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Three dimensional iron oxide /graphene aerogel hybrids as all-solid-state

flexible supercapacitor electrodes

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DOI: 10.1039/C6RA11106H

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Three dimensional iron oxide/graphene aerogel

hybrids as all-solid-state flexible supercapacitor
Cite this: RSC Adv., 2016, 6, 58994
electrodes†
Abdul Muqsit Khattak, Huajie Yin, Zahid Ali Ghazi, Bin Liang, Azhar Iqbal, Niaz Ali Khan,
Yan Gao, Lianshan Li* and Zhiyong Tang*

Received 29th April 2016
Accepted 12th June 2016
DOI: 10.1039/c6ra11106h
www.rsc.org/advances
Three dimensional (3D) iron oxide (Fe2O3)/graphene aerogel (GA) hybrid (Fe2O3/GA) was synthesized by
a novel in situ hydrothermal method. Due to the high surface area and sponge structure of GA, which
facilitate the access of electrolyte to the internal surface of the graphene film, this 3D Fe2O3/GA
composite consequently lead to a robust and superior hybrid material with higher capacitance and
better rate performance compared to that of the stacked Fe2O3/graphene (Fe2O3/G) hybrid when used
as electrode materials in supercapacitors (SCs). Furthermore, a highly flexible all-solid-state symmetric
supercapacitor device was fabricated by two pieces of our Fe2O3/GA hybrid electrode. The device is
suitable for different bending angles and delivers a high specific capacitance of 440 F g
1. 90%
capacitance was retained over 2200 cycles, indicating good cycling stability. These excellent
electrochemical performances suggest that Fe2O3/GA composites have an enormous potential in energy
application.

Cheng and co-workers7 reported graphene networks produced

Introduction
Due to their signicant advantages of high power density, high
rate capacity and long cycling life, supercapacitors play an
important role ranging from portable electronics to hybrid
electric vehicles, and other high power energy sources.1 With
the growing demand for portable and wearable energy storage
systems, exible supercapacitors are gaining more and more
interest.1c,2 Recently, graphene, due to its unique mechanical
strength, chemical stability, high conductivity and theoretical
specic surface area as well as low fabrication cost, has emerged
as an ideal candidate for exible electrochemical energy storage
devices.3 Much effort has been focused on designing graphene
into various exible structures, such as graphene paper,4 gra-
phene gel,5 transparent electrodes,6 and so on. However,
because of the aggregating nature of graphene due to strong p–
p interactions, the large surface area cannot be fully utilized,
especially at a high charge–discharge rate. To overcome the
overstacking problems of graphene sheets and obtain high rate
performance in supercapacitors, various three-dimensional
(3D) graphene bulk materials have been developed. Generally,
3D graphene is a structure which contains interconnected pores
that prevent the restacking of graphene sheets. For instance,
CAS Key Laboratory of Nanosystem and Hierarchy Fabrication, National Center for
Nanoscience and Technology, Beijing 100190, P. R. China. E-mail: lils@nanoctr.cn;
zytang@nanoctr.cn
† Electronic supplementary information (ESI) available.
10.1039/c6ra11106h
by chemical vapour deposition (CVD) and template method and
Shi and co-workers8 prepared a self-assembled graphene
hydrogel by a hydrothermal method. However, when being used
as an electrode material for supercapacitors, the capacitance of
graphene is relatively low (around 100 to 200 F g
1) because it
mainly stores energy through the electric double-layer capacitor
(EDLC) mechanism.9 Thus, preventing the self stacking of gra-
phene and combining graphene with redox materials, which
can take both advantages of EDLC from graphene and faradic
pseudocapacitance from redox materials remain important
scientic challenges.
Transition metal oxide is a category of pseudocapacitance
materials based on the redox pseudo capacitive (i.e. faradic)
charge storage process. Several transition metal oxide materials
including Fe2O3,10 MnO2,11 WO3/MoO3,12 Co3O4,13 and their
composites14 have been extensively investigated as electrode
materials. Among those, Fe2O3 is recognized a good candidate
because of its natural abundance, low cost, environmental
friendliness and high theoretical specic capacity (1005 mA h
g
1).15 However, low conductive nature and strong agglomera-
tion of the Fe2O3 particles during the charge and discharge
processes result in rapid capacity loss.16 To overcome these
problems, conducting carbon matrices like 2D and 3D graphene
sheets have been used to provide structural stability and high
conductivity.17 For example, Lee et al.18 reported a novel nano-
composite with a-Fe2O3 nanotubes anchored on reduced gra-
See DOI:
phene oxide displaying a high specic capacitance of 216 F g
1,
attributed to short ion diffusion length and improved electrical

