphite
anode, the cost of graphene (rGO) anode is signifcantly higher. Therefore,
graphene anode is not yet being widely used in commercial battery prod-
ucts [8]. Apart from directly using graphene as an anode, using graphene
composites/alloys/nanohybrids as the anode material is another method to
take both the cost and the performance of the battery into consideration. As
a form of carbon, graphene can be used to easily form a good quality com-
pound. With the addition of other elements, the cost can be decreased. Due
to the interface properties, the capacity, cyclic stability, and capacity reten-
tion can be improved. Successfully applied composites materials include
Si, SiC, SiO, Mo, MoS2, Ge, and Sn; metal oxides such as Co3O4, Fe3O4,
Fe2O3, SnO2, TiO2, SnO2, CuO, and MoO3; alloys like silicon/graphene, tin/
graphene, germanium/graphene; nanohybrids such as Mn3O4, SnO2, SnO2
and phosphorus, Sb2O3, Ag. However, despite the improvements in the per-
formance of batteries, there is a long waiting period before graphene-based
anode can go into commercial application.
Use of Graphene on Electrolyte: The traditional electrolyte for commercial
LIB is typically liquid phase (some shown as crystals under room tempera-
ture) solvent plus lithium salt (LiPF6 is the most common option). Apart
from electrodes, the electrolyte will infuence the internal resistance and
the capacity of batteries. Over the past two decades, with the development
of electrolyte materials, the capacity of LIB has improved signifcantly. The
graphene (rGO or GO) additives in the electrolyte can increase the con-
ductivity of the electrolyte. It can also beneft the wettability of the electro-
lyte on the electrodes. The problem which limits the large-scale application
of graphene electrolyte is the same as graphene anode: price and stability.
Still, considering the commercial proft and scientifc progress, industries

and researchers invest more time and resources in the research of solid-
phase electrolytes, which is expected to be the breakthrough of the next-
generation LIB.
19.3.3.2 Graphene/Graphene Family Materials on Fuel Cells

19.3.3.2.1 Working Principle of Fuel Cells
Apart from rechargeable LIB, a fuel cell is another type of electrochemical power
supplier, which is also a major focus of research investigations. Compared with a
rechargeable LIB, fuel cells are typical of large volume and non-rechargeable. Unlike
rechargeable batteries, the materials used for the electrode reaction are required to
be fed continuously into the system. Therefore, the working life of a fuel cell is sig-
nifcantly longer than rechargeable batteries. The working principle for a fuel cell is
shown in Figure 19.3. The schematic shows a proton exchange membrane (PEM) fuel
cell, whose most suitable working temperature is around 80 (determined by different
materials of the membrane). The oxidation reaction of the fuel (typically hydrogen)
will take place around the anode, where hydrogen loses ions and is oxidized to H+.
The generated H+ will transfer to the cathode through the polymer electrolyte mem-
brane and assist the reduction of the oxidizing agent (oxygen is the most commonly
used material). Unused fuel and oxygen as well as the reaction product (H2O) will
then leave the cell and can be recycled afterward.
To ensure a safe and compact structure, the electrodes are typically designed
as bipolar plates, with fow channels uniformly distributed on them. Figure 19.4
shows various designs of the fow channels including (a) straight parallel, (b) inter-
digitated, (c) pin-type, (d) spiral, (e) single-channel serpentine, and (f) multiple-
channel serpentine fow channel confgurations [9]. The fow channels assist the
FIGURE 19.3 Schematic of hydrogen–oxygen proton-exchange membrane fuel cell.

FIGURE 19.4 Scheme of typical fow feld confgurations (a) straight parallel; (b) inter-
digitated; (c) pin-type; (d) spiral; (e) single-channel serpentine; (f) multiple-channel (triple)
serpentine [9]. Adapted with permission from [9]. Copyright (2019) Copyright The Authors,
some rights reserved; exclusive licensee MDPI.
fow of gas and prevent direct contact between oxygen and hydrogen. A thin layer
of catalyst is also required, which is typically made of platinum. The material
used for the polymer electrolyte membrane is required to only allow hydrogen ions
to pass through from the anode to the cathode while preventing the oxygen from
passing through. It also should have reasonable strength and temperature resistance
to ft multiple working conditions. For the PEM fuel cell, the half-reaction on the
anode is written as:
H 2 = 2H + + 2e −
As for the cathode reaction, it is written as:
1
2H + + O 2 + 2e − = H 2 O
2
The overall electrode reaction is written as:
1
H2 + O2  H 2 O
2
Apart from H-O PEM fuel cells, there are many other fuel cells with different fuel
and electrode reaction mechanisms. Commonly applied fuel cells include solid oxide
fuel cells, alkaline fuel cells, molten carbonate fuel cells, and direct methanol fuel
cells. Different types of fuel cells have different effciencies, output power, and work-
ing temperatures while the reaction product from the electrode reaction is clean mate-
rial like water, which makes them environment-friendly. Theoretically, as long as the
fuel and oxygen are fed ceaselessly, the cell can function continuously. Therefore, in
applications, fuel cells are usually designed to be large to store more fuel. Another
advantage of a fuel cell is the fuel unit that can be replaced or reflled simply and
swiftly. Unlike compact LIBs, fuel cells are ideal for power systems of automobiles,
ships, aircraft, and submarines. However, to achieve maximum usage of fuel cells,
there is the need to establish a fuel (H2) reflling system (similar to the current gas
station network). Some countries (such as Japan) have decided to develop hydrogen
supply systems and networks to replace the existing fossil fuel supply system and
network, and they expect to achieve an eco-friendly society in the next few decades.
19.3.3.2.2 Approaches to Improve the Performance of Fuel Cells

Unlike LIB whose key parameters are the capacity, output voltage, and lifetime,
with the large dimension and simplicity of reflling the fuel, the operation time and
capacity are not that signifcant for a fuel cell. Instead, the low-temperature startup/
functionality, effciency as well as output rate to reach the maximum capacity are its
key parameters. The performance of a fuel cell can be optimized using the following
approaches:
1. Fuel: As the most essential constituent of a fuel cell, a fuel that contains a
large amount of chemical energy needs to be used. However, the develop-
ment time, which is typically 20,000h+ per prototype, and the development
cost that can be £10M+ (for fuel only) make the development of the fuel
for fuel cells a rather expensive undertaking. Therefore, the researches on
the type of fuel to use in fuel cells researches are focused on hydrogen.
Developing a new type of fuel is not realistic currently.
2. Structure: Optimizing the structure of a fuel cell to optimize the gas fow is
the most effective method to enhance a fuel cell’s performance. The internal
gas fow can be guided by multiple channel confgurations on the bipolar
plates, as shown in Figure 19.4, to increase the contact area of gas as well as
controlling the internal heat radiation to maintain a suitable working tem-
perature. Besides, the pressure, gas composition, reactant utilization, inter-
nal resistance, and the current density within the cell will also be infuenced
by the structure design, which will further result in the enhancement of the
fuel cell’s performance.
3. Catalyst: A catalyst layer is typically located between the electrodes and
the PEM, to boost the velocity of reaction and optimize the reaction util-
ity of raw materials. The main catalyst material is required to have a large
active surface area and activity. Platinum and platinum alloy are the most
commonly used catalyst materials. The catalytic properties of the catalyst
layer degrade over time due to corrosion/oxidation of platinum or aggrava-
tion of carbon impurity. This results in the reduction of catalyst activity
and slows down the reaction velocity, which infuences the output of a fuel
cell. Therefore, the optimization of the material of the catalyst layer is an
approach to enhance a fuel cell’s properties.
4. PEM: The PEM between the electrodes is one of the core components of a
fuel cell. It assists the transfer of H+ (protons) from the anode to the cathode
and resists the direct passage of electrons across it. The PEM acts similarly
to the electrolyte in LIBs. Besides, the PEM should have low gas perme-
ation rate to prevent direct contact between oxygen and hydrogen to prevent
the explosion. Good mechanical properties and good thermal/chemical sta-
bilities are also required to ensure its integrity while working. The chemical
or mechanical corrosion of PEM will increase its micro or macroporosity,
which will result in low effciency and increase gas permeation rate, which
increases the potential explosion risk of the cell. Thus, selecting a suitable
membrane material based on its working condition is a signifcant factor
related to a fuel cell’s performance and safety. For instance, a solid oxide
fuel cell uses a ceramic material to allow it to operate at high temperatures,
while for normal temperature conditions, a long-chain polymer is used to
make the cell compact.
19.3.3.2.3 Approaches to Improve the Performance of Fuel

Cells through Graphene Family Materials
Based on the principles outlined, the following methods are the most commonly
applied approaches to improve the performances of fuel cells using graphene.
Use of Graphene in Catalyst/Electrodes: The output requirement for a fuel

cell needs it to have a high velocity of the reaction. It is mainly determined
by the reaction velocity on the cathode. Thus, it needs a catalyst layer to
ensure the reaction speed. Rare metals have been proved to have a good
catalytic effect on fuel cell reactions. In this regard, platinum and its alloys
are the most common catalyst materials. Due to the high price of both
the platinum and its alloys, an approach to produce a not-to-highly price
catalytic layer is to dope the microstructure of a reduced quantity of tita-
nium and its alloys with a small quantity of graphene. This will enhance
the velocity of oxygen reduction reaction induced by the doped catalyst (by
improving the carrier transportation process of the H+ across the PEM and,
thereby, boost the oxidation–reduction reaction speed) and reduce its cost
at the same time. Furthermore, graphene doping in the catalyst layer on the
anode will also optimize the oxygen reduction reaction process, though not
as effective as the improved performance achievable by the graphene dop-
ing in the catalyst layer on the cathode [10].
Use of Graphene on Bipolar Plate: The bipolar plate in a fuel cell has mul-
tifunction. Apart from controlling the fow of the fuel gas and air, it also
functions as a medium to conduct electric currents. The most commonly
applied bipolar plate materials are copper and nickel, whose properties have
a high probability of degrading during while the operating process of the
cell unit. Although it does not signifcantly infuence the general perfor-
mance of the cell, stability and durability still need to be ensured while the
fuel cell is functioning. Adding some quantity of graphene to the bipolar
plate is a practical method to reduce the electrical resistance of the bipo-
lar plate to a relatively low value, and to slow down the corrosion of the
bipolar plate during the oxidation process. Moreover, using graphene-based

