Implementation of graphene in the development of lithium-ion

batteries
Andrés Mauricio Rúa Peláez1, León Carlos Berrocal Salgado2, Juan Pablo Ortiz Hernandez3
1
[email protected], [email protected], [email protected]
Facultad de Minas, Universidad Nacional de Colombia- sede Medellín.

Abstract

In this article, the broad world of graphene, a two-dimensional material with exceptional properties, will be explored. The different
methods of graphene synthesis and their impact on the quality and properties of the resulting material will be analyzed.
Furthermore, the unique characteristics of graphene will be introduced, emphasizing its high electrical conductivity, mechanical
strength, and its capacity to act as an ideal platform for electrochemistry. Lastly, the application of graphene as an anode in lithium-
ion batteries will be examined, encompassing aspects of its performance, advantages, and associated challenges.

Resumen
En este artículo, exploraremos el amplio mundo del grafeno, un material bidimensional con propiedades excepcionales.
Comenzaremos analizando los diferentes métodos de síntesis del grafeno y su impacto en la calidad y las propiedades del material
resultante. A continuación, se introducirá en las características únicas del grafeno, destacando su alta conductividad eléctrica, su
resistencia mecánica y su capacidad para actuar como una plataforma ideal para la electroquímica. Finalmente, se examinará la
aplicación del grafeno como ánodo en baterías de ión-litio abarcando aspectos de su rendimiento, ventajas y desafíos asociados.

Keywords: Anode, Battery, Cells, Functionalization, Graphene, Graphite, Synthesis.

1. INTRODUCTION case of batteries, the main search is for electrode materials

that provide a high charge density, high conductivity, but
In these times in which society is by far the largest which in general make them more efficient and increase
consumer of resources and energy, it is paradoxical to their life cycle. Lithium-ion batteries have been for some
think that it is also when people are more aware of the time an outstanding technology for use in electric
environmental impacts and damage being done to the vehicles, electronic devices. And since the
planet. Because of this duality, society is going through a implementation of this technology, the anodes that are
paradigm shift or evolution in which it seeks to increase used with lithium ions have been formed mainly by
its energy reserves but avoiding that this comes from graphite which is a mineral that has outstanding properties
fossil resources that threaten the atmosphere; therefore it for this task, however since 2004, when Konstantin
is not unusual that many of the technological advances Novoselov and Andre Geim succeeded in isolating a one-
and ongoing research are focused on the use of so-called atom-thick layer of carbon from graphite [5], it was
"renewable" energy, here come into play many minerals perceived that it has properties much more suitable for
and materials that by their properties are strategic and this task, the scientific community has poured a lot of
potentially key to a major and definitive leap in energy as resources into the research and development of methods
we know it. It should be noted that one of the branches for the synthesis of this glorious material so that it can be
that has advanced the most is in the storage and supply of applied industrially, however, many obstacles have been
this energy, therefore, technologies such as capacitors and encountered but also many advances which will be
batteries are a fundamental pillar in this transition. In the described in this article.

© Theauthors; license Universidad Nacional de Colombia.

 Rúa-Peláez; Berrocal-Salgado;Ortiz-Hernández. Junio. 2023

heat waves always propagate from the center to the edges.

2. DEFINITION 4. SYNTHESIS

The term "graphene", which has its root in the words Graphene is a material whose characteristics largely
"graphite" and "alkene", was first coined to describe a depend on the synthesis route used for its creation [4].
single two-dimensional sheet component of graphite. Since its discovery, different techniques have been
Graphene can be defined as an atom-thick sheet consisting developed to produce graphene materials with various
of a hexagonal arrangement of carbon atoms with 𝑠𝑝 2 morphologies (spheres, nanoparticles, nanotubes,
hybridization. nanowires, graphene sheets, porous carbon, aerogels, and
other graphene-based structures) [9]. These routes include
Graphene can be considered as the origin of all other physical and chemical methods such as mechanical
graphitic forms, as it can be packed one sheet on top of exfoliation, thermal decomposition of SiC, chemical
another, to form graphite (3D) or rolled up in the form of vapor deposition (CVD), exfoliation and reduction of
carbon nanotubes (1D) [3,7]. graphite oxides, liquid-phase exfoliation of graphite,
solvothermal synthesis, organic synthesis, and other
3. PROPERTIES methods [4]. However, some of these techniques have
limitations in terms of costs and industrial scalability,
Electronic Properties which hinders their application in large quantities.

