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PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
event shall the Royal Society of Chemistry be held responsible
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DOI: 10.1039/C8TA01683F
Journal of Materials Chemistry A
Journal of Materials Chemistry A Accepted Manuscript

REVIEW
Synthesis and Application of Iron-based Nanomaterials as Anode

of Lithium-Ion Batteries and Supercapacitors
Received 00th January 20xx,
Shijin Yua, Vincent Ming Hong Ngb, Fajun Wangc, Zhuohao Xiaod, Cuiyun Lia, Ling Bing Konga,b, *,
Published on 11 April 2018. Downloaded by Fudan University on 11/04/2018 04:13:50.
Accepted 00th January 20xx

Wenxiu Quee, * and Kun Zhouf *
DOI: 10.1039/x0xx00000x
Lithium-ion batteries and supercapacitors have great potential as power supplies in portable electronic devices and
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electric vehicles. Their performance depends greatly on the properties of electrode materials. Many attempts have been
devoted to the development of new electrode materials with advanced electrochemical performances. Due to their high
theoretical specific capacitance, low cost and non-toxicity, iron-based materials are considered as very promising
candidates as anode materials. However, low electrical conductivity and poor cycle stability are two major problems
plaguing iron-based materials. Nanomaterial design has emerged as a promising solution to these fundamental issues in
LIBs and SCs. Here, we review the synthesis of iron oxide (Fe2O3, Fe3O4) nanomaterials with various structures, including 1D
(nanorods, nanowires, nanotubes), 2D (nanosheets) and 3D (nanospheres, hollow nanostructures, flower-like structures,
nanoarrays). Nanocomposites, consisting of iron oxides and different supports (such as carbonaceous materials, other
metal oxides, polymers), are also covered in this review. Furthermore, the synthesis and structural characteristics of iron
hydroxides (FeOOH) and iron sulfides (FeS2) will also be elaborated. Finally, applications of iron-based nanomaterials in
LIBs and SCs are summarized. Ultimately, we wish to provide an in-depth and reasonable understanding on how to
effectively improve the electrochemical performance of iron-based anodes by selecting suitable nanostructures and
optimizing chemical compositions. Hopefully, these concepts and strategies can be extended to other nanomaterials, as a
reference for the future development in the areas of energy conversion, storage and environmental protections.
electric vehicles for power batteries and portable consumer

1. Introduction electronics also places high demands on the power density, energy
density, transparency and flexibility of energy storage systems.
Energy is one of the most important and hot research topics in
Electrochemical energy storage systems, which have the
recent decades. With the rapid consumption of fossil fuels and the
characteristics of high efficiency, high flexibility and versatility, are
environmental crisis, renewable clean energy has attracted
currently the most successful devices for energy storage
worldwide attention. Solar energy, wind, tidal energy and other
applications. Lithium-ion batteries (LIBs) and supercapacitors (SCs)
clean energy can be used to generate electricity, so that they have
are the most widely used electrochemical energy storage devices.
been extensively studied. However, there is a fatal flaw of energy
LIBs have the highest rechargeable energy density, while SCs can
instability in these clean energies. A high-energy-density storage
provide very high power density. Both devices usually consist of
system needs to be added to achieve the effect of cutting peaks and
cathode, anode, electrolyte and separator. Electrochemical energy
valleys in the smart grid. In addition, the rapid development of
storage is achieved by the charging/discharging of electrons/ions.
During charging and discharging, electrochemical reactions occur at
a. School of Mechanical and Electronic Engineering, Jingdezhen Ceramic Institute,
the electrodes. Therefore, the performance of electrode materials
Jingdezhen 333403, P. R. China. *Email: [email protected]; plays a decisive role in determining the performance of LIBs and
[email protected] (LB Kong) SCs.
b. School of Materials Science and Engineering, Nanyang Technological University,
50 Nanyang Avenue, Singapore 639798. Graphite carbons are the conventional anode materials for LIBs
c. Key Laboratory for Microstructural Control of Metallic Materials of Jiangxi
and SCs, which suffer the drawbacks of limited specific capacity (~
Province, Nanchang Hangkong University, Nanchang 330063, P. R. China.
d. School of Materials Science and Engineering, Jingdezhen Ceramic Institute, 372 mA h g–1) and cycling life. Therefore, new anode materials with
Jingdezhen 333403, P.R. China. high capacity, long cycling lifetime and high safety are urgently
e. Electronic Materials Research Laboratory, School of Electronic and Information
demanded. Significant achievements have been gained in the
Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China. *Email:
[email protected] (WX Que) search of alternative anode materials with high capacity, such as Si,
f. School of Mechanical & Aerospace Engineering, Nanyang Technological
intermetallic alloys and transition metal oxides. Although Si and
University, 50 Nanyang Avenue, Singapore 639798. Email: [email protected] (K
Zhou)
alloy materials have high theoretical specific capacities, they suffer
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
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Review Journal of materials Chemistry A
from large volume changes during lithium intercalation/- In the past decades, although many high-quality 64-66
Viewreviews
Article Online
deintercalation. For example, the volume expansion ratio of Si DOI: 10.1039/C8TA01683F
have been published, covering the preparation of iron-based oxides
electrodes after lithium insertion can reach 400%.53, 54 As one of and their applications in LIBs or SCs, no attention has been made to
transition metals, iron-based materials are considered as one of the low-dimensional nanostructured (1D and 2D) iron oxides. More
most promising anode materials for LIBs and SCs. Firstly, it has recently, a few of reviews67, 68 have referred to the preparations

multiple valence states (Fe0, Fe2+ and Fe3+) to provide rich redox and applications of iron oxides, but only emphasizing hollow
pairs, such as Fe0/Fe2+, Fe0/Fe3+ and Fe2+/Fe3+. Therefore, iron-based structures in energy storage and conversion. Moreover, there is a
material has a higher theoretical capacity than the graphite carbon lack of systematic review on the preparation and properties of iron
electrode. Secondly, iron-based materials have stable and wide oxide nanocomposites. In addition, the research on iron-based
operating windows at negative potentials and thus they are well hydroxides and FeS2 has made great progress, but so far there is no
suited for the fabrication of high-performance asymmetric relevant review regarding to their application in LIBs and SCs. Here,
supercapacitors (ASCs). Moreover, iron is the most abundant we attempt to provide a comprehensive review on the preparation,
transitional metal in the Earth's crust (Fig. 1a). In addition, its cost characterization and application of various iron-based materials,
price is roughly equivalent to that of commercial activated carbon, especially the newly emerged synthetic strategies in the past five
thus making it economically viable for large-scale applications. years. The applications of iron-based nanomaterials as LIBs and SCs
Lastly, it is less toxic and greener than other transition metal electrodes, the analysis of the relationship of different
oxides/hydroxides. Therefore, many papers have been published morphologies, composition and electrochemical performance are
regarding the synthesis and application of iron-based nanomaterials the main highlights of this review article.
over the past five years. (Fig. 1b-c)
2. Synthesis of Iron Oxide (Fe2O3)

Nanostructures
Among various iron-based materials, Fe2O3 has attracted a great
deal of attention, as anode of LIBs and SCs, due to its high
theoretical specific capacitance, abundant resources and excellent
environmental compatibility. Various methods have been used to
synthesize Fe2O3 nanostructures, such as hydro/solvothermal,
electrospinning, spray pyrolysis, sol-gel, vapor deposition and
electrodeposition. Unfortunately, it suffers from poor conductivity,
volumetric expansion and particle agglomeration. Nanostructures
have proven to be an effective solution to address these issues. In
this section, 1D, 2D and 3D Fe2O3 nanostructures are thoroughly
reviewed.
2.1 1D Fe2O3 Nanostructures
Generally, 1D nanostructure is defined as those that have high
aspect ratio of length along the longitudinal dircetion to width
Fig. 1 (a) Elemental abundance in the Earth's crust, (b) Line chart of the research
along the transversal axis. When they are densely packed into
trend of iron-based materials of LIBs and SCs in recent year, (c) Pie chart of the electrode materials, they have a large specific surface area and can
ratio of iron materials applied in LIBs and SCs form suitable internal voids. Various 1D iron oxide nanostructures,
such as nanorods, nanowires, nanoribbons and nanotubes, have
However, as an electrode material, iron-based materials been synthesized and applied not only to LIBs and SCs but also to
have poor conductivity and cycle stability. It has been waste treatment, sensors and catalysts.69-71
acknowledged that nanomaterials could be a promising 2.1.1 Fe2O3 Nanorods
solution to these issues. Nanomaterials have been studied for Fe2O3 nanorods can be synthesized by using various approaches,
decades and great achievements have been made, especially such as solution method, electrospinning method and
in the design and preparation of controlled nanostructures. At electrochemical deposition.57, 60, 72, 73 For example, Kim et al60 first
present, various iron-based nanostructures have been deposited and grew FeOOH nanorods by using electrochemical
developed, such as one-dimensional (1D) structures deposition processes on the surface of carbon nanofibers, from
(nanowires, nanotubes, nanorods), two-dimensional (2D) which Fe2O3 nanorods were obtained after calcination at 400℃. It
nanosheets and three-dimensional (3D) structures was found that length of the nanorods was increased with
(nanospheres, hollow nanostructures, flower-like increasing current density during the deposition. Cherian et al.57
nanostrucutres, arrays). These nanostructures can be obtained prepared Fe2O3 nanorods by using electrospinning and heat
by using various methods, such as sol-gel,56 chemical vapor treatment. Iron acetylacetonate (Fe(acac)3) was added to alcoholic
deposition,50 electrospinning,29, 57 hydro/solvothermal,6, 20, 58, 59 solution of polyvinylpyrrolidone (PVP) to form a PVP/Fe(acac) 3
electrochemical deposition,60 spray pyrolysis,61 detonation,62 composite precursor. The electrospun PVP/Fe(acac)3 nanorodes
corrosion32 and electron beam deposition51, 63. were calcined in air at 500 ℃ for 5 h to obtain Fe2O3 nanorods,
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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Journal of Materials Chemistry A Review
which had an average diameter of 150 nm. Microstructural analysis facilitated the controlling over the crystal morphology. 83
View Article Online
indicated that these Fe2O3 nanorods are formed through the 85 DOI: 10.1039/C8TA01683F
Srinivasan’s group studied the controlled formation of α- Fe2O3
assembly of Fe2O3 nanoparticles. nanorods by using different vicinal diamine derivatives, such as
In recent years, hydrothermal method has been widely used the ethylenediamine, N-methylethylenediamine, 2, 3-diaminobutane, 1,
prepare nanorods.74-77 For instance, Balogun et al.58 prepared α- 2-diaminopropane. Due to the electron density enhancement (+M

Fe2O3 nanorods by using a hydrothermal process. Zhang et al. 76 effect) and steric hindrance, the location and number of
deposited α-Fe2O3 nanorods on carbon cloth from FeCl3 and Na2SO4 substituents (H, H3C) affect the directional structure formation of
precursor solutions through hydrothermal treatment. The α-Fe2O3 ferric iron species. 1, 2-diaminopropane exhibits the strongest
nanorods are single-crystalline with diameters of 100-150 nm and shape controlling capability. The prepared nanorods have an
are vertically grown on the carbon fibers. Chen et al 16 obtained average length of about 390 nm, with an aspect ratio of about 5.0.
Fe2O3 nanorods with exposure of (001) and (010) planes by using a In this case, the H3C-groups at the same C amine group enhance the
hydrothermal method, with FeCl3 and NaOH precursor solutions. chelation ability of the iron species by increasing the electron
The resulting Fe2O3 nanorods have a very uniform size distribution density (+M effect), while causing less steric hindrance. It is
with an average length of about 496 nm, while their widths and observed that the shape control ability was decreased in the order
thicknesses are 50 and 15 nm, respectively, as shown in Fig. 2a-b. of 1, 2-diaminopropane > ethylenediamine ≥ 2, 3-diaminobutane >>
The sample has a specfic surface area of 26.81 m2 g–1, which is N-methylethylenediamine. Through the selection of the SCAs and
larger than that of Fe2O3 nanosheets. the adjustment of the Fe3+ concentration, the Fe2O3 nanorods could
be controlled to have lengths in the range from 240‒400 nm and
aspect ratios of 2.6‒5.7. The nanorods, with lengths of 240‒280 nm
and aspect ratios of 2.6‒3.0 exhibited optimized electrochemical
properties.
2.1.2 Fe2O3 Nanowires
Fe2O3 nanowires are mainly used for biocatalysis and sensors.69 In
recent years, they have been explored as electrode materials for
LIBs and SCs. Fe2O3 nanowires can be efficiently synthesized by
using the traditional methods, such as chemical precipitation.
Wang’s group2 mixed FeCl3 solution with NaBH4 aqueous solution to
obtain a precipitate, which was annealed at 500℃ to form Fe/Fe2O3
nanowires with a core-shell structure. The Fe/Fe2O3 nanowires have
lengths from several micrometers to tens of micrometers and
diameters of 80-130 nm. The shell thickness of the nanowire is
about 4.0 nm, as observed in Fig. 3a-b. Lu’s group29 developed Pt-
doped Fe2O3 nanowires by using electrospinning. The Fe2O3
Fig.2 SEM (a) and TEM (b) images of the Fe2O3 nanorods [Reprinted with
nanowires contained some micropores, with a diameter of about
permission from Ref. 16, Copyright 2016, Nature]. SEM images of the products
obtained at different volume ratios of aqueous FeCl 3 solution to 1, 2- 100 nm. Pt doping has a significant effect on morphology of the
propanediamine, (c) without 1, 2-propanediamine and (d) 1/1 [Reprinted with nanowires, as demonstrated in Fig. 3c-d. With increasing content of
permission from Ref.44, Copyright 2009, IOP]. Pt, the nanoparticles become more and more compact, so that the
porosity of the nanowires was gradually reduced, but the cracks on
The crystal structure of nanorods has a significant effect on their the walls became more obvious. With acetylacetone iron as
electrochemical properties.78-81 Controlling the morphology of the precursor and polyvinyl pyrrolidone as raw material, Sivakumar’s
nanorods is an effective strategy to improve the electrochemical team86 synthesized Fe2O3 porous nanofibres by using
properties of Fe2O3 as electrodes for LIBs and SCs. A variety of electrospinning. The nanofibers have diameters in the range of
shape controlling agents (SCA) have been used to assist the 700‒750 nm, with specific surface area of about 61 m2 g–1, average
hydrothermal synthesis of nanorods, in order to control their pore size of 5.7 nm and pore volume of 0.087 cm3 g–1.
morphologies.82, 83 With ferrous sulphate (FeSO4·7H2O) and sodium Bioinspired strategy is a new method to synthesize
acetate (CH3COONa) as raw materials, Chaudhari et al 84 nanomaterials. Hierarchical FeOOH nanostructure array was
synthesized porous Fe2O3 nanorods by using a wet chemical synthesized by using a bioinspired gas–liquid diffusion method at
approach. CH3COONa was used as the precipitating agent, which the air–water interface.87 Similarly, Huang and co-workers15
slowly released hydroxide ions during the reaction, so as to control fabricated a Fe2O3 nanowire network@graphene transparent film
the growth rate of the nanorods. Li et al.44 prepared uniform α- (FNW@Gr-TF) by using a bioinspired gas‒liquid diffusion method at
Fe2O3 nanorods with aspect ratio of >10 by using 1, 2- the air-solution interface. During the reaction process, NH3
propanediamine-assisted hydrothermal method. The results vaporized and diffused into the ferrous sulfate solution. At the gas-
showed that 1, 2-propanediamine not only provided OH- during the liquid junction, NH3 reacted with ferrous sulfate to form a yellow
formation of the Fe2O3 nanorods, but also played an important role film. Excess NH3 continued to diffuse into the solution, reacting with
in determining the morphology of the nanorods, as illustrated in the ferrous sulfate solution underneath the top layer, where
Fig. 2c-d. The SCA adjusted the substituents on the diamine unit to nanowires were developed from the nucleus and grew towards the
affect the electron density and the steric interaction, which solution. The reaction ended to generate Fe 2O3 nanowires with a

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diameter of 10.5 nm. Then, ITO/PET substrate and graphene sheets high as the template channels. Geng and co-workers 1 have
View Article Online
were respectively introduced as the substrate and the conductive DOI: 10.1039/C8TA01683F
synthesized a layer of Fe2O3 on the surface of silver nanowires to
layer. Nanowire layer with a thickness of about 500 nm showed a form Ag@Fe2O3 nanocables similar to the coaxial cable structure.
porous network structure. After the thin and transparent graphene When Ag was corroded by aqueous ammonia, the Ag@Fe2O3
wrapped the Fe2O3 nanowire layers, there are still many nanocables were transformed into hollow Fe2O3 nanotubes.

transparent holes, as seen in Fig. 3e-f. Representative SEM and TEM images of the Fe2O3 nanotubes are
shown Fig. 4a-b. Ma and co-workers14 have synthesized FeOOH
nanotubes with MoO3 nanorods as a template. By adjusting the
molar ratio of Fe3+ to MoO3 and the hydrolysis temperature of Fe3+,
nanotubes with different thicknesses and diameters can be
obtained. After calcination, the FeOOH nanotubes are transformed
into Fe2O3 nanotubes with wall thicknesses ranging from 50 to 128
nm, as illustrated in Fig. 4c. As the molar ratio of Fe3+ to MoO3 is 2:1
and the hydrolysis temperature of Fe3+ is 70℃, the resulting α-
Fe2O3 nanotubes are built up of nanoparticles with a diameter of 10
nm, as seen in Fig. 4d. The Fe2O3 nanotubes possess a BET surface
area of as high as 149 m2 g–1.
Fig. 3 SEM (a) and HRTEM (b) images of the Fe@Fe2O3 nanowires [Reprinted with
permission from Ref.2, Copyright 2016, Wiley]. SEM images of the products obtained
at different mole number ratios of Pt to Fe 2O3: (c) 0 and (d) 3 mol% [Reprinted with
permission from Ref.29, Copyright 2018, Elsevier]. SEM (e) and TEM (f) images of the
graphene wrapped Fe2O3 nanowires [Reprinted with permission from Ref. 15,
Copyright 2017, IOP]. SEM (g) and TEM (h) images of the Ag NWs@Fe 2O3 nanowires
[Reprinted with permission from Ref.1, Copyright 2015, Wiley].
Using the existing nanowires as a template, a metal oxide source

solution is coated on the surface of the nanowires to prepare the Fig.4 SEM (a) and TEM (b) images of the Ag nanowires@Fe2O3 nanotubes [Reprinted
with permission from Ref.1, Copyright 2015, Wiley]. SEM (c) and HRTEM (d) images of
metal oxide nanowires. Zhang's team88 has synthesized Fe2O3
the Fe2O3 nanotubes with the molar ratio of Fe 3+ to MoO3 2:1 at hydrolysis
nanofibers on the surface of carbon fibers by electrospinning. Geng temperature of 70 ℃ [Reprinted with permission from Ref. 14, Copyright 2015,
and co-workers1 have synthesized a layer of Fe2O3 on the surface of Springer]. SEM images of FeC2O4·2H2O (e), FeOOH precursor (f) and Fe2O3 nanotubes
silver nanowires to form Ag@Fe2O3 nanocables similar to the (g) [Reprinted with permission from Ref. 33, Copyright 2017, Elsevier]. SEM (h) and TEM
coaxial cable structure. As the iron source concentration increases, (i) images of the as-synthesized Fe2O3 nanotube and corresponding high resolution
TEM image showing the lattice fringes (inset) of the sample [Reprinted with
the Fe2O3 nanosheets become uniform and dense, and the
permission from Ref.48, Copyright 2017, Elsevier
thickness increases accordingly. Representative SEM and TEM
images of the Ag nanowires and Ag@Fe2O3 nanowires are depicted Sacrificial template method is a preparation of nanotubes
in Fig. 3g-h. strategy. For example, by using Cu nanowires as a sacrificial
2.1.3 Fe2O3 Nanotubes
template, Lou’s group90 has prepared Fe2O3 nanotubes by the
Template method is the most common preparation of nanotubes. substitution reaction method. The prepared Fe 2O3 nanotubes well
After preparing the Fe2O3 coating on the surface of the nano-metal replicated the Cu nanowire structure. The diameter of Fe2O3
wire, the metal wire template is etched to form the nano-tube. nanotubes is in the range of 50-100 nm, while the thickness of the
Chen et al.89 have thermally decomposed Fe(NO3)3 precursors to nanotube wall is about 10 nm. Despite the very thin nanotubes, the
prepare Fe2O3 nanotubes by using an anodic aluminum membrane wall thickness is very uniform and has good structural stability. Gu
as a template. After impregnation with Fe(NO 3)3·9H2O solution, the et al.33 chose FeC2O4·2H2O nanorod precursors as self-sacrificial
templates were dried under vacuum and annealed. The solution template to obtain uniform Fe2O3 nanotubes. During the growth of
impregnation and annealing process was repeated twice. NaOH FeOOH nanotubes, FeC2O4·2H2O nanorod precursors were used as
solution was used as an etchant to remove the alumina template. raw materials and initial framework. The FeOOH nanotubes were
The preparation process can well copy the template morphology. converted to hierarchical Fe2O3 nanotubes through heat treatment.
The Fe2O3 nanotubes arrange in an ordered manner by the alumina The Fe2O3 nanotubes well inherited the morphology and size of the
matrix. Similarly, the length of the Fe2O3 nanotubes is 60 microns as

