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Iron-Based Supercapacitor Electrodes: Advances and

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Challenges
Yinxiang Zeng, Minghao Yu, Yue Meng, Pingping Fang, Xihong Lu,* and Yexiang Tong

higher power density than batteries/fuel

Supercapacitors (SCs) have great promise as the state-of-the-art power source cells, which can play a role in bridging the
in portable electronics and hybrid vehicles. The performance of SCs is largely power and energy gap between batteries/
determined by the properties of the electrode material, and numerous efforts fuel cells and traditional capacitors. In this
regard, SCs hold great promises as new
have been devoted to the explorations of novel electrode materials. Recently,
and efficient energy storage device.[12–15]
iron-based materials, including Fe2O3, Fe3O4, FeOOH, FeOx, CoFe2O4, and Figure 1b–d show several examples of
MnFe2O4, have received considerable attention as very promising electrode designed flexible SC devices, which hold
materials for SCs due to their high theoretical specific capacitances, natural great potential applications for portable
abundance, low cost, and non-toxicity. However, most of these Fe-based SC electronic devices like wearable electronic
products and flexible displays.
electrodes suffer from poor conductivity and/or electrochemical instability,
According to charge storage mecha-
which seriously impede their implementation as high-performance elec- nisms, SCs can be divided into two classes:
trodes for SCs. To settle these issues, substantial efforts have been made in electrical double-layer capacitors (EDLCs)
improving their conductivity and cycling stability, and great processes have that are based on charge separation and
been achieved. Here, recent research advances in the rational design and accumulation at the electrode/electrolyte
synthesis of diverse Fe-based nanostructured electrodes and their capacitive interface, and pseudocapacitors that origi-
nate from the fast redox or intercalation
performance for SCs are presented. Besides, challenges and prospects of Fe-
reaction of the electrode material.[14,16–18]
based materials as advanced negative electrodes for SCs are also discussed. Pseudocapacitors with superior specific
capacitance and energy density (usually
10–100 times higher than that of EDLCs)
1. Introduction show great interest for practical applications.[14,18–21] Owing
to their multiple valence states of the metal ions and unique
With the rapid development of global economy, diminishing crystal structure that enables fast faradaic redox/intercalation
supply of fossil fuels and increasing environmental pollu- reaction, transition metal oxides and hydroxides have been
tion, sustainable and renewable energy resources are being widely explored as pseudocapacitors electrodes.[22–26] In recent
intensively pursued. Consequently, there is an urgent demand years, advanced achievements have been made in the tran-
for efficient and renewable energy resources as well as effi- sition metal oxides/hydroxides electrode materials, and the
cient, low-cost and environmentally friendly energy storage common operating potential windows of some typical metal
devices.[1–6] Among various energy storage devices, Superca- oxides/hydroxides are summarized in Figure 2.[24,27–39] Of all
pacitors (SCs), also call electrochemical capacitors, are finding these metal oxides/hydroxides, iron based oxides/hydroxides
increasing applications in hybrid electric vehicles, roll-up dis- (e.g., single oxides: Fe2O3, Fe3O4, FeOOH, etc. and binary
plays, memory back-up systems and industrial power and metal oxides: MFe2O4 (M = Ni, Co, Sn, Mn, Cu), BiFeO3, etc.)
energy management in recent years.[7–11] Figure 1a shows the are receiving tremendous interests as desired electrode mate-
Ragone plot of various energy storage devices. Significantly, SCs rials for SCs because of their significant merits: (1) iron own
possess higher energy density than traditional capacitor and multiple valence states (Fe0, Fe2+, Fe3+, etc.) and rich redox
chemistry (Fe0/Fe2+, Fe0/Fe3+, Fe2+/Fe3+, etc.), enabling them
high specific capacitance.[27,40,41] (2) most of the transition
metal oxides/hydroxides are employed as positive electrodes
Y. X. Zeng, M. H. Yu, Y. Meng, Prof. P. P. Fang, while iron oxides/hydroxides have stable and wide working
Prof. X. H. Lu, Prof. Y. Tong
MOE of the Key Laboratory of Bioinorganic and
window in negative potential, making them very promising
Synthetic Chemistry as high-perfomance negative electrodes for asymetric superca-
KLGHEI of Environment and Energy Chemistry pacitors (ASCs).[42–44] (3) iron oxides/hydroxides are less toxic
School of Chemistry and Chemical Engineering and more environmental friendly compared to other transition
Sun Yat-Sen University metal oxides/hydroxides.[45–47] (4) iron oxides/hydroxides are
Guangzhou 510275, P. R. China
E-mail: luxh6@mail.sysu.edu.cn earth-abundant (iron is the richest transition metal element in
the earth’s crust) and inexpensive (e.g., less than $1 per kg for
DOI: 10.1002/aenm.201601053 Fe2O3), which are suitable for commerical applications.[34,48,49]

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Due to the various valence states of Fe and crystal structures,