58994 | RSC Adv., 2016, 6, 58994–59000 This journal is © The Royal Society of Chemistry 2016
 View Article Online

Paper RSC Advances

conductivity. Similarly Yang et al.19 reported novel a-Fe2O3

mesocrystals/graphene nanohybrid and porous a-Fe2O3/gra-
phene exhibiting high specic capacitance of 306 F g
1 and 343
F g
1, respectively. Although the combination of graphene and
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iron oxide is effective processing protocol to improve the elec-

trochemical performances, weak interaction between Fe2O3 and
graphene lead to severe restacking of graphene sheets and
subsequent agglomeration of Fe2O3 particles during charge/
discharge. To the best of our knowledge, a study of Fe2O3
particles supported on 3D graphene aerogel for exible all-solid-
state SC has not been reported to date.
Here, we combine 3D GA and Fe2O3 nanoparticles (NPs) to
fabricate a composite supercapacitor electrode. Fe2O3/G nano-
composites were simultaneously synthesized for comparison.
Compared with the Fe2O3/G nanocomposite, the produced
Fe2O3/GA hybrid material exhibits higher specic capacitance
(440 F g
1 at 0.45 A g
1), better rate performance and long-term
cycling stability due to the porous nature of graphene aerogel
which can help increasing electrical conductivity and surface
area of the composite electrodes. In addition, we also made the
all-solid-state symmetric supercapacitor by assembling two
pieces of as-made Fe2O3/GA electrodes. The fabricated super-
capacitor exhibit an outstanding electrochemical performance
with specic capacitance of 311 F g
1 at a current density of 3 A
g
1 when bent to 90 degree. The device demonstrates good
exibility and shows high capacitance retention of 89% aer
2200 cycles.
Experimental
Synthetic procedures
The synthetic route of Fe2O3/GA is schematically illustrated and
explained in our previous work.20 Graphite oxide was obtained
from the natural ake graphite through a modied Hummers'
method.21 The as-prepared graphite oxide was fully washed by
ultrapure water, followed by sonicating for 60 min to obtain
aqueous GO dispersion. To synthesize Fe2O3/GA hybrid,
aqueous GO dispersion (20 mL, 3 mg mL
1) and FeCl2$4H2O
solution (10 mL, 0.3 M) were mixed rst, followed by adding
NH3$H2O solution (50 mL, 28 wt%). Aer mixing, the Fe2+ ions
were absorbed through electrostatic interactions or coordina-
tion on surface oxygen containing groups (Fig. 1). The mixture
was then sealed in a Teon-lined stainless-steel autoclave,
subsequently heating the mixture at 180  C for 12 h to give rise
to the nucleation sites of tiny Fe2O3 NPs. Further reduction of
GO sheets leads to self-assembled hydrogel structure with