polymer composites as the plate material is a good method to optimize the
performance of the cell unit, although the cost of the plate might be higher.
Use of Graphene on PEM/Electrolyte: As introduced in the previous section,
the PEM needs to have good mechanical properties and selective permitted
ability. The most commonly used PEM material includes poly(vinyl alcohol)-
based composites, Nafon copolymer, and sulfonated-polyetheretherketones
(SPEEK) [11]. The properties of these plastic-based materials can be modi-
fed easily by graphene micro-fller through the wet mixing method. The
graphene-modifed composites have better ionic conductivity and enhanced
mechanical properties, which results in a higher power density and longer
lifetime of the cell. Besides, graphene can also enhance PEM with opti-
mized thermal stability and water absorption capacity, allowing the cell unit
to function under various environmental conditions. Alternatively, instead
of using graphene as micro-fllers to optimize the solid-state electrolytes, it
can be directly used as a bulk or solid piece electrolyte. Nevertheless, the
bulk/solid piece electrolyte technologies are not as mature as modifying
PEM using micro-fllers.
19.3.4 DISCUSSION
In this section, the application of graphene in the battery and fuel cell felds has
been introduced. Although graphene has good electrical conductivity and a large
surface area, which is ideal for battery and fuel cell performance enhancement, due
to limitations of current technology and price, graphene has not been widely applied
in commercial battery or fuel cell products yet. Offsetting aside the issue of current
technology, the future applications of graphene in batteries or fuel cells depend on
the categories of these electrochemical units. Table 19.3 shows the categorization of
electrochemical cells based on their application scenario, accessibility, and price.
TABLE 19.3
Categories of Electrochemical Power Suppliers
Category Properties Price
Commercial Usually cheap and disposable (some are rechargeable), low power Less than £5
density. Can be directly used in daily life on low-power electric
devices such as controller, mouse, and toy.
Moderate The majority can be represented by a lithium-ion battery, widely £10–100,
applied on mobile devices, tablets, and wearable devices. depending
Rechargeable, able to constantly function for more than 10 hours. on properties
Usually sealed and requires assembly by an experienced technician.
Advanced Usually has special requirements such as high working temperature, More than
high output power (e.g., fuel cell), and long working time (more £1,000
than 24 hours). It is usually large and is unlikely to be sold
separately to private customers as it is usually in-built as part of a
system such as a vehicle.
For the commercial category, the cost of graphene enhancement of their proper-
ties far outweighs the performance enhancement. From the mechanism or technol-
ogy point of view, graphene should be able to improve its performance. However,
from cost consideration, with one gram of graphene worth more than 50 pieces of
batteries, the cost–beneft ratio is very small. Besides, such batteries can only be
used once, which is a waste of precious graphene material. Therefore, graphene is
not suitable to be used to enhance their performance. As for advanced high power
density electrochemical units like H-O fuel cells, because of their large dimension,
large quantities of graphene will be required to improve their performance. This will
further increase the cost of the cell unit, not to mention their original high price.
Apart from this, for a fuel cell, the simpler and more cost-effective approach is to
optimize its structure.
Graphene is more likely to be applied in the optimization of moderate category
batteries like LIB as long as the cost of graphene can be further reduced and its
enhancement effect can be further improved. Technically, increasing the interlayer
distances in a graphite electrode can improve the performance of a LIB, which can
be achieved by using advanced manufacture technologies to produce graphene elec-
trodes in which the layer-by-layer distances are increased. Commercially, there are
three main reasons for graphene to be applied in a moderate category battery like
LIB. First, the quantity of graphene used to optimize a LIB is relatively small, which
makes the increment of cost also be relatively small. Second, the recycling industry
of LIB is already mature. With the development of technology, the expensive gra-
phene content is possible to be re-used. Third, as the LIB is widely applied in mobile
phones, product customers are willing to pay more money, to experience the latest
technology, which makes it have bright market potential. Researchers and factories
are currently trying hard to bring the graphene-enhanced LIB into daily use.
19.4 SUMMARY AND PROSPECTIVE

In this chapter, the information on graphene family material, basic knowledge of bat-
tery and fuel cell, and the applications of graphene in the battery and fuel cell feld
have been briefy introduced. Nowadays, with investment from national governments
around the world, more and more graphene industrial parks are being built globally.
Researchers are trying their best to overcome the technical diffculties and to seek
opportunities for the application of graphene. As a star material over the past decade,
graphene has already proven its bright application potential in various felds includ-
ing material, energy, and medical felds. However, due to its high price, mature gra-
phene-based battery products can be hardly found in the market, even if the market
is looking for a next-generation mobile device battery. The authors predict that with
the development of technology to solve the technical challenge of mass production of
high-quality graphene, graphene-based LIBs can be expected to become ubiquitous
within the next decade.
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20 2D Transition Metal
Dichalcogenides (TMD)-
Based Nanomaterials
for Lithium/Sodium-ion
Batteries
Tian Wang, Ashok Kumar Kakarla, and Jae Su Yu
Kyung Hee University
CONTENTS
20.1 Introduction .................................................................................................. 341
20.2 Structure and Properties of 2D TMDs ......................................................... 343
20.3 Preparation Processes ................................................................................... 343
20.3.1 Hydrothermal/Solvothermal Method................................................ 343
20.3.2 Chemical Vapor Deposition Method ................................................ 347
20.3.3 Exfoliation Method........................................................................... 349
20.4 Applications .................................................................................................. 349
20.4.1 Application in Lithium-ion Batteries................................................ 349
20.4.2 Application in Sodium-ion Batteries ................................................ 353
20.5 Conclusion and Outlooks.............................................................................. 357
References.............................................................................................................. 358
20.1 INTRODUCTION
Fast-growing consumption of energy has drawn great attention to exploring sus-
tainable, clean, and low-cost energy storages devices. The traditional fossil fuels-
based energy supply systems are expected to be replaced by renewable energy, such
as solar energy, wind energy, and so on [1,2]. However, the intermittent issue of
renewable energy hinders its practical application. As an alternative solution, elec-
trochemical energy storage (EES) devices, such as rechargeable batteries, become
increasingly important for research and development. The application areas range
from portable electronics to the electrifcation of transportation and coupling with
renewable energy sources for powering the electrical grid [3,4]. Nowadays, recharge-
able battery devices are playing an important role in smart electronics, portable
electronic devices, and electric vehicles, by which our lifestyle is transformed [5].
DOI: 10.1201/9781003178453-20 341

Meanwhile, the substantial progress in battery technology will also build a stable
foundation for the successful realization of a carbon-neutral society in the energy
transition [6].
Lithium-ion batteries (LIBs) have been more interested in energy storage systems
as the power source for portable electronic devices since their frst commercializa-
tion by Sony in 1991. LIBs been also considered as the most promising energy stor-
age system for large-scale applications. The energy density of LIBs is also steadily
increasing at a rate of 7–8 Wh kg−1 year−1. Up to now, the state-of-the-art LIBs have
reached an energy density of 250 Wh kg−1 at the battery level (for 18,650 type cells).
Meanwhile, the energy densities of 235 Wh kg−1 and 500 Wh L−1 at the battery pack
level demanded by the market are also increasing [7,8]. Sodium-ion batteries (SIBs)
have captured widespread attention because of their abundant resources, low cost,
and similar electrochemistry to LIBs [9,10]. Figure 20.1a displays the components
of a rechargeable LIB/SIB. During the discharge process, Li/Na ions de-intercalate
from the anode after crossing the separator and intercalate into the cathode material.
The charge process is reversed. There are many achievements for LIBs that can be
easily applied for SIBs, which makes the rapid development of SIBs within only a
few years. However, the low energy density and limited cycle life of electrode materi-
als are of great challenge for the commercialization of SIBs [11]. Therefore, research-
ers are looking for more suitable electrochemically active materials to develop higher
energy density and power density batteries.
Since the successful preparation of graphene in 2004, two-dimensional (2D) nano-
materials attracted worldwide attention due to their unique properties. Layered tran-
sition metal dichalcogenides (TMDs), as typical graphene-like 2D nanomaterials,
have gained great interest in energy storage due to their X-M-X structure and unique
electronic and mechanical properties. The unique 2D architecture can enhance the
contact area between the electrode and electrolyte, offer more active sites for foreign
ions, and increase the ion migration kinetics. Meanwhile, compared with the graph-
ite anode, the higher voltage platform (usually above 1.0 V) of TMDs can effectively
avoid the formation of dendrite and ensure battery safety. These advantages suggest
that the TMDs are the ideal candidates for next-generation anode materials. In this
chapter, we present the recent progress in the synthesis and characteristics of 2D
TMD materials as an anode in Li/Na-ion batteries (Figure 20.1b). Meanwhile, the
FIGURE 20.1 (a) Components of a rechargeable LIB/SIB. (b) Synthesis and characteristics
of 2D TMD materials as an anode in Li/Na-ion batteries.
2D TMDCs-Based Nanomaterials 343
exciting progress of these 2D TMD materials used as an anode in Li/Na-ion batteries

is displayed. Finally, we conclude the improvement and prospects in the Li/Na-ion
storage performance of 2D TMD materials.
20.2 STRUCTURE AND PROPERTIES OF 2D TMDs

The layered TMDs usually possess two polymorphs, i.e., 1T and 2H which stand
for trigonal and hexagonal phases, respectively. The layered structures are similar
to graphite and the thickness of each monolayer is around 0.6–0.7 nm. Meanwhile,
they also have a common formula of MX2 in which M is a transition metal, from
groups 4 to 10 of the periodic table, and X is the chalcogens, respectively. The X-M-X
sheets are bonded by covalent force, while individual layers are held together by Van
der Waals force [12]. A variety of polytypes of the bulk crystals are formed by the
variations in stacking order and metal atom coordination. Therefore, a monolayer
MX2 displays different phases (trigonal prismatic or octahedral) according to the
coordination environment of M with X. For the H phase, M is in trigonal prismatic
coordination with X. For the T phase, M is in octahedral coordination with X. The
distorted T phase is named the T′ phase, which has the same coordination environ-
ment as the T phase [13].
Different polymorphs endow layered TMDs with different properties, leading to
the change in performance when being used in EES devices. For example, the 2H and
1T phase MoS2 structures are widely used in energy storage and conversion devices
due to their characteristic structure and rich physical and chemical properties [14].
However, the structure of the 2H MoS2 suffers from the large volume change during
the charging/discharging process and has a poor electronic conductivity, which hin-
ders the development of 2H MoS2 in Li/Na-ion batteries. Compared with 2H phase
MoS2, the 1T phase MoS2 presents a metallic transport behavior, which delivers fast
electron conduction. Besides, 1T MoS2 has a bigger interlayer spacing than 2H MoS2,
thereby enhancing the insertion/extraction of the foreign ion [14,15]. Therefore, 1T
phase 2D TMDs have been studied extensively in recent years.
20.3 PREPARATION PROCESSES

