Synthetic Metals 175 (2013) 6267

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Synthetic Metals
j our nal homepage: www. el sevi er . com/ l ocat e/ synmet
A novel multilayered architecture of graphene oxide nanosheets for high
supercapacitive performance electrode material
M. Zabihinpour
a,
, H.R. Ghenaatian
b
a
Department of Physics, Payame noor University, P.O. Box 19395-3697, Tehran, Iran
b
Faculty of Basic Science, JahromUniversity, Jahrom, Iran
a r t i c l e i n f o
Article history:
Received 11 November 2012
Received in revised form6 April 2013
Accepted 17 April 2013
Available online 28 May 2013
Keywords:
Supercapacitor
Specic capacitance
Multilayered graphene oxide nanosheet
Graphite oxide
a b s t r a c t
Multilayer graphene oxide (MGO) nanosheets have been prepared by a simple chemical method. The
MGO has been employed as a novel and low cost electrode material in construction of a high energy
aqueous symmetric supercapacitor MGO/MGO. Scanning electron micrographs reveal the formation of
nanosheet structure with thickness ranging from 30to 50nm The Fourier transform infrared spectroscopy
(FTIR) results conrm the existence of oxygenated functional groups in the MGO nanosheets. Cyclic
voltammetry (CV), galvanostatic chargedischarge (CD) and electrochemical impedance spectroscopy
(EIS) methods are carried out to characterize electrochemical performance of the symmetric superca-
pacitor MGO/MGO. The maximum cell applied potential 1.2 V is obtained associates with 60 F g
1
of
total electrode materials and maintains about 85% of the initial capacitance after 10,000 cycles. Further-
more, the symmetric supercapacitor MGO/MGO shows high specic energy, specic power and maximum
power values of 12 Wh kg
1
, 300 W kg
1
and 20,751 W kg
1
based on the total mass of the active elec-
trode materials, respectively, at a current density of 5mA cm
2
in 1M H
2
SO
4
. The performance of the
proposed supercapacitor has been compared with a symmetric supercapacitor based on graphite oxide
(GO).
2013 Elsevier B.V. All rights reserved.
1. Introduction
Supercapacitors are high-power density energy storage sys-
tems that in recent years have drawn much attention to their
because of their ability in storage and redeliverance of electri-
cal energy in a short time [1]. They can complement or replace
batteries in electrical energy storage and harvesting applications,
when high power delivery or uptake is needed. A notable improve-
ment in performance has been achieved through recent advances
inunderstanding charge storage mechanisms andthe development
of advanced nanostructured materials [25]. Performances of these
systems aredeterminedmainlybytheir electrodematerials [6]. The
main drawback of the supercapacitors is their lowspecic energy.
The specic energy (Wh kg
1
) of a supercapacitor is given by Eq.
(1) [7]:
Specic energy (SE) =
1
2
CV
2
=
IVt
2M3600
(1)
where Cis the specic capacitance (F g
1
), V is the working poten-
tial window(V), I is the discharge current (A), t is discharge time (s)
and Mis the amount of active materials (kg) in the supercapacitor

Corresponding author. Tel.: +98 9171912873.

