Ionics (2014) 20:1651–1663
DOI 10.1007/s11581-014-1262-5
REVIEW
A review of research on hematite as anode material
for lithium-ion batteries
Xiaodong Zheng & Jianlong Li
Received: 3 April 2014 / Revised: 15 September 2014 / Accepted: 16 September 2014 / Published online: 28 October 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract Hematite (α-Fe2O3) nanomaterials have been in-
vestigated intensively as a promising anode material for Li-ion
batteries due to their advantages such as high theoretical
capacity, low cost, environmental friendliness, high resistance
to corrosion, etc. However, their practical application is ham-
pered by poor capacity retention, low Coulombic efficiency,
and poor high-rate capacity. To overcome these drawbacks,
many effective works have been proposed. This review focus-
es first on the present status of α-Fe2O3 nanomaterials in the
field of Li-ion batteries including their features, synthesized
methods, modification, application and then on their near
future development.
Keywords Lithium-ion batteries . Anode . Hematite
Introduction
In recent years, rechargeable lithium-ion batteries (LIBs)
have attracted much attention and are considered the
most promising power sources for electric vehicles (EVs)
and hybrid electric vehicles (HEVs) due to their unique fea-
tures. Currently, conventional anode materials for LIBs are
mainly based on carbonaceous materials such as graphite,
which have been used in portable electronics for decades.
However, the present carbonaceous negative electrode, al-
though a commercial reality, is obviously lying behind the
X. Zheng : J. Li
College of Chemical Engineering, Qingdao University of Science
and Technology, 266042 Qingdao, China
X. Zheng (*)
Department of Chemical Engineering, Binzhou University,
256603 Binzhou, China
e-mail: zhxdbzu@163.com
requirements of high energy and high power application for
EVs and HEVs due to their relatively low specific capacity
(e.g., 372 mA h/g for graphite). Therefore, the tremendous
challenge has motivated intense research interest searching for
alternative anode materials with exceptional capacity as well
as high energy density and excellent cycling stability. As one
of the new generation anode materials, 3D transition metal
oxide (MxOy, where M is Co, Ni, Fe, or Cu) nanoparticles
demonstrate some attractive electrochemical performances [1,
2]. Among them, nanoscale hematite has been investigated
intensively due to its attractive advantages including high
theoretical capacity (1,007 mA h/g), high inherent density
(5.24 g/cm3), low cost, environmental impact, etc.
Different from traditional electrode materials for LIBs, the
reaction mechanism of Fe 2O 3 with Li relies on an
electrochemically induced conversion reaction [3].
During the discharge process, iron oxides are reduced
to metallic iron nanoparticles and Li2O. Fe0 nanoparti-
cles embedded in the Li2O matrix have been verified to
be electrochemically active, owing to the huge internal
contact surface between Li2O and Fe0, and the Li2O
matrix can be decomposed through the unique synergy,
and thus, lithium ion is released. Unfortunately, the reversibil-
ity of the conversion reaction is hampered by the insulating
character of Li2O [1, 3, 4], causing large irreversible capacity
loss and low Coulombic efficiency. Another challenge for iron
oxides is severe volume change (over 200 %) during
lithiation/delithiation process, resulting in structural degrada-
tion of electrode materials, even pulverization, and thus
breakdown of electrical conduction of the electrode and
rapid capacity fading. In addition, repeated formation/
decomposition of unstable thick solid electrolyte inter-
phase (SEI) films on the anode surface of iron oxides,
caused by catalysis of the nanosized Fe0, has been
verified as one of the causes influencing cycle stability
as well [4, 5].
1652 Ionics (2014) 20:1651–1663

To resolve the abovementioned drawbacks, several ap- Due to its insulative Li2O matrix, much of the capacity is
proaches have been proposed, such as the fabrication of lost in the subsequent delithiation process, and the oxidization
nanocomposites with decreased size or different morphologies product of Fe0 is not the original Fe2O3 but amorphous iron
and structures, surface modification with high electronic con- oxides. Therefore, the reversible reaction mechanism is pro-
ductivity materials, offering structural scaffold by employing posed as follows [6, 11, 14, 15]:
structural stable material, and so on. In this report, the latest
progress in research on hematite nanomaterials including their 2Fe0 þ 2xLi2 O↔2FeOx þ 4xLiþ ð4Þ
electrochemical characteristic, synthesis methods, surface −
modification, and application is reviewed. þ 4xe ð0:005−3:0 V; 0 ≤ x ≤ 1:5Þ