REVIEW

there are abundant stable phases for iron oxides/hydroxides, Yinxiang Zeng received her
such like α-Fe2O3, β-Fe2O3, γ-Fe2O3, Fe3O4, α-FeOOH, B.S. degree in materials
β-FeOOH, γ-FeOOH and δ-FeOOH.[40,50–52] For example, chemistry from Sun Yat-Sen
Figure 3 illustrates the crystal structure of three common Fe- University in 2015. She is
based materials (α-Fe2O3, Fe3O4 and α-FeOOH). These dif- currently a 1st year physical
ferent forms typically endow them distinctly different electronic chemistry master degree can-
and electrochemical properties, and also need specific syn- didate student at Sun Yat-sen
thesis conditions. For instance, α-Fe2O3 with corundum crystal University. Her research
structure exhibits more structure stability than β-Fe2O3 and focuses on the development
γ-Fe2O3, which enable it as preferable electrode choice for long- of nanostructured materials
life SCs.[52] Meanwhile, β-Fe2O3 and γ-Fe2O3 are considered as for application in supercapaci-
intermediary metastable phases in the evolution to α-Fe2O3.[50] tors and microbial fuel cells.
It was found that phase conversion to α-Fe2O3 is easy to occur
through thermal treatment at around 500 °C in air.[50,52,53] It is Xihong Lu received his BS
also conceivable that crystal forms play a crucial role in tuning degree (2008) and his PhD
the electrochemical performance of Fe-based electrodes. Inves- degree (2013) in Physical
tigation of the influence of crystal structure on electrochemical Chemistry from Sun Yat-Sen
performance is the foundation of rational design of advanced University, PR China. He is
Fe-based electrodes. now an associate professor
Considerable efforts have been paid to explore various ion- in the school of chemistry
based materials as SCs electrodes in recent years.[26,35,42,54–56] and chemical engineering at
The key challenge of current iron-based electrodes for SCs is Sun Yat-Sen University. His
their unsatisfied electrochemical and cycling performances as a research interests focus on
result of their poor electrical conductivity and structural stability the design and synthesis of
during the charge/discharge process. It is well known that the functionally nanostructured
morphology, composition, crystal phase and defect of iron based materials for applications in energy conversion and storage
materials have significant influence on their electrochemical devices such as supercapacitors, Li ion batteries, and
properties.[42,43,46,57] In this regard, some effective approaches microbial fuel cells.
including nanostructural design, componential regulation,
elemental doping, and phase/defect tailoring have been devel- Yexiang Tong received his BS
oped to compensate the aforementioned limitations of Fe based in General Chemistry in 1985,
materials.[42,43,45,49,58,59] Nanostructuring of Fe based materials MS in Physical Chemistry in
with desirable architecture such as nanorods (NRs),[42,60–62] 1988, and PhD in Organic
nanosheets (NSs),[40,45] nanotubes (NTs),[63,64] nanowires,[49,65] Chemistry in 1999 from Sun
nanoflowers[48] etc. is the most common strategy, which has Yat-Sen University. He is a
widely demonstrated to can dramatically increase the surface professor of Chemistry in
area as well as shorten the diffusion length for electron and ion the school of chemistry and
transport. On the other hand, incorporating iron-based mate- chemical engineering at Sun
rials with highly conductive materials (graphene,[27,55,56,58,66] Yat-Sen University. His cur-
carbon nanotube (CNT),[35,59] activated carbon,[67,68] PANI,[69,70] rent research focuses on the
PEDOT[43,71] etc.) to combine the merits and mitigate the short- electrochemical synthesis of
comings of both the components is also an efficient way to alloys, intermetallic compounds and metal oxide nano-
boost the conductivity and capacitive performance of iron-based materials, and investigation of their properties in energy
materials. Apart from the extrinsic modification approaches, conversion and storage.
some intrinsic modifications such as the introduction of oxygen
vacancies and foreign ion doping have also been proven to be
efficient approaches to remarkably boost the capacitance and
cyclic life of the Fe based materials.[42,43,51] 2. Fe2O3-Based Nanostructured Materials for SCs
In this article, we reviewed the recent achievements on the
design and synthesis of nanostructured Fe-based (e.g., Fe2O3, Among various Fe-based materials, Fe2O3, especially hema-
Fe3O4, FeOx, and FeOOH) materials and their composites for tite (α-Fe2O3), has received considerable concern as SCs
SCs. The relationships between morphology, component and electrode material owing to its superior environmental compat-
capacitive properties of these Fe-based electrodes are sum- ibility, abundant resource and high theoretical specific capaci-
marized. Moreover, the promising advantages of the Fe-based tance.[42,43,45,46,72,73] There are a variety of methods to synthesize
electrodes as negative electrode for ASCs are also highlighted. Fe2O3, such as sol-gel,[74,75] chemical vapor deposition,[76] elec-
Finally, we also discussed the challenges of the current Fe- trodeposition,[77] electrospun,[78–80] spray pyrolysis[81] and hydro-
based electrodes as high energy and high power negative elec- thermal method.[43,82] Currently, the specific capacitance of
trodes for SCs. Fe2O3 is still far below the theoretical value, resulting from its

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Figure 1. a) Ragone plot for different energy storage technologies. Optical photographs of b) the fabricated flexible asymmetric supercapacitors (ASC)
using Commercial pen ink as the active material. Reproduced with permission.[129] Copyright 2012, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
c) The flexible solid-state ASC based on PANI/MWCNT/PDMS film electrode. Reproduced with permission.[130] Copyright 2014, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim. d) The direct writing of a microdevice. Reproduced with permission.[17] Copyright 2013, Macmillan Publishers Limited.

poor electrical conductivity and insufficient ionic diffusion rate,
especially at high mass loading.[34,42,47,59]
To address these issues, many researchers have focused on
the preparation of Fe2O3 nanostructures with high surface area
and shorted diffusion pathway for irons and electrons.[45,48,60,83]
A variety of nanostructured Fe2O3 electrodes, including nano-
partilces,[72] nanobelts,[84] nanoflowers,[48] NS,[45] NRs,[60,83]
NTs[63,64] and nanowires[49,65] have been explored and showed
substantially enhanced capacitive performance. For example,
Zhu et al. reported hematite nanoparticles with narrow size
distribution, which yielded a high capacitance of 340.5 Fg−1 at
1 A g−1.[72] Highly ordered Fe2O3 NTs prepared by a sacrificial
template-accelerated hydrolysis treatment presented a specific
capacitance of 180.4 mF cm−2 (257.8 F g−1) at the current den-
sity of 1 A g−1. Additionally, a solid-state ASCs based on these
Fe2O3 NTs achieved a high energy density of 0.55 mW h cm−3
and good rate capability.[44]
In comparison to zero-dimensional (0D) and one-dimen-
sional (1D) nanostructures, two-dimensional (2D) nano-
structures such as nanosheets (NSs) are more beneficial for
increasing the contact area with electrolyte and shortening ion
Figure 2. The working potential windows of various electrode materials
in aqueous electrolyte. The acid-base property of electrolyte is marked
inside the braces, a for acid, b for basic and n for neutral.[24,27–39]
diffusion paths, and hence usually exhibiting superior capaci-
tive performance.[40,45,46] Recently, ultrathin α-Fe2O3 nanoflakes
(NFs) with enhanced electrochemical properties have been
reported by Li and his co-workers.[46] These ultrathin α-Fe2O3
NFs were fabricated by an electrochemically induced mor-
phological transformation method, as illustrated in Figure 4a.
Highly crystalline α-Fe2O3 NFs with an average thickness of
around 10 nm were successfully obtained after reducing NRs
at a negative potential of −1.2 V vs Ag/AgCl for 100 s, and
then annealed at 550 °C in vacuum. Benefiting from the
increased surface area and reduced charge transfer resistance
(from 23.16 Ω to 6.13 Ω, Figure 4b), the α-Fe2O3 NF electrode
delivered a remarkable areal capacitance of 145.9 mF cm−2
(100.6 F g−1) at a current density of 1 mA cm−2 (Figure 4c),
which was approximately an order of magnitude higher than
that of α-Fe2O3 NR electrode. Meanwhile, the α-Fe2O3 NF elec-
trode also exhibited a superior rate capability that could retain
as high as 81.1 mF cm−2 when the current density increased to
10 mA cm−2.
Oxygen vacancies are well known to serve as shallow donors
in Fe2O3, and have been proved to play an important role in
determining the surface and electronic properties of Fe2O3 nano-
structures.[85–88] Lately, Lu et al. demonstrated the conductivity
and capacitive properties of α-Fe2O3 NRs could be remarkably
boosted after introducing oxygen vacancies through a simple
and effective method.[42] Porous α-Fe2O3 NRs with abundant
oxygen vacancies were prepared through thermal treatment of
β-FeOOH NRs in N2 atmosphere (denoted as N-Fe2O3). It can
be seen from Figure 5a that the N-Fe2O3 NRs are polycrystal-
line structure and there are a large number of planar defects
in N-Fe2O3 NRs. Figure 5b shows the Mott−Schottky plots of
N-Fe2O3 NRs and Fe2O3 NRs obtained by thermally annealing
in air (denoted as A-Fe2O3). Due to the increased number of
oxygen vacancies, the N-Fe2O3 electrode showed a substantially
less precipitous slope, and its donor density was dramatically
increased by an order-of magnitude compared to the A-Fe2O3
electrode. As a consequence, the N-Fe2O3 electrode possessed
outstanding capacitive properties with high capacitance, good

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Figure 3. Schematic representation of the crystal structure of Fe-based materials a) α-Fe2O3, b) Fe3O4, and c) α-FeOOH.