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precursors. The Fe2O3 nanotubes retained tubular morphology, oriented and acid etching method.6, 95, 96 Lu et al.94 prepared
View ArticleFe2 O3
Online
without collapse after calcination. Many nanosheets are randomly nanodiscs by using hydrothermal method with DOI:NaAc
10.1039/C8TA01683F
as the control
distributed on the surface of the Fe2O3 nanotubes, as observed in agent. It has been well known that the hydrolysis of Fe 3 + produces
Fig.4e-g. The tubular structure and high surface area allow the H+, as shown in Eq. (1). As the concentration of H+ in FeCl3 solution
electrode material to provide more electroactive sites and greater is sufficiently high, the hydrolysis of Fe (H2O)63+ is inhibited. Without

scalability to alleviate volume changes during the charge-discharge the presence of NaAc, the number of Fe2O3 nuclei generated by the
cycles. hydrothermal processes is so less that the crystals grow very fast.
In addition to the template method, there are other methods With the presence of NaAc, two equilibrium reactions occur in the
that can be used to prepare Fe2O3 nanotubes, such as hydrothermal solution, as shown in Eqs (2) and (3). With increasing the amount of
and solution impregnation methods. With the aid of NH4H2PO4 NaAc, the original balance is broken. The concentration of H+ is
solution, Lee et al.59 prepared Fe2O3 nanotubes by hydrothermally decreased, while that of OH- is increased. Then, Eq. (1) will shift in
treating FeCl3 solution. The obtained nanotubes had an average forward direction, i.e, hematite precipitation takes place, thus
length of about 370 nm, with the wall thickness in the range of 15- producing a large number of nuclei. As a consequence, the crystals
40 nm. Xiang et al.48 adopted a hydrothermal and bio-stimulating will have relatively small size, which appear as hexagonal nanodisks
strategy to synthesize Fe2O3 nanotubes. Using tannic acid as coating with exposed (001) plane and thickness of only about 27 nm. The
agent, a composite coating was prepared on the surface of concentrations of OH- and H+ have a significant effect on
hydrothermally synthesized Fe2O3 nanotubes. The Fe2O3 nanotubes morphology of the final products.97
have lengths of 300-400 nm and an outer diameter of about 90 nm,
2Fe(H2O)63+ ↔ Fe2O3 + 6H+ + 12H2O (1)
as shown in Fig. 4h-i. Fig. 4h shows that Fe2O3 nanotubes contained
pores, as indicated by the arrows. CH3COO- + H+ →CH3COOH (2)
2.2 2D Fe2O3 Nanostructure
CH3COO- + H2O ↔ CH3COOH + OH- (3)
The lateral dimension of 2D nanosheets is at least two orders of
magnitude greater than the thickness, which well combine the
advantages of 0D and 1D nanostructures. 2D nanosheets have
unique mechanical properties that can be wrinkled and twisted or
even folded into 3D nanostructures. Therefore, 2D nanosheets have
the ability to buffer the lithiation/delithiation volume change of
lithium ions.91 In addition, nanosheets have a larger surface area
and shorter Li+ ion diffusion paths. They also provide 2D
transmission channels between layers to facilitate pseudocapacitive
storage of the electrodes.92 These superficial special electronic
structures make nanosheets well suited for energy devices, thus
attracting much interest in recent years.93
Chen’s group16 used a hydrothermal method to prepare Fe2O3
nanosheets with exposure of (001) plane. The nanostructure
exhibited a discharge capacity of 865 mA h g–1 at the rate of 200 mA
g–1 over 80 cycles, which is higher than that (456 mA h g–1) of Fe2O3
Fig. 5 SEM (a, b) images of the ultrathin Fe2O3 nanosheets. [Reprinted with
nanorods by 90%. Firstly, the (001) plane of hermatite has a high permission from Ref.6, Copyright 2017, Elsevier]. SEM images of the Fe2O3 nanosheets
packing density of Fe3+ and O2-, which is a key factor to high free of Ni2+ ions (c) and with 0.85 wt% of NiCl2 (d). [Reprinted with permission from
electronchemical performance. In comparison, (010) facet is the Ref.27, Copyright 2014, Royal Society of Chemistry]. SEM image (e) of the as-
mainly exposed crystal plane in nanorods, with a ratio of (010) synthesized Fe2O3 nanosheets [Reprinted with permission from Ref. 46, Copyright
2016, Royal Society of Chemistry].
plane to (001) plane to 77:23. The proportion of (001) plane in
nanosheets is almost 100%. Secondly, the charge transfer
resistances of Fe2O3 nanosheets is 53 Ω, which is smaller than that In order to better tailor the crystal morphology and explore the
(179 Ω) for Fe2O3 nanorods. As a result, Fe2O3 nanosheets offer crystal growth mechanism, studies indicated that it is possible to
more conductive pathway and lower Li+ migration resistance. control the directional growth of Fe2O3 nanocrystals by introducing
Thirdly, according to potentiostatic intermittent titration data, the foreign matters or ions. For instance, Al3 + and Ni2+ ions have been
average DLi+ value of nanosheets is 2.2 × 1010 cm2 s–1, which is shown to be suitable crystal growth control agents.98 Jin et al.6
increased by about 15.7% as compared with that of the nanorods. synthesized Fe2O3 nanosheets with a thickness of 1.3 nm by using
The high kinetic parameters are responsible for the discharge cycle hydrothermal method, as shown in Fig. 5a-b. It was found that the
stability and rate ability. addition of Al3+ is crucial for the formation of Fe2O3 nanosheets.
Due the anisotropic structure of Fe2O3 crystals, it is possible to Fe2O3 nanoparticles synthesized without the presence of Al3+ were
enlarge the exposure of (001) facet and control the growth of Fe2O3 irregular in shape. When Al3+ ions were added, they would be
nanostructures along the [001] direction.94 Fe2O3 nanosheets along adsorbed onto the (001) surface of the Fe 2O3 nanoparticles.
the [001] direction with preferentially exposed (001) facet have Therefore, Fe2O3 nanoparticles grew preferentially along the [100]
been grown by using hydro/solvothermal, template-assisted direction, while the growth of (001) is inhibited. Jin’s group 27
prepared Fe2O3 hexagonal nanoplates by using a molten salt method

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with the assistance of Ni2+ ions. The thickness and morphology of the of the surface deposition can be carried out simultaneously, with
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Fe2O3 nanoplates could be tailored by controlling the content of Ni2+. The DOI: 10.1039/C8TA01683F
the formation of a dense coating on the template surface.
Ni2+ ions were adsorbed onto the (001) facet through coordination Li’s group20 reported the synthesis of Ag-Fe2O 3 hollow spheres by
bonding with the O atoms, resulting in slower growth along the (001) using Ag@C nanospheres templates. Fig. 6a schematic diagram
planes. With increasing content of Ni2+, the nanosheets became more describing the synthesis process of Ag-Fe2O 3 nanospheres. The

and more uniform, the edges of the items are more and more sharply, Ag@C template has diameters of 650-700 nm and each sphere
and the thickness of nanoplates was decreases rapidly from 300 nm to consists of a carbon shell with a thickness of 230 nm and an Ag
50 nm, as demonstrated in Fig. 5c-d. core with a diameter of 150 nm. Ag-Fe2O 3 hollow spheres were
In addition to direct synthesis in solution, template and substrate obtained after the growth and annealing of Fe 2O3. The diameter
methods have also been employed to prepare 2D Fe2O3 of the Ag-Fe2O 3 nanospheres is about 600 nm, which is almost
nanostructures. Liu and co-worker51 fabricated Fe2O3 nanofilms by the same as that of the Ag@C template sphere. The surface of
using Al2O3 as the sacrificial layer. The Al2O3 films and the Fe the Ag-Fe2O 3 hollow nanospheres is covered with numerous
nanofilms were sequentially deposited on a glass substrate. Then, Fe2O3 nanorods which are 60-70 nm in length and 30-40 nm in
Fe nanofilms were obtained by etching the Al2O3 sacrificial layer width, as illustrated in Fig. 6b-c. In addition, the Ag nucleus was
with aqueous NaOH. After annealing in air at 450℃, 2D Fe2O3 decomposed into nano-sized particles of about 10 nm in size and
nanostructures were obtained, with thicknesses of 103‒165 nm. uniformly distributed on the surface of the Fe 2O 3 spheres. Chen’s
The Fe2O3 nanofilms were free-standing, with a relatively rough group61 fabricated ultrafine Fe2O 3 nanoparticles embedded in
surface due to the assembly of nanoparticles. Because of the nitrogen-doped hollow carbon spheres by pyrolyzing Fe-based
presence of internal differential stress, the Fe2O3 nanofilms were zeolite imidazole framework (Fe-ZIF). The Fe-ZIF precursor is
prone to wrinkling and bending. It is expected that such a structural composed of Fe2+ ions and 2-methylimidazolate linker. When the
feature should be very effective to buffer the lithium/delithiation Fe-ZIF precursor was annealed in air at 620 ℃ , the 2-
induced strain. Wu’s team46 synthesized a spinous Fe2O3 nanosheet methylimidazolate linker was converted to a nitrogen-doped carbon
hierarchical structures on Ni foam substrate by using a network as carbon and nitrogen sources. At the same time, Fe2+
hydrothermal process. The as-synthesized spinous Fe2O3 sample ions were oxidized to form Fe2O3 nanoparticles, which were
consists of a large number of nanosheets, with thicknesses at uniformly dispersed in the nitrogen-doped carbon network. This
nanometer scale, as seen in Fig. 5e. unique structure can effectively prevent agglomeration of the Fe2O3
2.3 3D Fe2O3 Nanostructures nanoparticles. In addition, Fe atoms served as catalyst to promote
The synthesis of 3D Fe2O3 nanostructures of Fe2O3 has been rapid carbonation of the carbon-containing linker, leaving a hollow
extensively reported in the open literature. Various 3D Fe2O3 structure. When such Fe2O3 nanospheres are used as electrode
nanostructures, such as spherical nanostructure,20, 61, 99, 100 hollow material of LIBs, the hollow structure can act as a reservoir for Li+
nanostructure,11, 38, 101 nanoarray,8, 25, 39 flower-like nanostructure4, ions and electrolytes, effectively accommodate huge volumetric
10, 102 and microbox structure, 103 have been synthesized, by using changes and shorten the path of Li+ ion diffusion and electron
different synthetic methods. transfer.
2.3.1 Spherical Structures
3D spherical nanostructures have been widely studied for the
applications not only in LIBs and SCs but also in water treatment
and sensors. In this section, the synthesis of 3D Fe2O3 spherical
nanostructures will be presented. Based on whether a template is
used or not, there are two categories: (i) template synthesis20, 61, 104
and (ii) template-free method.100,70,105
2.3.1.1 Template-based Approaches
Template synthesis is a simple and stable strategy to obtain
spherical nanostructures. By selecting specific template, one can
readily control shape, size and uniformity of the final products. In
general, template synthesis consists mainly of four steps: (1)
synthesis of the template, (2) modification of the template surface,
(3) deposition of the designed material and (4) deletion of the
template. Each step is important, but their importance is slightly
Fig. 6(a) Schematic illustration of template-guidance synthesis mechanism of the Ag-
different case by case. For instance, the second step to introduce
Fe2O3 nanospheres, (b) SEM images of the Ag@C templates and (c) Ag-Fe2O3
functional groups on the template surface can effectively solve the composites. [Reprinted with permission from Ref.20, Copyright 2017, Nature].
problem of incompatibility between the template surface and the
shell material. The third step requires effective deposition of the Similar to the traditional template, sacrificial template is also an
designed material on the shell material at the micro-nano level, effective approach in controlling the structural orientation and
which is generally considered to be the most challenging step. The determining shape and size of the sphere. However, the significant
second step of the template surface modification and the third step difference is that the sacrificial template is partially or completely
consumed during the reaction. The sacrificial template forms the

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shell structure by sacrificing the template itself, so that additional nanosphere surface. After polymerization and carbonization
View Articlein N2,
Online
surface functionalization steps can be omitted. Therefore, this droplets of the spray pyrolysis were convertedDOI: 10.1039/C8TA01683F
into FeOx-carbon
method is generally considered to be more efficient, especially composite spherical powders (Scheme 1-a-②). The FeOx powders
when the template is completely depleted during the shell were then reduced to dozens of nanometers of Fe nanocrystals and
formation process. These attractive features have been applied uniformly dispersed in the carbon microspheres (Scheme 1-a-③

widely to the formation of a variety of hollow spherical structures. and Scheme 1-b-①). In oxidizing atmosphere, the surface of Fe
A large number of special formation mechanisms can be proposed nanocrystal is partially oxidized to form a thin Fe2O3 layer (Scheme
to understand the process of sacrificial template synthesis of hollow 1-a-④ and Scheme 1-b-②). Due to the Kirkendall effect, Kirkendall
spheres, such as the Kirkendall effect106-110 and galvanic voids are generated in the vicinity of the Fe/Fe2O3 interface (Scheme
replacement99. 1-b-③). As the Fe nanocrystals are completely oxidized to iron
oxide, hollow Fe2O3 nanosphere agglomerates are formed (Scheme
1-a-⑤ and Scheme 1-b-④).
2.3.1.2 Template-free Approaches

Template synthesis of microspheres usually involves complicated
synthesis procedures and thus has high costs. Moreover, the

template residue can also affect the activity of the prepared
materials. Therefore, various template-free methods have been
developed to prepare complex microsphere structures 111, 112.
Hydrothermal method to obtain hollow nanospheres is based on
the Ostwald ripening process. Nanoparticles in the hydrothermal
solutions aggregate into spheres to reduce the total surface energy.
The growth process is at the continuous consumption of small
crystals or particles, thus leading to the formation of larger
nanospheres. Chai and co-workers113 synthesized Fe2O3@C
nanospheres (∼50 nm) by using a one-step hydrothermal method.
Small Fe2O3 nanocrystals (∼8 nm) were embedded in carbon
nanospheres. Due to the small size and well-crystallized structure,
these Fe2O3 nanocrystals would ensure a short diffusion distance
for electrons and ions. In addition, the carbon shells not only
provide high electrical conductivity, but also buffer the volumetric
expansion/contraction during the process of lithiation/delithiation.
Solvothermal method is developed on the basis of hydrothermal
method, which uses organic solvents rather than water. Pan's
group100 prepared Fe2O3 nanocrystalline microspheres consisting of
52 nm nanocrystals by using solvothermal reaction and thermal
oxidation. Zhu and Xu114 prepared Fe2O3 mesoporous microspheres
by using a surfactant-free solvothermal method combined with
precursor thermal transformation. Fe(NO3)3 and tartaric acid were
dissolved in dimethylformamide (DMF). After reaction at 160℃ for
8 h, ferrous tartrate (C4H4O6Fe) precursor microspheres were
obtained. The precursormicrospheres were further calcined in air at
Scheme 1 (a) Formation mechanism of the hollow Fe 2O3 nanosphere
320℃, resulting in γ-Fe2O3 mesoporous microspheres. The as-
aggregates through Kirkendall-type diffusion. (b) Chemical conversion prepared γ-Fe2O3 mesoporous microspheres have a high specific
process in the surface region of a Fe sphere in C matrix [Reprinted with
permission from Ref. 17, Copyright 2015, Royal Society of Chemistry]. surface area of 138.6 m2 g–1.
According to the previous studies, ammonia, L-arginine and
sodium hydroxide have all been used as hydrolysis-controlling
Yan’s group99 synthesized α-Fe2O3 hierarchical hollow spheres
agent, leading to nanopolyhedra, nanoparticles and nanoflakes. 115,
through galvanic replacement reactions with CuO nanospheres. The 116 Zhang’s group105 developed hierarchically porous Fe O
2 3
CuO nanospheres and FeCl2 were mixed in solution, sealed in an
microspheres with lysine as hydrolysis-controlling agent. It is well
autoclave and held at 170℃ for 30 min. In this process, Cu atoms in
known that the number of amino and carboxylic acid groups in a
the CuO nanospheres were replaced by Fe ions to form hollow α-
molecular structure determines the pH of an amino acid. Lysine
Fe2O3 nanospheres. Cho et al.17 used a combination of spray
molecules include two amino acids and one carboxylic acid group.
pyrolysis and nanoscale Kirkendall diffusion effect to synthesize
Because of its pH above 7, lysine can act as a hydrolysis control
new structures called ‘hollow nanoball agglomerates’. Scheme 1
agent to control the formation of Fe2O3 during hydrothermal
shows the formation mechanism of the hollow nanosphere
processes. With the hydrolysis of lysine, more and more OH - ions
aggregates and the chemical conversion process of FeOx-carbon
are produced in the hydrothermal reaction solution, so that pH

Journal
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value of the solution increases greatly. The Fe(OH)3 phase is then accommodates volume expansion on the one hand and reduces
View the
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dehydrated to obtain Fe2O3 particles. DOI:
loss of volumetric energy density on the other 10.1039/C8TA01683F
hand.
In addition to the hydro/solvothermal method, heat treatment
has been used to prepare microspheres, such as spray pyrolysis and
thermal annealing. Zhang et al.117 developed a ‘spray drying-

carbonization-oxidation’ strategy to prepare α-Fe2O3-graphitic
carbon (α-Fe2O3@GC) composite microspheres. The α-Fe2O3
nanoparticles with sizes in the range of 30‒50 nm are coated by
onion-like GC shells with thickness ranging from 5 to 10 nm. In this
particular structure, the α-Fe2O3 nanoparticles act as the main
active material and contribute most part of the capacity. Because of
its simple feature, this preparation process has attracted
widespread interest of the research community of LIBs. It can be
widely employed to synthesize other MOx-GC nanocomposites,
such as MnO2@GC, SnO2@GC, NiO@GC and Co3O4@GC. Kore et
al.118 synthesized mesoporous Fe2O3 nanoparticles by a using

solvent deficient approach. Without the use of any solvent,
ammonium bicarbonate (NH4HCO3) was grinded with a hydrated Fig. 7 FESEM (a, b) and TEM (c) images of the double-shell Fe2O3 hollow spheres
ferric nitrate nonahydrate (Fe(NO3)3·9H2O) to obtain a precursor. [Reprinted with permission from Ref.11, Copyright 2017, Elsevier]. TEM images of the
Then, mesoporous Fe2O3 nanoparticles were achieved after Fe2O3 particles prepared by spray pyrolysis at various temperatures, (d) 600℃, (e)
800℃, and (f) 1000℃. [Reprinted with permission from Ref.38 , Copyright 2015,
annealing at 350℃ for 2 h.
Royal Society of Chemistry].
2.3.2 Hollow Structures