Additionally, the capacities of nanosized α-Fe2O3 elec-

trodes would begin to increase slightly after cycling over a
Electrochemical characteristics of hematite
long period, and this phenomenon has been reported by sev-
eral groups on iron oxides [16–19], which may result from the
As with the other anode materials, particle size and morphol-
gradual release of the Li+ trapped inside the insulating Li2O
ogy have been identified as important aspects affecting the
formed during the initial dozens of cycles and from the re-
electrochemical performance of hematite (α-Fe2O3). Micron-
versible growth of a polymeric gel-like film on the surface of
sized α-Fe2O3 particles have previously demonstrated a large
the progressively pulverized particles [20, 21]. As the number
size-dependent effect on reaction with Li+, where a structural
of cycles increases, more and more Fe nanograins are pro-
transformation occurs from the hexagonal to cubic phase after
duced and the previous particles break up into much smaller
insertion of an equivalent of just 0.05 mol Li+ [6]. Further
ones due to the electrochemical milling effect [6, 16, 22]; thus,
lithiation leads to the formation of metallic Fe and amorphous
the inactive Li2O may contact with Fe0 and participate in the
Li2O. In the discharge process, the formation reaction of Fe0
reactions. On the other hand, the massive interface formed
and Li2O is reversible and cubic Li2Fe2O3 is formed. The
during cycling between nanoscale solid phases provides a
mechanism of electrochemical reaction of α-Fe2O3 and
pathway for ionic transport during the conversion process,
lithium is determined as follows [7, 8]:
and vast numbers of Li+ ions can be stored, resulting in the
enhancement of capacity. Although nanosized α-Fe2O3 parti-
α‐Fe2 O3 →α‐Lix Fe2 O3 →cubic Li2 Fe2 O3 ↔Fe0 ð1Þ
cles display a much better electrochemical performance than
þ amorphous Li2 O large particles, the large capacity loss and low Coulombic
efficiency as a result of volume change and poor conductivity
With the number of cycles increasing, the size of nanosized may still present a challenge.
metallic Fe gradually becomes larger than initial and presents
a large domain, which is electrochemically inactive, and thus
causes rapid capacity loss of the cell [9].
Synthesis method
Compared with large particles, nanosized (∼20 nm) α-
Fe2O3 particles are able to maintain their structural integrity
The reversible capacity and stable cycle of α-Fe2O3 are great-
(corundum phase) before conversion [6, 10], and 0.5 mol of Li
ly affected by properties, such as particle size, morphology,
could be reversibly intercalated into α-Fe2O3 nanoparticles in
structure, and crystallinity, which are strongly dependent on
the potential range of 4.0–1.5 V (vs. Li). When discharged to
the synthesis methods. For the purpose of fabrication of he-
0.9 V (vs. Li), up to 2 mol of Li can be intercalated, but these
matite nanoparticles with controllable size and shape, a variety
cannot be electrochemically extracted during the delithiation
of approaches have been successfully developed, and these
process without destroying the crystal structure. Further deep
synthesis techniques are briefly reviewed in the succeeding
discharge down to 0.005 V (vs. Li+/Li) can result in the
subsections.
reaction of more than 6 mol of Li with 1 mol of Fe2O3, and
the excess Li could be related to the electrolyte decomposition
Hydrolysis method
depending on the surface area of hematite nanoparticles. The
initial lithiation process is shown as follows [6, 11–13]:
The hydrolysis method is a simple and facile synthetic route
using trivalent iron salt and deionized water as raw materials,
Fe2 O3 þ 2Liþ þ 2 e− →Li2 ðFe2 O3 Þ ð4:0−0:9 VÞ ð2Þ and the process involves two stages that is shown as follows:
[Fe(H2O)]3+ →Fe(OH)3 →α-Fe2O3. The size of nanoparticles
can be controlled by adjusting the concentration of Fe(III) salt
Li2 ðFe2 O3 Þ þ 4Liþ þ 4e− → 2Fe0 ð3Þ
and hydrolysis rate, and the main disadvantage of this method
þ 3Li2 O ð0:9−0:005 VÞ is that the morphology cannot be easily controlled and the
Ionics (2014) 20:1651–1663
water needs to be kept boiling during the whole hydrolysis
process. Zhang et al. [23] prepared α-Fe2O3 nanoparticles
5 nm in diameter assembled into a mesoporous network using
Fe(NO3)3·9H2O and deionized water as reagents at 125 °C for
1 h, the surface area of which is 112 m2/g contributing to the
excellent cycling performance (1,009 mA h/g at 100 mA/g
after 230 cycles) and rate capability (reversible charging ca-
pacity of 420 mA h/g at 1,000 mA/g after 230 cycles). In
addition, after 30 cycles, the capacity showed a tendency to
increase, compared with the other results reported, and this
tendency appears sooner, indicating that the smaller the size of
the particles, the more significantly the electrochemical
grinding effect.
Direct thermal oxidation process
Direct thermal oxidation process is another easy and direct
route to prepare α-Fe2O3 nanoparticles, by which binder-free
α-Fe2O3 anode can be directly fabricated in a short time.
However, its drawbacks are also obvious such as uncontrol-
lability of the size and shape of nanoparticles that restrict its
application. Ding et al. [24] synthesized α-Fe2O3 nanoparti-
cles on the surface of an iron mesh current collector via direct
thermal oxidation process within 6 min, and the morphology
of the particle is irregular and the size distribution is inhomo-
geneous (from 200 to 300 nm). These particles tightly at-
tached on the surface of the iron mesh current collector, which
can be used directly as anode without any conductive addi-
tives or polymer binders. The obtained binder-free anode still
can maintain a large reversible capacity of 700 mA h/g at
400 mA/g and 530 mA h/g at 1,000 mA/g, respectively. The
outstanding electrochemical performances of the Fe2O3 anode
are mainly attributed to the improved electronic conductivity
provided by the iron mesh current collector.
Precipitation-calcination method
For the purpose of the fabrication of hematite nanoparticles
with controllable size and shape, several effective methods
have been successfully developed. Among them, the
precipitation-calcination method may be the simplest and
most popular chemical pathway to obtain hematite particles.
Generally, it is not possible to precipitate specific α-Fe2O3
nanoparticles directly in the desired size and shape, but the