simultaneously grown Fe2O3 NPs. Aer the as-prepared hydro-
gel was freeze dried, the Fe2O3/GA hybrid was obtained. For
comparison, Fe2O3/G nanocomposites were synthesized hydro-
thermally. In detail an aqueous solution (10 mL) of FeCl3$6H2O
(0.6 mmol) was added into an aqueous suspension of GO (40
mL). Aer continuous stirring for 2 h, 10 mL of NaOH (1.2
mmol) aqueous solution was added into the above mixture.
Finally, the mixture was sealed in a Teon-lined stainless steel
autoclave for hydrothermal reaction at 180  C for 12 h. The nal
product was washed several time with water and ethanol, and
then dried at 80  C for 12 h.
Fig. 1 Schematic representation of Fe2O3/GA composite formation
process by in situ growth method.
Materials
Graphite (CP grade, #300 mesh) and activated carbon (CP
grade) were purchased from Sinopharm Chemical Reagent.
FeCl2$4H2O and NH4OH (28 wt%, AR grade) were bought from
Longxi Chemical Reagent.
Characterization
Surface morphology and energy dispersive X-ray spectroscopy
(EDS) element mappings of the material were obtained under
a Hitachi S4800 scanning electron microscopy (SEM). Trans-
mission electron microscope (TEM) images were obtained on
a FEI Tecnai G2 F20 electron microscope operated at 200 kV.
Powder X-ray diffraction (XRD) patterns were recorded on
a Pananlytical X'Pert-pro MPD X-ray power diffractometer by
using Cu ka radiation (l ¼ 0.154056 nm). Thermogravimetric
analyzer (TGA, TA Instruments, USA) was used to obtain the
Fe2O3 content by heating our sample in air from 0  C to 800  C
at a heating rate of 20  C min
1. XPS spectra were performed by
an ESCALAB 250 Xi. XPS system of Thermo Scientic, where the
analysis chamber was 1.5  10
9 mbar and the X-ray spot was
set to 500 mm.
Electrochemical measurements
Electrochemical studies were carried out in a conventional
three-electrode and two-electrode symmetric supercapacitor
setup with room temperature. Briey, in three-electrode system
Fe2O3/GA on nickel foam as the working electrode, platinum
(Pt) foil and standard calomel electrode (SCE) were used as
counter and reference electrodes in 6 M KOH, respectively. The
working electrode was prepared by mixing 80 wt% active
materials, 8 wt% PVDF binder and 12 wt% carbon black in an
agate mortar. Then an appropriate amount of ethanol was
added to this mixture to make slurry, which was subsequently
coated on nickel foam and dried in an oven at 100  C for 10 h.
For two electrodes symmetric system the PVA–KOH gel elec-
trolyte was prepared as follows: 8 g of PVA powder was put into
60 mL distilled water and was fully dissolved at 85  C with
stirring. Then 6 g of KOH was added into the solution and