Due to its low density, high surface area and shell permeability,
Because of its simple process, spray pyrolysis is one of the most
hollow structure has attracted a great deal of attention in the fields
common methods to develop hollow structures. Spray pyrolysis
of energy storage and conversion, gas sensors and drug delivery. 119
temperature is the most critical factor affecting the number of
Hollow structure is usually composed of a core, a middle of the gap
shells. Kang’s group38 prepared yolk-shell structured Fe2O3 particles
and a shell. Expectedly, the interior voids in the Fe2O3 yolk-shell
by using a continuous spray pyrolysis method. Compact (non-
particles would provide extra space to alleviate structural
hollow) Fe2O3 spheroidal particles were prepared through spray
strain/stress during the charge/discharge process, when they are
pyrolysis of a sucrose-free solution. Sucrose concentration is one of
used as anode materials of LIBs. Yolk-shell and multi-ball nesting are
the key factors for the formation of the yolk-shell. The optimized
typical hollow structures. Hydrothermal is a common method to
concentration of sucrose in the spray solution was 0.7 M. The
prepare hollow structures. Lu’s group11 adopted a template-free
temperature of the preparation process can affect the rate of
hydrothermal synthesis to develop double-shell hollow Fe2O3
combustion of the Fe salt and carbon components, thus controlling
nanospheres, with K3[Fe(CN)6] and NH4H2PO4 as the raw materials.
the formation and internal structure of the yolk-shell structured
In the early stages of hydrothermal reaction, single-shell hollow
particles. The microsized carbon-Fe2O3 composite particles had
spheres were formed due to the Ostwald ripening process. When
yolk-shell structures after the reaction of sucrose polymerization
the reaction was carried on, H+ ions from NH4H2PO4 corroded the
and carbonization, repeated combustion and shrinkage. When the
inner shell, forming a multi-shell hollow nanosphere structure. The
temperature was 600℃, the combustion rate of the composite
diameter of the ball is about 400 nm, which consists of a large
particles was slow, while the Fe2O3 particle had a yolk-shell
number of primary particles with diameters of tens of nanometers.
structure with four shells. Due to rapid combustion and Ostwald
Multilayered internal structures can be clearly observed from
ripening process, the shell number of the carbon-Fe2O3 particles
cracked nanospheres, as demonstrated in Fig. 7a-c. The diameter of
was reduced to two, as the temperature was increased to 1000℃.
the inner sphere is about 250 nm. The thicknesses of the inner shell
Representative SEM and TEM images are shown in Fig. 7d-f. The
and the outer shell are 60 and 30 nm, respectively, while the
rate of temperature change is another important factor affecting
distance between the two shells is about 60 nm. Yu’s group101
the number of shells. Yu's group120 prepared α-Fe2O3 multi-shelled
developed a novel structure of iron oxide/carbon. The α-Fe2O3
hollow spheres by using a spray drying method. From the broken
nanoparticles were prepared by using a hydrothermal method.
part of the microspheres, it was observed that the microspheres
Then, tetraethoxysilane and dopamine hydrochloride were used for
have a multi-shell structure. According to the mechanism of non-
hydrolysis and carbonization. Finally, the SiO2 layer was etched
uniform shrinkage, the process of the shell formation is closely
away with NaOH to form a hollow multi-layer shell Fe2O3 sphere.
related to the rate of temperature change. At lower rates (0.5℃
The internal void space will allow the active material to freely
min–1), fewer shells are produced, corresponding to single-shell
expand without damaging the outer protective shell. However, the
hollow spheres and yolk-shell structures. At higher rates (2 and 5℃
void space will affect the performance of the volume energy
min–1), more shells were formed and multilayer hollow spheres
density. They optimized the void space by adjusting the thickness of
were obtained.
the sacrificial layer of silicon oxide, so that the electrode material

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2.3.3 Flower-like Structures precursor of Fe2O3 and the flower-like structure View self-assembly
Article Online
Flower-like structure has high specific surface area, which is process. When ethylene glycol forms an ironDOI: 10.1039/C8TA01683F
alkoxide with FeCl 3, H+
conducive to the diffusion and adsorption of ions and electrons. ions are generated as a by-product. Hydrolysis of urea produces OH-
Various flower-like structures have been prepared and used as ions to neutralize H+ ions, which favors the precursor synthesis.
electrode materials for LIBs and SCs.121-123 Shivakumara's team124 Liang et al.42 prepared 3D flower-like Fe2O3 nanostructure through

synthesized flower-like α-Fe2O3 nanostructures by using glycol- urea-assisted hydrothermal route. Representative SEM image of the
mediated self-assembly. Flower petals in the nanostructure have nanostructures is shown in Fig. 8d. Urea and NaOH played key roles
many independent pores. These pores and the flower-shaped in the formation of Fe2O3 microflora. Similar aids have been
structure provide a larger surface area. Wang's group125 obtained reported in the literature.121, 122 Liang et al.31 found that sodium
ferric (III)-hydroxide precursor hydrolyzed from FeCl3 solution and citrate played a very important role in the formation of Fe2O3
flower-like Fe2O3 structure was achieved through heat treatment. flower-like microspheres obtained by using hydrothermal synthesis.
No templates or catalysts are required in this process. The On the one hand, the introduction of citric acid chelated with iron
individual flower-shaped structure was made up of dozens of self- ions to reduce the concentration of free Fe3+ in the solution and the
assembled nanosheets with a thickness of about 20 nm. Cao and co- formation rate of Fe2O3 nanoparticles. On the other hand, citrate
workers4 prepared flower-shaped 3D Fe2O3 nanosheets on copper acted as a shape regulator and control agent. The diameter of Fe2O3
foil. FeSO4·7H2O, urea and NH4F were dissolved in deionized (DI) flower-like microspheres was about 6.8 μm. This flower structure
water. The solution and the pretreated copper foil were had a rough surface, which consisted of numerous randomly
hydrothermally treated at 80℃ for 12 h. The product was finally arranged rice-like granular particles, as demonstrated in Fig. 8e.
annealed in Ar at 450℃. In the early stages of reaction, the 2.3.4 Nanoarrays
nanoparticles first aggregated into flower-like dodecahedrons. With large surface area and hierarchical structure, nanoarrays,
Then, petals grew out and started to divide. Large petals divided which could provide high surface area and short transmission paths
into layered nanosheets, thus leaving enough room between them for electron and ion conduction, are ideal candidates for electrode
and finally forming the 3D framework (Fig. 8a). The flower-like materials of SCs. There are various strategies to prepare
Fe2O3 structure has a high BET specific surface area of 16.1 m2 g–1. nanoarrays, which can be roughly divided into top-down and
Lu’s group10 prepared a porous α-Fe2O3 microscopic flower-like bottom-up categories. The former mainly involves etching,
structure, which was derived from FeSO4(OH) precursors removing unnecessary parts and preserving the desired material
synthesized by using a simple ethanol-mediated method. array. The latter is a step-by-step growth of a given material,
Fe2(SO4)3·xH2O was added to absolute ethanol and stirred for 3 h, removing the intermediate process material, leading to hierarchical
followed by hydrothermal reaction at 150℃ for 24 h. The resulting array structure. Fe2O3 nanoarray is mainly prepared by using
yellow colored precursor was calcined at 700℃, yielding hybrid bottom-up method.
structure of Fe2O3 with an average diameter of about 2 μm. The
flower-like structure is composed of a large number of
nanoparticles nanoporous bodies, as illustrated in Fig. 8b-c.
Fig. 8(a) SEM image of the 3D flower-like Fe2O3 [Reprinted with permission from
Ref.4, Copyright 2015, Wiley]. (b, c) SEM images of the as-prepared porous α-Fe2O3
microflowers. [Reprinted with permission from Ref. 10, Copyright 2017, Elsevier]. (d)
SEM image of the Fe2O3 microflowers. [Reprinted with permission from Ref. 31,
Copyright 2014, Elsevier]. (e) SEM image of the α-Fe2O3 microflowers. [Reprinted
with permission from Ref.42, Copyright 2013, Elsevier].
Fig. 9 (a) SEM images of the NiCo2S4 NNAs and (b) hierarchical NiCo 2S4@Fe2O3 core-
shell NNAs. [Reprinted with permission from Ref. 8, Copyright 2016, Elsevier]. (c)
In order to better control the flower-like structures, various Schematic illustration of fabrication of the Fe2O3/Ppy nanostructure and (d) TEM
adjuvants are used during the synthesis of iron oxides. Wang et al image of the Fe2O3/PPy. [Reprinted with permission from Ref. 25, Copyright 2017,
102 synthesized Fe O with a 3D flower-like structure with urea as Wiley]. (e) TEM image of the NiNTAs@Fe 2O3 nanoneedles. [Reprinted with
2 3
the control agent. Urea plays a decisive role in the synthesis of the permission from Ref.39, Copyright 2017, Wiley].

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In order to solve the problem of low conductivity of iron oxide, ℃, Fe2O3 nanoparticles grew up, forming porous Fe2OView
3 microboxes.
Article Online
materials with high conductivity are usually used in either the core Further increase in annealing temperature DOI:resulted
10.1039/C8TA01683F
in further
or the shell of the arrays. Zhai’s group8 designed and fabricated growth of the Fe2O3 nanocrystals, thus leading to the formation of
hierarchical core-shell heterostrucure composities which consisited nanoplatelets. Fe2O3 hierarchical microboxes were produced at 650
of NiCo2S4 nanoneedle arrays (NNAs) and Fe2O3 nanorods (NRs). A ℃. Therefore, morphology and structure of the Fe2O3 microboxes

free-standing NiCo2S4 NNAs with diameters of 50-100 nm and a could be controlled simply through annealing temperature.
length of about 800 nm were grown on a Ti substrate, on which
Fe2O3 nanorods with a diameter of about 5 nm and lengths of 5‒15
nm were grown by using hydrothermal method, as illustrated in Fig. 3. Synthesis of Ferriferous Oxide (Fe3O4)
9a-b. The Fe2O3 nanorods were directly grafted onto the NiCo2S4 Nanomaterials
NNAs to provide a large active surface area for electrochemical
3.1 Low-dimensional Nanostructures
reactions. The NiCo2S4@Fe2O3 sample had a Brunauer-Emmet-Teller
(BET) specific surface area of 58.5 m2 g–1, which is much larger than Due to its magnetic properties, low-dimensional Fe3O4
that of Fe2O3 (21.6 m2 g–1). The high conductivity of the core nanomaterials are widely used in data storage, magnetic resonance,
(NiCo2S4 NNAs) and the high specific surface area of the shell gas sensors, spintronic devices and biomedical fields. Fe3O4 is also
(porous Fe2O3) would ensure a high charge storage capacity of the an attractive anode material for LIBs and SCs, owing to its high
Fe2O3 composites. capacity, environmental friendliness and high electrical
Several special treatment methods have been used in the conductivity. However, the stress caused by the volume expansion
preparation process to improve the stability of the nanoarray, such during charging and discharging leads to poor cycle stability of the
as sacrificial template or adhesive film layer. Hu’s group25 Fe3O4 electrode and low rate capability. In this case, low
synthesized tectorum-like Fe2O3/polypyrrole (PPy) nanoarrays. The dimensional Fe3O4 nanostructures could be solution to these
preparation process includes the growth of Fe2O3 nanoarrays from problems. This is because nanostructures ensure a high contact
sacrificial ZnO templates and the in-situ vapor-phase polymerization area with the electrolyte and can buffer strain and volume changes
of PPy on surface of the nanoarrays. The formation of the to avoid structural changes or cracks. Gupta’s team127 synthesized
Fe2O3/PPy on the conductive carbon cloth is shown in Fig. 9c. The nearly monodisperse Fe3O4 nanocrystals by using a wet chemical
ZnO nanorods with diameters of 100-300 nm were transformed into method, with an average particle size of 8 ± 2 nm. Zhang et al.128
tectorum-like Fe2O3 nanoarrays in Fe(NO3)3 aqueous solution. The prepared carbon-encapsulated Fe3O4 nanoparticles by using a
surface of the Fe2O3 nanoarray was coated with PPy layer with an hydrothermal reaction combined with heat treatment. It was found
optimized thickness of 3 nm by adjusting the amount of PPy. The that crystal morphology and particle size of the Fe3O4 nanoparticles
length and diameter of the Fe2O3/PPy arrays were about 1 μm and could be controlled by adjusting the concentration of iron nitrate
250 nm, respectively. The array was made up of nanosheets that and glucose solution during the reaction process.
are tens of nanometers in thickness, as demonstrated in Fig. 9d. The 1D nanowire can promote the transport of electron and lithium
PPy shell was uniformly attached to surface of the Fe2O3 cores. Xia’s ion, which is advantageous for achieving high rate performance.
team39 deposited iron oxide nano-needles on ultrafine Ni nanotube Manthiram’s group129 prepared Fe3O4 single crystal nanowires and
arrays (NiNTAs) to form NiNTAs@Fe2O3 nanostructures with a carbon-coated Fe3O4 nanowires by using a microwave assisted
hybrid core-shell structure. ZnO nanorod arrays were used as the hydrothermal method. Xia and co-workers130 synthesized Fe3O4
template, while an Au film was sputtered on its surface before an nanotubes by using a two-step hydrothermal method. Firstly, Fe2O3
ultrathin Ni film was coated through electrodeposition. Finally, nanotubes were obtained by using a hydrothermal method. Then, a
Fe2O3 nano-needles were deposited. Interestingly, the thin layer of thin carbon layer was coated on surface of the nanotubes by using
Au (thickness of about 5 nm) sputtered on the ZnO nanorods with another hydrothermal treatment step. The Fe2O3 nanotubes were
an average diameter of 150 nm ensured the uniform growth of the completely reduced and converted to Fe3O4 nanotubes after
Ni nanofilm on the ZnO nanorod. Representative TEM image of the thermal annealing. O'Neill et al.131 prepared 1D Fe3O4 nanowires by
nanostructure is shown in Fig. 9e. Without the presence of the Au using a spray deposition method. They were wrapped with carbon
film on the ZnO nanorods, uniform Ni film could not be formed, nanotubes to form composite electrode for SCs. Doong’s group 132
instead, the Ni film was non-uniform and discontinuous, composing deposited Fe3O4 nanoparticles on the surface of halloysite
of large Ni particles. nanotubes to get Fe3O4 nanotubes by using a coprecipitation
2.3.5 Other Structures method.
Zheng et al.126 prepared an iron oxide hollow nanoshuttle, which
was used as electrode of SCs. The hollow nanoshuttles had average
wall thickness and length of 30 nm and 100 nm, respectively. Zhang
and co-workers103 synthesized a series of Fe2O3 microboxes with
various shell structures by annealing Prussian blue (PB) microcubes.
The microboxes were made up of numerious nanoparticles. As the
annealing temperature was increased, the particles on the surfaces Fig. 10 SEM images of the Fe−ethylene glycolate nanosheets with different
grew up accordingly. The Prussian blue microcubes were converted thicknesses, synthesized at different concentrations of sodium citrate: (a) 370
nm/10 mM, (b) 110 nm/15 mM and (c) 23 nm/20 mM. [Reprinted with permission
into hollow Fe2O3 microboxes by thermally induced oxidative
from Ref.23, Copyright 2016, American Chemical Society].
decompostion at 350℃. When the annealing temperature was 550

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The unique structure of 2D nanosheets also ensures high smooth. However, if the content was too high (98 View wt%), the
Article Online
conductivity, while the spacing in between the sheets is able to microspheres had a macroporous sponge-like DOI: 10.1039/C8TA01683F
structure and the
alleviate the problem of volume expansion. Gu et al.133 prepared surface was rather rough. Wan’s group140 synthesized porous 3D
Cu/Fe3O4 core–shell nanorod array by using a hydrolysis-coupled nanohybrids. N-doped carbon (NC) was used to encapsulate the
redox reaction. Thin Fe3O4 nanosheets are uniformly assembled on Fe3O4 nanoparticles. The Fe3O4@NC nanoparticles were connected

the Cu nanorods. Ding et al.23 used sodium citrate as the surfactant by nitrogen-doped graphene to form a conductive network of 3D
to induce the growth of Fe-O into hexagonal ultrathin nanosheets. interconnects. The resulting 3D nanostructures exhibited am ultra-
The addition of sodium citrate not only neutralizes H+ as OH- donor, low density (8.47 mg cm–3).
but also acts as a surfactant to direct the growth of the nanosheets Hollow porous structures have attracted much interest due to
and prevent their aggregation. In the process of growth, Fe-O layers their specific morphology. The hollow and porous structure offers a
and ethylene glycolate anion layers stack alternatively and high specific surface area and a large number of pores, providing a
crystallize in the c-axis direction. Therefore, the citrate groups large contact area between the electrode and the electrolyte and
coordinate with the Fe3+ ions exposed on the (001) plane through thus producing more redox activation sites. More importantly, the
their carboxyl and hydroxyl ligands, which can inhibit the deposition hollow structure may provide sufficient space to mitigate the
and aggregation of Fe-glycolate along the c-axis direction. As the mechanical stresses caused by the volume changes during the
concentration of sodium citrate was increased from 15 mM to 20 repeated Li+ insertion/extraction. Therefore, hollow structured
mM, average thickness of the Fe-ethylene glycolate nanosheets was electrode will have high cycling stability. Various methods have
decreased from 370 nm to 23 nm, because the growth in the c-axis been employed to prepare hollow porous Fe3O4 nanostructure,
direction was more severely inhibited than that in the a-b direction such as self-assembly, ion exchange, solid state decomposition and
as the sodium citrate concentration was increased. Fig. 10a-c shows chemical etching.141-145
SEM images of the Fe−ethylene glycolate nanosheets obtained at
different concentrations of sodium citrate. In addition, the Fe–
ethylene glycolate nanosheets tended to be curved, preventing
them from close packing in the thickness direction. Similar results
have been reported by others in the literature.94, 97 Xin et al.134
prepared a hierarchical structure of Fe3O4 nanosheets by annealing
nanosheet ferric alkoxide precursors in N2. Huang et al.135 deposited
porous Fe3O4 nanosheets by using chemical bath. The nanosheets
consisted of nanoribbons with a width of less than 10 nm.
3.2 3D Nanostructures
Due to special physical reasons such as Ostwald ripening,136
spherical or flower-shaped 3D Fe3O4 nanostructures have been
synthesized through stacking. Sun’s group137 synthesized Fe3O4
microflowers by using a solvothermal method combined with
subsequent thermal annealing. When the Fe3+ solution was mixed
with urea and ethylene glycol, burst nucleation occurred, resulting
in the aggregation of supersaturated nuclei. Subsequently,
Fig. 11 (a, b) SEM images of the Fe3O4 hollow microspheres [Reprinted with
nanoparticles began to form and grow. Due to Ostwald ripening, permission from Ref.19, Copyright 2013, Wiley]. (c, d) SEM and TEM images of the hollow
these nanoparticles with an average size of 10 nm were Fe3O4 nanostructure (inset: magnified image). [Reprinted with permission from Ref. 45,
interconnected and assembled into nanosheets with an average Copyright 2014, Royal Society of Chemistry]. (e) SEM image revealing the hierarchical
thickness of 60 nm. In order to minimize the energy of the system, porous structure of the C-C-Fe3O4 hollow spheres. [Reprinted with permission from
Ref.7, Copyright 2015, Elsevier].
the nanosheets are crosslinked together to form a microflower with
diameters of 3‒6 μm. Zhu and Xu114 prepared Fe3O4 mesoporous
microspheres by using a solvothermal method without the use of
surfactants. Fe(NO3)3 and tartaric acid were dissolved in Hollow nanostructures include hollow spheres, multi-shell hollow
dimethylformamide solvent and reacted at 160℃ for 8 h to prepare structure, hollow nanocapsules and yolk-shell structure. Lou's
ferrous tartrate (C4H4O6Fe) precursor microspheres. The group19 synthesized a hollow microsphere composed of Fe3O4
microspheres were further calcined in N2 at 400℃, leading to Fe3O4 nanoplates by using a solvothermal method. The uniform sphere
mesoporous microspheres. The as-prepared Fe3O4 mesoporous with a diameter of about 5 μm was hollow inside, whereas the wall
microspheres had a high specific surface area of 122.3 m2 g–1. He’s of the sphere is made up of nanoplate through stacking. These
group138 fabricated Fe3O4@C nanospheres with ferrocene as the Fe wedged plates had a certain curvature to construct the spherical
sources by suing a solvothermal method. Suh’s group 139 prepared structure, as demonstrated in Fig. 11a-b. Similar Fe3O4 hollow
Fe3O4@carbon microspheres through suspension polymerization spheres were reported by Geng and co-workers45 by using a
combined with heat treatment. Surface morphology of hydrothermal method combined with heat treatment. The Fe 3O4
microspheres varied with the content of Fe3O4 nanoparticles. With hollow nanospheres had an average diameter of about 200 nm,
lower content (72 wt%), the microsphere surface was relatively with a rather rough surface. The hollow spheres were made of
nanocrystals with a diameter of about 10 nm, as seen in Fig. 11c-d.