20.3.1 HYDROTHERMAL/SOLVOTHERMAL METHOD
The hydrothermal/solvothermal method is a low-cost and high-effciency synthetic
method that can synthesize most TMD nanomaterials, which has been intensively
investigated. The materials synthesized via hydrothermal/solvothermal method have
advantages of high phase purity, uniform size distributions, and controllable mor-
phology. Compared with conventional synthetic methods, hydrothermal synthesis
is more excellent in several aspects. For example, the compounds with elements in
oxidation states are diffcult to attain, especially important for transition metal com-
pounds. However, the hydrothermal method is easy to achieve in closed systems [16].
Over the past decade, many 2D TMD materials with different morphologies have
been reported by the hydrothermal/solvothermal method. The typical representatives
are MoS2 and WS2, and their corresponding carbon nanocomposite materials, etc.
FIGURE 20.2 (a) Schematic illustration of the tubular MoS2 hierarchical structures.
(Adapted with permission from [17]. Copyright (2020) American Chemical Society.) (b)
Formation process of MoS2/graphene heterostructure and (c, d) TEM and HRTEM images
and (e) the corresponding elemental mapping images. (Adapted with permission from [18].
Copyright (2017) American Chemical Society.) (f) Schematic illustration and (g) TEM images
of the VO-MoS2/N-RGO. Adapted with permission from [19]. Copyright (2018) Wiley-VCH.
(h) Schematic illustration for the preparation of MoSe2/MXene@C. Adapted with permission
from [20]. Copyright (2019) American Chemical Society. (i) TEM and (j, k) HRTEM images
of the WS2 nanochains. Adapted with permission from [21]. Copyright (2018) Elsevier.
As shown in Figure 20.2a, the tubular MoS2 hierarchical structure was prepared
by using ((NH4)6Mo7O24·4H2O) and thioacetamide (TAA) as a precursor and tetra-
methylammonium bromide (TMAB) as an additive. In this process, the addition of
TMAB helped to form a layered solid stick-like tetramethylammonium molybdate,
which acts as a template and intermediate during the formation of tubular MoS2
hierarchical structure [17]. Huang et al. reported a facile method to prepare the
MoS2/graphene heterostructure with MoS2 nanospheres grown on the graphene. At
frst, the graphite was exfoliated by ions and modifed with functional groups to
form a functionalized graphene. In the following hydrothermal reaction, the func-
tional groups on the graphene led to the MoS2 nucleation and growth (Figure 20.2b).
In this architecture, the MoS2 nanospheres anchored on the functionalized graphene

not only decreased the aggregate of MoS2 but also prevented graphene layers from
restacking. The transmission electron microscope (TEM) (Figure 20.2c) and high-
resolution TEM (HRTEM) images (Figure 20.2d) displayed the hexagonal structure
of the MoS2/graphene heterostructure, which indicated a large layer spacing (larger
than 0.64 nm). The elemental mappings also suggested a uniform distribution of
MoS2 on graphene (Figure 20.2e) [18].
High-effciency ion-based secondary battery electrode materials need to meet
rapid ion mobility during the design process. In this regard, designing electrode
materials with a vertical ion diffusion path is an ideal choice. Therefore, Park et al.
introduced a vertically oriented MoS2 with spatially controlled geometry on nitrog-
enous graphene sheets (VO-MoS2/N-RGO) by the solvothermal method. In their
research, the VO-MoS2/N-RGO was synthesized by an l-cysteine/MoO42− gel pre-
cursor in a mixed N, N-dimethylformamide and water solvent. In the case of select-
ing a suitable precursor, by controlling the heating rate of the nucleation process, the
vertical arrangement structure was obtained (Figure 20.2f). Figure 20.2g displayed
the TEM image of the VO-MoS2/N-RGO. The uniform layer number distribution
and large layer spacing are availed for the insertion/extraction of the foreign ion. As
a consequence, with a longer nucleation time, a denser MoS2 on the basal surface
was formed [19].
The 2D TMDs have high surface energy usually, which causes the nanosheets to
agglomerate, which results in the rapid capacity fading when used as electrode mate-
rials. Zhang et al. presented a rational design and fabrication of hierarchical carbon-
coated MoSe2/MXene hybrid nanosheets (MoSe2/MXene@C) as an anode material
to prevent the 2D MoSe2 sheets from restacking (Figure 20.2h). In this architecture,
the highly conductive MXene substrate could effectively improve electronic conduc-
tivity. Meanwhile, the carbon layer further enhances the stability of the composite
structure [20]. Du et al. introduced a metallic 1T′ phase dominated WS2 (1T′-D WS2)
nanostructure by a one-pot colloidal synthesis approach. In this study, oleic acid and
oleylamine were used as the reaction solvent and 1T′-D WS2 nanostructure was suc-
cessfully prepared at 280°C [21]. Figure 20.2i showed the TEM image of the 1T′-D
WS2 with a dominant size of ~162 nm. Meanwhile, the HRTEM images revealed that
the entire WS2 was composed of closely stacked thin nanosheets (Figure 20.2j and k).
Recently developed ternary sulfdes, such as Ni-Co-S, have attracted wide atten-
tion in EES due to their high stability, rich active sites, and excellent electronic
conductivity. In our previous work, we reported nanosliver decorated Ni0.67Co0.33S
forest-like nanostructures on Ni foam (nano-Ag@NCS FNs/Ni foam) via a facile
wet-chemical method, followed by a light-induced growth of nano-Ag onto NCS
[22]. In desirable growth, the NCS FNs were obtained on Ni foam by rapid nucle-
ation and precipitation of nickel (Ni2+), cobalt (Co2+), and thiosulfate (S2O32−) ions
(Figure 20.3a and b). Then, the nano-Ag was anchored on NCS FNs/Ni foam by a
facile photoreduction method at room temperature (Figure 20.3c). Hetero-network-
based MoS2@Cu2MoS4–210 (MS@CMS obtained at 210°C) 3D nanofowers (NFs)
and Co-nanoparticles-containing MS@CMS-210 (Co-MS@CMS-210) 3D NFs were
successfully prepared by a hydrothermal synthesis method [23]. As shown in Figure
20.3d, copper oxide (Cu2O) nanospheres (NSs) were prepared by the co-precipitation
346
FIGURE 20.3 (a) Preparation of growth environment, (b) schematic illustration for the growth of NCS NFs/Ni foam, and (c) photoinduced growth of
Ag nanoparticles on the NCS NFs/Ni foam. Adapted with permission from [22]. Copyright (2019) Wiley-VCH. (d) Schematic illustration for the prepa-
ration of the Cu2O NSs, MS@CMS, and Co-MS@CMS-210 hybrid products at different temperatures. (Adapted with permission from [23]. Copyright
(2021) Elsevier.) Schematic illustration for the preparation process of (e) Co-MOF/Ni foam, (f) CoNi2S4 NTs/Ni foam, and (g) Cu(Co-Ni)2S4 NTs/Ni
2D Nanomaterials
foam. Adapted with permission from [24]. Copyright (2021) Elsevier.

method. Then, the formed uniform Cu2O NSs were employed as a template to pro-
duce a series MoS2@Cu2MoS4 under different temperatures. Finally, the Co-MS@
CMS-210 was obtained by using the Co-nanoparticles induced MS@CMS-210 3D
NF. Metal-organic framework (MOF), as a new class of organic–inorganic hybrid
materials, has shown great potential as an attractive template for the feld of energy
storage devices. Yu et al. introduced Cu(Co-Ni)2S4 nanotubes on Ni foam (Cu(Co-
Ni)2S4 NTs/Ni foam) using synchronous etching and multi-ion doping enabled MOF
precursor [24]. Initially, the MOF precursor was synthesized on Ni foam with a facile
aqueous solution process, which provided Co2+ and Ni2+ ions during the solvothermal
process (Figure 20.3e). Figure 20.3f was the preparation of the CoNi2S4 NTs/Ni foam
by the multi-ion-exchange process. Then, the MOF/Ni foam and Cu foam were added
into the sulfur-contained solution to form hollow structured Cu(Co-Ni)2S4 NTs/Ni
foam (Figure 20.3g). In this architecture, the in situ doping Cu enhanced the elec-
trochemical conductivity. The hollow structure increased the electroactive surface
area. Therefore, this ternary architecture system indicates signifcant potential for
Li/Na-ion battery electrode materials.
20.3.2 CHEMICAL VAPOR DEPOSITION METHOD

Chemical vapor deposition (CVD), which is a bottom-up method for preparing 2D
TMD materials can be used to prepare high-quality 2D materials on different types
of substrates. Meanwhile, the CVD method can also be used to grow layered TMD
nanomaterials on other kinds of electrochemically active materials, resulting in
hybrid electrode materials. In this method, the precursors are exposed to the sub-
strate under conditions of high temperature. When the kinetic and thermodynamic
conditions required for the chemical reaction are reached, the 2D ultrathin products
are deposited on the substrate. As shown in Figure 20.4a, Wang et al. reported a
large-area multilayer MoS2/WS2 heterostructures on the SiO2/Si substrate via the
CVD method. The reaction process was mainly based on the instability of MoO3
and WoO3 at 650°C, which could be easily volatilized into the gaseous state. Then,
a thin layer of MoS2/WS2 flm was deposited on the substrate after the reaction of
gaseous MoO3 and WoO3 with sulfur vapor [25]. Wang et al. discovered that strong
light absorption and fast intralayer mobility could not be well developed in the usual
reported monolayer/few-layer MoS2 structures. Therefore, large-area, high-quality,
and vertically oriented few-layer MoS2 (V-MoS2) nanosheets were prepared by
CVD method [26]. Figure 20.4b displayed the morphology of the prepared MoS2
nanosheets. The cross-sectional image of the V-MoS2 (Figure 20.4c) indicated that
the height was about 2 µm with a bright and nearly transparent vertically oriented
structure [26]. The V-MoS2/Si heterojunction displayed an excellent lateral photo-
voltaic performance in the wide range of visible-near-infrared light and prominent
linearity without applying an external bias voltage.
Recently, Ly et al. reported the CVD growth of 2D MoS2 into a deep kinetic regime
via KCl as a catalyst and the plasma pretreatment on growth substrates (Figure 20.4d).
By this method, they achieved an unprecedented nonequilibrium high-index facet-
ing and unusual high-symmetry shapes in 2D materials [27]. During the preparation
of the 2D TMD materials via the CVD method, the substrates played a signifcant
FIGURE 20.4 (a) Schematic diagram of the CVD grown MoS2 and MoS2/WS2 flms.
(Adapted with permission from [25]. Copyright (2018) Elsevier.) (b) Top-view and (c) cross-
sectional SEM images of V-MoS2. Adapted with permission from [26]. Copyright (2018)
Wiley-VCH. (d) Schematic diagram of the catalyzed kinetic growth. Adapted with permis-
sion from [27]. Copyright (2020) American Chemical Society. (e) Schematic diagram and
(f) SEM image of triangular-shaped WS2 crystals grown onto a h-BN fake. Adapted with
permission from [28]. Copyright (2014) American Chemical Society. (g) Synthesis prog-
ress and (h) of the MoS2 quantum dots interspersed in MoS2 nanosheets. Adapted with per-
mission from [29]. Copyright (2014) American Chemical Society. (i) VS2 NH3 precursor
with NH3 molecules intercalated into the S-V-S layers and (j) AFM image of the exfoliated
VS2 nanosheets. Adapted with permission from [30]. Copyright (2011) American Chemical
Society.
role in limiting the physical properties of atomic-layer materials. Therefore, a suit-

able substrate directly determines the morphology and properties of the 2D TMDs.
Kitaura et al. reported direct CVD growth of WS2 onto high-quality hBN by a 3-fur-
nace CVD setup [28]. Figure 20.4e showed the atomic structure diagram of the WS2/
hBN heterojunction. As shown in Figure 20.4f, there were some dark triangles with
about 3 μm on hBN, which indicates the formation of WS2 crystals with a triangular
shape.
20.3.3 EXFOLIATION METHOD