Graphene exhibits a dipole electric field effect and charge This article will focus on the most important and
carriers can move in this material continuously if the promising routes for industrial-scale graphene
temperature is manipulated, suggesting that ultrahigh production. However, special mention will be given to the
velocities of up to 15000cm2V-1s-1. In suspended graphene mechanical exfoliation method or "tape method," as it was
and decreasing impurities, velocities of up to 200000 the precursor to all current routes. Despite its ability to
cm2V-1s-1 cans be obtained at room temperature [2]. generate one or a few layers of high-quality graphene,
mechanical exfoliation is a complex method for
Mechanical Properties producing large masses of graphene, making it
impractical for industrial applications [7]. On the other
The defect-free graphene has a Young's modulus of 1 TPa hand, graphene synthesis by chemical vapor deposition
and a fracture toughness of 130 GPa [9]. By reducing the (CVD) is practical but not cost-effective for large-scale
oxide by means of a hydrogen plasma, the modulus production. Nevertheless, it has been recognized as one of
decreases to a value of 0.25 TPa. With this in mind, the the most promising processes for generating high-quality
materials can be assembled by graphene platelets graphene sheets, particularly for electronic applications.
improving their mechanical characteristics.
Now we will focus on two widely used and relatively cost-
Optical Properties effective methods: liquid-phase exfoliation or thermally
expanded graphite exfoliation, and reduction of graphene
The transmittance decreases linearly with the number of oxides [1]. In the liquid-phase exfoliation method,
layers n in the graphene except for photons with an energy expanded graphite or isolated graphite flakes are obtained
of less than 0.5 eV. Even so, it is a material with an ultra- through the thermal expansion process of intercalated
fast photo-response of up to 40 GHz used as a transistor graphite compounds, commonly known as expanded
for optoelectronic devices for communications or sensing. graphite or EG. These flakes are dispersed in solvents
such as tetrabutylammonium hydroxide (TBA) or oleum
Thermal properties to weaken the intermolecular forces between the graphene
layers. Exfoliation is facilitated by the application of
Conductivity is determined by phonon transport, which external forces and generate high-quality graphene sheets.
means, diffuse conduction of electrons at high The method's high scalability and cost-effectiveness
temperature and ballistic conduction (in a specific render it highly appealing for the large-scale production
direction without being diffuse medium). In graphene, of graphene.