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He’s team7 prepared Fe3O4 double carbon-shelled hollow spheres, β-FeOOH during annealing, some pores were left on View the Article
surface of
Online
where a double C-C-SiO2 hollow sphere was used as a hard the materials. At the same time, the core DOI: 10.1039/C8TA01683F
volume shrank at high
template. 2, 4-Dihydroxybenzoic acid-formaldehyde was coated on calcination temperatures, creating void spaces inside the carbon
surface of the C-C-SiO2 particles through in-situ polymerization. Fe3+ shell. The β-FeOOH@PDA core-shell nanostructure was then
ions were locked through the electrical attraction between the transformed to Fe3O4@N-C yolk shell nanostructure. The Fe3O4@N-

negatively charged RF-COO- and the positively charged Fe3+ ions, C nanocapsules exhibited a BET surface area of 94.2 m2 g–1.
which were converted to iron oxide during the subsequent In addition, there are many reports on the synthesis of
pyrolysis. Then, double-layered hollow C-C-Fe3O4 microspheres nanobeads, nanocages and hollow nanotubes. Based on directional
were obtained by carbonizing the resin layer and removing the assembly and Ostwald ripening, Xie’s group147 fabricated a hollow
intermediate silica layer. The as-prepared C-C-Fe3O4 hollow spheres Fe3O4 nanobead by using a solvothermal method. Using kapok fiber
had a typical hierarchical porous structure. The first layer was a as a microtubule biotemplate, Du et al.148 synthesized Fe3O4 hollow
macropore with diameters of 50-100 nm, as clearly observed from nanotubes. Song’s group149 prepared hollow nitrogen-doped
the broken shell in which the holes were well connected one Fe3O4/carbon nanocages with hierarchical porosities by carbonizing
another (white arrow in Fig. 11e). The second layer was a polydopamine coated Prussian blue.
mesopore/micropore in the carbon wall that was thinner than 3
nm. The C-C-Fe3O4 microspheres had a high specific surface area of

317.3 m2 g–1 and a pore volume of 0.591 cm3 g–1, indicating that 4. Synthesis of Iron oxide (Fe2O3, Fe3O4)
most of the pores in the shell were connected to the opening Nanocomposites
outside the spheres.
Volume changes and powder agglomeration are the major
Prussian blue (PB) templates have also been used to synthesize
problems suffered by the transition metal oxide (MOx) electrode
hollow microcapsules. Xu’s group145 prepared Fe3O4/VOx hollow
material. In order to solve these problems, the first approach is to
microcapsules through a template reaction between PB cube and
design and fabricate various types of nanostructures such as
Na3VO4. The synthesized PB cube was a 3D mini cube with a
nanotubes, nanowires, nanospheres, hierarchical structures. The
uniform size. Addition of Na3VO4 resulted in the conversion of PB to
nanostucture material can provde a high specific surface area and
multi-component composites near the surface by hydrolysis and ion
short electron-transmission distance, which improves large contract
exchange. An interlayer gap appeared between the shell and the
area between active material and electrolyte, high rate capability
remaining PB core. The reaction occurred from the outside to the
and cycling performance during the lithium insertion/extraction
inside. As the reaction time was extended to 20 min, the core
process. The second strategy is that MOx composities with other
disappeared and an open hollow micro-cassette was formed.
materials, to reduce agglomeration and volume changes during the
Yolk-shell is a special type of hollow nanostructures consisting of
charge/discharge cycles. The third effective method is design and
an outer shell and an inner core, with a gap between them, which
synthesis of a hybrid electrode.74, 150-156
can be prepared by using a variety of methods. The first step is to
In this section, we will focus on the complexing of iron oxide with
prepare a multi-layer core-shell structure, from which the middle
other materials, and review the synergistic effects of the various
layer is then removed, thus leaving gap to achieve yolk-shell
components and enhance the electrochemical behavior. Firstly, the
nanostructure. There are two main ways to remove the middle
composites of different carbonaceous supports such as iron oxide
layer. One is the corrosion method. Guan’s group 146 synthesized a
and amorphous carbon, carbon nanotubes, graphene and carbon
yolk-shell Fe3O4@C composite with a high loading ratio of 90 wt%
cloth will be reviewed. Then, the nano-hybrid structures formed by
by using a modified Stöber method. Firstly, 3-aminopropyltriethoxy-
iron oxide and other metal oxides will be introduced. Finally, the
silane was applied to modify the NH2 groups. Then, Fe3O4 spheres
composite with other polymer conductors will be given.
were coated with a SiO2 layer. Secondly, a carbonaceous layer was
4.1 Iron Oxides and Carbonaceous Nanocomposites
deposited through hydrothermal reaction, followed by thermal
annealing. Finally, NaOH solution was used to etch the SiO 2 layer. In The involvement of carbonaceous materials can not only reduce
this way, middle-hollow Fe3O4@C yolk-shell spheres were obtained, electrode resistance and increase lithium ion and electron transport
in which Fe3O4 was a core, carbon layer with 10 nm thickness was rates, but also provides a buffer layer to mitigate the volume
the shells and the void thickness between the Fe3O4 core and changes and agglomeration of the activated particles during the
carbon shell was about 80 nm. A similar yolk-shell Fe3O4 cycling process. Various carbonaceous materials have been adopted
nnaostructure was prepared by Yang’s group47. The main difference to form composites with iron oxide. According to the carbon
is that they used ionic liquids as the sources of carbon and nitrogen. sources, they are classified into graphene, carbon nanotubes and
Another way to remove the middle layer is to generate a gas other carbonaceous materials.
through chemical reaction, thus forming the voids. Chen’s group 12 Graphene is a sp2-bonded carbon atom with a 2D single-atom
prepared yolk-shell Fe3O4@nitrogen-doped carbon (Fe3O4@N-C) thickness, which has the characteristics of high specific surface
nanocapsules by using a hydrothermal method combined with area, excellent electrical conductivity and mechanical flexibility.
thermal annealing. Spindle-like β-FeOOH nanoparticles were When graphene and iron-based composite materials are used as
prepared through hydrothermal reaction first. Dopamine was electrode of LIBs, the graphene layer not only acts as a structural
coated on surface of the β-FeOOH nanoparticles as carbon source buffer layer to effectively accommodate the volume change, but
and nitrogen source to form β-FeOOH@PDA core-shell also promotes electron conduction and shortens lithium-ion
nanostructure. As water molecules ran away from the spindle-like transport pathway. Moreover, the combination of graphene sheets

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and nanoparticles can also effectively inhibit the re-accumulation of morphology. The rGO NSs had high surface area and View
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graphene and the iron-based nanoparticles. Also, the composite edge, which was favorable for the attachmentDOI:
of10.1039/C8TA01683F
the nanoparticles.
maintains a high active surface area. In recent years, many iron Fe3O4 nanoparticles about 50-200 nm in size were uniformly
oxide and graphene composites have been reported in the open dispersed in the framework of rGO nanoparticles. The edges of the
literature34, 157-163. Yu’s group164 prepared Fe2O3/graphene hybrids rGO NSs prevented the agglomeration of the Fe3O4 nanoparticles,

by using a liquid phase lift off method, in which highly conductive which would increase electrochemical capacity and stability of the
few-layer graphene sheets and covalently bound Fe2O3 composite. Fu's team41 synthesized Fe3O4 nanospheroids with
nanoparticles were employed to build up a sandwich structure. necklace-like structures on carbon nanofibers (CNFs) by using a
Tour’s group165 fabricated a Fe2O3/Fe3C-graphene nanoporous solvothermal method. Ferric chloride and CNFs were added to the
composite by using a chemical vapor deposition. In this composite, ethylene glycol solution and then hydrothermally treated in an
the graphene layer coated on the surface of the nanoporous autoclave at 200℃ for 16 h. The resulting Fe3O4 nanospheres had a
material is mainly used for its conductive effect. The introduction of diameter of about 300 nm and were uniformly strung on the CNFs,
FeC increases the structural stability of the nanoporous composite, as illustrated in Fig. 12d-e. The mass content of Fe3O4 was about
which provides more capacity due to the interfacial lithium storage 86%. The Fe3O4/CNF necklace could be directly sprayed onto a large
effect. area current collector to form a binderless electrode, with
Zapien’s group166 prepared Fe3O4 nanoparticles and graphene promising performances for LIBs and SCs.
composites by using a thermal evaporation-induced anhydrous
strategy. The Fe3O4 nanoparticles with sizes of 10-20 nm were
uniformly anchored onto graphene sheets, which prevented the
agglomeration of the graphene sheets. Choi and Kang3 prepared
Fe3O4/graphene composite powder by using a spray pyrolysis
process. During the drying process, the graphene sheets were bent
due to shrinkage. A plurality of curved graphene sheets were
agglomerated into the hollow Fe3O4/graphene balls (Fig. 12a-b). Fig.
12j shows formation process of the hollow Fe3O4/graphene balls
and the mechanism of lithium intercalation/deintercalation. BET
surface area of the Fe3O4/graphene balls was up to 130 m2 g–1. Hu
et al.167 prepared a sandwich-structured graphene-Fe3O4-carbon
composite. The composite was characterized with high mass
content of Fe3O4 (85%), ultrafine Fe3O4 particles (~5 nm) and high
carbon layer coverage of the Fe3O4 surface. Zhao et al.168 prepared
a carbon-coated Fe3O4 quantum dots/graphene composite by a
hydrothermal method. In that composite, the graphene nanosheets
showed curly and wavy morphology, while the Fe3O4 nanoparticles
with sizes of 7-10 nm were immobilized on the graphene
nanoplatelets.
Gao et al.169 synthesized a quasi-hexagonal Fe2O3 nanoplates/-
graphene composite by using a solvothermal method. It was found
that, as the concentration of FeCl3 was increased, the morphology
of the Fe2O3 nanosheets became more and more regular. Fe 2O3
nanosheets with sizes of 20-80 nm were uniformly dispersed on the
surface of rGO, so that their agglomeration was prevented. Xu’s
group170 prepared Fe3O4@graphene composites on graphene by Fig. 12 (a, b) SEM and TEM images of the Fe3O4/graphene hollow balls [Reprinted
etching an FeAl alloy. The Al was selectively leached from the FeAl with permission from Ref.3, Copyright 2014, Elsevier]. (c) SEM images of the 3D rGO
alloy with NaOH solution. During the etching process, the number NSs [Reprinted with permission from Ref.28, Copyright 2017, American Chemical
of octahedron nanoparticles was increased and the shape became Society]. (d, e) SEM and TEM images of the Fe3O4/CNF necklaces. [Reprinted with
permission from Ref.41, Copyright2015, Royal Society of Chemistry]. (f, g) SEM and
more and more regular. Longer corrosion time (48 h) was conducive
TEM images of the Fe2O3/SWCNT composites [Reprinted with permission from Ref. 50,
to the formation of uniform Fe3O4 octahedron. Fe atoms underwent Copyright 2017, IOP]. (h, i) TEM images of the urchin-like Fe3O4@N-C composites
natural oxidation and aggregation to produce Fe3O4 octahedrons of [Reprinted with permission from Ref.55, Copyright 2016, Elsevier]. (j) Schematic
about 500 nm in size. The positively charged Fe3O4 octahedron was illustration of formation of the hollow Fe3O4/graphene balls and the lithium
intercalation/deintercalation mechanism [Reprinted with permission from Ref. 3,
fixed on the graphene by using an electrostatic assembly method.
Copyright 2014, Elsevier].
Kumar and co-workers28 synthesized 3D hybrid composite of
Fe3O4 nanoparticles embedded in the network of reduced graphene
oxide nanosheets (rGO NSs) by using in-situ microwave method. Due to its super high conductivity, carbon nanotubes (CNTs) can
The rGO NSs had a cotton-like fluffy structure, as observed in Fig. be used as the conductive substrate and skeleton of composite
12c The surface of the rGO NSs presented a microscopic open electrode materials.60 Its composites have been studied extensively
structure and interconnects with each other to form a network as electrode materials for energy storage systems, including both

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LIBs and SCs. Gao et al.171 prepared a hybrid film which is composed sources. During high temperature carbonization, α-FeOOH was
View Article Online
of α-Fe2O3 nanoparticles and single-walled carbon nanotube converted to oxide and the outer carbon DOI: shell10.1039/C8TA01683F
also turned into
(SWCNT). Shang’s group50 synthesized Fe/SWCNT films by using a hollow carbon tubes, as shown in Fig. 12h-i. On the one hand, water
chemical vapor deposition method, which was converted to molecules evaporated from the α-FeOOH framework, leaving pores
Fe2O3/SWCNT composite film through thermal annealing. When the in the original spinous process surface. On the other hand, the

annealing temperature was increased from 450℃ to 600℃, the appearance of the carbon shell remained unchanged, forming a
mass fraction of Fe2O3 was increased from 63 to 96%, while the hollow carbon tube. The Fe3O4@N-C urchin-like microspheres
Fe2O3/SWCNT composites still maintained porous network exhibited a BET surface area of 72.6 m2 g–1, which was much larger
structure, as demonstrated in Fig. 12f-g. The interconnected Fe2O3/- than that (47.7 m2 g–1) of the Fe3O4 microspheres. The Fe3O4@N-C
SWCNT networks, which contain highly loaded active materials, urchin-like microspheres were made through the stacking of
have a synergic effect and are promising anode materials for LIBs. nanorods with sizes of 20-50 nm and lengths of 500-800 nm. The
Yu et al.172 prepared quadrangular carbon nanotube (q-CNT)- thickness of the carbon shell was 5-8 nm and the pore size was 5-25
Fe3O4-C composite by using hydrothermal method. Cheng’s team173 nm. Therefore, urchin-like Fe3O4@N-C was a mesoporous material.
reported nanoporous Fe2O3-5 wt%CNT composites as electrode of It is expected that this porous structure of the carbon shell would
SCs by using a nitrogen atmospheric pressure plasma jet method. provide an effective internal transport path and offer sufficient
Wang et al.174 prepared Fe-Fe2O3@N-doped C nanoparticles internal void space to relieve the volumetric expansion during
uniformly anchored to N-doped carbon nanotubes (NCNTs). The lithiation/delithiation.
nano-Fe-Fe2O3 particles had core-shell structure, consisting of a Fe- 4.2 Iron Oxides Nanocomposites with Other Metal Oxides
Fe2O3 core and an N-doped C shell with an average diameter of Due to their higher theoretical capacities (1494 mA h g–1 for SnO2,
about 10 nm. The N-doped C shell effectively interconnected the 1232 mA h g–1 for MnO2, and 890 mA h g–1 for Co3O4), SnO2, MnO2
Fe-Fe2O3 with the CNTs scaffold, which can improve the and Co3O4 have been chosen to construct the heterostructures with
mass/charge transfer properties and structural stability. Sun’s iron oxide. Solvothermal and hydrothermal methods are the most
group63 developed Fe2O3@CNTs composites by depositing Fe2O3 commonly used ones to prepare Fe2O3/SnO2 heterostructures. Liu’s
nanoparticles on carbon nanotubes through atomic layer team186 and Yang’s team187 synthesized Fe3O4@SnO2 and
deposition. The Fe2O3 nanoparticles were uniformly distributed on Fe2O3@SnO2 core–shell nanorods by using hydrothermal process.
the CNTs. The size of Fe2O3 nanoparticles was increased with Yu’s group188 grown 1D SnO2 nanorods on 2D Fe2O3 nanoflakes to
increasing number of atomic layer deposition cycles. form a comb-shaped heterostructure. Jin et al.189 prepared SnO2
In addition, explosive detonation is the process of generating hollow spheres by using solvothermal method first, onto which a
very high temperatures and pressures in a very short period of layer of Fe2O3 was coated. The hierarchical Fe2O3/SnO2 hollow
time, where a large amount of heat is released due to the spheres offer breathable aggregate which can buffer the volume
conversion of the chemical energy involved in the energy molecules expansion during the charge/discharge process. Moreover, the
into heat energy. In recent years detonation has been used to unique porous structure of the hollow sphere and nanosized
prepare bamboo-like carbon nanotubes.175 Chen’s team62 has network can provide faster ion diffusion and better cycling stability.
prepared a Fe3O4-Fe@CNT composite by detonation method. In the In addition, flame-assisted spray method has been employed by Li
preparation process, bamboo carbon nanotubes wrapped with et al.190 to decompose iron and tin precursors to prepare core-shell
Fe3O4/Fe flakes were prepared by one-step detonation using Fe2O3@SnO2 heterostructures. He’s group191 prepared a N-doped
ferrocene as carbon source and using hexane to generate high amorphous carbon coated Fe3O4@SnO2 coaxial nanofiber by using
temperature and high pressure. Fe3O4 flakes and iron nanoparticles electrospinning technology combined with chemical bath
were generated during the detonation assisted decomposition and deposition.
were finally encapsulated in carbon nanotubes. The resulting Yang’s group9 prepared MnO2/Fe2O3 dendrites nanorods through
carbon nanotubes have a bamboo-like structure, presenting a hydrothermal reaction. MnO2 nanorods with diameters of 30-120
multi-section entangled morphology. Nanotubes (about 18-20 nm were employed as the skeleton of the dendritic nanorods.
nodes) are more than 600 nm in length and 20-30 nm in diameter. During the hydrothermal process of FeOOH, a large number of tiny
In addition to graphene and carbon nanotubes, a variety of other Fe2O3 nanorods were deposited on the surface of the nanorod
carbonaceous organic and inorganic materials have been used as framework. The Fe2O3 nanorods with an average diameter of 30 nm
carbon sources. Graphite and porous carbon were used as inorganic and a length of 140 nm were deposited perpendicularly onto the
carbon sources to prepare iron oxide and carbon composites by sides of the MnO2 nanorods, resulting in typical branched
Yang et al.176 and Ye et al.177. Sucrose178, glucose179, melamine180, nanostructures, as demonstrated in Fig. 13a-d. The Fe2O3 branches
ethylene glycol181, petroleum pitch182, petroleum alkali lignin183, were arranged nearly quadruplicate on the side of the MnO 2
gelatin56 and other organic matter as a carbon source, have been nanorods, forming high yields of branched nanostructures. The
widely studied. Polymers can also be used as a carbon source. For specific surface area of the dendritic nanorodes reached 32.7 m2 g–
instance He et al.184 and Pan et al.185 synthesized iron oxide/carbon 1. These branched nanostructures should be beneficial to increase
composites with polyacrylonitrile and polydimethyldiallylammo- reaction sites and interface area during the discharge/charge
nium as carbon sources, respectively. Chen et al.55 prepared N- process, thus achieving high specific capacity. Wang’s group192
doped urchin-like Fe3O4@C composite by using hydrothermal prepared α-Fe2O3 nanotube@MnO2 nanosheet hierarchical
method. Urchin-like hydroxyferric oxide (α-FeOOH) was used as a networks for electrodes of SCs. Zhao et al.32 obtained Mn3O4/Fe3O4
template and polydopamine (PDA) was used as carbon and nitrogen