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RSC Advances
stirred vigorously until the powder was completely dissolved
and solution became clear.
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Fabrication of all solid-state supercapacitor electrodes
In both cases, prior to the device fabrication, nickel foam sheets
(2.5 cm  1.5 cm) were pressed under pressure of 10–15 MPa
for 1 min by a pressing machine and were cleaned with acetone
for 20 min, washed thoroughly with deionized water and
absolute ethanol. These pressed sheets were then used as
support and current collector. The active material was pasted on
these sheets. The prepared electrodes were immersed in the
PVA–KOH gel solution for 30–60 min and then taken out. Aer
vaporizing the excess water at room temperature, the two elec-
trodes were assembled. When the gel electrolyte solidied,
a robust and highly exible, all-solid-state symmetric super-
capacitor was prepared.
The electrochemical performance of the assembled devices
ware studied on a CHI660D electrochemical workstation using
cyclic voltammetry (CV) at various scan rates, galvanostatic
charge–discharge (CD) at different current densities from 0.45 A
to 8 A and electrochemical impedance spectroscopy (EIS) in the
frequency range from 100 kHz to 0.1 Hz at open circuit poten-
tial. For quantitative considerations, the specic capacitance
was calculated as follows:
In the three-electrode measurement, the specic capacitance
is calculated from charge–discharge proles using the following
equation:
Cs ¼ (I  t)/(V  m)
For two electrodes symmetric system the following equation
is used to calculate the specic capacitance22:
Cs ¼ 2  I  dt/m  DV
where Cs (F g
1) is specic capacitance of the supercapacitor, I
(A) corresponds to the discharge current, DV (V) is the potential
window, Dt (s) is the discharge time, and m (g) refers to the mass
of active materials on the one electrodes.
Results and discussion
Fig. 1 shows the typical preparation process of Fe2O3/GA
composite. A possible reduction mechanism of Fe2+ and the role
of NH4OH can be described as follows
GO + Fe2+ / Fe3+ (1)
Fe2+ + NH3$H2O / Fe2O3 + NH4+ (2)
Our way of synthesis of these Fe2O3/GA hybrid is more
general because of (i) the use of low valence metal ions (Fe2+)
salts as precursors guarantee the exclusive growth of metal
oxide NPs on the surface of GO sheets23 (ii) avoid the use of as-
synthesized Fe3O4 NPs and specic organic solvents and
58996 | RSC Adv., 2016, 6, 58994–59000
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stabilizers or surfactants like PVP etc.24 and (iii) high loading of
metal oxide NPs in the hybrids.
The morphology and microstructure of the as-prepared Fe2O3/
GA were elucidated by means of Scanning Electron Microscopy
(SEM), Transmission Electron Microscopy (TEM) and X-Ray
Diffraction (XRD). SEM images show that the Fe2O3/GA
composite exhibits a hierarchical and interconnected porous
network composed of randomly oriented graphene sheets,
(Fig. 2a) similar to those of previous graphene aerogel. The
results also revealed uniformly dispersed framework with
continuous pores of several micrometers. The unique 3D porous
structure can largely prevent the aggregation of graphene sheets
caused by p–p interaction and van der Waals force, which may be
benecial to the rapid transport of electrolyte.25 While stacked
graphene sheets have numerous wrinkles and folds without
obvious pores (Fig. S1†). Moreover, magnied SEM image of
Fe2O3/GA clearly shows that Fe2O3 NPs are uniformly encapsu-
lated within the graphene layers with high density, indicating an
efficient hybridation of Fe2O3 NPs and graphene sheets (Fig. 2b).
It is important that the encapsulation of Fe2O3 NPs within the
graphene sheets avoid direct contact between Fe2O3 particles and
electrolyte. Such 3D porous frameworks promote the electro-
chemical activity and stability of the composites.26 TEM charac-
terization show the uniform distribution and intimate contact
between the graphene sheets and Fe2O3 nanoparticles with
diameters of 15–60 nm (Fig. 2c). Elemental distribution mapping
and HRTEM results (Fig. 2d) further conrm the Fe2O3/GA
nature. From Fe, O and C maps, we can clearly see that C is
everywhere, representing the graphene scaffold, while Fe and O
(Fe2O3) are also present. Moreover, the HRTEM image shows the
inter-planar spacing between lattice fringes is 0.25 nm, in
agreement with the (110) plane of a-Fe2O3.
The EDS spectra also verify the presence of the elements C, O,
Fe and Si. The signal of Si is from silica glass (Fig. S2†). The
powder XRD pattern of the composite indicates that the attached
Fe2O3 NPs are alpha phase (hematite) (JCPDS le card no. 33-
0664), consistent with the result of HRTEM characterization
(Fig. 3a). The absence of extra diffraction peaks demonstrates
high purity and crystallinity of the Fe2O3 particles. Remarkably,
Fig. 2Typical SEM, (a and b) TEM image, (c) elemental maps for C, Fe
and O and HRTEM of Fe2O3/GA composite (d).
This journal is © The Royal Society of Chemistry 2016