Exfoliation method is a top-down method to prepare TMD nanosheets. TMD
nanosheets are easily obtained by exfoliation when the Van der Waals force between
layers weakens. Among all the exfoliation methods, solvent-assisted and ion (Li+)
intercalation-assisted exfoliation are two common methods. Compared with the ion
intercalation-assisted method, the solvent-assisted exfoliation method is simple to
implement. Figure 20.4g displayed the synthesis process of MoS2 quantum dots inter-
spersed in few-layered MoS2 sheets. The MoS2 quantum dots were obtained by a
liquid exfoliation technique in organic solvents. At frst, the MoS2 powder was added
in 1-methyl-2-pyrrolidone and sonicated in an ultrasonic bath continuously for 3.5 h.
Then, the dispersion was sonicated with a sonic tip for another 3.5 h. After standing
12 hours, the liquid exfoliation of MoS2 was obtained by centrifugal treatment [29].
Figure 20.4h showed the TEM image of MoS2 quantum dots (∼2 nm) interspersed in
MoS2 nanosheets.
In addition to the mechanical stirring technology to prepare single/few-layer 2D
materials, ion intercalation technology is also used to exfoliate layered 2D materi-
als. However, the traditional ion exfoliation technology suffered from the residual
of the nonvolatile ions, which hindered the performance of the prepared materials.
NH3 is a micromolecule with very positive physical activity and chemical reactiv-
ity. Meanwhile, the excellent volatilization property makes no residue after the
evaporation. Zhang et al. introduced a unique NH3-assisted strategy to exfoliate VS2
fakes into ultrathin VS2 nanosheets stacked with less than fve S-V-S single layers
(Figure 20.4i) [30]. Atomic force microscope (AFM) image showed that the c param-
eter of VS2 was 5.73 Å and the thickness was 2.488 nm (Figure 20.4j), which denoted
that the product consisted of 4–5 single layers of S-V-S.
20.4 APPLICATIONS
20.4.1 APPLICATION IN LITHIUM-ION BATTERIES
LIBs have been applied as a major power source for portable electronic devices in the
past decades. Graphite is employed as a predominant anode material for commercial
LIBs. However, the low theoretical capacity of 372 mAh g−1 hinders its large-scale
application. It is a considerable research direction to develop alternative anode mate-
rials with improved Li-ion storage performance [31,32].
In recent years, the 2D TMDs have attracted considerable attention in LIBs due
to their unique properties [33]. Onion-like crystalline WS2 nanoparticles anchored
on graphene sheets as high-performance anode materials for LIBs were reported
by Inha Kim et al. [34]. The onion-like crystalline WS2 nanoparticles evenly coated
on graphene sheets (WS2@Gs) were synthesized via ball milling technique apply-
ing WO3 nanoparticles (~15 nm) and following sulfdation. The ball milling method
enabled uniform covering of WO3 nanoparticles on graphene sheets without aggrega-

tion and the sulfdation induced phase transformation of the WO3 to WS2 nanopar-
ticles (Figure 20.5a). The unique structured WS2@Gs nanocomposites exhibited
excellent Li-ion storage capability of 587.1 mA h g−1 at 200 mA g−1. Meanwhile, it
delivered an excellent reversible capacity of 371.9 mA h g−1 at 1,000 mA g−1 and good
stability with a capacity retention of 62% after 500 cycles.
As shown in Figure 20.5b, 1T-MoSe2 with expanded interlayer spacing of 10.0 Å
in situ grown on single-wall carbon nanotube (SWCNT) flm was prepared through
a solvothermal technique [35]. Related with X-ray absorption near-edge structures,
1T-MoSe2/SWCNTs amalgamated structures could provide robust chemical and
electrical inclusion between SWCNT flm and 1T-MoSe2 nanosheets in a form of
FIGURE 20.5 (a) Schematic illustration of the synthesis process and crystalline features
of WS2@Gs. Adapted with permission from [34]. Copyright (2019) Elsevier. (b) Schematic
illustration of the electrochemical process and (c) cycle performance of the 1T-MoSe2/
SWCNTs. Adapted with permission from [35]. Copyright (2017) American Chemical Society.
(d) Synthesis process and (e) rate and cycle performances of the MoSe2/NFC nanomateri-
als. Adapted with permission from [36]. Copyright (2020) American Chemical Society. (f)
Formation mechanism of the MoS2@C nanospheres. Adapted with permission from [37].
Copyright (2017) American Chemical Society. (g) Schematic illustration and SEM image of
the WSe2/RGO. (h) Cycle performance of the WSe2/RGO. Adapted with permission from [38]
Copyright (2018) Elsevier.
C-O-Mo bonding, which gains good effciency electron/ion transport pathway and
structural stability, thus directly enabling high-performance Li-storage properties.
The cycling performance of 1T-MoSe2/SWCNTs delivered a capacity of 971 mAh
g−1 at 300 mA g−1 after 100 cycles with a capacity retention of 89% (Figure 20.5c),
owing to the strong C-O-Mo bonding and 1T-MoSe2/SWCNTs accommodates vol-
ume variation during the continuous lithiation/de-lithiation process. The poor cycle
performance induced by the vast capacity alteration on the charge/discharge method
severely limited its practical application in LIBs. Recently, Liang et al. reported 3D
hierarchical MoSe2/N, F co-doped carbon (MoSe2/NFC) heterostructure assembled
by ultrathin nanosheets for LIBs [36]. Here, 3D hierarchical MoSe2/NFC hetero-
structure was obtained by one-pot hydrothermal process, followed by N, F co-doping
method that utilized NH4F as fuoride and nitrogen sources (Figure 20.5d). N, F co-
doped carbon was executed to enhance the conductivity and the constrain volume
expansion of MoSe2 during the charge/discharge process. Figure 20.5e depicted the
rate capability of all the electrodes at different current densities. As compared to
the MoSe2 (C1) and MoSe2/C (C2), the MoSe2/NFC (C3) displayed the capacities of
853.9, 782.1, 713.2, 663.2, 621.2, 563, and 452.9 mAh g−1 at 0.1, 0.5, 1, 2, 3, 4, and
5 A g−1, respectively. Such improved rate capability was assigned to the 3D hierar-
chical structure assisted Li-ion diffusion and the integrated F, N co-doped carbon
increased the electronic conductivity. The cycling performance for all the electrodes
was obtained at a rate of 0.1 A g−1. MoSe2 (D1) and MoSe2/C (D2) showed lower
capacities of 535.3 and 669.9 mAh g−1 and the MoSe2/NFC (D3) provided excellent
capacity of 838.9 mAh g−1 after 200 cycles. From the above results, the MoSe2/NFC
again confrms that the 3D hierarchical structures can deliver more active sites for
Li-ion storage.
Zhang et al. prepared the petal-like MoS2 nanosheets by the combination of hydro-
thermal, co-condensation, and annealing methods [37]. As shown in Figure 20.5f, a
modern methodology for cost-effective preparation of petal-like MoS2 nanosheets
internal hollow mesoporous carbon spheres (HMCSs) and yolk–shell architecture
MoS2@C was developed. The HMCSs could effectively control the expansion of
MoS2 nanosheets and enhanced the electronic conductivity and structural solidity
of the hybrid material. The yolk–shell MoS2@C delivered an excellent discharge
capacity of 993 mAh g−1 at 1 A g−1 and also provided a good high-rate performance
at 10 A g−1 of 595 mAh g−1. The yolk–shell structure ensured good cycling capability
and excellent rate performance, which are desirable for LIB applications. In another
investigation, the WSe2/RGO hybrid nanostructures were constructed by the WSe2
nanosheet template in situ grown on RGO nanosheets via a simple solvothermal
route (Figure 20.5g) [38]. Compared with WSe2 nanosheets, the capacity of WSe2/
RGO reached about 528 mAh g−1 at 0.2 C after 80 cycles (Figure 20.5h). The key role
of graphene nanosheets effectively prevented the WSe2 nanosheets from aggregation.
Yang et al. reported the MoSe2 nanosheet arrays with layered MoS2 hetero-
structures for superior hydrogen evolution and Li-storage performance. The MoSe2
nanosheet arrays with layered MoS2 heterostructures were fabricated by the exfolia-
tion of MoS2, followed by solvothermal method. The MoS2 nanosheets were grown
during the exfoliation process. Subsequently, a solvothermal growth was applied to
prepare MoSe2 (syn-MoSe2) [39]. Schematic illustration of the synthesis route was
FIGURE 20.6 (a) Synthesis route and (b) rate and (c) cycle performances of the MoS2-
MoSe2 heterojunction. Adapted with permission from [39]. Copyright (2017) American
Chemical Society. (d) Schematic illustration of the preparation route and (e) cycle perfor-
mance of MoSe2-CoSe2/NGA. Adapted with permission from [40]. Copyright (2019) Elsevier.
(f) Fabrication process of 1T@2H WS2@CFC and (g) schematic illustration of the composite
for LIBs. Adapted with permission from [41]. Copyright (2018) Elsevier. (h) Preparation of the
1T MoS2/NiMoO4 composite electrode. Adapted with permission from [42]. Copyright (2019)
American Chemical Society.
displayed in Figure 20.6a. The MoS2-MoSe2 heterostructures showed attractive elec-