E-mail address: m zabihin@pnu.ac.ir (M. Zabihinpour).
(includingpositive andnegative electrode weight). BasedonEq. (1),
twomainstrategies areenvisionedtoimprovethespecic energyof
supercapacitors: (i) using of nanomaterials with high surface area
and (ii) increasing working potential window (V). The stability
and the nature of the electrolyte and the electroactive material of
a supercapacitor are important parameters for determination of its
operating working potential [8].
Based on the charge-storage mechanisms, supercapacitors
can be classied into two categories: (i) the electric double layer
capacitors (EDLCs), mainly by using conducting porous materials
such as the pure carbon [9], in which the capacitance arises from
the charge separation at an electrode/electrolyte interface. (ii) The
multielectron-transfer Faradic reaction at or within 2-dimensional
surfaces of the electroactive materials [2,10] such as transition
metal oxides [11], electrically conducting polymers (ECPs) [12] and
heteroatom-containing carbon materials [13]. Supercapacitors can
store energy by using a single or combination of the charge storage
mechanisms. Lowspecic capacitance of the pure carbon materials
is a big drawback [14]. To overcome this problem, heteroatom-
containing carbon materials which have various functional groups
such as oxygen, nitrogen, boron and dispersed metal on their
surfaces, have been considered in the supercapacitor eld [9,15].
Recently, carbon materials with some oxygen containing func-
tional groups (such as COOH, CO, and others) show promising
pseudocapacitance characteristics [16]. Their abilities arise from
0379-6779/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.synthmet.2013.04.023
M. Zabihinpour, H.R. Ghenaatian / Synthetic Metals 175 (2013) 6267 63
Fig. 1. Scanning electron micrographs of (a) MGO nanosheets, (b) GO dense agglomerates.
contributing of electrochemically active and acidic functional
groups in the formation of EDLCs and Faradic reactions [1,6,9].
In this study, the MGO nanosheets have been prepared by a
simplechemical methodandusedas anewhighperformancemate-
rial in construction of a symmetric supercapacitor MGO/MGO in
aqueous electrolyte solution. This symmetric supercapacitor shows
both pseudo-capacitive behavior using EDLs formation and Faradic
reactions as energy storage mechanisms. The system demon-
strates a higher capacitance and specic energy than symmetric
supercapacitor GO/GO and can operate up to 1.2V in aqueous
media.
2. Experimental
2.1. Reagents and instrumentation
Graphite powders (raw samples) and analytical grade reagents
of KOH, HCl, Na
2
SO
4
, KClO
3
, and H
2
SO
4
were prepared fromMerk
or Fluka as supplied without further purication. All solutions were
prepared by using doubly distilled water. The electrolyte solutions
were degassed by using pure Argon during all experiments. All
electrochemical experiments were carried out by an Autolab Gen-
eral Purpose System PGSTAT 30 (Eco-chemie, The Netherlands). A
conventional three electrode cell was used in order to character-
ize the MGO and the GO using CV in potential windows 0.8 to
0.9V at scan rate 50mV s
1
. A MGO or GO plate (0.5mmthick and
1cm1cmarea) were used as the working electrode, a Pt wire and
Ag/AgCl (KCl, saturated) were utilized as the counter and reference
electrodes, respectively.
Symmetric supercapacitors were built in a home-made two
electrode cell: (i) MGO/MGO and (ii) GO/GO with two identical
MGO and GO electrodes, respectively. These were constructed
with 5mg cm
2
for each electrode using cellulose acetate as
separator in 1M H
2
SO
4
aqueous solution. Electrochemical inves-
tigations of the symmetric supercapacitors were performed as
follows: the CV and the CD experiments were done in cell applied
potential 0.01.2V at scan rates 50200mVs
1
and constant
current densities 540mAcm
2
, respectively. The EIS investi-
gations were performed at cell applied potential 1.2V and in
frequency range 10
2
to 10
5
Hz. Cycle life tests of the symmetric
supercapacitors MGO/MGO and GO/GO were done at a constant
chargedischarge current density of 5mAcm
2
for continuous
10,000 cycles.
Morphological studies of prepared samples were carried out
by using SEM (Philips XL 30). A Bomem (Quebec, Canada) MB102
FTIR spectrometer equipped with a DTGS mid-range detector,
CsI optics and a global source were employed to carry out the IR
measurements.
2.2. Preparation of MGO
The MGO was prepared fromnatural graphite based on the fol-
lowing procedures: the rawgraphite powder was added gradually
in the fuming nitric acid with ultrasonic radiation using an ultra-
sonic bath. Then mixtures temperature was xed at 70

C and this
product was oxidized using potassiumchlorate for 12h. In the next
step, the remaining liquid and solid particles were centrifuged and
solid product (GO) was repeatedly washed with 5% HCl solution
and distilled water and dried in an oven at 50

C for 24h. Finally, in

order topreparetheMGO, theGOpowder was dispersedin3MKOH
solutionusinganultrasonic irradiationanddispersedsolidparticles
were centrifuged in order to recover the MGO solid product. Subse-
quently, it was washed using doubly distilled water repeatedly and
dried in an oven at 50