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no apparent diffraction peak could be identied at 20–30 which
corresponds to the (002) diffraction peak of graphene. This
indicates that the Fe2O3 NPs were efficiently deposited on the
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graphene surface, suppressing the stacking of graphene layers.
More information about the chemical bonding states in Fe2O3
as well as the chemical element valence were obtained by typical
X-ray photoelectron spectroscopy (XPS) measurements (Fig. 3b–
d). In the high-resolution Fe 2p spectrum (Fig. 3b), the oxidation
state of spectrum for the Fe 2p core level shows two distinct peaks
located at 711.0 and 724.6 eV corresponding to a spin–orbit
couple of the Fe 2p3/2 and Fe 2p1/2 peaks, which are typical of Fe3+
of Fe2O3. In addition, these two peaks are accompanied by two
shake-up satellites situated at 719 and 732.6 eV corresponding to
Fe2+ and does not overlap either with Fe 2p3/2 or Fe 2p3/2
peaks.17,18 This result indicates that Fe2O3–GA contains no or only
trace amount of Fe3O4. The survey XPS spectrum demonstrates
that Fe2O3/GA hybrid consists of iron, oxygen, and carbon
(Fig. 3c). In C 1s spectrum, three peaks at 284.7, 286.6 and 289 eV
are assigned to C–C/C]C, C–O and C]O, respectively
(Fig. 3d).17,27 The low intensities of C–O and C]O functional
groups suggest the conversion of GO precursor to graphene. As
shown in Fig. S3,† in the case of O 1s, the spectrum can be
deconvoluted into two subpeaks positioned at 530.2 and 531.8
eV, in accordance with O–Fe and O]C, respectively.27
The interesting morphologies of the Fe2O3/GA hybrids show
promise for energy storage applications. We next evaluated the
electrochemical properties of the hybrid Fe2O3/GA-III (here III
refers to three-electrode system) using 6 M KOH aqueous elec-
trolyte. The typical CV curves exhibit one pair of obvious redox
peaks at about
0.687 V for the anodic scan and
1.02 V for the
cathodic scan, which are respectively ascribed to the oxidation
and reduction processes (Fig. 4a). Well dened redox peaks
conrm the faradaic behavior of the Fe2O3/GA-III product that
involves the reversible redox reactions Fe2+ 4 Fe3+.28
Fig. 3 XRD pattern (a) the narrow spectra of Fe 2p (b) XPS survey
spectra (c) and the narrow spectra of O 1s (d) of the Fe2O3/GA
composite.
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Apparently, the peak current density positively relates to the
scan rate without obvious shape change of the CV curve, indi-
cating a good rate capability for Fe2O3/GA-III. However, the
increased scan rate caused a positive shi of the anodic peaks
and a negative movement of the cathodic peaks. This
phenomenon indicates that the polarization of Fe3+/Fe2+ reac-
tion increases at a high charging/discharging rate.
The specic capacitances of the composites are calculated
from galvanostatic charge/discharge curves at different current
densities ranging from 0.4 A to 8 A. A high capacitance of 1045.3
F g
1 at 0.4 A g
1 is obtained for Fe2O3/GA-III (Fig. 4b). It could
be observed that the specic capacitance is still as high as 577 F
g
1 even at the current density of 8 A g
1, indicating good rate
capability. A well dened charge step (oxidation) at around