trochemical performance as well as good cycle life and rate capability. With differ-
ent current rates increasing from 0.1 to 1 A g−1, the MoS2-MoSe2@C delivered good
performance. Meanwhile, a lithiation capacity of 736 mA g−1 was obtained when the
current density returned to the initial current density, which implied the outstanding
rate capacity of MoS2-MoSe2@C electrode (Figure 20.6b). Figure 20.6c displayed
the cycling performances at 0.2 A g−1 for all the electrodes. The MoS2-MoSe2@C
electrodes delivered a capacity of 680 mAh g−1 and maintained a stable capacity
over 200 cycles with an excellent coulombic effciency of 98%. These properties of
MoS2-MoSe2 heterostructures make it a promising low-cost applicant for the anode
material of LIBs. Zhang et al. reported the MoSe2-CoSe2/N-doped graphene aerogel

nanocomposites by a single-step hydrothermal method [40]. Figure 20.6d showed
the preparation route of the MoSe2-CoSe2 nanocomposites. The porous (N-doped
graphene aerogel) NGA with lofty specifc surface area delivered a stable and con-
ductive network, which could accelerate electron transmission and shorten the dif-
fusion distance of Li ions. Figure 20.6e delivered the long-term cycling stability of
the MoSe2-CoSe2/NGA nanocomposites with a high current density of 1 A g−1. It
performed outstanding specifc capacity of 914 mAh g−1 after 200 cycles.
Wang et al. reported 1T@2H WS2 nanosheet arrays anchored on carbon fbers as
a fexible electrode for LIBs. The 1T phase WS2 unveiled inimitable performances
and represented the microstructure compared with 2H phase WS2 [41]. The unveiling
of N caused the phase change from 2H to 1T and the robust N-W bonds enhanced
the solidity of 1T WS2. Figure 20.6f and g represented the synthesis mechanism of
1T@2H WS2@carbon fber cloth (CFC) and composite for LIBs. Here, a carboniza-
tion technique was used to make fexible (CFC), and via hydrothermal method, the
2H WS2@CFC was fabricated. The evenly distributed carbon fbers are closely inter-
woven, and it was not only provided as the carbon matrix but also increased the rapid
transfer of Li ions during the lithiation/delithiation process. Li et al. developed a
conductive additive-free composite electrode using a composition of blade and spray
coating activities to create a two-layer composite electrode. Figure 20.6h displayed
the schematic procedure for forming the 1T MoS2/NiMoO4 composite electrode. A
mixture of binder and 1T MoS2 was coated on the copper foil and dried in a vacuum
oven. Then, the 1T MoS2/NiMoO4 composite electrode was obtained by spraying a
1T MoS2/NiMoO4 solution on the electrode [42]. When the 1T MoS2/NiMoO4 com-
posite was employed as an anode in LIBs, it delivered an excellent charge capacity
of 940.1 mAh g−1. The excellent performance is attributed to both the dexterously
designed electrode structure and the intrinsic electrochemical properties. This strat-
egy provides an effective method for improving the poor conductivity of active mate-
rials as an electrode in lithium metal batteries (LMBs).
20.4.2 APPLICATION IN SODIUM-ION BATTERIES

Rechargeable SIBs have shown great potential as a promising substitute for LIBs
due to their abundance and low cost. However, the large ionic radius of Na ion (0.106
nm) compared with that of Li ion (0.076 nm) leads to the slow kinetic characteristics
of Na-related electrode reactions, resulting in poor rate capability and low capac-
ity. Recently, 2D TMDs (such as MoS2, SnS2, WS2, and MoSe2) have been widely
employed for promising SIB electrodes due to their suitable interlayer spacing [43].
Xu et al. reported a controllable design of MoS2 nanosheets via a solvothermal
method [44]. Figure 20.7a showed the fabrication process and morphologies of MoS2
nanosheets. Here, solvothermal method was helpful to construct a sequence of MoS2
nanosheets (dozens of layered MoS2: DL-MoS2, few-layered MoS2: FL-MoS2, and
ultrasmall MoS2: US-MoS2) anchored on a nitrogen-doped graphene (NG) to form
hybrid electrodes. The prepared MoS2 nanosheets showed tunable size and number
of layers with interplanar spacing, owing to the switching of solvents and raw mate-
rials. The excellent electrochemical behavior resulted in the controllable design of
354
FIGURE 20.7 (a) Synthesis procedure and morphologies of the DL-MoS2@NG, FL-MoS2@NG, and US-MoS2@NG (Scale bars, 100 nm). Adapted
with permission from [44]. Copyright (2018) Wiley-VCH. (b) Schematic illustration of the fabrication and (c) SEM image of the SnS2 nanosheets
assemble hierarchical tubular structure. Adapted with permission from [45]. Copyright (2018) Elsevier. (d) XRD pattern and (e) TEM image of the SnS2/
rGO/SnS2 composite. (f) Discharge/charge curves of the SnS2/rGO/SnS2 electrode. (Adapted with permission from [46]. Copyright (2019) American
Chemical Society.) (g) XRD pattern and (h) TEM image of the MoSe2/N, P-rGO. (Adapted with permission from [47]. Copyright (2017) Wiley-VCH.)
(i) Synthesis route of the nanostructured MoSe2@HCNS. Adapted with permission from [48]. Copyright (2018) Wiley-VCH. (j) Synthesis process of
2D Nanomaterials
WS2/rGO nanomaterials. Adapted with permission from [49]. Copyright (2019) Elsevier. (k) Schematic illustration for the formation of the H-WS2@NC.
(l–q) TEM images and HRTEM images of the H-WS2@NC. Adapted with permission from [50]. Copyright (2020) Elsevier.
MoS2 nanosheets with more active S edges on the surface and increased interplanar
spacing for Na-ion storage.
In another study, the SnS2 nanosheets assembled hierarchical tubular structures
using metal chelate nanowires were fabricated via solvothermal synthesis by Zhao
et al. [45]. Figure 20.7b represented the schematic illustration for the preparation
of the SnS2 nanosheets-assembled hierarchical tubular structures (SnS2NS⊂HTSs).
During synthesis, the SnS2 nanosheets were grown on cobalt-nitrilotriacetic acid
chelate nanowires (Co-NTA CNWs), and the Co-NTA CNWs were completely dis-
solved, extending to the formation of SnS2 NS⊂HTSs without further calcination
and/or chemical etching process. Figure 20.7c showed the SEM image of the SnS2
NS⊂HTSs. The image exhibited well structural solidity without obvious distortion in
presence with sustaining the high-temperature annealing. Therefore, this electrode
material delivered an excellent electrochemical performance.
Owing to the layered structure with high capacity, the SnS2 materials have
attracted much attention in the EES. Recently, Jiang et al. reported a sandwich-like
SnS2/graphene/SnS2 with expanded interlayer distance via hydrothermal synthesis
[46]. Figure 20.7d showed the XRD pattern of the as-obtained sandwich-like SnS2/
rGO/SnS2 composite. The enlarged interlayer spacing of SnS2/rGO/SnS2 composite
showed 5.27 and 8.03 Å by the insertion/extraction of Li/Na ions with fast transport
dynamics. Figure 20.7e suggested the sandwich-like structures, which was formed
by SnS2 nanosheets evenly deposited on both the sides of rGO surface. The SnS2/
rGO/SnS2 nanocomposites exhibited a high revocable capacity of 1,860 mAh g−1 at
0.1 A g−1. After 100 cycles, they even provided a revocable capacity of 1,133 mAh g−1
(Figure 20.7f). Such a high reversible capacity and good cycling performance
indicated that the SnS2/rGO/SnS2 nanocomposites have a huge promise in recharge-
able SIBs.
Owing to the large spacing (0.64 nm), the MoSe2 electrodes showed improved
features for SIBs. Niu et al. reported MoSe2 treated N, P co-doped carbon via the
combination of hydrothermal technique and calcination process [47]. Figure 20.7g
displayed the XRD pattern of the MoSe2/N, P-rGO. All the remaining peaks were
well matched with the hexagonal phase MoSe2. Figure 20.7h was the high-magni-
fcation SEM image of MoSe2/N, P/rGO sample. The 3D network would help the
electrolyte penetration into the core and extended the space to assist the volume
variation upon cycling. The lattice fringe interlayer spacing was calculated to be 0.68
nm, matched well with the (002) plane of MoSe2. In another investigation, Liu et al.
reported few-layer MoSe2 nanosheets with extended (002) planes confned in hol-
low carbon nanospheres (HCNS) (Figure 20.7i) [48]. In this architecture, the HCNS
could prohibit the restacking of MoSe2, which allowed the development of evenly
enclosed few-layer MoSe2 nanosheets with an extended interlayer spacing formation.
The interlayer spacing was expanded to 1.02 nm, which was substantially larger than
its intrinsic (002) plane of 0.64 nm. The large interlayer spacing reduced the barrier
of Na ions and improved the migration kinetics of Na ions, thus exhibiting excellent
Na-storage performance.
WS2 has a large interlayer spacing (0.62 nm), which is conducive to the storage
of Na ions. However, WS2 exposes weak conductivity with decreased oxidoreduc-
tion kinetics and huge volume change during cycling, so it is diffcult to achieve as
356
TABLE 20.1
Summary of the Electrochemical Performance in the Reported Literature
Current Density
Materials Method (mA g−1) Cycle Number Capacity (mAh g−1) CE/CR (%) Ref.
2D TMD nanomaterials for LIBs
C@WS2@Gs Electrical explosion and 1,000 500 496.1 61.9 (CR) [34]
Ball milling
1T-MoSe2/SWCNTs Solvothermal 300 100 971 ~98.0 [35]
MoSe2/NFC Hydrothermal 100 200 838.9 ~99.0 [36]
MoS2@C Hydrothermal 1,000 200 993 ~100 [37]
WSe2/RGO Solvothermal 62.8 (0.2 C) 80 528 ~99.0 [38]
MoS2-MoSe2 Liquid phase ultrasonic- 200 200 ~680 ~98.0 [39]
assisted exfoliation
MoSe2-CoSe2/NGA Solvothermal 1,000 200 914 ~99.0 [40]
1T@2H WS2@CFC Hydrothermal 100 200 1130 ~100 [41]
2D TMD nanomaterials for SIBs
MoS2@NG Solvothermal 1,000 1,000 198 ~100 [44]
SnS2 Solvothermal 50 50 414 58.5 [45]
SnS2/rGO/SnS2 Hydrothermal 100 200 1357 96.6 [46]
MoSe2/N,P-rGO Solvothermal 500 1,000 378 87 [47]
MoSe2@HCNS Solvothermal 1,000 1,000 502 ~98.3 [48]
WS2/rGO Hydrothermal 100 70 522.3 99 [49]
H-WS2@NC Hydrothermal 100 200 473 99.1 [50]
2D Nanomaterials
an anode material for SIBs. In order to solve these issues, Song et al. reported self-
assembled nanohoneycomb WS2 modifed with graphene [49]. Figure 20.7j illus-
trated the production method of WS2/rGO by a self-assembly development under
hydrothermal activity. The synthesized cetyltrimethylammonium bromide (CTAB)
acted as a surfactant and helped to form WS2 nanofbers, and these nanofbers were
grown on the rGO to form WS2/rGO composites. The unique structure not only
enhanced oxidation–reduction kinetics but also buffered the volume extension,
thereby achieving an outstanding electrochemical performance.
Hu et al. reported the self-assembled conductive interlunar-extended WS2
nanosheets anchored on nitrogen-doped carbon matrix (H-WS2@NC) for rapid and
steady sodium storage [50]. Figure 20.7k showed the schematic illustration for the
formation of the H-WS2@NC microfower buds and the time-dependent tests were
conducted out to examine the structural growth. The ultrathin WS2 nanosheets were
randomly constructed for 2 hours. When the reaction time was increased to 6 h,
the randomly constructed WS2 nanosheets were self-assembled to form 3D hier-
archical solid microfowers (S-WS2@NC). As the reaction proceeded to 12 hours,
the WS2 microfower buds and a few of monolayer WS2 nanosheets were obtained
(Figure 20.7l–q). When the reaction time was increased to 24 hours, the well-
defned 3D hollow hierarchical microfower buds were formed (H-WS2@NC). The
nano-microstructure collectively incorporated the performances of few layers and
increased interplanar space of 2D WS2 nanosheets as well as N-doped carbon amal-
gamation 3D hierarchical hollow porous structure. The H-WS2@NC showed excel-
lent structural stability with high revocable performance, prominent cycling stability,
and rate performance as an anode for SIBs.
20.5 CONCLUSION AND OUTLOOKS