synthesis can be actualized by the transformation of hematite
precursor nanoparticles [25, 26]. Ma et al. [27] proposed a
facile two-step route to synthesize two kinds of hierarchical
porous flower- and cube-like α-Fe2O3 assemblies consisting
of nanoparticles with sizes of around 150 nm by the
precipitation-calcination method, which is favorable for in-
dustrial mass production. The precursors, α- and β-
FeF3·3H2O with flower- and cube-like morphology, respec-
tively, were fabricated using ethanol, FeCl3, and HF as the
1653
starting materials in different solvents. After calcination at
600 °C for 4 h under N2 atmosphere, the precursors were
converted to hierarchical hematite, and the original morphol-
ogies of FeF3·3H2O precursor were entirely preserved, as
shown in Fig. 1. The formation mechanism was associated
with crystalliferous water, which not only formed a large
number of pores inside when escaped, but also provided
oxygen sources for the formation of Fe2O3 leading to the
connection of nanoparticles and thus preserving the morphol-
ogies of the precursors. Yao et al. [28] prepared porous α-
Fe2O3 nanorods by thermal decomposition of FeC2O4·2H2O
precursor precipitate that were readily synthesized through
poly(vinyl alcohol)-assisted precipitation process. The α-
Fe2O3 product integrally inherited the morphology of the
precursor; after calcination, the α-Fe2O3 nanorods with an
elongated shape became porous, were composed of intercon-
nected nanoparticles, and delivered an enhanced rate capabil-
ity even cycling at 1 C rate (897 mA h/g after 100 cycles) that
was attributed to the small interfacial kinetic resistance mainly
caused by the large interfacial area between the nanostructured
electrode and the electrolyte solution.
Hydrothermal/solvothermal synthesis
In terms of homogeneous nucleation and grain growth, hy-
drothermal or solvothermal synthesis has shown to be advan-
tageous over other methods, such as milder conditions and
versatility. The preparation conditions, such as the concentra-
tion of the reagent, reaction temperature, reaction duration,
etc., play an important role in determining the morphologies
and structures of the α-Fe2O3 nanocrystals [15, 29–34]. In
addition, under hydrothermal conditions, many α-Fe2O3
nanomaterials with different structures can also be selectively
Fig. 1 SEM images of the flower-like (a) α-FeF3·3H2O and (b) α-Fe2O3.
And SEM images of the cubic (c) β-FeF3·3H2O and (d) α-Fe2O3.
(Reproduced with permission from [27]. Copyright 2012 Royal Society
of Chemistry)
1654
synthesized by adjusting solvents [35–37] and controlling
hydrolysis rate [38], with or without surfactants or templates
[39–42]. Zhang et al. [38] synthesized hierarchically porous
α-Fe2O3 microspheres with a diameter of 1.75 μm assembled
by well-crystalline nanoparticles of about 50 nm by using
lysine as a hydrolysis-controlling agent, and they further
discussed the formation mechanism of α-Fe2O3 microspheres.
During the hydrothermal process, with the hydrolysis of ly-
sine, more and more OH− come into being and the pH value of
the solution increases greatly, which results in the forma-
tion of Fe(OH)3 phase, and finally, Fe2O3 forms through
dehydration of the hydroxides. Through comparison with
other amino acids, it can be concluded that the property of the
hydrolysis-controlling agent, controlling the variation of the
pH value of the solution, plays an important role in the
formation of unique hierarchical microspheres. Zhu et al.
[42] reported a template-free preparation of hollow α-Fe2O3
with a unique cocoon-like structure by a one-pot hydrothermal
method without any surfactant in a short reaction time of 3 h
only, and oxalate ions released from decomposition of dimeth-
yl oxalate played an important role in guiding the formation of
the unique hollow cocoon-like nanostructures, and the forma-
tion mechanism is illustrated in Fig. 2. With the linear guiding
property of oxalate ions toward cations, nanorods are formed,
which tend to aggregate to form nanococoons to minimize
surface energy of the system. Subsequently, due to possessing
higher surface energy caused by aggregation of smaller pri-
mary units, the inner core area is easily dissolved compared
with the external shells. The low-density cores are dissolved
and are redistributed to surfaces to minimize energy and form
the hollow structures. The hollow interior and porous shell
structure of the nanococoon with building subunit aggregation
Fig. 2 a Illustration of the
proposed formation mechanism
for hollow nanococoons; b ex situ
electron microscope images for
samples prepared at 15, 30, and
75 min and 3 h of reaction, and
the reaction time is labeled in each
corresponding FESEM (top) and
TEM (bottom) images
(reproduced with permission from
[42]. Copyright 2014 American
Chemical Society)
Ionics (2014) 20:1651–1663
can effectively accommodate the volume change during the
charge/discharge process and provide shorter distance for the
transportation of Li+ ions.
Sol-gel synthesis
The synthesis of hematite by sol-gel synthesis can offer many
advantages such as tailor-made materials due to good process
control, homogeneous multicomponent systems due to
mixing in liquid medium, low temperature for material pro-
cessing, etc. The disadvantage of this method is that the sol
consists of a large amount of organic solvent that leads to high
synthetic cost. Woo et al. [43] reported the synthesis of nano-
scale α-Fe2O3 material by a sol-gel-mediated reaction inside
reverse micelles, which by employing reverse micelle as
reactor effectively overcomes the formation of a single piece
of gel and synthesized monodisperse α-Fe2O3 nanorods with
uniform size.
Template synthesis method
As an assisted method, template synthesis can be employed by
various synthetic techniques, such as sol-gel synthesis, ther-
mal decomposition, solvothermal preparation, and so on.
Generally, the employed materials in template synthesis can
be simply classified into hard templates and soft templates
[44]. Hard templates normally possess well-confined void,
which is in the form of channels, pores, or connected hollow
space. Soft templates usually consist of organic surfactants
and polymers, which are relatively flexible in shape. By using
template, many nanoparticles of α-Fe2O3 with a unique
hollow structure can be fabricated [45–49]; however, the
Ionics (2014) 20:1651–1663 1655