rate capability and exceptional stability. Remarkably, a high
areal capacitance of 277.3 mF cm−2 was achieved by the N-Fe2O3
electrode at a scan rate of 10 mV s−1, while only 152 mF cm−2
for the A-Fe2O3 electrode (Figure 5c). Moreover, the N-Fe2O3
electrode could retain more than 35.3% of its initial capaci-
tance as the scan rate increases from 10 to 400 mV s−1 even at
a high mass loading (4.3 mg cm−2). When using the N-Fe2O3
NRs as anode and a MnO2 electrode as cathode, the assembled
ASC device could reach a stable electrochemical voltage of 1.6 V
with a maximum high energy density of 0.41 mW h cm−3 as
well as a maximum power density of 0.1 W cm−3 (Figure 5d).
This oxygen vacancy strategy may open up new opportunities
for improving the electrochemical performance of Fe2O3 based
electrodes and other metal oxide electrodes.
Combining Fe2O3 with conductive carbon materials or poly-
mers is another widely used method to improve the poor con-
ductivity of Fe2O3.[34,47,54,58,69,89,90] With the synergistic effect
from the large capacitance of Fe2O3 and excellent conductivity
of these conductive materials, these Fe2O3-based composites
exhibited superior electrochemical performances than the pris-
tine Fe2O3.[54,58,59,73,91] Lee et al. reported a facile hydrothermal
approach to prepare Fe2O3 NTs/reduced graphene oxide
(rGO).[54] The specific capacitance of the Fe2O3-rGO compos-
ites was calculated to be 215 F g−1 at a scan rate of 2.5 mV s−1,
which was 7 times higher than that of Fe2O3 (30 F g−1). Simi-
larly, a novel hierarchical composite architecture of Fe2O3
nanoparticles, graphite foam and carbon nanotubes (GF-CNT@
Fe2O3) with remarkable capacitive performance was developed
by Guan et al.[59] As illustrated in Figure 6a, GF-CNT with high
electrical conductivity and surface area was first constructed via
a CVD method, followed by coating with crystalline Fe2O3 using
atomic layer deposition (ALD) techniques. SEM image clearly
demonstrated the CNTs were uniformly coated with many small
nanoparticles, and no aggregation was observed (Figure 6b).
Figure 6c depicts the CV curves of bare GF-CNT and GF-CNT@
Fe2O3 electrodes. Note that the CV curve of GF-CNT@Fe2O3
electrode showed apparent redox peaks, while a rather rectan-
gular curve was observed for GF-CNT electrode. The oxidation

Figure 4. a) Schematic illustration of the morphological evolution of a hematite NR. b) Nyquist plots collected at the open circuit potential. c)
Histograms of the maximum areal capacitance of the NR and NF electrode. Inset shows the cyclic voltammogram (CV) curves of the two electrodes.
Reproduced with permission.[46] Copyright 2015, Elsevier.

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Figure 5. a) HRTEM image of N-Fe2O3 NRs, inset in Figure a is the enlarged HRTEM image that recorded from the white dashes rectangle of Figure
a, and the red arrows and zig-zag arrangements indicate the defects of the N-Fe2O3. b) Mott−Schottky plots of A-Fe2O3 and N-Fe2O3 samples obtained
at each potential with 10 kHz frequency in the dark in a 1 M KOH electrolyte. c) Areal capacitance and capacitance retention of A-Fe2O3 and N-Fe2O3
NR electrodes calculated from CV curves as a function of scan rate. d) Volumetric capacitance and energy density calculated for the MnO2//Fe2O3-ASC
device based on the discharge curves collected at 4 mA cm−2 as a function of the potential window. Reproduced with permission.[42] Copyright 2014,
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Figure 6. a) Growth procedure of GF-CNT@Fe2O3 starting from graphite foam. b) SEM image of GF-CNT@Fe2O3. c) CV curves of GF–CNT@400Fe2O3
(prepared with ALD cycles of 400) and GF–CNT. d) Cycling tests of GF–CNT@400Fe2O3. Reproduced with permission.[59] Copyright 2015, American
Chemical Society.

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Figure 7. a) Schematic of the fabrication process for the Ti-Fe2O3@PEDOT on carbon fabrics. b) Nyquist plots of the pristine Fe2O3, Ti-Fe2O3 and
Ti-Fe2O3@PEDOT electrodes. c) CV curves collected for the pristine Fe2O3, Ti-Fe2O3 and Ti-Fe2O3@PEDOT electrodes at a scan rate of 100 mV s−1.
d) Cycling performance of the pristine Fe2O3, Ti-Fe2O3 and Ti-Fe2O3@PEDOT electrodes collected at a scan rate of 100 mV s−1 for 30000 cycles. The
inset is the first and 30000th CV curves collected for the Ti-Fe2O3@PEDOT electrode. Reproduced with permission.[43] Copyright 2015 Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.

peak at ≈−0.7 V and reduction peak at ≈−1.1 V can be well
assigned to the pseudocapacitive reaction of Fe3+ species in the
electrolyte. At a high current density of 20 mA cm−2, GF-CNT@
Fe2O3 electrode delivered a remarkable areal capacitance of
470.5 mF cm−2, which is ≈4 times higher than that of GF-CNT
(93.8 mF cm−2). In addition, the GF-CNT@Fe2O3 electrode
also expressed excellent cycling ability with 111.2% capacitance
retention even after 50000 cycles of charge-discharge at a high
current density of 20 mA cm−2 (Figure 6d).
Inspired by the role of the oxygen vacances,[42] Zeng et al.
recently developed a new strategy that combines Ti4+ ion
doping and poly(3,4-ethylenedioxythiophene) (PEDOT) coating
to further boost the capacitive properties and cycling durability
of the Fe2O3 electrode as negative electrode for ASCs.[43] The
conductivity of Fe2O3 could be markedly improved after Ti4+
doping since Ti4+ dopant is an electron donor by substituting
Fe3+ and reducing Fe3+ to Fe2+ (accompanying with the produc-
tion of oxygen vacancy). Additionally, as a stable and conductive
polymer, PEDOT coating could increase the conductivity of the
Fe2O3 and act as a flexible buffering layer to prevent its struc-
ture from destruction/degradation. The Ti-Fe2O3@PEDOT core
shell NRs with significantly improved capacitive performance
were prepared via a two-step process, which included the hydro-
thermal growth of Ti-Fe2O3 NRs on a flexible carbon cloth sub-
strate and electrodeposition of PEDOT shell on the surface of
these NRs (Figure 7a). This core/shell architecture by using
Ti4+ doped Fe2O3 NRs as the core and a highly stable, conduc-
tive PEDOT layer as the shell can afford a large surface area
and efficient charge transport as well as accessible diffusion
of the electrolyte, thus exhibiting excellent conductivity and
enhanced capacitive performance. As shown in Figure 7b, the
charge transfer resistance (related to the semicircle) of the Ti-
Fe2O3 electrode was much smaller than the pristine Fe2O3 elec-
trode, indicating that Ti4+ doping could effectively improve the
conductivity of Fe2O3 electrode. In addition, coating ultrahigh
conductive PEDOT shell on Ti-Fe2O3 NRs can further reduce
the charge transfer resistance of the electrode. In comparison
to the Fe2O3 and Ti-Fe2O3 electrode, larger current density and
capacitance could be clearly identified for the Ti-Fe2O3@PEDOT
electrode (Figure 7c), revealing that Ti4+ doping and PEDOT
coating could considerably improve the capacitive properties
of Fe2O3 electrode. The as-prepared Ti-Fe2O3@PEDOT core/
shell electrode achieved a large areal capacitance of 1.15 F cm−2
at 1 mA cm−2, while only 0.46 F cm−2 for Fe2O3 electrode and
0.81 F cm−2 for Ti-Fe2O3 electrode at the same current den-
sity. Moreover, the Ti-Fe2O3@PEDOT electrode expressed
extraordinary electrochemical durability with 96.1% reten-
tion of the initial capacitance after 30000 cycles (Figure 7d),
which was substantially higher than that of Fe2O3 (81.8%) and
Ti-Fe2O3 (80.7%) electrodes. Further, a flexible solid-state ASC
device with an extraordinary energy density of 0.89 mW h cm−3
and impressive rate capability was achieved based on this Ti-
Fe2O3@PEDOT as the anode. In addition to PEDOT, PANI has
been adopted to improve the capacitive performance of Fe2O3
NWs electrode, too.[69,70] Three-dimensional (3D) Fe2O3@
PANI core-shell NWs could deliver an areal capacitance of
103 mF cm−2 at 0.5 mA cm−2, much higher than that of pure
Fe2O3 (33.93 mF cm−2).[70]
Besides conductive polymer coating, C coating is also an
effective approach to improve the electrochemical performance
of Fe2O3 owing to the excellent conductivity, superior chem-
ical and thermodynamic stability, and lightweight characteris-
tics of carbon materials.[92–94] For instance, Jayan Thomas and
his co-workers demonstrated that the capacitive performance
of Fe2O3 NRs was dramatically improved after coating a thin
carbon shell with a thickness of ≈6 nm, and the specific capaci-
tance of Fe2O3@C NRs reached 90.8 F g−1 at 20 mV s−1.[94]
More interestingly, they developed a novel coil-type asymmetric
supercapacitor electrical cable (CASEC) with superior bend-
ability and mechanical-electrochemical stability based on the