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nano-flower by etching Mn5Fe5Al90 alloys. In this case, the more with iron oxide. Owing to high Li-insertion voltage and Viewzero-strain
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active components of the alloys are removed, so that voids are DOI: 10.1039/C8TA01683F
insertion, spinel Li4Ti5O12 has attracted considerable attention.195-198
formed inside the materials. NaOH solution was used as the etchant Diao’s group199 synthesized a core-shell α-Fe2O3@ Li4Ti5O12
to selectively etch the Al atoms from the Mn5Fe5Al90 alloy. Then, the composite through a facile hydrothermal reaction. The spinel
exposed Fe and Mn atoms were rapidly oxidized to form oxide Li4Ti5O12 wrapped α-Fe2O3 ellipsoids, which broke the vast majority

nuclei. The oxide nuclei aggregated into nanoflower structures in of the contacts between the active material α-Fe2O3 and the
the alkaline environment. The individual nanoflower-like structure electrolyte. The core-shell α-Fe2O3@Li4Ti5O12 composite can
consisted of an array of regularly-shaped hexagonal nanosheets. prevent the formation process of solid electrolyte interface (SEI)
Hexagonal nanosheets had side lengths of 600-900 nm and layer, thus minimizing the initial capacity loss. Gao’s group52
thickness of about 150 nm, as revealed in Fig. 13e-f. fabricated α-Fe2O3 nanosheet@Ni(OH)2 nanosheet hybrid
Using ZnO as a sacrificial template, Tu’s group43 prepared composite by using a two-step hydrothermal method. The α-Fe2O3
hierarchical Fe2O3@Co3O4 nanowire arrays. The Co3O4 nanowires nanosheet was wrapped with wrinkled Ni(OH)2 nanosheet, as
were first fabricated by using a hydrothermal process. The observed in Fig. 13i-j. Xiang et al.200 embedded RuO2-Fe2O3
nanowires were then immersed into a Zn source solution and heat nanoparticles into ordered mesoporous carbon (OMC) by using
treated to form the intermediate template ZnO@Co3O4 nanowires. impregnation and in-situ heating method. The RuO2-Fe2O3
Finally, the nanowires were transferred to a Fe source reaction nanoparticles were uniformly dispersed in the pore walls of the 2D
solution. After the replacement reaction, Fe2O3@Co3O4 nanowires mesoporous carbon. The average particle size of RuO2-Fe2O3 was
were formed, as shown in Fig. 13g-h. Wu’s team193 synthesized 1.96 nm. The RuO2-Fe2O3/OMC composites had a large pore volume
Fe2O3@Co3O4 composites by using a two-step hydrothermal of 1.01 cm3 g–1, an appropriate pore size of 4.3 nm and a high
method. The α-Fe2O3 nanosheets were covered with a layer of well specific surface area of 768 m2 g–1. The nanocomposite particles
aligned Co3O4 particles. Similarly, Yang et al.194 fabricated Co3O4 would not block the mesoporous channels and also enhance the
nanowire@Fe2O3 nanorods by using hydrothermal method. electron and ion conduction.
4.3 Iron Oxide Nanocomposites with Conductive Polymers
Conductive polymers can be used to improve the electrochemical
performance of energy storage devices, thus having attracted a
great deal of interest in recent years.201, 202 Polyaniline (PANI) has a
small particle size and high electrical conductivity, which can
enlarge high specific surface area and provide fast electron
transport. PANI not only acts as a host material for
insertion/extraction of Li+ ions but also serves as an intermediate
between the active material and the electrolyteto facilitating the Li+
ion insertion/extraction process. Wang et al.203 developed
Fe2O3/PANI composite through the in-situ polymerization of aniline,
while the Fe2O3 was synthesized by using hydrothermal synthesis.
Lee’s group24 fabricated a hierarchical Fe2O3@PANI core-shell
hollow structure, in which urchin-like Fe2O3 spheres were
synthesized by using a template-free sonochemical method. PANI
was then coated on surface of the Fe2O3 spheres. Fig. 14a shows a
schematic diagram of the synthesis process. A representative TME
image of the Fe2O3@PANI nanocomposite is shown in Fig. 14b.
Fig. 13 SEM images of (a) MnO2 nanorods, (b) branched nanorods of MnO2/FeOOH
and (c) branched nanorods of MnO2/Fe2O3. (d) Schematic diagram of formation of Fig. 14 (a) Schematic diagram illustrating the procedure to fabricate hierarchical
the MnO2/Fe2O3 branched nanostructures [Reprinted with permission from Ref. 9, Fe2O3@PANI through simultaneous in- and exterior construction, (b) TEM images of the
Copyright 2013, Wiley]. (e, f) SEM images of the Mn3O4/Fe3O4 sample after Fe2O3@PANI samples [Reprinted with permission from Ref. 24, Copyright 2013, Wiley].
dealloying Mn5Fe5Al90 alloy for 10 h in 2 M NaOH solution [Reprinted with permission
from Ref.32, Copyright 2015, Elsevier]. (g, h) SEM and TEM images of the
Fe2O3@Co3O4 nanowire array [Reprinted with permission from Ref. 43, Copyright As an ultra-stable conductive polymer, poly (3, 4-ethylenedioxy-
2013, Elsevier]. (i, j) SEM and TEM images of the α-Fe2O3@Ni(OH)2 nanosheet thiophene) (PEDOT) not only can effectively improve the
hybrids [Reprinted with permission from Ref. 52, Copyright 2016, Nature]. conductivity of the material, but also can be used as a protective
layer to prevent structural damage.204, 205 Lu’s group206 designed
and prepared Ti-doped Fe2O3@PEDOT nanorod arrays on carbon
In addition to the above three oxides, there have also been cloth. In the composites, Ti doped Fe2O3 nanorods form the core,
reports on other oxides used to form complex heterostructures conductive PEDOT layer is the shell, and the carbon cloth is the

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carrier. Ti4+ partially replaced Fe3+ and some Fe3+ ions were polymerization process combined with carbonization. ViewThe
Articlein-situ
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accordingly reduced to Fe2+. In this way, the donor concentration in DOI: 10.1039/C8TA01683F
polymerization not only inhibited the agglomeration and growth of
Fe2O3 was significantly increased, thus making it possible to the metal oxide particles, but also provided excellent conductivity
increase its capacitance. The unique core/shell composite should be pathways after carbonization. Sun’s group212 prepared reduced
a promising candidate of electrode, with high conductivity, the large graphene-Fe3O4-SnO2-C quaternary hybrid nanocomposites by using

interfacial area for the reaction and enhanced diffusion of a homogeneous precipitation method and solvothermal treatment.
electrolyte ions. Nanosized Fe3O4 and SnO2 were uniformly dispersed on the
Polypyrrole (PPy) and poly (ST-AN) (PSA) have also been used to reduced graphene nanosheets and were entirely encapsulated by
combine with iron oxide to make high performance electrode the outermost carbon layer to form a sandwich-like buffer
materials. Shen’s group207 directly heated iron oxide foil to obtain structure. The multi-particle layers were stacked to form nanopores
iron oxide nanoflakes in the air, which were then coated with with an average size of 5.8 nm. These structural features would
conductive PPy layer through chemical polymerization. Zhang et enhance the LIBs electrode performance of the composites.
al.208 synthesized a PSA-Fe3O4@C mesoporous microsphere by using
hydrothermal method.
4.4 Multi-component Nanocomposites Based on Iron Oxides
Multi-component nanocomposites (ternary or quaternary) based on

iron oxide have also been developed. Xie’s group209 proposed a
hybridization strategy for layered assembly of TiO2 nanorods and
Fe3O4 nanoparticles on pristine graphene (PG) sheets, so as to
construct TiO2/Fe3O4-PG ternary heterostructures. Each of the three
components contributed in a mutually supportive manner,
demonstrating a significant synergy in terms of composition and
morphology. In the composition, TiO2 as the primary active material
can fully maintain the high cycle stability of the composite, Fe3O4 as
a secondary active material can provide high capacity, while
graphene ensures sufficient conductivity. At the microscopic level,
Fe3O4 nanoparticles and TiO2 nanorods acted as spacers to prevent
Fig. 15 (a, b) SEM and TEM images of an individual Fe 3O4-TiO2-carbon composite
the re-stacking of the graphene nanoplatelets. Graphene nanofiber, with the inset showing the TEM image of an Fe3O4 nanoparticle [Reprinted
nanosheets served as a mounting substrate that also prevented with permission from Ref.21, Copyright 2016, American Chemical Society]. (c, d) SEM
agglomeration of the TiO2 nanorods and Fe3O4 nanoparticles. and TEM images of the MnOx/Fe2O3/PPy nanotube [Reprinted with permission from
Ref.37, Copyright 2017, Elsevier].
Huang’s group21 prepared a nanofibrous Fe3O4-TiO2-carbon ternary
composite by using natural cellulose as a structural support and
carbon source. A layer of TiO2 was deposited on the cellulose 5. Synthesis of Iron Hydroxide (FeOOH)
surface by using a sol-gel process. Then, Fe3O4 nanoparticles were Nanomaterials
grown the TiO2-cellulose substrate through hydrothermal reaction,
followed by carbonization and thermal annealing. In this way, the Due to its attractive negative potential window and high theoretical
Fe3O4 nanoparticles with a diameter of about 30 nm and a length of specific capacitance, FeOOH is emerging as a new anode material in
less than 100 nm were anchored to the surface of the TiO 2 coated recent years. FeOOH particles with various shapes and
carbon nanofibers. Due to the loss of water molecules during the compositions have been developed as electrodes of supercapacitor.
calcination, pores were formed inside the Fe3O4 particles, as With large surface area and high ion mobility, 1D coaxial
depicted in Fig. 15a-b. The BET specific surface area of the Fe3O4- nanostructured materials have shown great potential to imporve
TiO2-carbon composite was 258 m2 g–1, while the average pore size electrochemical performances. In order to develop electrode
was about 3.9 nm. materials with high energy density and high power density, Wei et
Using MnOx/Fe2O3 nanotubes as a template, Jin et al.37 al.213 prepared FeOOH@PPy, a composite of 1D FeOOH
synthesized MnOx/Fe2O3/polypyrrole(PPy) nanotubes through nanoparticles wrapped in ultra-thin polypyrrole. Lou’s group214
polymerization. The MnOx/Fe2O3/PPy nanotubes exhibited a rough prepared layered urchin-like α-FeOOH solid sphere or hollow
surface. The thin PPy layer was grown uniformly on the MnOx/Fe2O3 sphere by adjusting the amount of glycerol in the reaction system.
nanotubes to form 1D nanostructures, as demonstrated in Fig. 15c- Specific surface area of the α-FeOOH hollow sphere can reach 96.9
d. The combination of multiple components created more internal m2 g–1. Chen’s group18 used electroplating to synthesize iron
spaces that can effectively buffer the volume change and inhibit the oxyhydroxide lepidocrocite (γ-FeOOH) nanosheets with different
aggregation of the materials during the charge and discharge lamellar channels. These nanosheets had smooth surfaces, with an
process. Duan’s team210 prepared Fe3O4@C@Mn3O4 multilayer average length of about 1.4 μm and thicknesses of 30‒50 nm.
core-shell porous spheres by using bovine serum albumin as the Different nanosheets intertwine to form multiple 2D channels, as
carbon source. revealed in Fig. 16a. As a result, Li+ ions can reversibly insert/leave
Guo et al.211 developed SnO2-Fe2O3@C ternary nanocomposites the 2D channels in between the [FeO6] octahedral subunits, thus
for lithium battery electrode by using a sol-gel in-situ improving the pseudocapacitve effect. Yu’s group215 prepared
fluorine-doped β-FeOOH nanorods on carbon cloth. The

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introduction of fluoride anions enhanced the conductivity of the nanostructures on Ni foam through electrodeposition. This
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materials. Fluorine doped β-FeOOH as the electrode material can nanostructure has a large number of surfaceDOI: 10.1039/C8TA01683F
active sites, while the
solve the low energy density problem. amorphous characteristics of the FeOOH would promote the
diffusion and reaction of electrolyte ions, thus improving the
capacitive properties of the materials.

With the rapid development of wearable electronics, fiber SCs
have been considered as promising energy storage devices for
wearable applications, due to their advantages of small size, light
weight, high flexibility and good weaving.220, 221 Lee’s group49
developed nanostructured FeOOH/polypyrrole (PPy) on carbon
fiber (CF) through electrodeposition. The 1D FeOOH nanowires
Fig. 16 (a) SEM images of the γ-FeOOH NS [Reprinted with permission from Ref. 18, were grown vertically on the carbon fibers, thus leading to the
Copyright 2014, Wiley]. (b) TEM image of the as-prepared α-FeOOH@MnO2 formation of open porous structures, as illustrated in Fig. 16c. PPy
SEM of
[Reprinted with permission from Ref. 35, Copyright 2017, Springer]. (c) was subsequently applied to the FeOOH/CF, while the porous
FeOOH/PPy on carbon fibers [Reprinted with permission from Ref.49, Copyright morphology was still retained. The diameter of the FeOOH
2017, Royal Society of Chemistry]. nanowires in the composite was about 10 nm, while the thickness
of the PPy coating was about 3 nm. Yuan’s group 222 prepared Ti-
doped FeOOH quantum dot (QD)/graphene (GN) composites. The
FeOOH has also been incorporated with other materials, such as composites were then uniformly dispersed on a bacterial cellulose
metal oxides and carbonaceous materials, to form composites. (BC) substrate for form flexible capacitor electrode. The Ti-doped
Zhang et al.216 synthesized a CoFe2O4/FeOOH hierarchical electrode FeOOH QD/GN material acted as the active material, while the BC
nanocomposite for supercapacitor by using a hydrothermal ensured flexibility and mechanical strength of the flexible SCs.
method. Flower-like CoFe2O4/FeOOH nanostructure was obtained Electronic devices such as foldable displays and self-powered
by adjusting the urea content. Lv et al.35 obatined urchin-like α- transparent LCD displays require electrode materials to have not
FeOOH@MnO2 core-shell hollow microspheres by using a two-step only high power/energy density but also high transparency. In order
hydrothermal method. The first step was to prepare urchin-like α- to meet these requirements, asymmetric transparent flexible
FeOOH hollow spheres composed of nanorods. The second step supercapacitors have emerged. The application of carbon materials
was to grow ribbon-shaped MnO2 nanostructures on surface of the in transparent electrodes is limited by their low theoretical specific
hollow spheres to form urchin-like α-FeOOH@MnO core-shell capacitance and low transmittance. Due to their high specific
hollow microspheres. As shown in Fig. 16b, the middle black part is pseudocapacitive effect, transition metal hydroxide materials can
FeOOH while the outer white bar is MnO2. Hao’s group217 prepared be used as transparent microstructured electrodes. Zhang et al. 223
a FeOOH nanoparticle modified nitrogen-doped graphene fabricated transparent graphene-coated FeOOH nanowire arrays
composite. In the synthesis process, urea acted as not only a and Co(OH)2 nanosheet films by using a bioinspired method. Both
reductant and dopant for N-doped graphene, but also a hydroxyl nanostructures were encapsulated in a graphene shell and
donor for the precipitation of the metal hydroxides. FeOOH exhibited a porous structure, which have been evaluated as
nanorods were grown on graphene sheets through the combined transparent asymmetric pseudocapacitor electrode. The unique
action of N-doped graphene and urea. Zhang’s group218 developed structure of the composite materials provided a large effective
ultrafine α-FeOOH nanorods/graphene oxide composites as the contact area and high electrical conductivity, offering a 3D
electrode material of supercapacitors by using a hydrothermal transmission path for ions and electrons. O'Neill and co-workers131
method. Graphene oxide and iron acetate were used as the raw employed a spray deposition method to prepare mesoporous
materials through direct reaction without the use of any additives. porous composite electrodes, in which 1D Fe3O4/FeOOH nanowires
The α-FeOOH nanorods had an average diameter 6 nm and an were entangled with carbon nanotubes. FeOx and carbon
average length of 75 nm. nanotubes, with similar size, were closely ‘entangled’ together after
Although iron hydroxide is a promising supercapacitor electrode spraying. Self-supporting networks were formed by friction,
in terms of its crystal structure, the material is hard to expand or whereas voids with diameters of 50-250 nm were formed in
contract to limit ion penetration and diffusion. In comparison, between the two 1D materials. Transparent electrode materials
amorphous materials could exhibit excellent electrochemical require some porosity to improve electrode transparency, but voids
performances due to the disordered structure. Wu’s group36 reduce material density and capacitance. Therefore, a trade-off
synthesized amorphous FeOOH/MnO2 composites, which were should be established between the two aspects.
made into electrodes on PET, paper and textile substrates by using
screen printing. The supercapacitors on all three substrates were
highly flexible and could be bent without sacrificing device 6. Synthesis of Iron Sulfide (FeS2) Nanomaterials
performance. Xia’s group30 prepared amorphous FeOOH quantum Iron sulfide (FeS2) has the typical characteristics of metal sulfides,
dots/graphene hybrid nanosheets. The amorphous FeOOH high theoretical capacity (890 mA h g–1), low cost and
quantum dots with an average size of 2 nm were tightly anchored environmentally friendliness, which is considered as promising
on the graphene sheets, forming continuous mesoporous nanofilm. electrode materials. FeS2 can be used as either cathode or anode
Wong’s group219 prepared amorphous fish scale FeOOH because its voltage platform occurs at about 1.5 V.224-227 However,

Journal
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FeS2 electrode has poor electrochemical reversibility. During the Besides synthetic carbon, graphene and carbon nanotubes have
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first discharge, highly active Fe0 and high resistance Li2S are formed, also been used to form composites with FeSDOI: 2, in10.1039/C8TA01683F
order to improve
which cannot be completely reversed. In addition, the produced the conductivity of the electrode material and enhance the
lithium polysulfides (Li2Sx, 2 <x <8) have high solubility in the mechanical strength and structural stability. Lee’s group 13 used
electrolyte solution and diffuse to the lithium metal electrode to reduced graphene oxide to coat FeS2, leading to FeS2/rGO

form insoluble Li2S on the surface. The presence of Li2S and sulfur microspheres. The FeS2 nanoparticles were wrapped with rGO
results in an increase in resistance, thus leading to serious capacity sheets on the surface, which can effectively protect polysulfide
deterioration and irreversible electrode destruction. Therefore, electrolyte. This structure is also expected to reduce the charge
various strategies have been developed to solve these problems. 228 transfer resistance and improve the structural stability of the
One strategy is to use a liquid electrolyte that has a functional composite. Shen’s group5 prepared FeS2/graphene oxide composite
group to inhibit of dissolution of the polysulfide. Another strategy is by using a hydrothermal method. The cubic FeS2 microparticles had
to coat the electrode material with a layer of polymer or carbon to diameters in the range of 0.5-1 μm. The FeS2 particles were
effectively reduce the polysulfide dissolution in the electrolyte. assembled from cube-shaped blocks with sizes of 200-300 nm,
Covering a layer of carbon on the surface of FeS2 can effectively resulting in a rough surface. The particles were uniformly anchored
prevent the polysulfides from dissolving. Carbon coating was to the graphene oxide sheets, as shown in Fig. 17a. Han’s group232
previously formed through solid-phase reactions, such as ball synthesized FeS2@hierarchical porous carbon (HPC) composites by
milling FeC2O4·2H2O powder, S powder and glucose mixture.229 reacting FeS2 nanocrystals with HPC. The Fe ions adsorbed in the
Nanostructures of FeS2 electrodes have been proven to exhibit HPC were first calcined to form Fe3O4 and then reacted with sulfur
enhanced electrochemical performances. Wang’s team230 in vacuum to obtain FeS2. The HPC would ensure a high conductive
synthesized 1D porous FeS2@C nanowires as anode materials of network, while its porous structure would have a buffer effect for
LIBs. The composite nanowires consist of an inner core of FeS2 and the volume change. Park and Sridhar233 prepared FeS2-CNF
an outer thin amorphous carbon layer. The 1D FeS2@C composites, in which FeS2 was crosslinked to carbon nanofibers
nanostructures have short distances for electron transport and ion (CNFs). Through microwave pyrolysis, ferrocene was decomposed
diffusion, high surface area for the reaction, and more space to into iron, followed by sulfation with L-cysteine, so that the resulting
accommodate volumetric changes in lithium ion insertion/removal FeS2 nanoflakes were crosslinked with CNFs. Tao’s team234
processes. The carbon layer outside the nanowires can inhibit the developed pyrite modified sulfur-doped carbon (FeS2@S-C) fibers
internal polysulfide dissolution in the electrolyte. Yang’s team231 by using biological templates. Cotton was used as the biological
utlized a hydrothermal method to polymerize glucose on the template and served as the carbon source. The FeS2 nanoparticles
surface of FeS2 nanocrystals, followed by carbonization through were uniformly attached to the carbon fibers.
thermal annealing, thus form FeS2@C composites. Yu’s group226 In order to increase the specific area of FeS 2, porous structures
synthesized FeS2@C porous nano-octahedra by using a self- and flower-shaped structures have been proposed. He et al.26
sacrificing template routes. During carbonization of the carbon-rich synthesized FeS2 anchored on 3D graphene foam by using
polysaccharide layer coated on FeS2 octahedra, the partially hydrothermal method. During the hydrothermal reaction, FeS2
encapsulated FeS2 was decomposed into FeS to a certain degree. particles self-assembled into cauliflower-shaped nanostructures
Hydrochloric acid was used to remove the acid-soluble FeS, leaving with sizes of 1-2 μm, as demonstrated in Fig. 17b. The cauliflower-
void space that can buffer the volumetric expansion of lithium like structure would be able to reduce the volume expansion and
intercalation. prevent the FeS2 aggregation during cycling. Shen’s group235
prepared a flower-like FeS2/graphene airgel composite by using a
hydrothermal self-assembly method. Ma et al.40 fabricated porous
micro/nanostructured FeS2 microspheres (PPMS) by using
solvothermal method. The PPMS was a stack of nanosheets that
have many pores of about 100 nm in size, as seen in Fig. 17c.
The electrical conductivity of marcasite (m-FeS2) is higher than
that of pyrite p-FeS2, due to its lower semiconductor gap, stronger
Fe-S bonds and less S-S interaction. Therefore, m-FeS2 should be
more suitable as electrode material. However, m-FeS2 is rarely
studied due to the difficulty in synthesis. Zhang’s group22 prepared
m-FeS2 and carbon nanofiber composites (m-FeS2/CNFs) with a
cluster structure by using hydrothermal method. The m-FeS2
particles were uniformly distributed on the CNFs and intertwined
with the CNFs to form a grape-like hybrid morphology, as illustrated
in Fig. 17d. When Li+ ions are inserted, the m-FeS2/CNFs composite
Fig. 17 (a) SEM image of the FeS2/RGO composite [Reprinted with is transformed into a mimosa leaf-opening shape. In the same way,
permission from Ref.5, Copyright 2015, Royal Society of Chemistry]. (b) SEM image of it turns into a closed mimosa when Li+ ions are detached.
the 3D GF-FeS2 [Reprinted with permission from Ref. 26, Copyright 2016, Elsevier]. (c)
SEM image of the pyrite porous microspheres [Reprinted with permission from
Ref.40, Copyright 2017, Elsevier]. (d) SEM image of the m-FeS2/CNFs composite
[Reprinted with permission from Ref.22, Copyright 2017, American Chemical Society].