template-assisted synthesis suffers from many disadvantages

such as low yield, high cost, and contamination from removal
of the template. Xu et al. [50] successfully synthesized
multishelled α-Fe2O3 hollow microspheres composed of hi-
erarchical assemblies of 20–30 nm nanocrystals by using
carbonaceous microsphere sacrificial templates, which were
based on the calcination of Fe3+ ion-infused carbonaceous
microsphere templates and through adjusting the concentra-
tion of Fe3+ ion to tailor the number of multishells, the shell
thickness, and porosity of the hollow microspheres; the TEM
images are shown in Fig. 3. Among these as-prepared sam- Fig. 4 Synthesis of branched core-shell Fe 2 O 3 @C nanotubes
ples, thin, porous, hollow microspheres with three concentric (reproduced with permission from [51]. Copyright 2014 Royal Society
of Chemistry)
multishells showed the best cycling performance, demonstrat-
ing excellent stability and a reversible capacity of up to
1,702 mA h/g at a current density of 50 mA/g, and the specific capacity of 1,012 mA h/g after 300 cycles at a current
additional multishells increased the specific surface area, the density of 1 A/g, even after 1,000 cycles at a current density of
number of active reaction sites, and the volumetric capacity of 4 A/g, and the specific capacity could be still kept at
the hollow spheres. Moreover, the thin shells were more 482 mA h/g.
robust and maintained their morphology after 50 cycles, while
the thick shell hollow microspheres cracked and disintegrated Molten salt synthesis
causing loss of electrochemical contact and significant de-
crease in capacity, indicating that shells should be thin enough Molten salt synthesis is a relatively new method for nanopar-
to buffer the volume changes associated with lithium cycling, ticle preparation, by which synthesis temperature and time can
yet barely thick enough to maintain the structural integrity of be greatly decreased owing to the quicker diffusion of reac-
the electrode. Gu et al. [51] developed a novel design of tants in the liquid media. Moreover, since the molten salt
hierarchical carbon-coated α-Fe2O3 nanotubes by hydrother- always existed between the resultant powders during the
mal reaction between branched MnO2/Fe2O3 nanorods and reaction, the aggregate phenomena of resultant products can
glucose at 190 °C for 5 h, which is illustrated in Fig. 4. The be effectively reduced as well. Hassan et al. [16] prepared
resulting nanotubes realize all these controls in one particle in nanosized α-Fe2O3 with crystal size in the range of 20–40 nm
terms of their nanoscale size, 1D shape, hollow structure, by a molten salt method using the mixtures of LiNO3 and
hierarchical surface, and carbon coating and deliver a high LiOH·H2O for the molten salt at 300 °C for 3 h, which

Fig. 3 TEM images of α-Fe2O3

multishelled hollow microspheres
produced at 500 °C: a thin single
shell, b thin double shell, c thin
triple shell, d thick single shell, e
thick double shell, and f thick
triple shell (reproduced with
permission from [50]. Copyright
2013 Royal Society of
Chemistry)
1656
achieves excellent cycling performance and rate capability.
The authors also found that the capacity of the α-Fe2O3
electrode showed two major trends. For the first 100 cycles,
the capacity showed a decreasing trend, while for the range
between 101 and 600 cycles, the capacity trend was increasing
and the cubic structure of α-Fe2O3 has been modified to a
needle-like structure, resulting in even after the sample has
experienced long cycling (more than 600 cycles), the capacity
of the electrode still reaching 655, 419, 320, and 239 mA h/g
at 10, 20, 30, and 40 C, respectively. This phenomenon is
attributed to the effects of electrochemical milling, the chang-
ing of the morphology of a material, and the reduction of the
particle size.
Microwave heating method
Microwave heating method has many advantages to synthe-
size high-purity nanoparticles with narrow particle size. The
greatest advantage of microwave irradiation is that it can be
uniformly and rapidly absorbed by reactants through a reac-
tion container and thus leads to a more homogeneous nucle-
ation and a shorter crystallization time than conventional
heating method. Kijima et al. [52] synthesized ultrafine
α-Fe2O3 nanoparticles with an average diameter of less
than 10 nm and a large surface area of 217 m2/g by
microwave heating within 120 s, which can provide a
better accommodation for the structural strains and shorten
the Li+ diffusion path, thus leading to improved electrochem-
ical performance.
Electrospinning technique
Electrospinning is probably by far the most effective method
to fabricate 1D continuous nanofibers with diameters ranging
from tens of nanometers to several micrometers by applying a
high voltage on a polymer solution or melt. In recent years,
electrospinning has been explored as an advantageous and
easy method to synthesize electrode materials for lithium-ion
batteries. Chaudhari and Srinivasan [53] synthesized an inter-
connected 1D hollow structure of α-Fe2O3 nanofibers by
electrospinning technique using ferric acetylacetonate
(Fe(acac)3) and polyvinylpyrrolidone (PVP) as precursor and
further calcination at 500 °C for 4 h. The formation mecha-
nism suggested that during the electrospinning process, the
composite fibers of Fe(acac)3-PVP consisted of a rigid outer
shell with a fluid-like interior core with a large amount of
solvent anions forming a gel layer on the surface of the fiber,
which has an important function to maintain the fiber texture
during heat treatment. During calcination, evaporation of or-
ganic compounds (PVP and solvents) occurs, and diffusion of
Fe(acac)3 particles to the inner surface of the outer shell results
in solid fibers. The pressure inside the fibers increases when
the rate of gas evolution is larger than that of gas diffusion
Ionics (2014) 20:1651–1663
through the fibers’ surface, resulting in crystallized hollow
fibers. The as-prepared α-Fe2O3 hollow nanofibers exhibit
excellent cycle stability and rate capability, and at 1, 2, and
10 C, the initial capacity of the sample is 1,276, 948, and
538 mA h/g, respectively. Cherian et al. [54] reported the
synthesis of macroporous α-Fe2O3 nanorods with an average
diameter of 150 nm and a length of 1 μm, which are composed
of interconnected nanosized particles. Compared with the
microdimension of mesoporous particles, these interconnect-
ed nanofiber electrodes rendered a good electrical conduction
path within the particle and, thus, markedly reduced carbon
content generally requiring a high content to achieve an elec-
trochemical performance.
Electrostatic spray pyrolysis/deposition
The electrostatic spray technique is a novel technology by
which a liquid drop in a high voltage electrical field can be
divided into droplets with a much smaller diameter than
conventional spray drying. On this basis, some convenient
approaches have been developed to synthesize nanostructured
electrodes such as electrostatic spray pyrolysis and deposition
methods. García-Tamayo et al. [55] prepared α-Fe2O3 nano-
structured composite electrode in one step via the electrostatic
spray pyrolysis method, which are directly formed by
precursor solutions containing iron salts dissolved in N-
methylpyrrolidone (NMP) together with polyvinylidene
fluoride (PVDF) as binder. The nanocomposite electrode
was able to cycle and exhibit a good eletrochemical perfor-
mance without any conductive additive, despite the poor
electrical conductivity of iron oxide and the insulating prop-
erties of PVDF. However, the absence of carbon black partly
limits the electron percolation between the nanoparticles; thus,
at a certain point, with increasing electrode thickness, a con-
ductive additive is needed to sustain the applied current den-
sity without losing capacity, and the thickness of the thin layer
should be controlled in the range of micrometers. Wang et al.
[56] reported the preparation of porous carbon-free α-Fe2O3
thin film by electrostatic spray deposition. Compared with
other α-Fe2O3 thin film electrodes, the porous thin films
exhibit relatively better electrochemical property in a wide
temperature range from 5 to 55 °C, which could be attributed
to the large contact area between Fe2O3 particles and electro-
lyte and the much reduced diffusion distance of Li+.
Based on the above discussion, a comparison of different
synthesis methods has been compiled as shown in Table 1. In
terms of size and morphology control of hematite nanoparti-
cles, precipitation-calcination and hydrothermal/solvothermal
synthesis seem to be the optimal methods and are more
suitable for mass production. As an emerging technique,
electrospinning became a superior alternative to obtain 1D
hematite nanofibers. For fabricating hematite nanoparticles
with a hollow structure, the template method was often
Ionics (2014) 20:1651–1663 1657