0.67 V and a discharge step (reduction) at around
1.0 V can
be observed (Fig. 4b inset). These voltage platforms correspond
to oxidation and reduction of Fe2O3 nanoparticles, respectively.
The CD results agree well with the above CV characterizations.
The Fe2O3/GA and Fe2O3/G composites were next tested in
two electrode system by means of cyclic voltammogram (CV),
galvanostatic charge/discharge (CD) measurements and elec-
trochemical impedance spectroscopy (EIS). The CV curves of
both two-electrode Fe2O3/GA and Fe2O3/G SC devices measured
at potential scan rate of 50–500 mV s
1 show slight distortions
from the quasi rectangular shape, which indicates good
capacitive behaviour of the composites (Fig. 5a and b). Here the
disappearance of redox peaks in the two electrode system is
observed which is normally seen in redox active materials. The
reasons are not clear yet.29 Moreover, the increasing scan rate
dose not inuence the shape of the CV curves signicantly,
indicating good electron conductivity in the composites.
However, by comparing the current response of the CV curves,
the Fe2O3/GA SC exhibited much higher current density than
Fe2O3/G SC, leading to a larger area of the closed curve thus
a higher specic capacitance (Fig. 5a). As tested at scan rate of
100–1000 mV s
1, device shows good capacitive behaviour with
perfect CV curves indicating fast and successive reversible
charge–discharge property owing to the porous 3D framework
of the graphene aerogel (Fig. S4†). No obvious change in CV
curves was observed aer 500 cycles at scan rate of 100 mV s
1,
which suggest the stable nature of Fe2O3/GA composite
(Fig. S5†). Galvanostatic charge–discharge (CD) curves of Fe2O3/
GA and Fe2O3/G SC at different current densities are then tested.
Fig. 4 Electrochemical performance of Fe2O3/GA-III in three elec-
trode system; (a) CV curves of Fe2O3/GA-III at various scan rates, (b)
capacitance at different current densities. The inset shows first three
CD cycles at 0.4 A current density.
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Fig. 5 Two-electrode supercapacitor performance of Fe2O3/GA and
Fe2O3/G. CV curves of Fe2O3/GA SC (a) and Fe2O3/G SC (b); charge/
discharge curves of Fe2O3/GA SC (c) and Fe2O3/G SC (d).
The CD curves for both devices are relatively symmetrical and
linear which indicate a good electrochemical capacitive behav-
iour of the devices with excellent reversibility (Fig. 5c and d).
The specic capacitances of the Fe2O3/GA SC from the discharge
curves are calculated to be 440 and 393 F g
1 at a current density
of 0.45 and 1.5 A g
1, respectively. In contrast, the Fe2O3/G SC
shows lower values of 357 F g
1 at 0.45 A and 338 F g
1 at 1.5 A.
These results are consistent with the CV characterizations
above. A common feature of both two SCs is the linear charging
and discharging proles indicating better capacitive perfor-
mance. Furthermore, the devices showed no IR drop in CD
curves representing a negligible intrinsic resistance of the
electrode, which could be attributed to the superior conduc-
tivity of the composite.
When discharge current density was increased to 8 A g
1, the
Fe2O3/GA SC still exhibited considerable capacitance of 300 F
g
1, in contrast with 171 F g
1 for Fe2O3/G SC, indicating high
rate capability of Fe2O3/GA SC (Fig. 6a). The capacitance of the
Fe2O3/GA reported here at a current density of 1.5 A g
1 is also
higher than that of many metal–oxide based anode materials
and comparable to or even higher than that of the cathode