This chapter reviewed recent progress in the preparation of 2D TMD-based nano-
materials and their applications in Li/Na-ion batteries. A series of TMD and TMD-
based nanomaterials prepared by hydrothermal/solvothermal, CVD, and exfoliation
techniques were summarized. Meanwhile, we summarized the current studies of
the 2D TMDs for Li/Na-ion anode. Some related electrochemical performances
were summarized in Table 20.1. Although 2D TMD materials are considered to
be an ideal choice for the anode of Li/Na-ion batteries, some issues need to be
improved. (a) The large-scale preparation method to obtain 2D TMD materials is
still a challenge. (b) Even though the large specifc surface area of 2D TMDs is con-
ducive to the pseudocapacitive behavior, thereby providing battery capacity, a series
of side reactions with electrolytes cause the irreversible consumption of electrolytes,
which results in low effciency. (c) Although the introduction of carbon materials
can improve the stability and conductivity of the 2D TMD materials, the tap density
of the electrode material will be reduced, resulting in a low volumetric energy den-
sity. Therefore, it is necessary to fnd a simple, low-cost, and high-effciency syn-
thetic method for large-scale production of 2D TMDs. Meanwhile, rational design
of 2D TMDs-based architectures will also be a promising mothed to improve the
electrochemical performance.
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Index
2D 2–4, 6–10, 12, 14, 21–26, 28, 30–32, 37–42, BN see boron nitride (BN)
44–49, 53–66, 68, 90, 91, 95, 99, 101, boron nitride (BN) 22, 38, 41, 49, 62, 213, 214, 235
105, 111–118, 120, 122, 124, 133, 140, bottom-up 23, 54, 57, 68, 112, 141, 166, 196, 347
141, 144, 146, 156, 162, 164–166, Brunauer, Emmett and Teller (BET) 208, 209, 309
169–171, 176–188, 192, 193, 197–199,
201, 202, 205–210, 213–218, 224–226, cadmium sulfde (CdS) 128, 196, 250, 252,
228, 229, 231–233, 235, 237–239, 247, 256, 258
256, 258, 259, 264, 291–295, 297, 304, cadmium telluride (CdTe) 72, 112, 128, 246, 249,
307–310, 316–318, 321, 342, 343, 345, 251, 252, 256, 264
347–349, 357 capacitance 25, 26, 27, 54, 66, 67, 83, 119, 120,
122, 124, 164, 165, 167, 169, 170, 184,
active sites 2, 6, 9, 25, 53, 57, 58, 61, 64, 65, 68, 104, 186, 187, 194, 195, 198, 200, 201, 214,
111, 122, 162, 165, 167, 170, 177–183, 229, 232, 233, 312
178, 179, 180, 181, 182, 183, 185, carbonitrides 2, 10, 22, 23, 90, 186
195–197, 196, 197, 209, 295, 304, 307, carbon nanotube (CNT) 12, 26, 27, 47, 54, 125,
308, 311, 315–317, 316, 317, 342, 345, 351 165, 170, 193, 194, 199, 350
alkali metal ion batteries 79 catalyst 6, 8, 9, 75, 77, 79, 91, 104, 116, 126, 142,
alkaline fuel cells 129, 334 180, 181, 182, 183, 193, 195, 267, 307,
amorphous 25, 72, 126, 128, 249, 255, 264, 309 311, 334, 335, 347
anode 10, 27, 53, 54, 75, 77–82, 85, 116, 129, 131, cathode 27, 53, 54, 62, 75, 77, 78, 79, 81, 82, 85,
165, 168, 170, 186, 188, 195, 196, 216, 116, 129, 165, 168, 198, 235, 239, 265,
235, 236, 265, 266, 271, 283, 309, 326, 266, 272, 273, 305, 309, 328, 329, 331,
328, 329, 331, 332, 334, 335, 342, 343, 333, 334, 335, 342
345, 349, 352, 357 CdS see cadmium sulfde (CdS)
aqueous rechargeable metal ion batteries CdTe see cadmium telluride (CdTe)
(ARMIBs) 81 chemical vapor deposition 23, 57, 112, 126, 141,
ARMIBs see aqueous rechargeable metal ion 162, 163, 185, 188, 193, 323, 347
batteries (ARMIBs) chemistry 7, 10, 24, 185, 197, 200, 205, 225, 226,
ASCs see asymmetric supercapacitors (ASCs) 282, 287, 327
asymmetric supercapacitors (ASCs) 27, 82, 85 chronoamperometry 178
atomic force microscopy 114, 149 CNT see carbon nanotube (CNT)
atomic layer 4, 124, 144, 162, 178, 218, 294, CO2 reduction reaction (CO2RR) 8, 9
304, 348 CO2RR see CO2 reduction reaction (CO2RR)
composite 22, 25, 26, 27, 42, 54, 67, 105, 124,
ball milling 23, 28, 39, 40, 41, 55, 169, 224, 225, 126, 129, 131, 133, 167, 169, 186, 196,
228, 349 198, 199, 206, 207, 208, 209, 211, 212,
bandgap 3, 4, 5, 28, 29, 31, 32, 37, 59, 72, 73, 90, 213, 214, 215, 216, 217, 224, 225, 226,
91, 92, 99, 101, 104, 105, 118, 128, 228, 229, 231, 232, 233, 235, 236, 237,
129, 140, 152, 192, 193, 194, 201, 202, 238, 239, 249, 256, 258, 264, 271, 274,
229, 246, 248, 249, 252, 256, 258, 259, 275, 285, 325, 330, 345, 353, 355
271, 281, 283, 284, 285, 287, 291, 293, conductivity 2, 6, 8, 9, 12, 22, 25, 26, 27, 28, 31,
294, 295, 297, 304 32, 62, 63, 78, 81, 104, 119, 120, 122,
batteries 1, 3, 6, 7, 10, 12, 25, 53, 59, 79, 80, 81, 124, 125, 168, 170, 176, 177, 179, 181,
82, 85, 110, 111, 118, 124, 165, 168, 182, 184, 185, 186, 187, 188, 192, 195,
176, 177, 181, 184, 186, 188, 206, 231, 196, 197, 198, 199, 200, 201, 206, 207,
233, 235, 247, 285, 293, 304, 322, 325, 208, 210, 212, 213, 214, 216, 217, 226,
326, 327, 328, 330, 331, 332, 333, 337, 228, 232, 235, 248, 257, 264, 269, 270,
338, 341, 342, 343, 353, 357 271, 273, 276, 283, 284, 286, 291, 293,
bimetallic 8, 9, 309, 311 294, 304, 308, 311, 315, 318, 324, 325,
black phosphorus 28, 30, 31, 32, 117, 205, 229, 331, 332, 337, 343, 345, 347, 351, 353,
233, 239, 291 355, 357
361
362 Index
density-functional theory (DFT) 5, 90, 91, 92, 95, electrolyte 9, 24, 26, 27, 41, 45, 47, 53, 67, 73, 75,
105, 281 77, 78, 79, 81, 82, 83, 85, 119, 120,
devices 2, 3, 10, 21, 25, 28, 30, 53, 54, 64, 82, 85, 124, 131, 162, 170, 184, 185, 186, 187,
86, 91, 92, 99, 104, 105, 118, 120, 124, 194, 198, 199, 200, 206, 208, 209, 210,
140, 142, 185, 188, 192, 206, 248, 249, 211, 212, 214, 216, 217, 231, 235, 266,
259, 264, 266, 268, 269, 271, 272, 273, 275, 282, 308, 312, 317, 330, 331, 332,
274, 275, 276, 282, 285, 286, 287, 288, 334, 336, 337, 342, 355
292, 293, 294, 296, 297, 327, 328, 341, electronic 140, 141, 170, 176, 177, 183, 185, 187,
342, 343, 347, 349 188, 192, 193, 194, 195, 200, 201, 206,
DFT see density-functional theory (DFT) 229, 248, 258, 281, 282, 283, 285, 286,
di-chalcogenides 3 287, 291, 293, 307, 308, 311, 315, 316,
dielectric 62, 83, 97, 152, 153, 157, 265 317, 318, 323, 325, 341, 342, 343, 345,
direct methanol fuel cell (DMFC) 214, 334 349, 351
DMFC see direct methanol fuel cell (DMFC) electron transport layer (ETL) 38, 265, 266, 272,
doping 6, 28, 30, 32, 57, 58, 59, 85, 92, 104, 105, 281, 282, 283, 284, 285, 286, 287
115, 118, 181, 193, 195, 196, 197, 198, energy 1, 2, 3, 4, 5, 6, 8, 12, 13, 21, 22, 25, 26,
201, 202, 206, 226, 281, 282, 283, 284, 27, 28, 30, 31, 32, 41, 53, 54, 61, 62,
286, 287, 288, 307, 310, 312, 315, 316, 65, 66, 68, 71, 72, 73, 75, 78, 79, 80,
317, 331, 336, 347, 351 81, 82, 83, 86, 90, 91, 92, 95, 99, 101,
DSCs see dye solar cells (DSCs) 102, 104, 105, 110, 111, 112, 113, 116,
DSSCs see dye-sensitized solar cells (DSSCs) 118, 119, 120, 124, 125, 126, 129, 131,
dye-sensitized solar cells (DSSCs) 128, 251, 264, 133, 140, 141, 153, 154, 156, 162, 164,
265, 266, 267, 273, 274, 275, 276, 282, 167, 169, 170, 176, 177, 179, 180, 181,
283, 285 184, 185, 186, 187, 188, 192, 193, 194,
dye solar cells (DSCs) 72, 73 195, 198, 201, 208, 211, 212, 213, 214,
217, 225, 231, 232, 233, 239, 246, 247,
EDLC see electric double layer capacitor (EDLC) 248, 249, 250, 251, 254, 256, 258, 259,
effciency 1, 2, 3, 7, 9, 10, 22, 27, 41, 45, 55, 72, 263, 264, 265, 266, 267, 270, 271, 273,
77, 91, 97, 99, 102, 104, 105, 112, 120, 276, 279, 280, 283, 284, 286, 287, 293,
125, 126, 128, 129, 131, 133, 177, 180, 294, 295, 304, 305, 307, 308, 312, 317,
195, 198, 199, 200, 208, 212, 237, 250, 326, 327, 331, 335, 338, 341, 342, 345,
251, 252, 255, 256, 258, 259, 280, 348, 357
281, 284, 285, 287, 293, 295, 297, 307, energy density 1, 2, 7, 26, 79, 81, 82, 85, 124, 129,
309, 312, 316, 328, 335, 336, 343, 351, 162, 164, 167, 184, 185, 192, 194, 231,
353, 357 232, 305, 330, 342, 357
electric double layer capacitor (EDLC) 12, 26, 83, engineering 12, 21, 26, 101, 129, 141, 197, 200,
85, 184, 185, 198, 211, 231 205, 218, 265, 285, 288
electrocatalysis 5, 6, 9, 179, 182, 304, 309 etching 22, 23, 24, 38, 47, 49, 55, 112, 163, 164,
electrocatalytic 2, 6, 8, 9, 10, 129, 305, 308, 310, 168, 169, 170, 176, 193, 194, 200, 201,
316, 317, 318 212, 217, 228, 347, 355
electrochemical 1, 3, 10, 12, 22, 23, 24, 27, 38, 53, ETL see electron transport layer (ETL)
67, 68, 77, 78, 81, 82, 83, 85, 90, 102, evaporation 62, 115, 116, 125, 128, 193, 209, 349
105, 111, 119, 120, 124, 126, 128, 165, exfoliation 13, 24, 38, 39, 40, 41, 42, 43, 44, 45,
170, 176, 177, 178, 180, 184, 185, 186, 46, 56, 112, 113, 141, 146, 149, 163,
188, 195, 197, 198, 200, 206, 216, 225, 166, 168, 169, 176, 177, 178, 179, 180,
228, 231, 233, 235, 250, 252, 308, 309, 182, 186, 188, 206, 215, 226, 228, 229,
310, 311, 312, 317, 318, 326, 333, 337, 231, 267, 275, 294, 349, 351, 357
338, 341, 347, 352, 354, 355, 357
electrode 2, 7, 10, 12, 25, 26, 27, 45, 46, 62, 66, FDTD see fnite-difference time-domain
67, 73, 75, 77, 79, 80, 81, 82, 83, 85, (FDTD)
102, 104, 118, 119, 120, 124, 125, 126, feld enhancement 96, 97, 99
129, 131, 162, 164, 165, 166, 167, 168, fnite-difference time-domain (FDTD) 90,
170, 177, 179, 182, 184, 185, 186, 187, 95, 97
188, 192, 196, 199, 201, 231, 232, 233, frst principles calculation 91
234, 235, 237, 252, 256, 265, 266, 273, fexible 25, 27, 28, 38, 72, 105, 119, 120, 133, 170,
275, 287, 297, 308, 309, 310, 312, 326, 180, 185, 194, 195, 199, 259, 291, 292,
327, 328, 330, 331, 333, 334, 338, 342, 293, 294, 295, 297, 353