Table 1 Comparison of characteristics of different synthesis methods

Synthesis method Morphology Size Advantages Disadvantages Reference

no.

Hydrolysis method Irregular 5 nm The synthetic route is simple Uncontrolled morphology and [23]
and the size can be controlled high energy consumption
by adjusting the
concentration of salt and the
hydrolysis rate
Direct thermal Irregular 200–300 nm Binder-free and carbon-free α- Uncontrolled morphology and [24]
oxidation Fe2O3 electrode can be size and inhomogeneous
directly fabricated within thickness of electrode
several minutes
Precipitation- Regular and Tens of nanometers Controlled morphology and size High requirement of precursor [27, 28]
calcination controlled morphology and size
Hydrothermal/ Regular and Tens of nanometers The nanoparticles have better High requirement of [15, 29–42]
solvothermal controlled dispersion, and different equipment and safety
synthesis structures can be selectively
synthesized by adjusting
preparation conditions
Sol-gel synthesis Nanorods Diameter is less than The reaction can be conducted High synthetic cost and long [43]
10 nm at room temperature and the reaction time
particles have a narrow
distribution
Template synthesis Hollow structure Shell thickness is from As an assisted method, it can be Complicated synthetic route [45–51]
method several to tens of employed by various and high synthetic cost
nanometers methods to produce hollow
nanoparticles with thin shell
or even multishells
Molten salt synthesis Irregular 20–40 nm Synthesis temperature and time High synthetic cost [16]
can be greatly decreased, as
well as aggregate phenomena
of resultant products
Microwave heating Irregular Diameter is less than Shortest crystallization time and High requirement of [52]
method 10 nm homogeneous nucleation equipment and safety
Electrospinning Nanofibers or Diameter is from tens to The most effective and easy High requirement of [53, 54]
technique nanorods hundreds of method to fabricate 1D equipment and synthetic
nanometers continuous nanofibers cost
Electrostatic spray Irregular Thickness of thin films is Homogeneously dispersed High requirement of [55, 56]
pyrolysis/ from several to tens of hematite thin film electrode equipment and synthetic
deposition micrometers can directly form in one step cost