C for 24h. Then, the powders were plated by

mixing 80wt% of MGO or GO powder with 15wt% acetylene black
powder and 5wt% of poly(tetraouroethylene) (PTFE).
3. Results and discussion
3.1. SEMand FTIR
Morphology and dimension of the as-prepared MGO and GO
were investigated by scanning electron microscopy (SEM) and the
results are shown in Fig. 1a, a

, b and b

, respectively. As shown
in Fig. 1a and a

, the structure of the MGO is consisted of some

nanosheets with thickness between 30 and 50nm The results
obviously demonstrate that the dense agglomerated GO can be
readily exfoliated as individual MGO nanosheets in the presence
of ultrasonic irradiation and KOH solution [17].
64 M. Zabihinpour, H.R. Ghenaatian / Synthetic Metals 175 (2013) 6267
Fig. 2. FTIR of the MGO nanosheets.
Previous studies [18] showthat the surface charge (zeta poten-
tial) of as-prepared graphene oxide sheets is highly negatively
charged when dispersed in water. The proposed mechanism can
be explained by ionization of the carboxylic acid and phenolic
hydroxyl groups using KOH in aqueous medium. So, exfoliation of
the GO is due to electrostatic repulsion forces between negatively
charged GO layers. Moreover, formation of the stable MGO col-
loids is attributed to electrostatic repulsion forces against van der
Waals interactions between the graphene layers [18]. These results
showthe critical role of KOH addition and ultrasonic irradiation in
preparation of the MGO nanosheets.
The FTIR spectra of the MGO are shown in Fig. 2. Similar to
FTIR spectra of the GO [19], the MGO (Fig. 2) depicts a strong OH
peak at about 3400cm
1
and other C O functionalities, COOH at
1720cm
1
andCOC/C OHinthe range 13841051cm
1
. The spec-
trum also shows a C C peak at 1619cm
1
corresponding to the
remaining sp
2
character.
3.2. Cyclic voltammetry studies
Cyclic voltammetry is one of the most suitable electrochemical
methods for estimating the difference between the Faradic and the
non-Faradic phenomena in electrochemical systems. Fig. 3 shows
cyclic voltammograms of the raw graphite, the GO and the MGO
in 1M H
2
SO
4
and the MGO in 1M Na
2
SO
4
electrolyte solutions
at scan rate of 50mV s
1
in three electrode cell congurations. As
Fig. 3shows, the larger current densityresponse of the MGO andthe
GO electrodes than raw graphite electrode is due to participation
oxygen-containing functional groups in formation of the EDL and
Faradic reactions. Predominantly, the MGO and the GO s voltam-
mograms showa couple of oxidation and reduction peak between
0.1 and 0.6V (versus Ag/AgCl) which are results of the transition
between quinone/hydroquinone states and are typical for carbon
materials with oxygen-containing functionalities [20]. The higher
current density response of the MGO nanosheets (Fig. 3) is due to
shorteningthediffusionandmigrationlengthof theelectrolyteions
during the fast charge/discharge process and increase the partici-
pation of the MGO electrochemical reactions. These results conrm
that the MGO nanosheets could be reversibly charged/discharged
using Faradic and non-Faradic phenomena better than the GO and
in the stable form.
The CV studies were also conducted across a wide working
potential windowof 0.01.2Vtoevaluate boththe Faradic andnon-
Faradic charge storage mechanisms and to determine a suitable
operating working potential window of the symmetric supercap-
acitors MGO/MGO and GO/GO. Fig. 4a and b shows the cyclic
voltammograms of both symmetric supercapacitors at different
scan rates 50200mV s
1
in 1M H
2
SO
4
solution. It is worth men-
tioning that during the charge process of these systems (anodic
Fig. 3. Cyclic voltammograms of the rawgraphite, the GOandthe MGO in1MH
2
SO
4
and the MGO in 1MNa
2
SO
4
electrolyte solutions at scan rate of 50mV s
1
in three
electrode cell conguration.
branches), the potential of the electrodes are split and in the
discharge process (anodic branches) electrode potentials will be
equaled nally.
The rectangle shape of the CV curves of the MGO/MGO cell
(Fig. 4a) at higher scan rates conrms that this system has a good
supercapacitive performance. Whereas, the parallelogramshape of
CVproles (Fig. 4b) of the GO/GOsystemis due toits higher internal
resistance than the MGO/MGO cell. Moreover, larger normalized
currents of the MGO/MGOthan the GO/GOat the same voltage scan
rates are due toshorteningthe diffusionandmigrationlengthof the
electrolyte ions during the fast charge/discharge processes [21].
The specic capacitance of a supercapacitor could be calculated
according to Eq. (2):
Specic capacitance (F g
1
) =