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Figure 8. a) Illustration of the structure of a CASEC. b) Schematic of the configuration to measure dual functionality of CASEC. c) Before the power was
turned on (open circuit), the voltage of a precharged CASEC showed 1.575 V. d) After the power was turned on (LED on), the voltage of the precharged
CASEC still showed 1.575 V. Reproduced with permission.[94] Copyright 2015, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
as-synthesized Fe2O3@C NRs as anode (Figure 8a). Due to the
unique cable structure, this CASEC delivered a high volumetric
specific capacitance of 2.46 F cm−3 and a maximum energy
density of 0.85 mW h cm−3. The long-term bending stability of
the CASEC device was tested under different bending condi-
tions, and good capacitance retention of 93% was achieved after
4000 cycles at a scan rate of 200 mV s−1, indicative of excellent
flexibility and electrochemical stability. Moreover, to verify the
dual functionality of the CASEC, the voltage of fully charged
energy storage part of a CASEC was measured. The results
indicated that the voltage always remained at 1.575 V whether
the LED was turned on or off (Figure 8b, c and d), proving that
the electrical cable part of the CASEC would not interfere with
the charge retention capability of energy storage part.
Table 1 summarizes the specific capacitance and cycling per-
formance of most recently developed Fe2O3 and its composites
electrodes. From the table we can see that Fe2O3-based mate-
rials are usually tested in alkaline and neutral electrolyte and
have a suitable operating voltage window in negative poten-
tial. Moreover, most of the specific capacitance and cycling
properties of the Fe2O3-based electrodes are barely satisfactory
and there is plenty of developing room for Fe2O3-based mate-
rials. In general, developing unique nanostructure and porous
structure, adjusting pore size distribution and hybridizing the
Fe2O3-based materials with various carbonaceous supports may
be beneficial for ionic/electronic diffusion and structural sta-
bility, contributing to higher capacitance, better rate capability
and longer cycling performance.[8,19,42,94,95]
3. Fe3O4-Based Nanostructured Materials for SCs
Fe3O4 has become one of the highly desirable candidates for SCs
due to its preferable electrical conductivity (≈200 S cm−1), high
specific capacitance, abundant availability on earth and envi-
ronmental friendly.[35,96–99] Recent reports have demonstrated
that the Fe3O4 nanostructures with high surface area exhibited
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promising capacitive properties.[97,100–102] In this regard, various
approaches including hydrothermal method,[102,103] sol-gel tech-
nique,[100] electroplating[104] and electrospinning[101] have been
widely used to prepare nanostructured Fe3O4 electrodes with
rational morphology and architectures. Fe3O4 cubes prepared
by an environmentally benign hydrothermal process achieved
a high capacitance of 118.2 F g−1 at a relative large current of
6 mA, but only remained about 88.7% of its initial capacitance
after 500 cycles.[102] Meanwhile, Fe3O4 nanoparticles synthe-
sized by a sol-gel technique delivered a high specific capaci-
tance of 185 F g−1 at 1 mA cm−2.[100] However, its capacitance
underwent fast decay after 200 cycles. Such the poor capacitive
performance and bad cycling stability are mainly due to the
easy reunion nature of Fe3O4 during the charging/discharging
process, which results in a low surface area and structural
pulverization.
The key to settle these aforementioned limiations of Fe3O4
nanostructures is suppressing their aggregation.[35,41,97,105]
Wang et al. developed a facile ultrasonic method to synthe-
size Fe3O4 nanoparticles with a high specific surface area of
165.05 m2 g−1 by employing FeCl3 and ethanolamine (ETA)
(denoted as UH-Fe3O4).[97] The HRTEM image of UH-Fe3O4
nanoparticles in Figure 9a revealed an atomic lattice fringe
spacing of 0.297 nm that indexed well to the (220) plane of the
Fe3O4 structure. As depicted in Figure 9b, the minor charge–
discharge platform demonstrated slight redox reactions occur-
ring during the charge–discharge process. The as-synthesized
Fe3O4 nanoparticles yielded a high specific capacitance of
207.7 F g−1 at 0.4 A g−1 and retained more than 43.5% of its
initial capacitance as the current density increased to 10 A g−1,
showing their good rate capability. Additionally, ETA and ultra-
sound process were found to be crucial to tune the dispers-
ibility and capacitive performance of the Fe3O4 nanoparti-
cles. Figure 9c compares the specific capacitance of H-Fe2O3
(without ETA and ultrasound), H-Fe3O4 (without ultrasound)
and UH-Fe3O4 electrodes as a function of cycling number.
Due to the low specific surface area (0.46 m2 g−1), the specific
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Table 1. A summary of the Fe2O3 and its composites according to electrolyte, potential, specific capacitance and cycling performance.