employed, but this method presents complicated synthetic
routes including coating of Fe precursors and subsequent
conversion of the precursor layer into hematite as well as core
template removal. Hence, developing template-free ap-
proaches to obtain hollow hematite nanoparticles has attracted
more attention, such as the self-assembly approach [41]. From
the results, it is well understood that although these methods
often furnish particles with narrow size distributions, they tend
to require re-optimization for each desired particle size, shape,
or structure.
Surface modification of nanosized α-Fe2O3
Surface modification of nanosized hematite using high elec-
tron conductivity materials such as carbon-based materials,
organic compounds, etc. has been proven to be helpful in
enhancing the cyclability of α-Fe2O3 by improving the con-
ductivity and further inhibiting volume expansion and de-
creasing the surface area to retard the side reactions between
the electrode and the electrolyte by coating.
Surface modification by carbon materials
Synthesis of active material/C composites has been regarded
as an effective and popular approach to improve the electro-
chemical performance of various electrode in Li-ion batteries,
and like other electrode materials, compositing with carbon is
a feasible and promising way to enhance both cycling and rate
performances of hematite. Therefore, many researches on α-
Fe2O3/C composites have been reported in recent years in-
cluding carbon coating, loading Fe2O3 on various carbon
matrices, and so on.
1658
The carbon coating layer on the surface of α-Fe2O3 nano-
particles can play an important role in improving the electro-
chemical performance of α-Fe2O3 nanoparticles such as in-
creasing the electronic conductivity and inhibiting the volume
expansion; more importantly, it can act as barriers that effec-
tively suppress the aggregation of the inner nanocrystals and
stabilize SEI films [57]. Cheng et al. [58] reported the synthe-
sis of pseudocubic α-Fe2O3/C nanocomposites with sizes of
30–35 nm via in situ carbonization of oleic acid under Ar
atmosphere, by which the carbon layer with a thickness of
1–2 nm tightly wrapped α-Fe2O3 nanocrystals. Compared
with bare α-Fe2O3 nanoparticles, α-Fe2O3/C composites ex-
hibited better dispersity and less initial discharge capacities
(α-Fe2O3/C and bare α-Fe2O3 electrode reached 1,227 and
1,300 mA h/g, respectively) that are related to the decompo-
sition of electrolyte to form SEI films. α-Fe2O3/C composite
electrode displayed a reversible capacity of 688 mA h/g after
50 cycles at 0.2 C rate and 370 mA h/g after 20 cycles at 2 C,
whereas bare α-Fe2O3 electrode had only 521 and 55 mA h/g
capacity, indicating that carbon coating is a good way to
improve the cycle stability and capacity retention.
Recent studies [59–61] demonstrated that the electron
transport to and within the particles could be the main factor
limiting the rate of iron oxide electrodes, and the electrochem-
ical reaction was proportional to the total conductivity includ-
ing ionic and electronic conductivities. Therefore, another
effective method has been proposed, namely loading α-
Fe2O3 nanoparticles on the surface of a carbon matrix
possessing high electronic conductivity, such as acetylene
black (AB) [62, 63], vapor-grown carbon fibers (VGCFs) [7,
64], carbon nanofibers (CNFs) [65–68], carbon nanotubes
(CNTs) [69–71], activated carbon [72], graphite [73],
graphene [74–85], etc. Compared to other carbon matrices,
graphene sheets can more effectively improve the electro-
chemical performance of these active nanomaterials because
the ultrathin flexible graphene layers not only can provide a
highly conductive matrix for nanoparticles but also can effec-
tively prevent the aggregation and volume expansion-
contraction of nanoparticles during the charging/discharging
processes [86–88]. Zou et al. [89] reported the novel synthesis
of graphene nanosheet (GNS)-supported Fe2O3 nanorice by a
microwave-assisted hydrothermal technique, as shown in
Fig. 5. The Fe2O3-GNS rice-on-sheet composite showed a
high reversible capacity of 1,184 mA h/g upon cycling and
excellent rate capabilities at large currents. At a large current
of 1,000 mA/g, the Fe2O3-GNS rice-on-sheet composite ex-
hibited an initial reversible capacity of 825 mA h/g, and a high
capacity of 582 mA h/g could be retained after 100 cycles,
which could be ascribed to the synergetic effect between two
components of the Fe2O3-GNS composite. The electrical con-
ductivity and mechanical stability of Fe2O3 nanorice were
improved by GNS, and GNSs were separated and stabilized
by the Fe2O3 nanorice decoration; therefore, the intriguing
Ionics (2014) 20:1651–1663
features of a few layers of GNS could be preserved during
long-time cycling.
It is well known that nitrogen-doped graphene can keep
good mechanical properties as pristine graphene and provide
extra lone pair electrons resulting in an improved electrical
conductivity. Moreover, graphene containing nitrogen atoms
can induce many surface defects, and as a result, the Li+ can be
much easier to get insertion/extraction. Therefore, Fe2O3/ni-
trogen-doped graphene composite is more suitable for revers-
ible lithium-ion storage compared with Fe2O3/graphene [90,
91]. Wang et al. [92] successfully synthesized α-Fe2O3 hex-
agonal nanoplatelets sandwiched between graphene layers
(HP-Fe-G). Compared with the α-Fe2O3 nanoparticles loaded