IdV
sMV
(2)
where I is the response current density (A), V is the voltage (V),
s is the potential scan rate (Vs
1
), V is cell applied potential
range (V) and Mis the amount of active materials (g) in the super-
capacitor (includes positive and negative electrodes) [10,22]. The
specic capacitances of the symmetric supercapacitors MGO/MGO
and GO/GO at different voltage scan rate were calculated using Eq.
(2) based on the cyclic voltammograms (Fig. 4a and b) and are
shown in Fig. 4c. As it is shown, the specic capacitance of the
MGO/MGO cell at high scan rate 200mV s
1
is 49.6F g
1
which
is about twice of the specic capacitance of the GO/GO system
(25F g
1
) at some scan rate. While, at lower scan rate 50mV s
1
the specic capacitance of the MGO/MGOcell is 61F g
1
, and about
1.37 times more than the specic capacitance of the GO/GO cell
(44.3F g
1
). These results show facile diffusion of the electrolyte
ions at higher scan rates in the bulk of the MGO nanosheets in view
of the fact that the porosity of the MGO nanosheets are higher than
the GOdense agglomerates. So, the electrolyte ions are more easily
inserted and de-inserted in the MGO nanosheets.
3.3. Galvanostatic chargedischarge and performance evaluation
Galvanostatic charge/discharge experiments were consid-
ered to evaluate the electrochemical performance of the
MGO/MGO and the GO/GO cells. Fig. 5a and b shows the
galvanostatic chargedischarge proles of the symmetric super-
capacitors MGO/MGO and GO/GO at different current densities
(540mA cm
2
). As shown (Fig. 5a and b), the potential varia-
tions of both systems are almost sloping with some steps, which
agrees with the CV results (Fig. 4a and b). This is attributed to the
M. Zabihinpour, H.R. Ghenaatian / Synthetic Metals 175 (2013) 6267 65
Fig. 4. Cyclic voltammetry responses of the symmetric supercapacitors MGO/MGO
(a) and GO/GO (b), at different scan rates 50200mV s
1
in 1MH
2
SO
4
solution and
effect scan rate on specic capacitance of both symmetric cells (c).
potential-dependent nature of Faradic redox reactions of MGO and
GO. It means that upon exchange of the electrons from a neutral
segment of positive and negative electrodes, some local positive or
negative charge deformations occur and according to the charge
neutrality, the ions owto the electrodes.
The calculated specic capacitance of both symmetric cells
based on Eq. (3) versus current density has been shown in Fig. 5c.
Specic capacitance (F g
1
) =
It
VM
(3)
where I denotes the applied constant discharge current (A), t
is discharge time (s) and V is discharge potential window
(V) [23].
As it is shown(Fig. 5c), the specic capacitance of the MGO/MGO
cell at high current density 40mAcm
2
is 43.6F g
1
which is about
1.89 times more than the specic capacitance of the GO/GO
system (23F g
1
). While, at lower current density 5mAcm
2
the
specic capacitance of the MGO/MGO cell is 60F g
1
and about
1.42 times more than the specic capacitance of the GO/GO cell
(42.3F g
1
). The results reveal that the MGO nanosheets can
exhibit higher electrode/electrolyte interface areas and providing
more electroactive regions than the GO.
Another useful parameter used to evaluate supercapacitor per-
formance is equivalent series resistance (ESR), which refers to the
resistance that adds to the impedance due to imperfections within
the electrolyte and capacitors material [3]. It shows the power
properties of thesystemduringthedischargeprocess. TheESRanal-
yses of the MGO/MGO and the GO/GO cells were calculated using
the chargedischarge proles of Fig. 5a and b. The output potential
windowdropped sharply at the beginning of each discharge exper-