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7. Potential Applications discharging processes of LIBs are accompanied by charge and Online
View Article mass
transfer in between the electrodes. Therefore, DOI:the
10.1039/C8TA01683F
performance of
Iron-based materials have been extensively studied for a wide
the electrode greatly affects the performance of the battery.
range of applications in photocatalytic, water treatment, gas
Commercial graphite anode can provide lithium ion storage space
sensors, magnetic storage, superconductors, lithium batteries and
with little change in volume and thus has high structural stability,

super capacitors and other fields.54, 64-66, 236-247 As stated earlier, the
but its relatively low theoretical capacity (372 mA h g–1) limits its
applications of the iron-based materials only focus on lithium-ion
application in power supply with high energy density. Due to their
batteries and supercapacitors.
high theoretical capacity, iron-based materials have been
7.1 Lithium-ion Batteries (LIBs)
considered to be the next generation electrode materials of LIBs.
Because of its high energy density, absence of memory effect, light However, their poor conductivity and large volumetric changes
weight, small self-discharge, environmentally friendly features, during lithiation/delithiation cause rapid capacity decay and
lithium-ion batteries take the absolute dominance in the consumer unsatisfactory rate performance. To solve the above problems, two
electronics power market.54, 65, 89, 248 They are also considered as the strategies have been developed. One strategy is to increase the
preferred energy storage unit for electric vehicle powertrain and electrical conductivity and improve structural stability by using
smart grid energy storage systems. These emerging applications put composites. The other strategy is to utilize intricate structures, with
higher demands on the energy density of LIBs. Therefore, the large area to contact with the electrolyte and porosity to buffer the
performance of LIBs batteries must be significantly improved. It is volumetric change. Representative Fe-based materials and their
well known that LIBs are composed of anodes and cathodes, which electrochemical performances as anode of LIBs are listed in Table 1.
are separated by an ion-permeable membrane. Meanwhile, lithium
ions in the electrolyte connect the two electrodes. The charging and
Table 1 Representative Fe-based materials and their electrochemical performances as anode of LIBs
Materials Preparation method Structure Electrochemical performances Year Ref.

α-Fe2O3 hydrothermal porous microspheres 705 mA h g–1 after 430 cycles at 100 mA g–1 2013 105
γ-Fe2O3 Solvothermal nanospheres 1077.9 mA h g–1 after 140 cycles at 100 mA g–1 2015 100
Fe2O3 e-beam deposition+ etching nanomembranes 808 mA h g–1 after 1000 cycles at 2 C 2014 51
530 mA h g–1 after 3000 cycles at 6 C

α-Fe2O3 hydrothermal microflowers 877 mA h g–1 after 1000 cycles at 2 C 2015 4
Ag/α-Fe2O3 hydrothermal hollow spheres 953.2 mA h g–1 after 200 cycles at 100 mA g–1 2017 20
678 mA h g–1 after 200 cycles at 1A g–1

Fe3O4@C hydrothermal urchin-like 800 mA h g–1 after 100 cycles at 500 mA g–1 2016 55
Fe2O3@N-C pyrolysis spheres 1142 mA h g–1 after 100 cycles at 1 A g–1 2015 61
Fe3O4/C solvothermal hollow spheres 1300 mA h g–1 after 100 cycles at 100 mA g–1 2017 176
FeOx@C hydrothermal+hydrolysis+cor yolk shell 810 mA h g–1 after 1000 cycles at 0.2 C 2014 101
rosion
m-FeS2/CNFs hydrothermal grape-like 1399.5 mA h g–1 after 100 cycles at 100 mA g–1 2017 22
573.4 mA h g–1 after 1000 cycles at 5 A g–1

Fe2O3/CNT detonation bamboo-like 800 mA h g–1 after 100 cycles at 300 mA g–1 2017 62
Fe2O3@CNTs atomic layer deposition Tube-like 859.7 mA h g–1 after 400 cycles at 500 mA g–1 2017 63
Fe2O3/SWNT chemical vapor deposition Tube-like 1007.1 mA h g–1 after 100 cycles at 200 mA g–1 2017 50
567.1 mA h g–1 after 600 cycles at 2A g–1

FeS2@HPC vulcanization composite 720 mA h g–1 after 100 cycles at 1C 2016 232
FeS2/rGO solvothermal microspheres 970 mAh g–1 after 300 cycles at 890 mA g–1 2015 13
380 mAh g–1 after 2000 cycles at 8900 mA g–1

Fe3O4/graphene spray pyrolysis nanospheres 1050 mA h g–1 after 300 cycles at 2 A g–1 2014 3
690 mA h g–1 after 1000 cycles at 7 A g–1

MnO2/Fe2O3 hydrothermal branched nanorods 1028 mA h g–1 after 200 cycles at 1 A g–1 2013 9
SnO2-Fe2O3@C Polymerization++heat nanospheres 1000 mA h g–1 after 380 cycles at 400 mA g–1 2014 211
treatment
Fe2O3@polyaniline polymerization +chemical Unchin-like 893 mA h g–1 after 100 cycles at 0.1 C 2013 24
etching
poly(ST-AN) hydrothermal Mesoporous- 1293 mA h g–1 after 100 cycles at 500 mA g–1 2016 208
/Fe3O4@C microsphere 599 mA h g–1 after 100 cycles at 10 A g–1

Fe3O4@void@N-C Stöber yolk shell 860 mA h g–1 after 500 cycles at 1 A g–1 2016 47
500 mA h g–1 after 500 cycles at 2 A g–1

Fe3O4@N-C hydrothermal yolk shell 832 mA h g–1 after 150 cycles at 500 mA g–1 2017 12
Fe3O4/VOx@C hydrolysis+ion exchange microboxes 742 mA h g–1 after 400 cycles at 500 mA g–1 2017 145

Journal
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7.1.1. Iron-based Material and their Composite Electrodes of 907 mA h g–1 in the first cycle and 720 mA h g–1 after
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Articlecycles
Online
In order to improve the electrochemical performance of iron-based at 1C current density. DOI: 10.1039/C8TA01683F
materials, forming nanocomposites has been a widely used

strategy. For instance, carbon material is used as a shell to
encapsulate the iron-based materials to reduce their crushing and

agglomeration, so as to improve the cycle stability. Combination
with a material having excellent conductivity can effectively solve
the problem of poor electrical conductivity of iron-based materials.
In addition, the composites of iron-based materials and various
transition metal oxides have been developed to increase the
reversible capacity and cycle stability, due to the synergistic effect.
According to the components, iron-based composites will be
discussed in five categories, namely (i) iron-carbon composites, (ii)
iron-graphene composites, (iii) iron-carbon nanotube composites,
(iv) other metal oxide composites and (v) iron-polymer composites.
The coating of carbon increases conductivity of the electrode

and prevents agglomeration of the iron-based materials. A foam-
like Fe3O4/C composite electrode fabricated by Mu et al.56
possessed a reversible capacity of 1008 mA h g–1 at 200 mA g–1 over Fig. 18 (a) Cycling performances of the FeS2 microsphere/rGO and FeS2 electrodes and the
400 cycles. Compared with other Fe3O4@C composites, corresponding CE of the FeS2 microsphere/rGO electrode. (b) Cycling performances of the
FeS2 microsphere/rGO electrode at 10 C rate [Reprinted with permission from Ref. 13,
pomegranate-like Fe3O4@C nanoparticles128 exhibited an excellent
Copyright 2015, Royal Society of Chemistry]. (c) Rate capability and (d) cycling
initial specific capacity of 1215 mA h g–1, together with significantly performance of the Fe3O4@C/PrMGO composite [Reprinted with permission from
enhanced rate capability (573 mA h g–1 at current density of 1500 Ref.34, Copyright 2017, Elsevier].
mA g–1) and cycling performance (806 mA h g–1 after 100 cycles).
Such a high performance was attributed to the unique The synergy between graphene and iron-based nanoparticles has
pomegranate-like structure, because it could endure the been used to improve the performance of iron oxide based
mechanical deformation caused by the Li+ insertion/extraction electrodes.167, 183, 249 The Fe3O4 nanoparticles and graphene
reactions and prevent the Fe3O4@C nanoparticles from breaking. In composites reported by Zapien’s group166 had a specific capacity of
addition, the small sizes of the Fe3O4 nanocrystals and the carbon 868 mA h g–1 at 200 mA g–1 after 100 cycles. After 200 cycles at 1 A
spheres were 15 nm and 45 nm, respectively, which was g–1, the specific capacity was still as high as 539 mA h g–1, while the
responsible for the high interface area between the active material coulombic efficiency was above 99%. The reduced graphene oxide-
and electrolyte, thus shortening the migration distance of Li+ ions. coated FeS2 (FeS2/rGO) microspheres prepared by Lee’s group13
The N-doped carbon shell formed a stable layer of solid possessed a high capacity of 970 mA h g–1 after 300 cycles at a
electrolyte interface (SEI), reducing the initial capacity loss and current density of 890 mA g–1. The electrode capacity reached 380
increasing the reversibility of Fe3O4 for Li ion storage. N-doped mA h g–1 even after 2000 cycles at an ultra-high current density of
urchin-like Fe3O4@C composite prepared by Chen and co-workers55 8900 mA g–1 (10 C), as demonstrated in Fig. 18a-b. Due to the
showed a reversible specific capacity of 800 mA h g–1 at 500 mA g–1 stability of the hybrids structure and the synergistic effect of the
after 100 cycles. Chen’s group61 prepared ultrafine Fe2O3 internal components of the nanosheets, the reduced graphene-
nanoparticles embedded in nitrogen-doped hollow carbon spheres Fe3O4-SnO2-C quaternary hybrid nanocomposites preapred by Sun’s
(Fe2O3@N-C), with a capacity of 1573 mA h g–1 after 50 cycles at a group212 showed a reversible capacity of 868.6 mA h g–1, at a
current density of 100 mA g–1. The reversible capacity could be current density of 200 mA g–1, after 100 cycles. The reversible
maintained at 1142 mA h g–1 after 100 cycles at a high current capacity of 414.7 mA h g–1 was retained even at a high current
density of 1 A g–1. The unique structure of the ultrasmall Fe2O3 density of 2 A g–1.
nanoparticles uniformly distributed in the shell of nitrogen-doped The Fe3O4@C/porous reduced microcrystalline graphene
carbon spheres promoted rapid electrochemical kinetics and (PrMGO) composite prepared by Ma and co-workers34 showed high
effectively prevented the aggregation of the Fe2O3 nanoparticles reversible capacity and good cyclic stability. The structure of the
during the delithiation. In addition, the hollow structure effectively Fe3O4@C/PrMGO composites was stable against the high rate of
buffered the volumetric change and prevented the spheres from charge/discharge processes. As the current density was increased
crushing. from 100 to 3200 mA g–1 and then back to 100 mA g–1, the capacity
Sulfur-doped carbon has also been used to form composite of the composites recovered to 946.1 mA h g–1, which was even
electrode with iron oxide to improve the cycle stability and rate higher than that at the initial cycle. For the next 40 cycles, the
performance. For example, pyrite modified sulfur-doped carbon reversible capacity of the composite only slowly increased to 1106.4
(FeS2@S-C) electrode developed by Tao’s team234 showed mA h g–1. In addition, the specific capacity was maintained at 530
promising cycle stability and rate performance. After 100 cycles at a mA h g–1 after 200 cycles at a high current density of 1000 mA g –1.
current density of 100 mA g–1, a high capacity of 689 mA h g–1 was When the current was reset to 100 mA g–1, the reversible capacity
retained. The FeS2@hierarchical porous carbon composite immediately rose to 1015 mA h g–1. In the next 30 cycles, the
electrode prepared by Han’s group233 displayed a specific capacity

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reversible capacity increased dramatically to 1216 mA h g–1. The the interconnected voids in the flower-shaped structure. WhenOnline
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capacity retention of the 392th cycle reached 135.8%, as observed in DOI: 10.1039/C8TA01683F
Mn3O4/Fe3O4 electrode was charged and discharged at 300 mA g–1,
Fig. 18c-d. The high electrochemical performance could be ascribed the initial capacity was as high as 1510 mA h g–1 and the reversible
to the synergistic effect of the Fe3O4@NP NPs and the PrMGO capacity was 1040 mA h g–1 after 200 cycles.
substrate. After the rate test, the structure of the composite

material was further optimized and the contact between the
Fe3O4@C nanoparticles and the PrMGO nanosheet became more
intimate. In addition, PrMGO has not only provided plentiful
pleated microchips, but also offered appropriate void structures for
strain relaxation during the charging and discharging.
Fe-based and carbon nanotube/fiber composites demonstrated
similar enhanced electrochemical performances. In the marcasite
and carbon nanofibers composite (m-FeS2/CNFs) reported by
Zhang’s group22, during Li+ insertion, m-FeS2 microparticles were
converted to have a mimosa-like shape with open leaves. Once the
Li+ ions were detached, the m-FeS2 particles would return to closed
mimosa shape, as illustrated in Fig. 19a. This change in morphology
created opportunity for Li+ ion insertion, thus resulting in enhanced
electrochemical performance. The m-FeS2/CNFs electrode had a
high reversible capacity of 1399.5 mA h g–1 after 100 cycles at a
current density of 100 mA g–1. It also exhibited excellent cycling
performance with a reversible capacity of 573.4 mA h g–1 after 1000
cycles at a high current density of 5 A g–1. The m-FeS2/CNFs
electrode possessed excellent rate capability. As the current density Fig. 19 (a) Ex-situ SEM images of the lithium insertion/extraction process. (b) Cycling
performances of the pristine m-FeS2, pure CNFs and m-FeS2/CNFs composite at 0.1 A
was increased from 100 mA g–1 to 10 A g–1, a capacity of 782.2 mA h
g-1. (c) High-rate capabilities of m-FeS2/CNFs at various current densities [Reprinted
g–1 was still retained, as observed in Fig. 19b-c. with permission from Ref.22, Copyright 2017, American Chemical Society]. (d) Rate
The Fe2O3/SWCNT composite films developed by Shang’s group50 capability of Fe2O3, h-Fe2O3 and Fe2O3@PANI electrodes at different rates ranging
exhibited a reversible capacity of 1007.1 mA h g–1 at a current from 0.1 C to 10 C. [Reprinted with permission from Ref. 24, Copyright 2013, WILEY].
density of 200 mA g–1, together with a high rate capability of 384.9
mA h g–1 at 5 A g–1, while the discharge capacity was retained at a Conductive polymers not only provide high electrical conductivity
level of 567.1 mA h g–1 after 600 cycles at 2 A g–1. The Fe3O4- but also enhance the mechanical strength and stability of the
Fe@bamboo-like carbon nanotubes prepared by Chen’s team62 composites. For example, Lee’s group24 developed a hierarchical
maintained a Coulombic efficiency of over 97%, with a reversible core-shell hollow structure of Fe2O3@polyaniline (PANI). Comparing
capacity of nearly 800 mA h g–1 after 100 cycles at a current density with the urchin-like Fe2O3 without etching (Fe2O3) and PANI coating
of 300 mA g–1. The Fe2O3@CNTs composites prepared by Sun’s and the urchin-like hollow Fe2O3 without PANI coating (h-Fe2O3),
group63 with atomic layer deposition showed a high reversible the Fe2O3@PANI exhibited much higher reversible capacity and
capacity of 859.7 mA h g–1 after 400 cycles at a current density of long-term cycling stability. The capacity of the Fe2O3@PANI
500 mA g–1. The Fe2O3@CNTs electrode could achieve a high cycle electrode was 893 mA h g–1 at a current rate at 0.1 C up to 100
capacity of 464.4 mA h g–1 even at high current density of 10 A g–1. cycles, which is higher than 680 mA h g–1 of the non-hollow Fe2O3
Nanocomposites based on iron oxide with other oxides have and 732 mA h g–1 of the h-Fe2O3 based electrodes. As the current
been demonstrated to have promising electrochemical rate was raised from 0.1 C to 10 C, the capacity was still retained to
performances.32, 187, 188, 191 For instance, SnO2/Fe2O3 hollow sphere be 681 mA h g–1, which is much higher than that of the non-hollow
electrode exhibited a high initial discharge capacity of 1726.6 mA h Fe2O3 electrode and the h-Fe2O3 electrode, as depicted in Fig. 19
g–1.189 SnO2-Fe2O3@C ternary nanocomposites reported by Guo et (d). Due to the synergistic effect of the multiple components and
al.211 possessed reversible capacities of over 1000 mA h g–1 after the conductive polypyrrole layer, the MnOx/Fe2O3/polypyrrole
380 cycles at a current density of 400 mA g–1, due to the synergistic nanotubes synthesized by Jin and co-workers37 maintained a high
effect of SnO2, Fe2O3 and C. The Fe3O4@C@Mn3O4 multilayer core– reversible specific capacity of 1060 mA h g–1 at the current density
shell porous spheres synthesized by Zhang and co-workers210 had of 200 mA g–1 after 100 cycles. The specific capacity could be kept
an initial specific capacity of 1261 mA h g–1 at the current density of at 630 mA h g–1 even at a high current density of 5 A g–1. The poly
0.1 C. Also, the reversible capacity was retained to be 987 mA h g –1 (ST-AN) (PSA)-Fe3O4@C mesoporous microsphere prepared by
after 200 cycles. The branched nanorods of MnO2/Fe2O3 prepared Zhang and co-workers208 had both high cyclability and high rate
by Yang’s group9 presented a reversible specific capacity of 1028 performance. The flexible PSA@C conductive skeleton not only
mA h g–1 after 200 cycles at a current density of 1 A g–1. Even at a ensured high electrical conductivity, but also offered structural
current density of 4 A g–1, a reversible capacity of 881 mA h g–1 was integrity of the material. Besides, the layered mesoporous
still kept. The Mn3O4/Fe3O4 nano-flowers prepared by Zhao and co- structures promoted Li+ ion diffusion and provided more contact
workers32 showed excellent reversible capacity and cycle stability, area with the electrolyte. At a current density of 500 mA g–1, the
due to the synergistic effect of the different oxide components and reversible capacity of the PSA-Fe3O4@C electrode showed a slow

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increasing trend. After 100 cycles, the reversible capacity was as electrode curve had three stages, as illustrated in Fig. ArticleIn
View20c. the
Online
high as 1293 mA h g–1. The reversible capacity was maintained at first stage, the Ag-Fe2O 3 electrode showedDOI: 10.1039/C8TA01683F
a gradual increase in
928 mA h g–1, 677 mA h g–1 and 599 mA h g–1, at current densities of specific capacity before 60 cycles, due to the activation of the
2 A g–1, 8 A g–1 and 10 A g–1, respectively, after 100 cycles. electrode material. In the second stage, the electrode
7.1.2. Iron-based Nanoelectrode with Intricate Structure decomposition dominated from 60 to 125 cycles, so that the