Fe2O3 electrodes Electrolyte Potential [V] Specific capacitance Cycling performance

Fe2O3 nanotube [63]
1 M Li2SO4 –0.8–0 V 138 F g−1 at 1.3 A g −1 89% (500 cycles)
Fe2O3 thin film[131] 1 M NaOH −0.6–0.1 V 178 F g−1 at 5 mV s−1 –
Fe2O3 NR[60] 1 M H3PO4 −0.1–0.9 V 308 F g−1 at 0.1 A g−1 77% (1000 cycles)
Fe2O3 microspindle[132] 2 M KOH −1.5–0.5 V 558.7 F g−1 –
Fe2O3 nanoflower[48] 0.5 M Na2SO3 −0.8–0 V 127 F g−1 at 1 A g−1 80% (1000 cycles)
Fe2O3[133] 1 M Na2SO4 −1–0 V 283 F g−1 at 5 mV s−1 91% (3000 cycles)
V2O5-doped Fe2O3 [80]
3 M KOH −0.1–0.6 V 183 F g−1 at 1 A g−1 81.5% (200 cycles)
Fe2O3 fiber[79] 1 M LiOH −0.1–0.9 V 256 F g−1 at 1 mV s−1 80–82% (3000 cycles)
Fe2O3 nanowire [65]
2 M KOH −1.35–0 V 908 F g−1 at 2 A g −1 –
Fe2O3[134] 0.5 M Na2SO3 −0.8–0 V 300 F g−1 at 1 A g−1 73% (1000 cycles)
Fe2O3 nanoflake[46] 3 M LiCl −0.7–0 V 100.6 F g−1 at 1 mA cm−2 87.2% (5000 cycles)
Fe2O3 nanotube [44]
5 M LiCl −0.8–0 V 257.8 F g−1 at 1.4 A g −1 –
Fe2O3[83] 1 M Li2SO4 −0.6–0 V 116.25 F g−1 at 5 mV s−1 74.2% (1000 cycles)
Fe2O3 particle[75] 0.25 M Na2S2O3 −1.2–0.2 V 532.8 F g−1 at 1 A g−1 –
Fe2O3 NR[42] 5 M LiCl −0.8–0 V 89 F g−1 at 0.5 mA cm−2 95.2% (10000 cycles)
Ti-doped Fe2O3@PEDOT[43] 5 M LiCl −0.8–0 V 311.6 F g−1 at 1 mA cm−2 96% (30000 cycles)
Fe2O3/MnO2[135] 1 M KOH −0.1–0.6 V 838 F g−1 at 2 mV s −1 98.5% (1000 cycles)
grapheme/Fe2O3/PANI[69] 1 M KOH −1–0.1 V 638 F g−1 at 1 mV s−1 92% (5000 cycles)
Fe2O3@C[92] 2 M KOH −0.7–0.2 V 215 F g−1 at 2 mV s−1 88.9% (1500 cycles)
Fe2O3/OMPC[34] 1 M H3PO4 −0.1–0.9 V 294 F g−1 at 1.5 A g−1 82% (1000 cycles)
Fe2O3/carbon black [93]
2 M KCl −0.3–0.25 V 40.07 F g−1 at 10 mV s−1 80% (500 cycles)
Fe2O3 NTs-rGO[54] 1 M Na2SO4 −1–0 V 215 F g−1 at 2.5 mV s−1 –
Fe2O3 /graphene[95] 1 M Na2SO4 −1–0.3 V 343.7 F g−1 at 3 A g−1 95.8% (50000 cycles)
Fe2O3/graphene[136] 1 M Na2SO4 −1.2–0.2 V 226 F g−1 at 1 A g−1 –
γ-Fe2O3/graphene[137] 1 M Na2SO3 −0.8–0 V 224 F g−1 at 25 mV s−1 97% (1000 cycles)
Fe2O3@GNS[138] EMIMBF4 −1.8–0 V 143 F g−1 at 0.2 A g−1 –
Fe2O3/N-rGO [58]
1 M KOH −1.2–0 V 618 F g−1 at 0.5 A g−1 56.7% (5000 cycles)
Fe2O3/graphene[139] 2 M KOH −0.85–0 V 151.8 F g−1 at 1 A g−1 86% (1000 cycles)
−1 −2
Fe2O3 NP/rGO[140] 1 M Na2SO4 −1–0 V 504 F g at 2 mA cm –
Fe2O3/graphene[89] 1 M KOH −1.05–0.3 V 908 F g−1 at 2 A g−1 75% (200 cycles)
Fe2O3/graphene[91] 1 M Na2SO4 −1.2–0.2 V 306.9 F g−1 at 3 A g−1 92% (2000 cycles)
Fe2O3 /graphene[141] 3 M KOH −1.05–0.35 V 1095 F g−1 at 3 A g−1 91.1% (1000 cycles)

capacitance of the H-Fe2O3 was much lower than H-Fe3O4
and UH-Fe3O4. The value of H-Fe3O4 was higher than that of
UH-Fe3O4 in the initial 800 cycles, however, it diminished dra-
matically in the next 1200 cycles and only 73% of the initial
capacitance was retained over 2000 cycles. Such this decrease is
attributed to the agglomeration of H-Fe3O4 particles during the
charging/discharging process. In contrast, there was almost
no decay for UH-Fe3O4 electrode after 2000 cycles, revealing
the good cycling stability. Despite ultrasound can prevent the
aggregation of the Fe3O4 nanoparticles during the electrode
preparation to some extent, aggregation is still hard to avoid
during long-term cycling process since the nanoparticles own
high surface energy. Designing other Fe3O4 morphologies such
as NRs, NTs and NSs with ultrahigh surface area is more appre-
ciated. For instance, Fe3O4 nanorods prepared by hydrothermal
method delivered a high specific capacitance of 314 F g−1 at
5 mV s−1 in 2.5 M Li2SO4 solution.[103]
Another effective strategy to prevent the agglomeration of
the Fe3O4 materials is to integrate them with highly conduc-
tive carbon materials, and these composites exhibit outstanding
electrochemical properties.[27,41,105–107] Guan et al. demonstrated
the capacitance of Fe3O4 cubes was significantly enhanced by
three folds after combined with multi-wall CNTs,[35] achieving a
high specific capacitance of 117.2 F g−1 at a large current den-
sity of 10 mA cm−2. A kind of Fe3O4/AC composite electrode
prepared by a hydrazine method also showed enhanced capaci-
tive performance with a specific capacitance of 202.6 F g−1 at
10 mV s−1.[67] In comparison to CNTs and AC, graphene mate-
rials possess much better mechanical property, higher electrical
conductivity and exceptionally larger surface area.[108–111] In this

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Figure 9. a) HRTEM images of UH-Fe3O4 nanoparticles. b) Galvanostatic charge–discharge curves of UH-Fe3O4. c) Long cycle life of UH-Fe3O4,
H-Fe3O4 and H-Fe2O3 at 1 A g−1. Reproduced with permission.[97] Copyright 2013, The Royal Society of Chemistry.

regard, graphene materials are very attractive as host matrixes
in the fabrication of the Fe3O4-based composites.[27,55,112,113]
For example, Fe3O4/rGO composites constructed through
facile hydrolysis and annealing methods was able to deliver a
remarkable specific capacitance (350.6 F g−1 at 1 mV s−1), good
rate capability (50% retention from 1 to 100 mV s−1) and supe-
rior long-term electrochemical stability (nearly no decrease
after 10000 cycles), which outperform the pure rGO and pure
Fe3O4.[55] To meet the demand for fabricating flexible SCs, a
flexible 3D graphene sheet/Fe3O4 composite (GS/Fe3O4) paper
was developed as high-performance flexible electrodes.[98] Fe3O4
nanoparticles were anchored on 3D conductive network GS
homogeneously via covalent chemical bonding. The 3D GS
as a flexible and conductive scaffold not only can provide fast
electron transport channel, offering good electrical contact
with Fe3O4 nanoparticles, but also prevents the agglomeration
of the Fe3O4 nanoparticles. The HRTEM image revealed that
≈5 nm Fe3O4 nanoparticles were uniformly dispersed on the
GS surface (Figure 10a). Well-resolved lattice distance of 0.297
nm corresponded well to the (220) plane of Fe3O4, suggesting
that the Fe3O4 nanoparticles were highly crystalline with a cubic
structure. In this unique 3D layered structure, the synergistic
effects of combining Fe3O4 with grapheme can simultaneously
improve the dispersion of Fe3O4 nanoparticles and prevent the
restacking of GS, and therefore exhibiting excellent capaci-
tive performance. At a current density of 1 A g−1, the specific
capacitance of GS/Fe3O4 paper with 64.8%wt of Fe3O4) reached
368 F g−1 based on the total mass of the paper (Figure 10b),
which was substantially higher than the other counterparts
(GS/Fe3O4 with different content of Fe3O4). When the current
density increased to 5 A g−1, this GS/Fe3O4 paper also showed
a large specific capacitance of 225 F g−1. Additionally, the GS/
Fe3O4 paper has excellent cycling performance with 108.8%
specific capacitance retention after 1000 cycles test at 5 A g−1,