with graphene composites (G-Fe2O3), HP-Fe-G exhibits an
improved electrochemical performance (887 mA h/g at 1 C,
only 135 mA h/g at 1 C for G-Fe2O3) due to its unique
architecture: thin nanoplatelets, large enough sandwiched
spaces to buffer the volume expansion, and N-doped
graphene.
Similar to graphene, CNTs with unique tubular structure
are also usually employed as ideal substrates to incorporate
nanostructured active materials. Filling α-Fe2O3 nanoparticles
into CNTs can significantly improve the specific capacity and
cyclic stability by its high electrical conductivity and the
inhibitory effect of large volume expansion [93–95]. Yu
et al. [96] reported the synthesis of α-Fe2O3-filled CNTs
hybrid material, and the fabrication process is shown in
Fig. 6: an anodic aluminum oxide (AAO) template with a
channel size of 50 nm was used as a hard template, and
through chemical vapor deposition, the carbon coating layer
was uniformly distributed onto the inner surface of the
nanochannels. By immersing the C@AAO films into a solu-
tion of iron nitrate in ethanol and heat treatment at 400 °C in
Ar atmosphere, Fe2O3 nanoparticles derived from the
decomposition of Fe(NO 3 ) 3 were loaded inside the
carbon-coated channels of the AAO film. The AAO
template was further dissolved by NaOH aqueous solution,
and Fe2O3 nanoparticle-filled CNTs were obtained. The
Fe2O3-filled CNTs, consisting of 51.8 wt% Fe2O3 nanoparti-
cles, exhibited an improved electrochemical performance in
terms of high reversible capacity and excellent cycling stabil-
ity (811.4 mA h/g after 100 cycles at 35 mA/g), compared to
that of pure Fe2O3 (186.9 mA h/g after 80 cycles), which was
ascribed to the nanoconfinement effect and excellent electri-
cally conductive network from CNTs.
Surface modification by organic compounds
As one of the typical conducting polymers, polypyrrole (Ppy)
possesses remarkable conductivity, high electrical charge re-
serving ability, and good stability in air or water, which has
been used to coat electrode materials with low conductivity
[97–99]. Liu et al. [100] fabricated 3D, self-supported α-
Ionics (2014) 20:1651–1663
Fig. 5 Schematic illustration of the growth process of Fe2O3-GNS particle-on-sheet and rice-on-sheet composites (reproduced with permission from
[89]. Copyright 2011 American Chemical Society)
Fe 2O 3/Ppy composite electrode by a two-step process
consisting of direct heating of iron foil in air and subsequent
coating of conducting polymer Ppy on the α-Fe 2 O 3
nanoflakes. The α-Fe2O3 nanoflakes with thickness around
10–30 nm are separated by distance in the range of 60–300 nm
on the plane of the Fe foil, and the thin Ppy film is uniformly
deposited onto the surface forming a conformal coating
around each nanoflake without any coalescence between
them. The unique nanostructure can afford a highly conduc-
tive pathway for electron, a short ion diffusion length for ions,
a fast mass transport channel for electrolyte, and sufficient
void space among neighboring nanoflakes for accommodat-
ing large volume variations. The α-Fe2O3/Ppy composite
electrode can achieve a relatively high specific capacity of
0.42 mA h/cm2 at 0.1 mA/cm2 even after 100 cycles with a
nearly 100 % Coulombic efficiency, while the capacity of the
bare α-Fe2O3 nanoflakes after 100 cycles is 0.26 mA h/cm2,
which is 62 % that of α-Fe2O3/Ppy.
Fig. 6 A schematic presentation showing the preparation process of the
Fe2O3 nanoparticle-filled CNTs (reproduced with permission from [96].
Copyright 2012 Royal Society of Chemistry)
1659
Surface modification by “zero-strain”-type materials
A major drawback of α-Fe2O3 material is large volume ex-
pansion of the electrode caused by the intercalation/extraction
of Li, resulting in rapid capacity fading and poor cyclic
stability. In order to overcome this obstacle, core-shell-type
nanoheterostructure composites have been designed and syn-
thesized by coating the nanolayer of “zero-strain”-type mate-
rials on the surface of α-Fe2O3 nanoparticles. Due to the
negligible volume change during the charge/discharge pro-
cess, “the shell” can supply durable mechanical support to
tolerate the volume change of “the core” and prevent its
collapse and dissolution into the electrolyte and, thus, improve
the electrochemical performance.
Zhang et al. [101] synthesized mesoporous core-shell
nanocomposites with porous α-Fe2O3 nanorods as the core
and porous TiO2 as the shell by calcination treatment of
FeOOH@TiO2 core-shell nanorods. Due to the high capacity
of Fe2O3 core and durable outer shell of TiO2, as well as
the specific mesoporous nanostructures, the products
deliver an excellent electrochemical performance toward
lithium storage, including stable reversible capacity as high
as ∼860 mA h/g at high current density of 1 A/g, excellent
cyclic stability with ultralong cycling life over 1,000 cycles,
and outstanding rate capability. Chen et al. [102] further re-
ported a novel carbon-free core-shell-type α-Fe2O3/Li4Ti5O12
composite by fabricating lithium titanate coating on hematite
ellipsoids. Compared with naked α-Fe2O3 ellipsoids, the α-
Fe2O3/Li4Ti5O12 composites exhibit lower initial capacity loss,
higher reversible capacity, and better cycling performance for
lithium storage. The coating layer of Li4Ti5O12 effectively
avoided the formation of the SEI layer that reduced initial
capacity loss and improved the cyclic stability of hematite
ellipsoids by inhibiting the volume expansion.
1660 Ionics (2014) 20:1651–1663