345, 347, 352, 353, 355, 357 fow batteries 125
Index 363
fuel cells 6, 7, 129, 131, 176, 177, 179, 180, 181, membrane 75, 78, 79, 126, 133, 207, 208, 209,
206, 210, 211, 217, 304, 325, 326, 333, 210, 211, 212, 213, 214, 215, 216, 217,
334, 335, 337 218, 333, 334, 336
mesoporous 2, 165, 195, 199, 282, 283, 317, 351
GO see graphene oxide (GO) metal-air 1, 3, 82, 304
graphene 2, 3, 6, 10, 12, 21, 22, 26, 27, 28, 29, 30, metal-air batteries (MABs) 1, 3, 82, 304
31, 32, 37, 38, 39, 40, 41, 42, 45, 47, 49, metal carbides 22, 176, 186, 199, 247
54, 55, 56, 57, 58, 62, 63, 64, 65, 67, metal-organic chemical vapor deposition
68, 90, 99, 105, 111, 113, 114, 115, 116, (MOCVD) 141, 142, 144, 146, 153,
117, 118, 119, 140, 162, 163, 164, 165, 154, 156
166, 167, 168, 176, 177, 178, 181, 182, metal-organic frameworks (MOF) 8, 9, 182, 206,
184, 185, 186, 187, 188, 192, 194, 195, 304, 308, 309, 310, 312, 317, 347
196, 198, 206, 207, 208, 209, 210, 211, metal-sulfur batteries (MSBs) 81
212, 214, 224, 225, 226, 228, 229, 231, MFC see microbial fuel cell (MFC)
232, 233, 235, 236, 239, 247, 264, 266, microbial fuel cell (MFC) 131
267, 268, 270, 271, 272, 273, 275, 291, microscopy 5, 13, 97, 114, 149
292, 293, 294, 296, 297, 304, 310, 311, microwave 27, 66, 96, 113, 164, 166, 184, 196,
312, 316, 317, 318, 322–326, 331–333, 226, 250, 275
336–338, 342, 344, 345, 349, 350, 353, MOCVD see metal-organic chemical vapor
355, 357 deposition (MOCVD)
graphene oxide (GO) 26, 27, 29, 40, 56, 67, 97, MOF see metal-organic frameworks (MOF)
111, 119, 120, 133, 163, 164, 167, 181, moltencarbonate fuel cells (MCFCs) 75, 77, 334
184, 185, 193, 194, 195, 196, 208, 209, molybdenum disulfde (MoS2) 3, 113, 153, 154,
210, 211, 212, 218, 225, 232, 235, 239, 156, 214, 216, 232, 293
264, 267, 268, 269, 270, 271, 273, 275, mono/few-layer thick transition metal
276, 311, 323 carbonitrides (MXenes) 2, 3, 4, 5, 6,
21, 22, 23, 24, 32, 55, 90, 169, 170,
HER see hydrogen evolution reaction (HER) 176, 181, 182, 183, 185, 186, 188, 200,
heteroatoms 6, 176, 182, 198, 307, 311, 317 201, 205, 207, 217, 224, 239, 247, 294,
HFA see hydrofuoric acid (HFA) 295, 304, 318
hole transport layer (HTL) 126, 265, 266, 268, 269, morphology 25, 26, 57, 58, 59, 63, 67, 68, 117,
270, 271, 272, 273, 276, 281, 284, 285 163, 184, 188, 208, 214, 233, 246, 247,
HTL see hole transport layer (HTL) 251, 269, 270, 272, 276, 283, 284, 285,
Hummer’s method 56, 226, 323 318, 325, 335, 343, 347, 348
hydrofuoric acid (HFA) 22, 23, 24 MSBs see metal-sulfur batteries (MSBs)
hydrogen evolution reaction (HER) 3, 8, 90, 104,
105, 179, 180, 181, 182, 304, 305, 307, nafon 210, 211, 212, 213, 214, 215, 217
308, 309, 310, 311, 312, 315, 316, 317, nanolithography 112
318 nanoribbons 6, 37, 193, 194
hydrothermal 27, 66, 67, 68, 114, 119, 131, 164, nanosheet 8, 9, 111, 176, 177, 180, 184, 193, 195,
166, 167, 168, 216, 224, 232, 238, 239, 196, 208, 209, 212, 213, 214, 217, 235,
250, 251, 312, 343, 344, 345, 351, 353, 308, 309, 317, 351, 353
355, 357 NiFe-hydroxide 307
nitrides 2, 10, 22, 62, 90, 176, 181, 186, 213, 217,
laser ablation 112, 113 247, 294, 304
layered hydroxides (LDHs) 177, 179, 181, 182,
183, 185 OER see oxygen evolution reaction (OER)
lithium-ion batteries (LIB) 6, 53, 124, 165, 176, optoelectronic 2, 38, 90, 92, 112, 140, 206, 265,
177, 186, 187, 188, 195, 247, 322, 327, 267, 270, 282, 284, 291, 292, 294,
328, 330, 331, 332, 333, 335, 338, 342, 295, 297
351 organic solar cells (OSCs) 75
ORR see oxygen reduction reaction (ORR)
MABs see metal-air batteries (MABs) OSCs see organic solar cells (OSCs)
mechanism 12, 45, 46, 61, 64, 66, 80, 81, 83, 85, Ostwald ripening 144, 156
97, 102, 117, 124, 129, 141, 142, 146, oxygen evolution reaction (OER) 8, 9, 179, 181,
149, 169, 177, 184, 186, 188, 196, 207, 182, 183, 309, 311, 312
212, 218, 231, 233, 256, 276, 282, 287, oxygen reduction reaction (ORR) 8, 9, 75, 179,
305, 326, 331, 338, 353 181, 182, 183, 336
364 Index
photovoltaic 38, 58, 62, 63, 72, 73, 75, 90, 96, SOFCs see solid-oxide fuel cells (SOFCs)
99, 105, 111, 112, 141, 149, 264, 265, solar cells 3, 38, 62, 71, 72, 73, 75, 85, 99, 101,
268, 269, 270, 271, 272, 273, 276, 279, 110, 112, 118, 126, 128, 246, 247, 249,
294, 347 250, 251, 252, 254, 255, 256, 257, 258,
perovskite solar cells 73, 112, 264, 288 259, 264, 265, 266, 270, 273, 275, 280,
phase 4, 21, 22, 23, 24, 38, 58, 59, 85, 105, 114, 281, 282, 285, 288
116, 120, 128, 131, 133, 141, 144, 146, sol–gel 112, 114, 115, 116, 131, 250
150, 153, 156, 163, 167, 168, 182, 197, solid-oxide fuel cells (SOFCs) 75, 77, 78, 131,
198, 218, 225, 252, 266, 271, 308, 332, 217, 334
343, 345, 353, 355 solvothermal 27, 57, 66, 68, 112, 114, 117, 124,
phosphoric acid fuel cells (PAFCs) 75, 77 231, 311, 343, 345, 347, 350, 351, 353,
photocatalytic 91, 105, 116, 229 355, 357
photodetectors 140, 291 sonication 38, 41, 42, 43, 44, 47, 55, 56, 163, 186,
photoelectrochemical 90 209, 210, 211, 229, 267, 271, 274
photovoltaics (PV) 99, 128, 129, 249, 250, 254, specifc capacity 81, 164, 166, 168, 170, 188, 195,
255, 256, 257, 258, 259, 279, 280, 281, 196, 198, 199, 201, 353
282, 283, 285, 288 specifc energy 78, 79, 120
physical vapor deposition (PVD) 57, 60, 61, 62, specifc power 78, 120, 131
63, 68, 115, 129 sputtering 27, 60, 61, 62, 115, 116, 128, 129, 131,
piezoelectric 90, 101, 105, 140 287
plasma 29, 32, 47, 49, 58, 59, 114, 126, 194, 347 STM see scanning tunneling microscopy (STM)
polymer solar cells (PSCs) 265, 271, 281–287 structure 2, 3, 4, 6, 7, 8, 9, 10, 12, 14, 22, 24, 25,
porous 10, 25, 26, 64, 77, 83, 116, 124, 131, 162, 26, 27, 28, 30, 31, 32, 40, 49, 53, 54,
163, 164, 165, 167, 169, 170, 176, 182, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65,
194, 195, 199, 218, 308, 309, 312, 316, 66, 67, 73, 77, 82, 91, 92, 95, 96, 97,
353, 357 99, 101, 105, 111, 112, 114, 115, 117,
potassium-ion batteries (PIBs) 79, 165, 199 118, 124, 129, 140, 142, 152, 156, 162,
power conversion effciency (PCE) 111, 112, 126, 163, 164, 166, 168, 169, 170, 180, 184,
250, 251, 252, 265, 268, 269, 270, 271, 185, 186, 187, 192, 193, 194, 195, 196,
272, 273, 275, 281, 282, 283, 284, 285, 197, 198, 199, 200, 201, 205, 206, 207,
286, 287 210, 212, 213, 214, 216, 218, 229, 233,
power density 27, 104, 120, 129, 131, 162, 185, 247, 248, 251, 252, 265, 266, 268,
192, 194, 195, 212, 217, 231, 233, 337, 271, 280, 283, 285, 286, 287, 294, 295,
338, 342 296, 304, 308, 309, 310, 312, 315, 316,
proton-exchange membrane fuel cell (PEMFCs) 317, 318, 321, 322, 323, 333, 335, 338,
75, 78, 217 343, 344, 345, 347, 348, 350, 351, 353,
pseudocapacitors 12, 26, 82, 83, 231 355, 357
supercapacitor 12, 23, 25, 53, 82, 83, 118, 119,
Raman 37, 42, 49, 90, 96, 97, 118, 142, 144, 145, 120, 122, 167, 177, 184, 185, 194, 195,
146, 149, 325 198, 200, 231, 232, 239
rechargeable metal ion batteries 81 supercapacitors (SCs) 23, 25, 26, 255, 271
reduced graphene oxide (rGO) 26, 27, 29, 56, 58, surface area 2, 6, 7, 8, 10, 12, 21, 25, 26, 53, 54,
67, 111, 119, 120, 122, 163, 167, 194, 57, 62, 63, 64, 65, 68, 83, 90, 102, 105,
195, 196, 199, 212, 225, 226, 229, 232, 111, 112, 118, 119, 163, 164, 166, 167,
264, 267, 268, 269, 271, 272, 273, 274, 168, 169, 177, 179, 180, 181, 184, 185,
275, 293, 311, 312, 323, 325, 332, 345, 186, 188, 192, 194, 195, 196, 207, 208,
351, 355, 357 214, 231, 232, 237, 239, 273, 275, 276,
282, 292, 307, 308, 309, 316, 317, 335,
scanning probe microscopy 117 337, 347, 353, 357
scanning tunneling microscopy (STM) 64, 65,
325 tafel 305, 307, 309, 310, 311, 312, 315, 316
schottky 95, 99, 105, 286 tensile strength 208, 212, 213, 214, 217
SCs see supercapacitors (SCs) TFSCs see thin-flm solar cells (TFSCs)
Sensors 141, 176, 177, 188, 237, 239, 247, 249, thermoelectric 23, 90, 198
293, 295, 304 thin flms 9, 23, 57, 66, 111, 112, 116, 117, 119,
SIBs see sodium-ion batteries (SIBs) 120, 129, 141
sodium-ion batteries (SIBs) 6, 79, 165, 168, 196, thin-flm solar cells (TFSCs) 72
342, 353 TiO2 see titanium dioxide (TiO2)
Index 365
titanium dioxide (TiO2) 102 wafer 141, 142, 144, 145, 146, 149, 152, 153, 154,
TMCs see transition metal carbides (TMCs) 156, 157, 193, 214
top-down 23, 24, 38, 49, 54, 55, 56, 112, 166, 177, water splitting 8, 59, 91, 102, 104, 105, 177, 180,
188, 349 181, 304, 305, 309, 310, 311, 312, 318
transition metal 2, 21, 22, 23, 37, 38, 55, 57, 90, wavelengths 97, 150, 157, 267, 291, 292, 296
120, 140, 167, 176, 180, 181, 182, 183,
187, 196, 197, 200, 205, 214, 217, 224, X-ray diffraction (XRD) 40, 183, 325, 355
231, 237, 248, 266, 291, 294, 304, 308, X-ray Photoelectron Spectrometer (XPS) 118,
311, 316, 317, 342, 343 146, 210
transition metal carbides (TMCs) 22, 23, 317
transition metal dichalcogenides (TMDC) 2–4, Young’s modulus 53, 212, 214, 217, 324, 325
12, 22, 38, 39, 57, 59, 62, 67, 104, 140,
141, 142, 144, 146, 149, 156, 166, 167, zinc oxide (ZnO) 73, 128, 129, 226, 251, 252, 257,
182, 196, 197, 198, 202, 206, 239, 293, 258, 285, 286, 287
308, 318, 239, 342, 343, 347, 349, 357 zinc selenium (ZnSe) 252, 257, 258
turn of frequency 9 zinc sulfde (ZnS) 246, 249, 252, 256, 257, 258
zinc tellurium (ZnTe) 246, 252, 258
unzipping 38, 47, 48, 49 Zn-MnO2 124
ZnO see zinc oxide (ZnO)
V2CTx 14 ZnS see zinc sulfde (ZnS)
Volmer–Heyrovsky 305 ZnSe see zinc selenium (ZnSe)
Volmer–Tafel 305 ZnTe see zinc tellurium (ZnTe)
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2D Nanomaterials Chemistry and Properties Ram K. Gupta