The synthesis of complex structures, especially hollow or electrode performance decreased. In the third stage, the electrode
microporous structures, is a hotspot, which is a synthetic strategy capacity gradually increased from 125 to 200 cycles. The formation
to to improve the electrochemical performance of iron-based and decomposition of an organic polymer gel-like film provided
materials. In recent years, a variety of unique nanostructures have additional sites for lithium storage. In the whole process, the
been developed, which can alleviate volume changes during the external SEI layer may be damaged, spalled and reformed, resulting
lithium insertion/extraction process, provide more lithium in an unstable SEI layer during the cycling. When the structure is
intercalation sites, optimize the diffusion paths of ions and refined, a thin and stable SEI film is formed without splitting, and
electrons, shorten diffusion distances and reduce active material the reactivated electrode will exhibit excellent cycle stability over a
loss because of the repeat formation of SEI layer.66-68, 119 In this long period of time. This phenomenon, which the electrode
section, five categories of nanostructured electrodes will be performance first decreases and then increases, has been observed
discussed, i.e., spherical, hollow spherical, yolk-shell, nanobox and in other studies.47, 250-252
flower-like nanostructures.
Iron-based microspheres or mesoporous microspheres have good
electrochemical properties.114, 117 The unique structure of magnetite
(γ-Fe2O3) nanospheres prepared by Pan's group100 have been shown
to be able buffer the volumetric change during
lithiation/delithiation. The electrode had an initial charge capacity
of 1060 mA h g–1 at a rate of 100 mA g–1, with a steady cycling
capacity of 1077.9 mA h g–1 after 140 cycles. Hierarchically porous
Fe2O3 microspheres prepared by Zhang’s group105 via a lysine-
assisted hydrothermal process demonstrated excellent
electrochemical performance, because of the hierarchical porosity
and ordered microstructure. The initial specific capacity was 1079
mA h g–1 at a current density of 100 mA g–1, which was remained at
705 mA h g–1 after 430 cycles. The Fe3O4/graphene sphere prepared
by Choi and Kang3 achieved a reversible capacity of 981 mA h g–1
after 100 cycles at a current density of 2 A g–1. Due to the formation
of a polymer gel film on the active material and the decomposition
of the electrolyte, the discharge capacity of the Fe 3O4/graphene
nanostructures was gradually increased after 100 cycles, reaching
1050 mA h g–1 at the 300th cycle, as displayed in Fig. 20a-b. The
reversible capacity of the Fe3O4/graphene was preserved at 690 mA
h g–1 after 1000 cycles at a high current density of 7 A g–1. At a very
high current density of 30 A g–1, the electrode still had a stable
reversible capacity of 540 mA h g–1.
Hollow microspheres are promising candidates as electrode Fig. 20 (a,b) Cycle performances and long cycle performances of the Fe 3O4-decorated
materials with high electrochemical performances. The Fe3O4/C hollow graphene ball powders at 2 A g-1 and 7 A g-1, respectively [Reprinted with
hollow microspheres prepared by Wen’s group181 through permission from ref3, Copyright 2014, Elsevier]. (c) Cycling performance of the Ag-
ultrasonic spray pyrolysis were constructed from mesoporous Fe2O3 composites electrode at 1 A g -1 [Reprinted with permission from Ref. 20,
Copyright 2017, Nature]. (d) Cycling performance and corresponding columbic
carbon nanosheets that covered Fe3O4 nanoparticles. The reversible
efficiency of the Fe3O4@void@N-doped carbon electrode at a current rate of 2000 mA
capacity of Fe3O4/C composite was maintained at 600 mA h g–1 after g-1 [Reprinted with permission from Ref.47, Copyright 2016, Elsevier]. (e) Cycling
200 cycles at 1.0 A g–1, with a high value of 1030 mA h g–1 at low performance of the Fe3O4@N-C-700 at 500 mA g-1 [Reprinted with permission from
current density 0.1 A g–1. The Fe3O4/C composite with hollow Ref.12, Copyright 2017, Elsevier]. (f) Rate capability of the Fe2O3 nanomembrane
spheres synthesized by Yang et al.176 showed a stable electrodes [Reprinted with permission from Ref.51, Copyright 2014, Nature].
electrochemical cycle life. The initial capacitance was 1450.1 mA h

g–1, together with a high reversible capacity of 1300 mA h g–1 after As mentioned above, yolk-shell nanostructures have voids that
100 cycles at 100 mA g–1. can accommodate volumetric expansion during the lithiation
Compared with Fe2O 3 hollow spheres, the Ag-Fe2O3 hollow process. The FeOx@C yolk-shell structure reported by Yu’s group101
spheres prepared by Li’s group20 showed a higher capacity of 953.2 The showed high reversible capacity of 810 mA h g–1 and excellent
mA h g–1 at a current density of 100 mA g–1 after 200 cycles. The Ag- cycling stability (97.4% capacity retention at 100 cycles) at 0.2 C.
Fe2O3 electrode also exhibited a more stable capacity of 678 mA h The Fe3O4@void@N-doped carbon yolk shell composites prepared
g–1 over 200 cycles at 1000 mA g–1. It was found that the Ag-Fe2O3 by Yang’s group47 exhibited a high electrochemical performance,

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with a capacity of 860 mA h g–1 at a current density of 1 A g–1 after nanostructures provided a 3D conductive network Viewduring the
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500 cycles, which is more than double that of the cycling. The electrode exhibited excellent rateDOI:capability
10.1039/C8TA01683F
and high
Fe3O4@vacancies@carbon based electrode. The specific capacity of reversible capacity, with an initial discharge capacity of 1869.3 mA h
the Fe3O4@void@N-C first decreased and then increased, as g–1. After 1000 cycles, the reversible capacity was stabilized at 877.7
demonstrated in Fig. 20d. This is a typical characteristic of yolk-shell mA h g–1.

nanostructure electrode. Accordingly, Chen’s group12 well explained
this phenomenon, by observing micro-morphology changes during
the charging process. When the yolk-shell Fe3O4@nitrogen-doped
carbon (Fe3O4@N-C) nanocapsules were used as electrode,
reversible capacity decreased during the first 16 cycles and then
rose slowly. The reversible capacity of at second cycle was 815.7
mA h g–1 and reached the lowest level of 713 mA h g–1 at 16th cycle.
However, after 150 cycles, the reversible capacity was increased by
16.7% and remained at 832 mA h g–1 at 500 mA g–1, as seen in Fig.
20e. Fig. 21A shows morphologies of the Fe3O4@N-C capsules after
the 50th, 100th and 150th cycles. Due to the volume expansion
caused by the charge-discharge process, part of the Fe3O4 core
disassembled into small particles after the 50th cycle, as shown in
Fig. 21A(a, b). The disassemble of the Fe3O4 core into Fe3O4
nanoparticles was helpful to increase the number of active sites in
the electrode materials. With the process of cycling, the core
continued to decompose, as illustrated in Fig. 21A(c, d). The small
particles of Fe3O4 almost filled the entire carbon shell, while the
internal voids were greatly shrunk, but the number of the Fig. 21 (A) TEM images of the Fe3O4@C-N-700 nanocapsules after the (a, b) 50th cycle,
activation sites was greatly increased. After 150th cycle, the Fe3O4 (c, d) 100th cycle and (e, f) 150th cycle. (B) Schematic illustration of morphology and
core decomposed into smaller nanoparticles and remained volumetric change process of the Fe3O4@N-C nanocapsules during electrochemical
cycling [Reprinted with permission from Ref. 12, Copyright 2017, Elsevier].
completely enclosed within the carbon shell [Fig. 21A(e, f)]. The
volume expansion of the charge-discharge process broke the core
into small particles, which provided more activation sites and pores With a free-standing structure, Fe2O3 nanomembrane electrodes
that further boosted the electrochemical performance. Due to the prepared by Liu and co-workers51 showed an ultra-long cycling life
protection of the carbon shell, the spindle-like structure remained and a high capacity, with a reversible capacity of 808 mA h g–1 after
intact. Therefore, the electrode performance was not be degraded, 1000 cycles at 2 C. A high capacity of 530 mA h g–1 was hold after
due to the decompostition of the core, instead, the number of 3000 cycles at 6 C. The rate capability of the Fe2O3 nanomembrane
activation sites was increased. The morphology and volumetric was examined by two rounds of rate capability measurements at
change process of the Fe3O4@N-C nanocapsules during various current rates, as shown in Fig. 20f. The specific capacitance
electrochemical cycling was shown schematically in Fig. 21B. decreased from 899 mA h g–1 to 128 mA h g–1 as the current was
Square hollow nanobox is another common hollow structure. In increased from 0.2 C to 50 C. However, when the current rate
the Fe3O4/VOx@C hybrid hollow microboxes prepared by Xu’s returned from 50 C to 0.2 C, the reversible capacity was recovered
group,145 the outer carbon layer not only improved the conductivity to a high value of 946 mA h g–1. The rate capacity of the Fe2O3
of the electrode but also maintained the stability of the structure. nanomembrane electrode in the second round rate capacity
Hollow structures and nanopores smoothen the Li+ ion diffusion measurement process showed an almost the same level of that in
path and reduce volume expansion during charge-discharge. The the first round. Liu et al. believed that the 2D structural
Fe3O4/VOx@C electrode showed a reversible capacity of 742 mA h characteristics of the Fe2O3 nanomembranes was the key factor to
g–1 after 400 charge/discharge cycles at a current density of 500 mA improve the electrochemical performance. First of all, the unique
g–1. Similarly, the hollow nitrogen-doped Fe3O4/carbon nanocages mechanical wrinkling and bending of the Fe2O3 nanomembrane
with hierarchical porosities prepared by Song’s group149 had a effectively buffered the lithiation/delithiation induced strain. Due to
specific capacity of 878.7 mA h g–1 after 200 cycles at 200 mA g–1. the formation of the SEI layer, the thickness of the Fe2O3
The Fe3O4 microflowers synthesized by Sun’s team137 showed a nanomembranes was increased and wrinkled under the strain of
reversible capacity of about 1 A h g–1 at 100 mA g–1 after 50 cycles. repeated lithiation/delithiation. The nanomembranes maintained
He et al.26 anchored cauliflower-like FeS2 on 3D graphene foam to well layered structure without pulverization. Such a good
form 3D GF-FeS2 composites, which can be used directly as a free- mechanical stability of the nanomembranes can extend the cycling
standing and binder-free anode for LIBs without polymeric binders, life. Secondly, numerous 'mini-capacitors' were formed by the
conductive additives or metal current collectors. The 3D GF-FeS2 parallel Fe2O3 nanomembranes and electrolyte, which provideed
electrode maintained a specific capacity of 1080.3 mA h g–1 after excessive pseudocapactive contribution. 2D nanomembrane
100 cycles at a current density of 0.2 C. Cao and co-workers4 structured electrode can prolong the cycle life and improve the rate
prepared a similar flower-like structure in which 3D layered porous performance of high-rate batteries, which has been proved by
Fe2O3 nanosheets were stacked. The porous 3D layered Augustyn et al.92.

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DOI: 10.1039/C8TA01683F
Table 2 Representative Fe-based materials and their electrochemical performances as electrodes of SCs
Materials Specific Capacitance Rate capability Cycling stability year Ref.

Fe3O4 207.7 F g−1 at 0.4 A g–1 90.4 F g−1 at 10 A g–1 100% after 2000 cycles at 1 A g–1 2013 253
FeS2 317.8 F g–1 at 3 A g–1 195.1 F g−1 at 50 A g–1 81.1% after 1000 cycles 2016 254
C-C-Fe3O4 1153 F g–1 at 2 A g–1 514 F g−1 at 100 A g–1 96.9% after 1000 cycles at 5 A g–1 2016 7
Fe2O3/GP 3.08 F cm–2 at 5 mA cm–2 1.406 F cm–2 at 10 mV cm–2 95% after 5000 cycles at 100 mV s–1 2017 160
FeOOH QDs/graphene 365 F g–1 at 1 A g–1 189 F g–1 at 128 A g–1 89.7% after 20 000 cycles at 4 A g–1 2016 30
α-FeOOH 127 F g–1 at 10 A g–1 100 F g–1 at 20 A g–1 85% after 2000 cycles at 5 A g–1 2017 218
nanorods/GO
Fe3O4/rGO 455 F g–1 at 8 mV s–1 317 F g–1 at 27 mV s–1 95% after 9500 cycles at 3.8 A g–1 2017 28
RuO2-Fe2O3/OMC 1668 F g–1 at 1 A g–1 93% after 3000 cycles at 1 A g–1 2016 200
α-FeOOH@MnO2 597 F g–1 at 1 A g–1 443 F g–1 at 10 A g–1 97.1% after 2000 cycles at 1 A g–1 2017 35
Fe2O3/PPy 382.4 mF cm–2 at 0.5 mA cm–2 170.5 mF cm–2 at 10 mV s–1 97.2% after 5000 cycles at 100 mV s–1 2017 25
Ti-Fe2O3@PEDOT 1.15 F cm–2 at 1 mA cm–2 0.77 F cm–2 at 8 mA cm–2 96% after 30 000 cycles at 100 mV s–1 2015 206
NiNTAs@Fe2O3 418.7 F g–1 at 10 mV s–1 215.3 F g–1 at 64 A g–1 92.3% after 5000 cycles at 100 mV s–1 2017 39
amorphous 350.2 F g–1 at a 0.5 A g–1 159.5 F g–1 at 20 A g–1 95.6% after 10 000 cycles at 15 A g–1 2017 36
FeOOH/MnO2
Ti-FeOOH QD/GN/BC 3322 mF cm–2 at 2 mA cm–2 883 mF cm–2 at 50 mA cm–2 94.7% after 6000 cycles at at 8 mA cm–2 2017 222
7.2. Supercapacitors (SCs) current density of 2 A g–1. Even at a current density of 100 A g–1, the
Basing on structural characteristics and applications, the iron-based capacity still remained at 514 F g–1, with a rate capability retention
supercapacitors that are discussed in this section are classified into of 45%. As the current density was increased to 5 A g–1, the specific
three categories: nanocrystalline supercapacitors, asymmetric capacitance only decreased slightly from 914 F g–1 to 886 F g–1 after
supercapacitors and transparent flexible supercapacitors. Table 2 1000 cycles, with a loss of about 3.1%. It is believed that the
lists representative Fe-based materials and their electrochemical hierarchical porous structure of the outer carbon layer facilitated
performances as electrodes of SCs. ion diffusion and reaction with Fe3O4 species, as shown
7.2.1. Iron-based Nano-materials for Supercapacitors schematically in Fig. 22a. The synergistic effect between the outer
porous carbon layer and the uniformly distributed Fe3O4 species
In recent years, many efforts have been made to explore iron-based
was responsible for the enhanced capacitive performance.
materials for SCs. At present, the main challenge is their poor
Due to the large surface area and fast electron transport, the
electrical conductivity and structural stability during the charging
specific capacitance of the Fe2O3/graphene oxide paper (GP)
and discharging process. To solve these problems, nanostructure
prepared by Xie et al.160 was about 3.08 F cm–2 at a current density
design of iron-based materials is the most common strategy.
of 5 mA cm–2, which was about 14 times that of the Fe2O3/carbon
Nanostructures, such as nanorods76, 84, 255, nanosheets18, 46, 256,
paper (0.22 F cm–2). The Fe2O3/GP hybrid electrode retained about
nanotubes14, 59, 257 and nanowires15, 86 have been developed. The
95% of the initial capacitance after 5000 cycles. The Fe2O3
Fe3O4 nanoparticles synthesized by Yang’s group253 exhibited a
nanorods/Ag nanowires/coffee filter composites prepared by Hsu’a
specific capacitance of 207.7 F g–1 at 0.4 A g–1 and a good rate
group258 had a high reversible features and rate capabilities as
capability of 90.4 F g–1 at 10 A g–1. Using a sodium lauryl sulphate
electrode of supercapacitors, with an excellent specific capacitance
template, Chen et al.254 prepared pyrite FeS2 nanoribbons by using
of 287.4 F g–1, an energy density of 64.6 Wh kg–1 and a power
hydrothermal method, which possessed a capacitance of 317.8 F g–1
density of 18 kW kg–1. The N-doped graphene quantum
at 3 A g–1.
dots@Fe3O4-halloysite nanotube composites fabricated by Doong’s
Combining iron-based nanomaterials with highly conductive
group132 exhibited excellent electrochemical performances. In a
materials, such as carbon layer7, carbon nanotubes132, 258 and
neutral electrolyte solution, the specific capacitance of the
graphene30, 160, is an effective method to improve the electrical
electrode reached 418 F g–1 at a current density of 0.5 A g–1. In
conductivity of iron-based materials. Due to the synergistic effect of
addition, the nanocomposites also demonstrated high energy
the high capacitance of the iron-based material and the excellent
densities of 29 Wh kg–1 and high power densities of 5.2 kW W–1.
electrical conductivity of nanocarbon materials, these iron-based
After 3000 charge-discharge cycles, the original capacitance was
composites exhibited much better electrochemical performance
retained by about 82%.
than the pristine iron-based ones. In addition, they also have the
Incorporation of graphene could improve the electrochemical
effect of inhibiting mutual agglomeration. He’s team7 synthesized a
performance of iron-based materials.259 For example, the
C-C-Fe3O4 hollow sphere, with porous structure that allowed fully
amorphous FeOOH QDs/graphene hybrid nanosheets prepared by
contact of the active sites and thus promoted the interface redox
Xia’s group30 showed excellent pseudocapacitive effect, with a large
reaction. The uniform distribution of Fe3O4 on the porous carbon
specific capacitance of about 365 F g–1. At the same time, the
walls made a full use of the carbon conductive network. The C-C-
composite electrode had excellent cycle performance and excellent
Fe3O4 material achieved a maximum capacity of 1153 F g–1 at a

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rate performance. After 20 000 cycles, the capacitance was still spherical Fe3O4 nanoparticles, the contact area between the multi-
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retained by about 89.7% at a current density of 4 A g–1. At a current faceted Fe3O4 nanoparticles and the rGO DOI: nanoparticles
10.1039/C8TA01683F was
density of 128 A g–1, the capacitance was still at a high level of 189 F enlarged and the contact was more intimate. Kumar et al 28
g–1. When the lower cut-off voltage was extended to –1.0 and –1.25 anchored 3D Fe3O4 nanoparticles to the network of reduced
V, the specific capacitances were increased to 403 and 1243 F g –1, graphene oxide nanosheets (rGO NSs), with a large area CV curve at

respectively, as seen in Fig. 22b. The Fe2O3/FeOOH nanorods were a scan rate of 8 mV s–1, as illustrated in Fig. 22c-e. The Fe3O4
fixed on the graphene sheets, so that both the agglomeration of the nanoparticles were anchored in open spaces where rGO NSs were
Fe2O3 nanorods and the re-stacking of the graphene sheets were interconnected. The Fe3O4 nanoparticles inhibited the restacking of
prevented. The Fe2O3/graphene electrode prepared by Yang et al.161 rGO NSs, while the Fe3O4 nanoparticles were separated by the rGO
showed a high performance, with specific capacitance of 320 F g –1 NSs, thus leading to the high capacitive performance. At different
at 10 mA cm–2 and ideal electrochemical stability (capacitance scan rates of 8, 12, 18 and 27 mV s–1, the CV curves of the
retained at 97% after 500 cycles). Zhang’s group 218 synthesized Fe3O4/rGO hybrid electrode had no significant difference in shape
ultrafine α-FeOOH nanorods/GO composites as electrode materials except for the increase in area. The specific capacitance at 8 mV s–1
for supercapacitors, which had a large specific capacitance of 127 F was 455 F g–1. The electrode exhibited an energy density of 102.4
g–1 at a current density of 10 A g–1, an excellent rate performance Wh kg–1 and a power density of 2.027 kW kg–1. The rGO NSs
(100 F g–1 at 20 A g–1) and a good cycle performance with a capacity structure relieved the volumetric expansion or contraction of the
retention of 85% after 2000 cycles at 5 A g–1. Quan et al.162 Fe3O4 particles and confined them to the voids during the redox
prepared 2D α-Fe2O3/reduced graphene oxide (rGO) reaction, which ensured a high cyclic stability. The initial
nanocomposite electrodes, with a specific capacitance of 903 F g –1 capacitance was retained by 95% after 9500 cycles at a current
at a current density of 1 A g–1, which was much higher than those of density of 3.8 A g–1.
the bare α-Fe2O3 (347 F g–1) and rGO (167 F g–1). Examples of nanocomposites with other oxides to improve
electrochemical performance of iron-based materials are discussed
as follows. For instance, the α-Fe2O3@Ni(OH)2 nanosheet hybrid
composite prepared by Gao’s group52 reached a specific
capacitance of 356 F g–1 after 500 cycles at a current density of 16 A
g–1, with a capacity retention of 93.3%, due to the ample active sites
and shortened ion diffusion distance. Xiang et al.200 embedded
RuO2-Fe2O3 nanoparticles into ordered mesoporous carbon, which
exhibited a maximum specific capacitance of 1668 F g–1 at 1 A g–1,
much higher than that of the RuO2/OMC (1212 F g–1). The addition
of Fe2O3 promoted the uniform dispersion of the RuO2-Fe2O3
particles, thus reducing agglomeration and hence yielding good
reversibility. After 3000 cycles, the RuO2-Fe2O3/OMC composite
supercapacitor retained the initial capacity by 93%. The capacitance
of the RuO2-Fe2O3/OMC composite electrode was contributed by
both the double-layer capacitive and pseudocapacitive effects, thus
having a promising capacitor energy density. The electrode had an
energy density of 134 Wh kg–1 at a power density of 200 W kg–1.
Even at a power density of 6000 W kg–1, the energy density of the
electrode still could reach 80 Wh kg–1, which was nearly double that
of the RuO2/OMC one (48 Wh kg–1). Zhong et al.260 synthesized a
hierarchical heterostructure of Fe2O3 nanospheres on FeS2
nanosheets by using hydrothermal treatment, which had better
capacitor performance than the bare Fe2O3 electrode. The
composite electrode displayed a specific capacitance of 255 F g–1
Fig. 22 (a) Schematic diagram of hierarchical porous structure of the outer carbon layer
and good rate capability (145 F g–1 at a current density of 8 A g–1).
to facilitate ion diffusion and reaction with the Fe 3O4 in the inner core [Reprinted with 7.2.2. Asymmetric Supercapacitors (ASCs)
permission from Ref.7, Copyright 2015, Elsevier]. (b) Specific capacitances of the As discussed before, the low energy density has limited the
FeOOH/40G electrode in different voltage windows of -1 to 0 V and -1.25 to 0 V at development and application of supercapacitors. According to the
different scan rates [Reprinted with permission from Ref. 30, Copyright 2015, Wiley]. (c)
CV curves of the Fe3O4 NPs, 3D rGO NSs and 3D Fe3O4/rGO hybrids at a scan rate of 8
relationship between energy density (E), specific capacitance (C)
mV s-1. (d) CV curves of the 3D Fe3O4/rGO hybrids at different scan rates. (e) and voltage (V), E = 1/2 CV2, it is possible to increase the energy
Charge/discharge curves of the 3D Fe3O4/rGO hybrids at different current densities. density by increasing the specific capacitance (C) and the voltage
[Reprinted with permission from Ref.28, Copyright 2017, American Chemical Society]. (V). Because the voltage can be increased at separate potential
windows by configuring the positive and negative electrodes, the
The Fe3O4 nanoparticle/reduced graphene oxide composite development of asymmetric supercapacitors (ASCs) has become an
synthesized by Jiao’s team259 had a high specific capacitance of attractive strategy. ASCs are usually composed of a double-layer
220.1 F g–1 at 0.5 A g–1 after 3000 cycles. Compared with the electrode as power source and a battery-type Faraday electrode as