materials such as MnO2, Co3O4, V2O5, MoO3.30 Furthermore, to
exhibit the advantage of the Fe2O3/GA SC, the performance of
different FeOx/graphene nanocomposite based supercapacitors
are compared in Table S1.† The specic capacitance of the as-
prepared Fe2O3/GA SC is superior to that of many iron oxide
and graphene based composites. To further evaluate the dura-
bility of our devices, the cycling stability of the supercapacitor
was tested through a cyclic charge/discharge process at current
density of 3 A g
1. The as fabricated Fe2O3/GA SC device exhibit
328 and 297 F g
1 for the rst and 2200th cycles, respectively,
corresponding to 90.5% of capacitance retention. While the
Fe2O3/G SC shows 234 F g
1 and 190 F g
1 under the same
testing conditions, corresponding to only 81% capacitance
retention (Fig. 6b). The capacitance loss in the Fe2O3/G SC
might be mainly caused by volume changes as a result of
58998 | RSC Adv., 2016, 6, 58994–59000
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Fig. 6 Specific capacitance plot against the current density (a) cyclic
stability of both symmetric devices at 3 A g
1 (b) first four charge/
discharge curves of the Fe2O3/GA SC at 2.5 A g
1 (c) and Nyquist plots
of Fe2O3/GA and Fe2O3/G SCs (d).
restacking of graphene layers and subsequent particle pulveri-
zation. The 3D structure in the Fe2O3/GA SC electrode can
release the mechanical stress during charge–discharge process,
and therefore is benecial in maintaining the stability of the
electrode structure.26 The rst four galvanostatic charge–
discharge curves at 2.5 A g
1 is shown in Fig. 6c, corroborates
the result with cyclic stability. In order to investigate the resis-
tance of the composites, AC impedance spectral analysis (EIS)
for both devices was carried out. Nyquist plots were collected in
the frequency range of 100 kHz to 0.1 Hz at open circuit
potential (Fig. 6d). Z0 and Z00 refer to the real and imaginary
parts of the impedance. It can be observed that quantitatively,
all Nyquist plot curves are same (straight line) in shape, having
two distinct parts, a small semicircle arc at high frequency
region and a linear part at low frequency region. The arc usually
corresponds to the charge transfer limiting process and is
ascribed to the double-layer capacitance (Cdl) in parallel with
the charge transfer resistance (Rct).28,31 The inclined portion of
the curve (about 45 ) is ascribed to the Warburg impedance
representing ion diffusion in the electrolyte to the electrode
surface.32 It is noted that the Nyquist curve of the Fe2O3/GA SC
electrode exhibits very small arc and more straight line than the
corresponding Fe2O3/G SC electrode, indicating ideal capacitive
behaviour of the device and low resistance of the electrodes. The
higher capacitance of Fe2O3/GA SC electrode might due to the
synergistic effect of the combination of Fe2O3 nanoparticles and
the ne 3D interconnected framework structure of GA that serve
as “the highway” to promote and facilitate ion adsorption and
diffusion between the active material and electrode. The
uniform distribution of small sized Fe2O3 nanoparticles helps
to shorter electrolyte diffusion pathways, hence guaranteeing
the sufficient utilization of Fe2O3 particles.28,33
To further investigate the Fe2O3/GA composite for practical
application, all-solid-state exible supercapacitor devices were
fabricated, in which pressed Ni foam substrate was used as the
This journal is © The Royal Society of Chemistry 2016