Figure 10. a) HRTEM images of GS/Fe3O4-3 composite. b) Average specific capacitance of GS/Fe3O4 composites at different current densities. c) Cyclic
performance of GS/Fe3O4 composites at 5 A g−1. d) The CV cycles of the GS/Fe3O4-3 paper at different bending times (the inset is the digital photo of
GS/Fe3O4-3 paper). Reproduced with permission.[98] Copyright 2014, The Royal Society of Chemistry.

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Figure 11. a) Schematic diagram of the sequential fabrication steps for FeCHNPs. b-c) HRTEM images of FeCHNPs. d) Galvanostatic charge–discharge
curves of hybrid nanoparticles (current density: 2.0 A g−1). e) Calculated specific capacitance with various voltage scan rates of hybrid nanoparticles.
Reproduced with permission.[41] Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

as shown in Figure 10c. Furthermore, it is worth noting that
there is no capacitance loss after the GS/Fe3O4 paper electrode
was bended for 100 times (Figure 10d), which further proves
that the GS/Fe3O4 paper is a prospective candidate as flexible
SC electrode.
To further enhance capacitive performance of Fe3O4/carbon
composite, a number of abundant efforts have also been
attempted to design novel architectures.[41,105,114] More recently,
a kind of new carbon/Fe3O4/carbon hybrid nanoparticles
(FeCHNPs) with a shell-core-shell structure was developed and
yielded prominent electrochemical performance.[41] FeCHNPs
were synthesized using dual-nozzle electrospraying, vapor dep-
osition polymerization (VDP), and carbonization. Figure 11a
shows the schematic diagram of the fabrication process for
FeCHNPs. Firstly, vertically aligned FeOOH nanoneedles dec-
orated with polypyrrole (PPy) nanoparticles (FePNPs) were
prepared, followed by heat stirring reaction. Then, PPy-coated
FeOOH nanoneedles (PFePNPs) were fabricated by using VDP
to produce a precursor to the Fe3O4/carbon hybrid nanoparticles
(FeCHNPs), which were developed through the phase transi-
tion of FeOOH and PPy carbonization. As shown in Figure 11b,
there was a homogeneously coated carbon layer on the surface
of Fe3O4 nanoneedle. The HRTEM image reveals the thickness
of carbon layers is about 2 nm and the Fe3O4 nanoneedle is
mesoporous (Figure 11c). It is anticipated that the carbon core
and coated amorphous carbon layer will act as a conductive
channel for charge transport contributing to largely reduced
internal resistance and the coated amorphous carbon layer can
effectively inhibit the collapse of the Fe3O4 nanoneedles during
charge-discharge cycles. As expected, the FeCHNPs exhibited
the longest discharge time (Figure 11d), showing it has the best
capactive performance among these samples. The highest spe-
cific capacitance of the FeCHNPs reached 455 F g−1 at a scan
rate of 5 mV s−1 (Figure 11e), which was much higher than that
of PPy (105 F g−1), FePNPs (265 F g−1) and PFePNPs (370 F
g−1). When the scan rate increased from 5 to 50 mV s−1, the
FeCHNPs electrode showed the best rate capability with more
than 85% retention, which is beneficial for high power density.
Such the remarkable rate performance is due to the superior
conductivity of the FeCHNPs, which is confirmed by electro-
chemical impedance spectroscopy (EIS) analysis. The charge
transfer resistance (Rct) at the interface gradually decreased fol-
lowing each of the processing steps, indicating that the coated
conductive carbon layers could effectively facilitate interfacial
charge transfer at the electrolyte–electrode interface. The Rct
value of the FeCHNPs is the smallest (only 1.5 Ω), showing its
excellent conductivity.
4. FeOOH-Based Nanostructured Materials for SCs
In recent years, FeOOH is emerging as a new kind of anode
material for ASCs because of its attractive negative potential
window and high theoretic specific capacitance.[26,40,51,56,66,115]

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The capacitive behavior of FeOOH as anode in Li2SO4 solu- with a deposition time of 30 min achieved a high specific capaci-

tion was first investigated by Jin et al. in 2008.[115] Columned
β-FeOOH prepared by a hydrolysis process exhibited a pro-
mmising specific capacitance of 116 F g−1 at a current density of
0.5 A g−1 within potential window −0.85 to −0.1 V. Inspired by
this work, intensive effort has been devoted to exploring nano-
structured FeOOH electrodes for ASCs, and various FeOOH
nanostructures, including nanoparticles,[116] NSs,[40] NRs[51,56,61]
have been developed as ASCs electrodes.
The capacitive property of FeOOH electrode is greatly
affected by its crystal structure.[40,51,117] Recently, γ-FeOOH
NSs with a 2D layered structure have been demonstrated to
exhibit superior capacitive performance in negative potential
window.[40] γ-FeOOH with orthorhombic crystal structure has
the 2D permeable channels, which can facilitate the ion trans-
portation and possess good interlayer conductivity, favorable for
enhancing electrochemical performance. The γ-FeOOH NSs
were prepared on conductive carbon cloth via a simple one-
step electroplating approach without the assistance of any tem-
plates or surfactants. As presented in Figure 12a, free-standing
FeOOH NSs with smooth surface and an average thickness of
30–50 nm were uniformly grown on the surface of carbon cloth.
The mass loading and the specific capacitance of the FeOOH
NSs on carbon cloth could be readily adjusted by tuning the
deposition time. The optimized FeOOH NSs electrode obtained
REVIEW
tance of 310.3 F g−1 at 0.13A g−1 and still could retain 219.5 F g−1
at an ultrahigh discharge current of 12.6 A g−1, showing the
good rate capability of the γ-FeOOH NSs (Figure 12b). Further,
an ASC device in a mild aqueous electrolyte with the optimized
γ-FeOOH NSs electrode as anode and a MnO2 NSs electrode
as cathode was fabricated. Figure 12c displays the CV curves
of the MnO2 NS electrode and the γ-FeOOH NS electrode in
a Li2SO4 electrolyte collected at a scan rate of 5 mV s−1, which
indicates the as-fabricated ASC device may possess a wide
voltage window of 1.85 V. The symmetrical shape of charge/dis-
charge curves and small iR drops collected at different current
density with a cell voltage of 1.85 V reveal the good capacitive
behavior of the as-fabricated MnO2 NS//FeOOH NS ASC device
(Figure 12d). In addition, this ASC device could deliver a max-
imum power density of 16 000 W kg−1 at an energy density of
37.4 Wh kg−1.
In addition to γ-FeOOH, β-FeOOH has recently drawn wide
attention as SCs electrodes for its tunnel-type framework struc-
tures that can greatly facilitating electrolyte transport.[51,117]
However, the capacitive performance of β-FeOOH is ultimately
limited by its poor electrical conductivity. A promising strategy
to improve the conductivity of β-FeOOH is to introduce appro-
priate dopants of F.[51] Yu and his co-workers demonstrated
that the conductivity of the β-FeOOH NRs as well as their