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One commonly employed and extensively explored defects" are generated, while the addition or removal of
approach involves the reduction of highly oxidized carbon atoms in graphene sheets produces edges,
graphene oxide (GO) using various techniques such as deformations, and vacancies, known as "intrinsic
chemical, electrochemical, and thermal methods. defects." Therefore, it is critical to achieve a controlled
Exfoliated graphite sheets serve as the starting material chemical doping concentration in graphene for its
for producing reduced graphene oxide (rGO), application in electrochemical energy storage devices.
functionalized graphene sheets (FGSs), or chemically
converted graphene (CCG). The synthesis of graphene Edge functionalization
oxide typically involves the Hummers method, where
graphite undergoes a reaction with potassium Edge functionalization refers to the chemical or physical
permanganate (KMnO4) and concentrated sulfuric acid modification of graphene edges. It involves introducing
(H2SO4). As a result, GO sheets are heavily oxidized, functional groups or controlled defects at the edge sites of
containing an abundance of residual groups such as graphene to alter its chemical and physical properties [4].
epoxides, carbonyls, hydroxyls, and carboxylic acids This technique allows for the improvement of the
attached to their surface. There exist numerous techniques graphene's surface characteristics and harnesses its highly
for reducing GO to obtain rGO, including sonolysis, reactive edge sites to interact with different chemical
thermal, chemical, photochemical, photothermal, species. Edge functionalization can be achieved through
microwave-assisted and electrochemical reduction. various methods, such as chemical oxidation, ball milling,
deposition of atoms or molecules at the edge sites, among
others. These processes modify the chemical bonds and
5. GRAPHENE FUNCTIONALIZATION electronic structure at the edge sites, which can affect
electrical conductivity, adsorption capacity, chemical
Functionalization offers a highly effective strategy for reactivity, and stability of graphene. Surface
enhancing the performance of graphene and graphene functionalization plays a crucial role in creating graphene-
oxide. Through chemical or physical methods, these based materials with outstanding characteristics at both
materials can be modified by introducing covalent or non- the macroscopic and surface levels, which is essential for
covalent bonding interactions. This process allows for the efficient storage systems. It is particularly important to
tailored modification of their properties and opens new highlight that graphene edge sites are highly reactive and
avenues for their application in various fields. [1]. play a central role in covalent interactions with diverse
Generally, when functionalization is carried out through chemical species.
covalent interactions, the outer layer of graphene
structures is affected, resulting in the emergence of Topological and structural defects
defects and the loss of electronic characteristics. On the
other hand, non-covalent functionalization is often The improvement of the performance of graphene has
preferred as it does not alter the shape or electrical been approached through the functionalization of
properties of graphene but rather introduces new chemical structural and topological defects. This emerging strategy
groups. Over time, various functionalization techniques shows promise in optimizing your properties. Structural
have been developed, such as doping with heteroatoms, defects in graphene can play a crucial role, acting as
edge functionalization, and the introduction of electroactive sites or serving as anchors for other active
topological/structural defects, for the synthesis of species such as metals and heteroatoms [1]. It is important
graphene-based materials used in batteries. to highlight that defects in graphene have a direct impact
on its properties [2]. Therefore, proper management of
Doping with heteroatoms these imperfections can result in better performance of the
materials.
The introduction of heteroatoms, such as boron,
phosphorus, and nitrogen, into the graphene structure by
means of heteroatom doping can lead to an electronic
modification that optimizes its optoelectronic
characteristics. These chemical activities are especially
beneficial for electrochemical energy storage systems [1].
By incorporating heteroatoms into graphene, "extrinsic

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6. APPLICATION IN LITHIUM-ION voltages, can be estimated from a half-cell. Furthermore,