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exible current collector, and KOH/poly(vinyl alcohol) (PVA) gel
electrolyte was used as the solid electrolyte as shown schemat-
ically in Fig. 7a. The fabricated devices were examined by CV,
charge/discharge and cycling measurements. The exibility of
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the device was rst tested by CV at different bending angles of
90 and 180 (Fig. 7b). It is clear that the CV curves remained
unchanged, stable and nearly rectangular in shape indicating
high exibility and good electrochemical stability. The device
with bending angle of 90 was also tested at different scan rate.
With increasing scan rate, there is no obvious distortion of the
CV curves, indicating high rate capability (Fig. 7c). The CV curve
of the 90 bent device at 20 mV aer 2000 cycles is similar to
that of its initial state without any obvious change, showing
high exibility and excellent stability of the device (Fig. S6†).
Moreover, the long term cycling stability of the 90 bent
device was also tested by cyclic charge/discharge process at
current density of 3 A g
1 with capacitance retention of 89%
aer 2200 cycles (Fig. 7d). By comparing the cycling perfor-
mance of the bended and planner devices carefully, one can
notice that no signicant difference in device performance was
observed aer bending, further demonstrating the ultra exible
and stable nature of the Fe2O3/GA SC electrode (Fig. S7†). In
addition, electrochemical impedance spectroscopy (EIS)
measurement was carried out to investigate the reason for the
excellent capacitive performance of the bent device and its
relationship with ionic and electronic resistance. Nyquist plot of
the bent device before and aer 2000 CV cycles shows that at
very high frequencies, the intercept at real part Z0 (ionic resis-
tance of electrolyte) value is almost the same for both imped-
ance spectra. The semi circular loop at high frequency is too
small to identify, indicating the small interfacial charge-
transfer resistance and good electrical conductivity of the elec-
trode material. The slope of the impedance plot (about 45 ) at
low frequency increases and tends to become purely capacitive;
this implies that bending effect is negligible and the charge
Fig. 7 Schematic and optical images of the flexible supercapacitor in
different bending states, (a) CV curves of the device at scan rate of 100
mV s
1 when bent to 0 , 90 and 180 , (b) CV curves of 90 bent device
at different scan rates, (c) and capacitance of 90 bent device over
2200 cycles at 3 A g
1 (inset showing first 10 CD cycles at 3 A g
1) (d).
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Fig. 8 TGA curve of the Fe2O3/GA (a) and Ragone plots of energy
density versus power density for our symmetric SCs (b).
transfer between the Fe2O3 and the conductive GA sheets is
a fast process, revealing the ultra exibility of the device28b–d
(Fig. S8†).
TGA measurement carried out in the air was used to deter-
mine the loading amount of Fe2O3 in the Fe2O3/GAs. As shown
in Fig. 8a, the TGA curve displays a signicant weight loss at
approximately 350  C and a constant weight above 500  C. The
miniscule weight loss (<7%) that appeared below 300  C is most
likely attributed to the evaporation of adsorbed water mole-
cules. The major weight loss from 350 to 500  C was approxi-
mately 34%, indicating the combustion of graphene. Therefore,
the content of Fe2O3 in Fe2O3/GAs was calculated to be 59%.
The Ragone plot given in Fig. 8b compares the energy density
and power density of the Fe2O3/GA and Fe2O3/G in two-electrode
symmetric SCs. The Ragone plots verify that the Fe2O3/GA SC
operated at 0.8 V delivered the highest energy density of 9.8 W h
kg
1 under a power density of 90.1 W kg
1 higher than Fe2O3/G
SC (7.9 W h kg
1 under almost the same power density). Even
when the power density is increased to 1600 W kg
1, the energy
density of our Fe2O3/GA SC still maintains 6.7 W h kg
1. It is
clear that Fe2O3/GA SC exhibits much better performance in
terms of both energy density and power density than Fe2O3/G SC
device. The results of this work are comparing favourably with
earlier related reports.
Conclusions
In summary, a novel class of Fe2O3/GA hybrid was successfully
synthesized through hydrothermal method and the material
showed good performance as lightweight solid-state, exible
symmetric SC device. Compared with the nonporous Fe2O3/G
composite, the Fe2O3/GA composite show much higher capaci-
tance and cycle stability. In addition, all-solid-state exible
supercapacitor devices were fabricated by the as prepared
Fe2O3/GA composite, which show excellent exibility and
stability nature. This rationally designed 3D graphene and
metal oxide composite network based SC makes it a promising
candidate as electrode material for a exible SC. Moreover,
further optimization of the fabrication process on the simple
and low-cost assembly of this exible and lightweight device
may also improve its performance as efficient electrode material
for its practical use in adhesive tape-like or wearable
electronics.
RSC Adv., 2016, 6, 58994–59000 | 58999

RSC Advances
Acknowledgements
This work was supported nancially by National Key Basic
Published on 13 June 2016. Downloaded by National Center for NanoScience and Technology, China on 22/06/2016 04:03:18.
Research Program of China (2014CB931801, Z. Y. T.), National
Natural Science Foundation of China (51472054, L. S. Li,
21475029 and 91427302, Z. Y. T.), Instrument Developing
Project of the Chinese Academy of Sciences (YZ201311, Z. Y. T.),
CAS-CSIRO Cooperative Research Program (GJHZ1503, Z. Y. T.),
and “Strategic Priority Research Program” of Chinese Academy
of Sciences (XDA09040100, Z. Y. T.).
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