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energy source, which not only operate over a wider voltage range, MnO2 is another widely used cathode material for ASC
View device.
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but also provide high energy density. As a result, ASCs are expected The γ-FeOOH nanosheets developed by DOI: Chen10.1039/C8TA01683F
et al.18 showed
to be potential candidates for the applications in the field of hybrid excellent pseudocapacitive performance, reaching an extraordinary
vehicles, MEMS, handheld electronic devices and sensors. In recent power density of 9000 W kg–1. ASCs made of γ-FeOOH NSs and 2D
years, a great progress has been made in cathode materials, but the MnO2 as anode and cathode materials delivered a maximum power

anode materials are still under development. Currently, the main density of 16 000 W kg–1 and an energy density of 37.4 Wh kg–1,
anode material is carbon, whose specific capacity does not match when charging/discharging in a mild aqueous electrolyte at a
that of the cathode. In addition, the working voltage of the maximum cell voltage of 1.85 V. The tectorum-like
assembled ASCs is usually lower than 2 V due to the limitation of Fe2O3/polypyrrole（PPy）nanoarrays fabricated by Hu’s group25
the cathodic-anodic potential window in aqueous electrolytes. Very gave high electric-storage properties due to intriguing hierarchical
excitedly, the amorphous scale-shaped FeOOH nano-electrode nanoarchitecture of the composite. The Fe2O3/PPy electrode had an
synthesized by Wong’s group219 showed a high pseudocapacitance area capacitance of 382.4 mF cm–2 at a current density of 0.5 mA
of 1.11 F cm–2 or 867 F g–1. An asymmetric supercapacitor was cm–2, which was retained to be 170.5 mF cm–2 even at 10 mV s–1.
assembled using the FeOOH and Co-Ni double hydroxides as anode The initial capacity was retained by 97.2% after 5000 cycles. A solid
and cathode, reaching a power density of 1831.6 W kg–1 or 15.3 asymmetric supercapacitor made of the Fe2O3/PPy anode and
mW cm–3. The asymmetric ultracapacitor could supply a high MnO2 cathode exhibited a high energy density of 0.22 mWh cm–3 at
energy density of 86.4 Wh kg–1 or 0.7mW h cm–3. a power density of 165.6 mW cm–3. Lu’s group206 developed Ti-
Carbonaceous materials have been used as one of cathode doped Fe2O3@poly(3, 4-ethylenedioxythiophene) (PEDOT)
materials to construct ASCs. Shen et al.261 synthesized nanorodes array electrode, with a surface capacitance of 1.15 F cm –
Fe3O4@carbon nanosheet composites by using ammonium ferric 2 at 1 mA cm–2, much higher than the that for the original Fe O
2 3
citrate as the precursor and graphene oxide as the structure- electrode (0.46 F cm–2). Also, the device showed a very good cycling
directing agent, which were used as positive electrode, while stability, with a retention of above 96% after 30 000 cycles. The
porous carbon was employed negative electrode. The asymmetric asymmetric supercapacitor was assembled with the Ti-doped
supercapacitors achieved a maximum energy density of 18.3 Wh kg– Fe2O3@ PEDOT nanorodes arrays and MnO2 as the anode and
1 at a power density of 351 W kg–1, in the electrolyte of KOH/PVA cathode materials, which showed a maximum energy density of
gel. He’s team7 reported an asymmetric supercapacitor, with 0.89 mWh cm–3 and an ultrahigh stability with 96.1% capacitance
double carbon-shelled C-C-Fe3O4 and activated carbon (AC) as the retention over 30 000 cycles.
two electrodes. At current densities of 1 and 8 A g–1, the
corresponding specific capacitances were 117 and 50 F g –1,
respectively. When cycled at a current density of 1.5 A g–1, an initial
capacity could be retained by 96.7% after 8000 cycles. The ASC
devices had energy densities in the range of 17-45 W h–1, at power
densities ranging from 400 to 8000 W kg–1.
The Fe3O4/reduced graphene oxide (rGO) composite electrode
prepared by Lin et al.262 exhibited a high capacitance of 661 F g–1 at
1 A g–1. An asymmetric supercapacitor (ASC) was constructed with
the Fe3O4/rGO as the anode and NiO/Ni3S2/3D-graphene as the
cathode, which had a maximum capacitance of 233 F g–1 at a scan Fig. 23 (a) CV curves of the NiCo2S4@Fe2O3 electrode collected from 5 to 800 mV s-1 in
rate of 5 mV s–1, corresponding to a maximum energy density of a potential window between 0 and -1 V vs. SCE. (b) Galvanostatic charge/discharge
82.5 Wh kg–1 at a power density of 930 W kg–1. Due to the 1D curves of the NiCo2S4, NiCo2S4@Fe2O3 and Fe2O3 electrodes collected at a current
coaxial nanostructures and the presence of the fine integrated density of 2.5 A g-1 [Reprinted with permission from Ref. 8, Copyright 2016 Elsevier].
conductive layers, the FeOOH@PPy electrode prepared by Wei et
al.213 provided a specific capacitance of 1140 F g–1 at a current
density of 1 A g–1, which was twice that of the bare FeOOH. Optimal Hierarchical heterostructure and hybrid core structure have been
energy density of the ASC device reached 39.1 Wh kg–1 at a power shown to be able to provide rich active sites.75 For example, a
density of 800 W kg–1. Similarly, the core-shell α-FeOOH@MnO2 hierarchical heterostrucure compositie NiCo2S4@Fe2O3 NRs was
heterostructures synthesized by Lv et al.35 showed much higher prepared by Zhai’s group8, with CV curves to have an undistorted
electrochemical performances than the α-FeOOH hollow-fiber rectangular shape over a wide range of scan rates (5‒800 mV s–1),
microspheres. The specific capacitance of the α-FeOOH@MnO2 indicating that the composite electrode had good
electrode reached 597 F g–1 at a current density of 1 A g–1, which pseudocapacitieve performance and high rate capability, as
was more than twice that achieved by using the α-FeOOH electrode revealed in Fig. 23a-b. Compared with the electrodes based on
(232 F g–1). When the current density was increased to 10 A g–1, the NiCo2S4 and Fe2O3, the NiCo2S4@Fe2O3 electrode exhibited superior
capacitance was still retained by 74.2%, higher than 60% for the α- capacitive performance, which was evidenced by the fact that the
FeOOH electrode. After 2000 cycles, the capacitance retention was charge-discharge curve was more symmetrical. The NiCo2S4@Fe2O3
as high as 97.1%, also higher than 93.2% for the α-FeOOH electrode delivered a high specific capacitance of 342 F g–1 at a
electrode. The ASC device had a maximum energy density of 34.2 current density of 5 mV s–1. The enhance capacitance performance
Wh kg–1 at a power density of 815 W kg–1. was attributed to the composite structure with the highly

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conductive NiCo2S4 scaffolds and the grafted Fe2O3 NRs. According a scan rate of 10 mV s–1, at least 100 times higher than Viewthat
Articleof the
Online
to the Nyquist plot, the NiCo2S4@Fe2O3 electrode possessed an carbon material electrode transparent device. DOI:The
10.1039/C8TA01683F
volume energy
electrode transfer resistance (Rct) of 0.76 Ω, implying the presence density of the FNW@Gr-TF electrode was 8 mWh cm–3, which was
of a rapid Faraday reaction between the NiCo2S4 and Fe2O3 equivalent to 18.6 times212 that of the transparent electrode
particles. An ASC was constructed with the NiCo2S4@Fe2O3 capacitor based on FFT-GP (430 μWh cm–3)264. The value was also

nanoneedle arrays as anode and MnO2 nanosheet arrays as much larger than that of the carbon film (47 μWh cm–3)264 and that
cathode. Because the voltage of the ASC device was increased to of the graphene layer supercapacitor (50 μWh cm–3)263. The
2.3 V, the energy density could be significantly increased. In a transmissivity of the FNW-TF electrode was about 62.5% at a
neutral aqueous solution, the ASC device provided a volumetric wavelength of 550 nm. Due to the polymer (PVA) electrolyte and
energy density of 2.29 mWh cm–3 at an average power density of the counter electrode, the assembly supercapacitor transmittance
196 mW cm–3. Moreover, the ASC maintained an energy density of was decreased to 42.9%. There is no significant change in the CV
1.08 mWh cm–3 even at a high power density of 2063 mW cm–3, curve when the ultracapacitor device was bent at 0°, 30°, 60° and
demonstrating excellent power capacity. 90°, as seen in Fig. 24a. This outstanding flexibility makes it great
The nickel nanotube arrays (NiNTAs)@Fe2O3 electrodes prepared potential in the wearable and folding appliance industries.
by Xia’s team39 had excellent capacitive properties, with a specific The rapid growth of flexible/wearable consumer electronics
capacitance of 418.7 F g–1 at 10 mV s–1, which eas much higher than requires that energy storage devices not only have excellent
those of the Fe2O3 thin film (76.4 F g–1) and the Fe2O3 nanorod electrochemical properties, but also have the tolerance to fold and
(177.1 F g–1). The NiNTAs@Fe2O3 nanoneedle electrode retained an bend.265, 266 Flexible capacitors usually require the use of flexible
ultra-high specific capacitance of 215.3 F g–1 even at a high current substrates, such as PET, textiles, carbon cloth, stainless steel sheet,
density of 64 A g–1. Meanwhile, the electrode exhibited a minimum papers and fibers. The amorphous FeOOH/MnO2 composites
equivalent series resistance (Rs) of 2.3 Ω and a charge-transfer prepared by Wu’s group36 had high specific capacitance, good rate
resistance (Rct) of 2.3 Ω. The ultrafine and hollow Ni nanoframe capability and cycling stability as transparent capacitor electrodes.
structure is extremely advantageous for electron collection and fast The composite electrode delivered a specific capacitance of 350.2 F
Faraday reaction. At the same time, this type of special structure is g–1 at a current density of 0.5 A g–1. The specific capacitance was
also beneficial to the cyclic stability of the electrode. After 5000 remained at 159.5 F g–1 even as the current density was increased
cycles at 100 mV s–1, the liquid-state ASC showed excellent cycling to 20 A g–1. In addition, after 10 000 cycles at a current density of 15
stability, with a capacitance retention of 92.3%, while the solid- A g–1, the capacitance was retained by 95.6%. The SCs could be
state ASC had a retention of 79.3%. In addition, the CV curve of ASC printed on different substrates, including PET, paper and textiles,
device was almost unchanged in shape, indicating its high which could power a 1.9 V yellow LED, with large bending and
reversibility and cycling stability. The NiNTA@Fe2O3 nanode-needle stretching, as demonstrated in Fig. 24b-d.
electrodes achieved a maximum energy densities of 34.1 Wh kg –1
and 32.2 Wh kg–1, corresponding to power densities of 3197.7 W
kg–1 and 3199.5 W kg–1, in an aqueous electrolyte and a quasi-solid
gel electrolyte, respectively.
7.2.3. Transparent Flexible Supercapacitors (TFS)
Transparent supercapacitors have wide applications in the fields of
transparent smartphones, implantable medical devices and
smart/wearable devices15. Previous studies have focused on carbon
material based films, such as carbon films, 2D rGO films, 2D CVD
vinyl graphene films, 2D carbon nanotube films 223, 263, 264. There is
always a contradiction between the mass load and optical
transmittance. A high mass load can produce a high capacitance but
with result in a decreased transparency. So far, the electrochemical
performance of transparent supercapacitors is still far below that of
opaque supercapacitors. In this case, the transition metal oxide iron
oxides are explored as potential electrode materials for transparent Fig. 24 (a) CV curves of the supercapacitors based on the FNW@Gr-TF under the bent
states at a scanning rate of 100 mV s -1 [Reprinted with permission from Ref. 15,
flexible supercapacitors.
Copyright 2017, IOP]. (b) Photographs of the all printed solid-state flexible SC devices
Huang and co-workers15 fabricated a Fe2O3 nanowire on PET, paper and textile substrates. (c) Photographs after bending. (d) Photograph of
network@graphene transparent film (FNW@Gr-TF) electrode the SCs after bending in series to light up a yellow LED [Reprinted with permission from
material, in which graphene wrapped the Fe2O3 nanowires, forming Ref.36, Copyright 2017, Elsevier].
a fast 3D conductive network structure. The graphene layer also
adhered the active material onto the ITO layer, greatly improving Lokhande’s group267 prepared MnO2 and Fe2O3 thin films on
the stability of the electrode material. Due to the graphene highly flexible stainless steel sheets. Asymmetric flexible solid
encapsulation effect, the initial capacitance of FNW@Gr-TF supercapacitors (FSS-SC) were assembled by using the MnO2
electrode could be retained by over 92% after 10 000 cycles, much nanosheet as anode and the Fe2O3 nanosheet as anode, with
higher than 16.1% for the FNW-TF without graphene. The Na2SO4/carboxymethylcellulose (CMC) gel as separators and
FNW@Gr-TF electrode had a specific capacitance of 3.3 mF cm–2 at electrolytes, respectively. This flexible ASC had a maximum specific

Journal
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capacitance of 92 F g–1 and an energy density of 41.8 Wh kg–1, monitored with an in-situ scanning electron microscope (SEM).
View Article Online
making it suitable for the integration with portable electronics. Atomic force microscope (AFM) was used DOI: 10.1039/C8TA01683F
to study the interface
Wu’s team193 synthesized two hybrid composites, α- electrochemistry of silicon nanowires. In-situ transmission electron
Fe2O3@MnCo2O4 and α-Fe2O3@Co3O4, on a flexible carbon cloth. microscopy (TEM) was used to directly observe the dynamic
Area capacitances of 490 mF cm–2 and 1073 mF cm–2 at 1 mA cm–2 behavior and transformation mechanism of Ti3Sn/NiTi alloy and

were observed for the α-Fe2O3@MnCo2O4 and α-Fe2O3@Co3O4 Fe2O3/graphene. The formation of dendrites on the lithium metal
composites, respectively. After 6000 charge/discharge cycles, the anode and the passivation of the SEI layer was clarified in self-
capacities of the α-Fe2O3@MnCo2O4 and α-Fe2O3@Co3O4 discharge measurement. These advanced technologies could also
composites were retained by 74.6% and 77.8%, respectively. be used to study the electrochemical reaction mechanism of iron-
The Ti-doped FeOOH QD/GN/BC flexible anode prepared by based materials, which will guide the design and synthesis of new
Yuan’s group222 exhibited a high area capacitance of 3322 mF cm–2 nanostructures.
and a specific capacitance of 235.6 F g–1 at 2 mA cm–2. After 6 000 (4) Applications of iron-based electrode materials in new areas. It
cycles, the capacitance retention reached 94.7%. ASC devices was is well known that different applications put different requirements
assembled with the Ti-doped FeOOH QD/GN/BC and Mn3O4/GN/BC on structure and performance of the electrodes. For example,
as the anodes and cathodes, which delivered an ultrahigh area transparent flexible electrode for smart wearable device requires
energy density of 0.541 mWh cm–2 and an ultrahigh volume energy high light transmittance and mechanical flexibility, while the
density of 9.02 mWh cm–3, over the operating voltage range of 0– electrochemical performance should not be compromised.
1.8 V. At the same time, the capacitor had a good capacity retention (5) Optimization and simplification of the synthetic methods for
in bent states. The graphene-coated FeOOH nanowire arrays and large scale applications. At present, most of synthetic processes are
Co(OH)2 nanosheet thin-film transparent electrodes prepared by complicated and thus not cost-effective, which is not suitable for
Zhang et al.223 showed good transparency with a transmittance of commercial applications. As a result, it is crucial to develop a
50.5% at 550 nm. When operated at 1.8 V, the asymmetric flexible simple, low-cost and scalable method to precisely control the
ultracapacitor made of Co@Gr-TF//Fe@Gr-TF exhibited a high chemical composition and physical structure.
specific capacitance of 5.5 mF cm–2 and a high energy density of In short, the developments of iron-based nanomaterial and their
1.04 mWh cm–3, together with a capacity retention rate of 83.5% applications as electrode are still in the research stage, thus having
after 10 000 cycles. a long way to go in terms of commercial applications. Hopefully, by
comprehensively summarizing the recent research progress, this
review will provide as a reference for the follow-up researchers in
8. Conclusions and Perspectives this interesting and perspective field and promote the development
Here, we present a comprehensive review that highlights the of iron-based electrode materials.
significant progress made in the design and preparation of iron-
based nanomaterials over the last five years. It includes 1D, 2D, and
3D nanostructure design and synthesis of Fe2O3/Fe3O4,
Conflicts of interest
nanocomposites of iron oxides with various carbonaceous supports, There are no conflicts to declare.
other metal oxides and polymers, and recent research hotspots—
iron hydroxide (FeOOH) and iron sulfides (FeS2). In addition, the
application of iron-based nanomaterials in LIBs and SCs was Acknowledgements
reviewed according to the classification. For future research on This work was supported by the Natural Science Fund of China
iron-based electrode materials, it is believed that we should focus (51762023), the Jiangxi Provincial Department of Education, the
on the following aspects. Training Program of Outstanding Young Scientists in Jiangxi
(1) Design and synthesis of new nanostructured iron-based Province (20171BCB23070), Jingdezhen Science and Technology
materials. The preparation of new structures, such as grape-like Bureau, the Key Laboratory for Microstructural Control of Metallic
structures and complex hollow spherical structures, has promoted Materials of Jiangxi Province (JW201523006), and Special Fund for
the development of iron-based materials. Therefore, it is an Visiting Scholars in the Development Plan of Young Teachers in the
important research direction for these materials. Undergraduate Colleges and Universities of Jiangxi Province.
(2) Formation mechanism of the nanostructures. Although
several new structures have been prepared, they are either
accidentally obtained or relied on experiences. Therefore, the References
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Synthesis and Application of Iron-based Nanomaterials as Anode

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electric vehicles for power batteries and portable consumer

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2. Synthesis of Iron Oxide (Fe2O3)

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Using the existing nanowires as a template, a metal oxide source

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2.3.1.2 Template-free Approaches

synthesis procedures and thus has high costs. Moreover, the

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al.118 synthesized mesoporous Fe2O3 nanoparticles by a using

2.3.2 Hollow Structures

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nm. The C-C-Fe3O4 microspheres had a high specific surface area of

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