Figure 12. a) SEM images of γ-FeOOH NS electrodes (deposition time of 30 min). b) The gravimetric capacitances as functions of charge-discharge
specific current. Inset: Charge-discharge tests of γ-FeOOH NS. c) Comparison of CV curves of MnO2 NS electrodes and FeOOH NS electrodes in
a three-electrode cell at a scan rate 5 mV s−1. d) Galvanostatic charge/discharge curves of MnO2 NS-CC//FeOOH NS-CC hybrid supercapacitors at
different specific current from 0.4 to 8.4 A g−1. Reproduced with permission.[40] Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Figure 13. a) Calculated density of state plots for F-doped β-FeOOH sample. Here, the Fermi level is set to 0 eV for clarity. b) SEM image of typical
sample. c) Galvanostatic charge/discharge curves of the typical sample, Sample-1, Sample-2, and control sample-based supercapacitor at a current
density of 2.0 mA cm−2. d) Specific areal capacitance of typical sample, Sample-1, Sample-2, and control sample as a function of the current density.
Reproduced with permission.[51] Copyright 2015, Elsevier.

capacitive performance could be significantly boosted after
doping with appropriate F.[51] Theoretical calculation reveals
that β-FeOOH is a semiconductor with a direct band gap of
1.05 eV, which accounts for its relative low conductivity. After F
doping, the band gap of β-FeOOH will reduce to about 0.2 eV,
and there are finite density of state around both sides of the
Fermi level (Figure 13a), and hence a metal-like conductivity of
F-doped β-FeOOH. As shown in Figure 13b, metal-like F-doped
β-FeOOH NRs were successfully synthesized on carbon cloth by
a facile hydrothermal method. These NRs have a width of about
11 nm and a length of 40–70 nm. Figure 13c compares the gal-
vanostatic charge/discharge curves of the pristine β-FeOOH
and F-doped β-FeOOH NRs with different F dopant at a current
density of 2 mA cm−2. The F-doped β-FeOOH NRs prepared
with 32.0 mmol NH4F (denoted as typical sample) exhibited the
longest discharge time, showing the largest capacitance. The
areal capacitance of typical sample electrode reached as high as
1.12 F cm−2 at a current density of 1 mA cm−2, which is sub-
stantially larger than that of the pristine β-FeOOH NRs (con-
trol sample) and other F-doped β-FeOOH NRs (sample-1 and
sample-2) (Figure 13d). Moreover, all the F-doped β-FeOOH
samples yielded superior rate capability than the pristine
β-FeOOH sample due to the improved conductivity as a result
of F doping. Also, a high-performance symmetric SC device
based on the typical sample electrode was assembled and deliv-
ered a maximum energy density of 1.85 mW h cm−3 and power
density of 11.11 W cm−3 with good cycling stability (almost no
decay after 5000 cycles).
Like Fe2O3 and Fe3O4, incorporation of FeOOH with gra-
phene is another effective approach to enhance the conduc-
tivity and charge-storage capability of FeOOH.[56,66,118] A kind
of FeOOH NRs/graphene composite with a specific capacitance
of 165.5 F g−1 in Na2SO3 solution was achieved by using fer-
rous as a reducing agent of graphite oxide (GO) upon a hydro-
thermal process.[66] Similarly, Xiao et al. reported a one-pot
hydrothermal method to prepare FeOOH NRs/rGO composites
and studied their capacitive performance as SCs electrodes.[56]
Their results reveal that the electrochemical performance of the
FeOOH/rGO materials largely depends on the quantity of rGO
and size of FeOOH NRs. The FeOOH NRs/rGO composite
contained 82.6 wt% and 66.1 wt% FeOOH exhibited specific
capacitances of 501.71 and 537.14 F g−1 at a current density of
2 A g−1 in 1 M NaOH, respectively, which are much higher than
the value of pristine FeOOH NRs (156.43 F g−1). Despite these
achievements, the capacitive performances of most current
FeOOH electrodes are not yet satisfied, especially for rate capa-
bility and cycling stability. For instance, more than 14.5% of its
initial capacitance was decreased for the FeOOH NRs/graphene
composite after 500 cycles,[66] which is far away from their prac-
tical application and need further enhancement.
5. FeOx-Based Nanostructured Materials for SCs
FeOx with uncertain composed of iron and oxygen with
varying proportions, have also been extensively studied by