BATTERIES these metrics are excellent for evaluating an anode
material for LIBs.
Ideal anode characteristics
Graphene anodes
The "ideal" material for the anode of a lithium-ion battery
(LIB) should possess certain specific characteristics. It Since the discovery of graphene, there has been a study of
should be able to accommodate many lithium ions per its potential use as a host for lithium ions. However, there
formula unit, with insertion/desertion potentials very have been challenges encountered, such as reduced
close to that of metallic lithium. Additionally, it should be capacity compared to the theoretical expectation for
stable during the charge and discharge cycle and have reduced graphene oxide (rGO). Surprisingly, the
excellent gravimetric capacity (mAhg-1) as well as rGO/C60 composite has shown additional capacities,
volumetric capacity (mAhcm-3) at a sufficiently high mass although it diminishes after a few cycles. It has also been
loading (mgcm-2). It should not exhibit a sudden change observed that the stacking of graphene layers negatively
in properties that affect the voltage between charge and affects its ion storage properties. These confirmed
discharge and compromise the energy efficiency of the challenges have led to the need for addressing the design
battery, and it should have minimal irreversible capacity and stability of graphene anodes. Additionally,
during the first cycle [4]. Of course, to achieve adequate unexpected findings have emerged, such as the fact that
charge capacity, the material needs to exhibit good mixed the high surface area of graphene, typically considered
conductivity, i.e., high electrical and ionic conductivity. advantageous, becomes a disadvantage in this application
Furthermore, it is preferable for the material to be cost- as it leads to significant irreversible capacity and cycle
effective and environmentally friendly. Due to these instability [4].
properties, it is easier to understand why graphite has been
the preferred material for anode creation for several Subsequently, advances were made in understanding the
decades. However, since the emergence of graphene as a lithium-ion storage mechanism, revealing differences
revolutionary material that improves almost all properties between single-layer and multi-layer graphene. It was
of graphite, significant research efforts have been made to found that monolayer graphene is not an efficient host for
make the implementation of this material the key to the lithium ions. Doping graphene with boron was proposed
future of LIBs. to overcome the capacity limitations of pure graphene.
Research on doping, functionalization, and the
Cell configurations and electrochemical tests development of complex hierarchical graphene
architectures demonstrated that nitrogen- and boron-
Lithium-ion batteries are characterized by two cell doped graphene exhibited large reversible capacity and
configurations: half-cell and full-cell. In the half-cell impressive high-rate performance. In summary, despite
configuration, the anode material is studied as the positive promising results, significant challenges have been
electrode, while metallic lithium serves as the negative encountered in the use of graphene as an electrode
electrode. On the other hand, in the full-cell configuration, material in lithium-ion batteries. Different approaches,
a lithium oxide is used as the positive electrode [4,5]. such as graphene doping and functionalization, as well as
Although the intrinsic electrochemical properties of a the introduction of structural defects, have been explored.
material can be evaluated using the half-cell While improvements in electrochemical performance
configuration, in practice, this configuration does not have been observed, issues like irreversible capacity in the
allow for assessing its applicability in real batteries [6]. In first cycle and high delithiation voltage persist. Various
practice, an excess of lithium is employed in half-cells, structures and preparation methods have been
which helps mitigate charge consumption during the investigated, but clear progress in practical applications
cycle. However, in a full cell, the supply of lithium is has not yet been achieved. Furthermore, the mechanisms
limited, and parasitic reactions become an obstacle that of lithium-ion diffusion in graphene and the effects of
must be carefully addressed. It should be noted that when volumetric parameters on the evaluation of graphene-
testing a LIB anode in half-cell configurations, it is not based anodes have been studied.
possible to determine its energy density or power.
However, these properties, along with gravimetric and
volumetric capacity, as well as lithiation and delithiation