iment, proportional to the ESR of the systems. The ESR () could
be calculated according to Eq. (4):
ESR =
E
charge
E
discharge
2I
(4)
where I, E
charge
andE
discharge
are the appliedconstant discharge cur-
rent (A), the output potential windowof the cell at the endof charge
and at the beginning of discharge after the Ohmic drop (V), respec-
tively [3]. These average values of 1.5 and 8 () for the MGO/MGO
and the GO/GO systems, respectively, were obtained at constant
chargedischarge current density of 5mAcm
2
. These lowinternal
resistance value of the MGO/MGOcell conrms that this systemhas
higher power characteristic than the GO/GO cell.
The good performance of the symmetric supercapacitor
MGO/MGO was highlighted using the Ragone plots derived from
theresults of thegalvanostatic dischargecurves (Fig. 5aandb) using
Eqs. (1) and (5) and are shown in Fig. 5d.
Specic power (SP) =
IV
2M
(W kg
1
) (5)
As a result, it is concluded that the MGO/MGO system exhibits
promising performance compared to the GO/GOsystem. For exam-
ple, at a constant current density of 5mA cm
2
, the high specic
energy of 12Wh kg
1
was obtained at the corresponding specic
power of 300Wkg
1
for the MGO/MGO cell, whereas the specic
energy of 8.45Wh kg
1
was obtained for the GO/GOsystem. So, the
specic energy of the symmetric supercapacitor MGO/MGO was
signicantly enhanced upon raising the specic capacitance of the
MGO/MGO cell. These results clearly show that application of the
MGO nanosheets as electroactive electrode materials can be one
of the best ways for fabrication of high energy supercapacitors. The
outstanding performance of the MGO nanosheets material is due to
decrement of ion mobility limitation during the chargedischarge
processes and facile formation of the EDLCs and Faradic reaction
[16].
The symmetric supercapacitors MGO/MGO and GO/GO
were subjected to a prolonged cycle-life test at a constant
chargedischarge current density of 5mAcm
2
for continuous
10,000 cycles and these cycling performances are shown in
Fig. 6.
As it is seen, the symmetric supercapacitor MGO/MGO repre-
sents high specic capacitance of 60F g
1
at initial cycles, which
was decreasedslowly to51F g
1
after 10,000cycles (15%decrease).
Whereas, the GO/GOalternative revealeda lowspecic capacitance
of 42.3F g
1
which was decreased sharply to less than 15F g
1
after
10,000 cycles (65% decrease). This high attenuation in the capac-
itance of the GO/GO system can be reasonably attributed to the
66 M. Zabihinpour, H.R. Ghenaatian / Synthetic Metals 175 (2013) 6267
Fig. 5. Galvanostatic chargedischarge curves of symmetric supercapacitors MGO/MGO (a) and GO/GO (b) at different constant current densities 540mA cm
2
in 1M
H
2
SO
4
solution and effect of current density on specic capacitance of both symmetric cells (c) and Ragon plots relating power density to achievable energy density of both
symmetric systems (d).
agglomeration of the GO. Conversely, the modest decrease of the
capacitance of the MGO/MGO cell suggests good cycle stability can
be reasonably attributed to the surface negative charges of the
MGO nanosheets which prevent aggregation and reducing its sur-
face area. So, from the results, it can be expected that the MGO
nanosheets feature good performance as supercapacitor materials
in the aqueous solutions.
Fig. 6. Dependence of the specic capacitance of the symmetric supercapacitors
MGO/MGO and GO/GO with cycle number at chargedischarge current density of
5 mAcm
2
.
3.4. EIS analysis
The EIS analysis is a powerful andnondestructive methodwhich
can be used to separate different processes and evaluate the kinet-
ics of the under investigation systems. This method has often been