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Figure 14. a) HRTEM of 40-h FeOx-carbon nanofoam. b) Specific capacitance vs potential of deliver a maximum specific capacitance of
bare carbon nanofoam (black), 20-h FeOx-carbon nanofoam (red), and 40-h FeOx-carbon nano- 366 F g−1 in 1 M NaOH.[124] Yu et al. reported
foam (blue) in 2.5 M Li2SO4 at 5 mV s−1. Reproduced with permission.[121] Copyright 2015,
American Chemical Society.
researchers.[119–122] For instance, a well-dispersed mesoporous
FeOx nanowires/CNT composite electrode fabricated via
spray deposition gave a maximum capacitance of 312 F g−1
at 2 mV s−1 in an aqueous Na2SO3 electrolyte.[120] Gao et al.
demonstrated FeOx/rGO composites using the unique benzyl
alcohol route, where benzyl alcohol acting as a reactant for
FeOx formation as well as a reducing agent for GO to form
rGO NSs.[119] A high specific capacitance of 126 F g−1 was
achieved for FeOx/rGO electrode in a negative potential range
from −0.8 to 0 V.
The electrochemical properties of nanoscale iron oxides
may be further enhanced by distributing them onto the high
surface-area, electrically conductive carbon substrates. Notably,
electroless deposition of conformal, nanoscale FeOx coatings
were generated at the interior and exterior surfaces of carbon
nanofoam paper substrates via redox reaction with strong oxi-
dant K2FeO4.[121] The HRTEM image demonstrated that no
obvious distinguish of the two materials was observed for the
FeOx-coated domains (Figure 14a). It can be clearly discerned
that the overlap section of the FeOx and carbon regions by a
gradual change in the intensity of the gray level and lack of
lattice fringes. Occasionally the location of the oxide domain
near an edge allowed distinct lattice fringes of the oxide to
be discerned. All of the results showed that though homoge-
neously distributed within the nanofoam structure, the FeOx
did not exhaustively coat on all of the surfaces of carbon. The
specific surface area of carbon nanofoam was 533 m2 g−1 and
reduced to 431 m2 g−1 for the 40-h FeOx-carbon nanofoam
(40 h deposition). Similarly, the cumulative pore volume and
mean pore size gradually decreased with FeOx deposition.
Benefiting from the pseudocapacitance of FeOx, improved
charge storage upon incorporation of FeOx was evident in
the comparison of CV curves in Figure 14b. All of the curves
exhibit a semirectangular shape, indicating capacitive or pseu-
docapacitive behavior for all three electrodes. The optimal 40-h
FeOx-carbon nanofoam yielded specific, volumetric and areal
−1 −3 −2
capacitances of 84 F g , 121 F cm , and 0.85 F cm , respec-
tively at a scan rate of 5 mV s−1, with 3 to 7 fold enhancement
relative to that of carbon nanofoam.
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6. Iron-Based Binary Metal Oxides
REVIEW
Nanostructured Materials for SCs
In addition to single iron oxides/hydrox-
ides, iron-based binary metal oxides such
as MFe2O4 (M = Ni, Co, Sn, Mn, Cu) and
BiFeO3 have also attracted a lot of attention
recently.[123–126] These binary metal oxides
containing one or more electrochemical
active/inactive ions can exert the syner-
gistic effect of pure oxides and have better
electrical conductivity than pristine mental
oxides.[71,123,127] For instance, CoFe2O4 nano-
flakes synthesized on stainless steel substrate
by a chemical bath deposition method could
that NiFe2O4 nanoparticles directly grown on
flexible carbon cloth by a surfactant-assistant
hydrothermal method showed remarkable
specific capacitance (1135.5 F g−1 in 1 M H2SO4) and excellent
rate capability (more than 80% retention as the current density
increases from 2 to 100 mA cm−2).[128]
Multi-shelled hollow sphere nanostructure is recognized
as promising and fascinating nanostructure for application in
SCs electrodes due to its more active surface area, fast elec-
tron transfer and ion diffusion. Notably, multi-shelled CoFe2O4
hollow microspheres with tunable layers were prepared via
a facile one-step process using cyclodextrin as a template.[123]
The number of shells can be controlled by adjusting the ratio of
water to ethanol. As shown in Figure 15a, the increasing con-
tent of ethanol would allow more solution to further penetrate
into the carbonaceous spheres and more adsorption of Fe3+
and Co2+, contributing to multi-shelled CoFe2O4 hollow micro-
spheres. TEM images revealed that CoFe2O4 hollow micro-
spheres with triple-shelled was obtained (Figure 15b) and the
diameters of hollow spheres became larger with an increasing
number of shells because of the wetting properties of water
and ethanol. CV curves of the multi-shelled CoFe2O4 elec-
trodes with obvious redox peaks indicated the Faradic pseudo-
capacitive nature of the electrode. The initial capacitance of the
triple-shelled CoFe2O4 electrodes was clearly superior to other
counterparts and reached 1450 F g−1 at 1 A g−1 in 6 M KOH
(Figure 15c). With elastic multi-shelled structures, the triple-
shelled CoFe2O4 electrodes also yielded good rate capability
with a high capacitance of 1231 F g−1 at 20 A g−1. Moreover,
the triple-shelled CoFe2O4 electrodes also showed promising
durability with 98% capacitance retention after 500 cycles. Such
good performance can be ascribed to the increased ion-acces-
sible surface area, fast ion diffusion, lower internal resistance
and good structural stability of the multi-shelled hollow micro-
sphere structures.
On the other hand, the conductivity and stability of the iron-
based binary metal oxides can be improved by compositing
with other highly conductive materials such as graphene[125,126]
and PEDOT.[71] The MnFe2O4 nanocube decorated flexible gra-
phene NSs with PANI wrapped electrode presented a high spe-
cific capacitance of 338 F g−1 in 1 M NaCl electrolyte, which is
10 times larger than the pristine MnFe2O4 nanocube electrode
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REVIEW

Figure 15. a) Illustration showing enhancement of the pore infiltration and complexing ability of Fe3+, Co2+ in infusion solutions of increasing ethanol
content. b) TEM images of CoFe2O4 triple-shelled hollow microspheres after calcination at 550 °C. c) Rate-capability test for CoFe2O4 spheres at various
current densities (1–20 A g−1). Reproduced with permission.[123] Copyright 2016, Springer.

(32 F g−1).[122] Sen et al. reported that a high specific capacitance
of 251 F g−1 was achieved by PEDOT-NiFe2O4 nanocomposite,
much higher than that of the NiFe2O4 electrode (127 F g−1).[71]
7. Conclusion and Perspective
Fe-based materials have shown their potential as high-per-
formance electrode materials for SCs because of their good
electrochemical behavior, environmental benign, abundant
resource and low cost. Various single iron metal oxides/hydrox-
ides (Fe2O3, Fe3O4, FeOOH, etc.) and binary metal oxides
(CoFe2O4, NiFe2O4, etc.) have been extensively studied as SCs
electrodes. Each of them possesses its own advantages and
disadvantages, which we have highlighted in the front. Cur-
rently, the main problems of most Fe-based electrodes for prac-
tical applications are their low conductivity and poor structural
stability, which seriously limit their capacitive performance and
cycling life. In comparison with bulk materials, nanostructures
have remarkable merits of increased electrode/electrolyte con-
tact area for reactions, faster charge transfer rate and shorter
ion diffusion pathway. A large number of iron-based nanostruc-
tures with desirable morphologies, including 0D, 1D, 2D, and
3D architectures, have been developed and exhibited improved
electrochemical properties. Furthermore, tailoring composite
nanostructures via componential and defect control, which
combine with a conductive and/or active phase (integration
with an electrically conductive phases, introduction of oxygen
vacancies, or element doping), could also substantially boost
the capacitance and electrochemical stability of these Fe-based
electrodes.
Despite these exciting achievements, the electrochemical
performances of most Fe-based electrodes are still far from sat-
isfactory industrial application. In the view and analysis of the

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published literatures, the following aspects could be considered
in the future development of high-performance Fe based elec-
trodes: (1) Since the redox reactions only occur on the outermost
surface layer of Fe-based electrodes, the thickness of Fe-based
electrodes should be thin enough and the electrochemical active
sites of the electrode should be maximized. Designing unique
nanostructure and porous structure, optimizing pore size dis-
tribution may increase the active surface area. (2) Fe-based
materials has various crystal structure and these crystal forms
play a crucial role in optimizing the electrochemical properties
of Fe-based electrodes for SCs. Investigation of the influence of
crystal structure on electrochemical performance is the founda-
tion of rational design of advanced Fe-based electrodes. (3) The
conductivity of most Fe-based electrodes are poor, integrating
them with highly conductive materials is an effective way to
overcome the obstacle. Rationally design porous structure with
high surface area to form hierarchical microstructure may be
helpful to decrease the formation of dead volume and achieve
higher capacitance. Furthermore, interfacial interaction force
between these two materials is weak, not helpful for charge
transport. A structure of iron oxides/Fe/iron oxides NTs would
be a considerable solution. (4) Some underlying mechanism
of the Fe-based electrodes in the aqueous electrolyte remains
unanswered, especially regarding electron transfer and charge
storage mechanisms during the electrochemical interface pro-
cesses. We believed that understanding some fundamental
mechanism could provide a direction for the structure design
of Fe-based electrodes. (5) In recent year, flexible energy storage
devices are receiving tremendous interests and more efforts
should go into investigating Fe-based electrodes with excellent
mechanical flexibility since the current related researches is
limited. Future studies could focus on the development of flex-
ible substrate and polymer electrolytes.
Acknowledgements
We acknowledge the Financial support from the National Natural
Science Foundation of China (21403306, 31530009 and 21273290),
Guangdong Natural Science Foundation for Distinguished Young
Scholar (2014A030306048), the Fundamental Research Foundations
for the Central Universities (15lgpy24), Tip-top Scientific and Technical
Innovative Youth Talents of Guangdong Special Support Program
(2015TQ01C205), Science and Technology Planning Project of
Guangdong Province (2015B090927007) and Pearl River Nova Program
of Guangzhou (201610010080).
Received: May 19, 2016
Revised: June 22, 2016
Published online: August 22, 2016
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