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Graphene compound anodes still required to overcome these challenges and achieve
optimal performance in terms of power, energy and long-
Several types of composite anodes containing graphene term cyclability [8].
have been developed with the aim of increasing storage
capacity and preventing layer stacking. Examples include 7. DISCUSSION
compounds of rGO with nanoparticles of SnO 2, copper
oxide, silicon oxycarbide, and titanium dioxide (TiO), In the various consulted articles, it is evident that the
among others [5,8]. However, many of these compounds authors are aware of the significant implications that the
did not show significant improvements in electrochemical industrial application of graphene would have,
properties compared to graphite. Deficiencies in cycle particularly in contexts such as batteries, as the world is
stability and low coulombic efficiency were also undergoing an energy transition that requires new
observed. One positive aspect was that the presence of technologies to store and distribute energy effectively.
graphene was found to increase the charge capacity Considering this, it is easy to understand why the
compared to other carbonaceous compounds [4]. Some of widespread use of graphene has not yet been achieved.
the most promising advancements were achieved with Firstly, there are technical and economic challenges
compounds containing SnO2, NiO, and MoS2 due to their associated with large-scale production of graphene.
high gravimetric capacities. However, they exhibited Secondly, there is a lack of certainty or insufficient
limited lifespan and unsatisfactory electrochemical evidence regarding a significant increase in battery
reversibility. Different hybrids containing graphene along efficiency when implementing this material. Thirdly,
with other phosphides, metal oxides, and intermetallic there is a lack of consensus on the real metrics used in
compounds were also developed. These hybrids showed experiments conducted over the years. Without this
improved gravimetric capacities and cycling stability. agreement, it is difficult to align advancements towards a
However, most of them had the disadvantage of high common goal.
delithiation voltage and an irreversible capacity in the first
cycle exceeding 30%. Hybrid materials incorporating a However, despite these challenges, energy issues, the lack
three-dimensional graphene matrix were reported, which of alternatives, and the scarcity of raw materials such as
proved beneficial in reducing material resistance and lithium continuously drive extensive research efforts to
enhancing mechanical stability and high-rate storage achieve favorable outcomes that enable the application of
capacity. However, these porous materials had relatively graphene in various emerging technologies, including
low density, sacrificing volumetric capacity. It is batteries.
important to highlight that although practical
implementation challenges still exist, these compounds 8. CONCLUSIONS
continue to show indications that they will be a highly
viable option for constructing LIB anodes. El graphene has emerged as a revolutionary material with
unprecedented potential in a wide range of scientific and
Complete cells made up of graphene anodes and anodes technological applications, particularly highlighting its
containing grapheme promising use in lithium-ion battery anodes. Its versatile
synthesis, combined with its exceptional properties,
Different complete cells containing graphene as anode positions it as a promising candidate for electrode use in
have been reported, e.g., cells containing rGO/𝑇𝑖𝑂2 electrochemical devices. Although there are still
anodes coupled to 𝐿𝑖𝐹𝑒𝑃𝑂4 cathodes, rGO/𝐹𝑒3 𝑂4 anodes challenges to overcome, graphene continues to be the
coupled to a commercial 𝐿𝑖1.2 𝑁𝑖0.2 𝑀𝑛0.6 𝑂2 cathode, or subject of intensive research, and its impact on industry
𝐿𝑖𝐶𝑜𝑂2 or 𝐿𝑖𝑀𝑛2 𝑂4 cathodes [4]. In general, it is and society is expected to continue growing in the coming
observed that complete cells using graphene-containing years.
materials as anodes exhibit stable charge/discharge
capacities, but often face challenges such as irreversible Compared to other materials, carbon-based components
capacities in the first few cycles, low coulombic exhibit unique characteristics in the field of energy
efficiencies, poor capacity retention and poor storage. Their low cost, controllable microscopic
electrochemical performance in some cases. Although structure, adjustable electrical conductivity, and capacity
significant progress has been made in graphene-based for surface modification set them apart. Specifically,
whole cell research, more research and development are various carbon materials have played a fundamental role

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in lithium metal batteries. However, these advances have [6] Tavassol, H., Jones, E. M., Sottos, N. R.,
posed significant challenges, such as large-scale synthesis &Gewirth, A. A. (2016). Electrochemicalstiffness
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significant progress has been made in investigating the
[7] Wen, Y., Liu, H., &Jiang, X. (2023). Preparation
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composites as anodes. It is important to note that the lack lithium-ion batteries. Journal of Alloys and
of standardization in battery testing represents a hurdle to Compounds, 170885.
the advancement of this application. In many cases,
properties have been reported based solely on half-cell [8] Wu, Z., Sun, K., & Wang, Z. (2022). A Review of
configurations, implying that such measurements should the Application of Carbon Materials for Lithium
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measurements.
[9] Zhu, Y., Murali, S., Cai, W., Li, X., Suk, J. W.,
Potts, J. R., &Ruoff, R. S. (2010). Graphene and
It is evident that a revolution with the use of graphene has
graphene oxide: synthesis, properties, and
not yet been fully realized. However, the potential of this applications. Advancedmaterials, 22(35), 3906-
material to reshape the current paradigm in various 3924.
technologies is equally evident. Therefore, it is essential
to continue investing in research on the use of graphene
and explore all possible avenues and alternatives to
achieve efficient results with its implementation.

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