used to study the power sources and electrochemical systems,
especially supercapacitors.
Here, the impedance spectra of the symmetric supercapacitors
MGO/MGO and the GO/GO were performed in 1.0M H
2
SO
4
elec-
trolyte at frequency range 10
2
to 10
5
Hz and shown in Fig. 7 in cell
applied potential 1.2V. As it is seen, the almost vertically straight
lines and semicircle in low and high frequencies of both systems
denitely demonstrate the pseudocapacitive behaviors. From the
intersecting point at high frequency with the real axis, the inter-
nal resistances of the supercapacitor MGO/MGO is less than the
GO/GO system. To better evaluate the performance of these two
systems, the experiment data were tted to the equivalent circuit
model shown in Fig. 7 and were represented in Table 1. Due to
the porous surface of the MGO and the GO electrodes, constant
phase elements CPE
dl
and CPE
F
are used to express C
dl
and C
F
in the
equivalent circuit. The impedance of the constant-phase element
is dened as Z
CPE
=[Q(j)
n
]
1
with 1n1, where Q, and n
are the frequency-independent constant representing capacitance,
angular frequency and a correction factor between 0 and 1, respec-
tively. The mean error of the modulus is less than 1% implying that
the parameter values obtained from EIS tting via such proposed
circuit are reliable. The analysis of Z () is based on Eq. (6):
Z() = R
s
+Z
I
() +Z
F
(W) (6)
M. Zabihinpour, H.R. Ghenaatian / Synthetic Metals 175 (2013) 6267 67
Table 1
Electrical parameters for the supercapacitors MGO/MGO and GO/GO evaluated fromEIS test at applied voltage 1.2 (V) in 1.0MH
2
SO
4
solution.
Cell Rs () R
ct1
() R
ct2
() CPE
dl
CPEF
C
dl
(F cm
2
) n
1
CF (F cm
2
) n
2
MGO/MGO 1.79 0.65 370 0.02 0.68 0.57 0.95
GO/GO 6.09 1.04 740 0.016 0.62 .38 0.89
Fig. 7. Equivalent circuit model and EIS plots of the symmetric supercapacitors
MGO/MGO and GO/GO at cell applied potential 1.2 (V) in 1.0M H
2
SO
4
solution.
The solid lines represent the tting results according to this equivalent circuit.
1
Z
I
()
=
1
R
ct1
+Z
W
+jC
dl
(7)
1
Z
F
()
=
1
R
ct2
+jC
F
(8)
Every element has physical meaning where , R
s
, Z
I
, Z
F
, R
ct1
,
R
ct2
, C
dl
, Z
W
and C
F
are the angular frequency, solution resistance,
impedance of modied lm/electrolyte interfaces, bulk faradic
impedance, ionic charge-transfer resistanceof theredoxtransitions
of the polymer lms, double layer capacitance, Warburg diffu-
sion impedance and bulk faradic pseudocapacitance, respectively
[2426]. As it is seen in Table 1, the double layer capacitance and
bulk faradic pseudocapacitance of the MGO/MGO is much higher
than the GO/GO system which is consistence with the results of
the CV and CD experiments. Also, the R
ct1
in both cases is lower
(approximately 500 times) than the R
ct2
, which suggests a higher
rate of energy storage by the electrically double layer formation as
compared to the Faradic reactions.
4. Conclusion
Nanostructured MGO has been prepared by chemical oxida-
tion followed by ultrasonic irradiation in the presence of KOH
and is used for constructing of a new high energy symmetric
supercapacitor. This systemshows very promising energy storage
characteristic up to 1.2V. Based on the obtained results, the specic
capacitance, specic energy and specic power of 60F g
1
,
12Wh kg
1
and 300Wkg
1
were calculated, respectively. This
study highlights and opens a new rich world of possibilities to
develop carbon materials with large facile synthesis and low cost
for supercapacitor applications.
Acknowledgement
I would like to thank the Payam e Nour University Research
Council is gratefully acknowledged for their nancial support.
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