Application of hematite as coating material Synthesizing composites with other oxides

Modifying conventional anode material Zhou et al. [106] reported the synthesis of SiO/Fe2O3 com-
posite (5 wt% Fe2O3) by mechanical milling, which shows
Spinel Li4Ti5O12 has been regarded as one of the promising considerably better cyclability than that of SiO and milled
alternative anode materials to carbon for many years; howev- SiO, with 71 % charge capacity retention (1,335 mA h/g) with
er, its intrinsic low electronic conductivity (10−9 S/cm) seri- respect to the first charge capacity after 50 cycles. Luo et al.
ously prevents Li4Ti5O12 to be commercialized. To improve [107] fabricated TiO2/Fe2O3 core-shell arrays on carbon tiles
its electronic conductivity, several effective approaches have (CTs). The as-prepared sample can exhibit 497 and 422 mA h/g
been proposed, including modifying the surface by coating for the first discharge and charge capacities at a current density
conductive materials. Generally, the voltage range of of 120 mA/g, respectively, and after 150 cycles, it can show
Li4Ti5O12 electrode is between 2.5 and 1.0 V, and in this good capacity retention with 480 mA h/g, as well as high-rate
cutoff voltage range, the reaction product of Fe2O3 and lithi- capability, which is higher than the sum of TiO2/CNTs and
um is LixFe2O3 (0<×<2) that possesses a much higher CNTs, indicating a synergistic effect between the constituents
conductivity than Li2O and hematite [14], thus leading of the composite structure on electrochemical performance.
to a good cycling stability. Compared with conventional Zeng et al. [108] reported the large-scale synthesis of a
coating material, such as carbon, Fe2O3 has a higher SnO2/α-Fe2O3 composite nanotube array on a stainless steel
density and capacity, which further increases the specific substrate. The array electrode shows a large areal capacity,
volume capacity of Li4Ti5O12 electrode. Wang et al.
[103] reported the fabrication of spinel Li4Ti5O12 coated
by hematite thin layer less than 15 nm via a facile
hydrolysis method combined with further heat treatment.
At 2 C rate, the Fe2O3-modified Li4Ti5O12 anode mate-
rial delivered a reversible capacity of 135.1 mA h/g after
300 cycles and maintained 93 % of its initial capacity, whereas
the corresponding values for the pristine lithium titanium
oxide (LTO) are 89.6 mA h/g and 9.2 %, respectively. This
superior electrochemical performance is mainly attributed to
the better conductivity of LTO/hematite electrode, thus reduc-
ing the polarization of LTO.

Modifying electrode materials based on conversion reactions

Zhang et al. [104] synthesized a novel architecture of a

core-shell-structured FeF3/Fe2O3 composite with an in
situ Fe2O3 coating layer by a simple heat treatment
process utilizing FeF3 as precursor. By comparing the
electrochemical performance of the pristine FeF3 and the
FeF3/Fe2O3 composites, it was found that the in situ Fe2O3
coating, even with small amounts of Fe2O3 (0.6–5.2 wt%),
had a beneficial impact on electrochemical performance due
to the high electrochemical activity of Fe2O3 coating layer in
the 2.0–1.2 V region.
Xiong et al. [105] reported a Co3O4 nanowire array mate-
rial coated by Fe2O3 nanoparticles (the mass ratio of Co3O4
and Fe2O3 is around 3:4) via the aid of the hydrothermal
synthesis and sacrificial hydrolysis method. The obtained 1D
integrated electrode combines the merits of Co3O4 and Fe2O3
and exhibits high capacity and good cycle stability Fig. 7 a Voltage vs. specific capacity of α-Fe2O3 electrode in a lithium
cell. EC:DMC, LiPF6 electrolyte. b Comparison between cycle life of α-
(1,005.1 mA h/g after 50 cycles at a current density of Fe2O3 electrode in a lithium cell under standard cycling conditions and
200 mA/g) due to the elegant synergistic effect of two elec- under a limited capacity regime (reproduced with permission from [109].
trochemically active materials. Copyright 2011 Elsevier Ltd)
Ionics (2014) 20:1651–1663
good rate capability, and high Coulombic efficiency, which is
much better than many of the previously reported thin film
and 3D nanostructured anodes. The reasons could be attribut-
ed to a synergistic effect between SnO2 and Fe2O3 as well as
the porous and ordered nanotubes that provide increased
electrochemical reaction kinetics.
Performance of lithium-ion batteries using hematite
as anode
As mentioned above, many effective approaches have been
proposed to improve the electrochemical performance of he-
matite, but their main drawbacks such as poor reversibility and
capacity retention still severely limited the practical applica-
tion of α-Fe2O3 as anode material in lithium-ion battery.
However, considering its much higher theoretical capacity
(1,007 mA h/g) than that of cathode materials (e.g.,
170 mA h/g for LiFePO4), it is possible to obtain an extensive
electrode life by cycling under controlled capacity conditions.
Hassoun et al. [109] reported a novel lithium-ion battery
formed by coupling α-Fe2O3 anode with a LiFePO4 cathode
that was cycled for several hundred times by limiting the
anode capacity to a value matching that of the cathode. They
found that under a 300 mA h/g capacity limit, the hematite
electrode can exhibit a prolonged and more stable cycle life
than that of the same electrode when cycled in an unrestricted
mode as shown in Fig. 7, and thus, they further evaluated the
performance of a full lithium-ion battery using the limited
capacity α-Fe2O3 anode combined with a LiFePO4 cathode.
The working voltage of the “lithium-ion” battery is at about
2 V, and the practical energy density of the system has been
estimated to be in the order of 100 Wh/kg which is of the same
order of magnitude as that of commercial cells in the market. It
is worth noting that the Fe2O3 anode, even if with a lower
gravimetric capacity regime, still maintains a remarkably
higher volumetric capacity compared to the standard graphite
(i.e., 1,700 A h/l vs. 760 A h/l).
Conclusion
In this review, we have summarized the recent progress in
research on nanoscale α-Fe2O3 as anode materials for Li-ion
batteries. As discussed above, several elegant strategies
aiming to boost the electrochemical performance and promote
the practical application of α-Fe2O3 have been extensively
developed, including fabrication of nanoparticles with differ-
ent morphologies and sizes by various methods, modification
by various coating materials, limiting discharge/charge volt-
age range to improve cyclic stability, etc. Nevertheless, each
strategy applied alone commonly results in limited enhance-
ment in electrochemical performance. Therefore, it is more
1661
compelling to integrate multiple strategies, thus maximizing
their electrochemical advantages to meet the present energy
demands.
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