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2D Nanomaterials

and by CRC Press

© 2022 Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, LLC

Library of Congress Cataloging-in-Publication Data

ISBN: 978-1-032-01394-7 (hbk)

Chapter 1 Chemistry of 2D Materials for Energy Applications ...........................1

Chapter 2 Advanced 2D Materials for Energy Applications .............................. 21

Chapter 3 Top-Down Synthesis of 2D Nanomaterials........................................ 37

Chapter 4 Bottom-Up Synthesis of 2D Nanomaterials for

Chapter 5 Types of Energy Devices and Working Principles............................. 71

Chapter 6 Theoretical Considerations of 2D Materials in

Chapter 7 2D Nanomaterials Using Thin Film Deposition Technologies ........ 109

Chapter 8 Wafer-Scale Growth and High-Throughput Characterization

Chapter 9 Morphological Aspects of 2D Nanomaterials for

Chapter 10 Effect of Exfoliation on Structural and Electrochemical

Chapter 11 Tuning of Bandgap and Electronic Properties for

Chapter 12 Electrolyte Membrane for 2D Nanomaterials ..................................205

Chapter 13 Nanocomposites of 2D Materials for Enhanced

Chapter 14 Recent Developments in Group II-VI Based Chalcogenides

Chapter 15 Photovoltaic Application of Graphene Oxide and Reduced

Chapter 16 Revolutionizing the Field of Solar Cells by Utilization of

Chapter 17 2D Materials for Flexible Photo Detector Applications................... 291

Chapter 18 2D Nanomaterials for Electrocatalytic Hydrogen Production ......... 303

Chapter 19 Application of Graphene Family Materials for

Chapter 20 2D Transition Metal Dichalcogenides (TMD)-Based

Ram K. Gupta, Associate Professor

Junaid Ahmad Faheem K. Butt

Mangesh Diware Yue Hao

Chia-Jyi Liu Jing Ning

Joseph Chennemkeril Mathew Vincent O. Nyamori

Immanuel Paulraj Rajesh Kumar Singh

Tian Wang Jae Su Yu

Yuyan Wang Changzhou Yuan

Maoyang Xia Jincheng Zhang

1.2 CHEMISTRY, STRUCTURES, AND

1.2.2 MXENES-BASED 2D MATERIALS

1.2.3 GRAPHENE-BASED 2D MATERIALS

FIGURE 1.3 Graphene-based catalysts are regulated by introducing defects, nonmetal-

1.3 ENERGY APPLICATION OF 2D MATERIALS

1.3.1 ELECTROCHEMICAL HYDROGEN EVOLUTION REACTION

1.3.2 ELECTROCHEMICAL OXYGEN EVOLUTION REACTION

1.3.3 ELECTROCHEMICAL OXYGEN REDUCTION REACTION

1.3.4 ELECTROCHEMICAL CARBON DIOXIDE REDUCTION REACTION

proposed directed effcient electron transmission by metalloporphyrins, to accom-

1.3.5 2D MATERIALS FOR ADVANCED BATTERIES

1.3.6 2D MATERIALS FOR SUPERCAPACITOR DEVICES

FIGURE 1.5 Supercapacitors fabricated using 2D materials. (a) Graphene@polymer core–

FIGURE 1.6 (a) Assembling pseudocapacitive electrodes with improved electrochemical

complicated systems customized for specifc applications. The compatibility of fat

briefy discuss conjugated microporous polymer (CMP)/MXene composites, super-

2.2 PREPARATION METHODS OF MXenes

2.2.1 CHEMICAL VAPOR DEPOSITION (CVD)

2.2.2 HYDROFLUORIC ACID

2.2.3 MOLTEN SALTS

2.2.4 ELECTROCHEMICAL ETCHING

2.3 CONJUGATED MICROPOROUS POLYMER/

Therefore, it would be benefcial to develop strategies of preventing restacking and

FIGURE 2.1 Classifcation of supercapacitors.

electrode/electrolyte; pseudocapacitors refer to their energy being stored through