ARTICLE
pubs.acs.org/JPCC
Preparation of Highly Conductive Graphene Hydrogels for
Fabricating Supercapacitors with High Rate Capability
Li Zhang and Gaoquan Shi*
Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China
bS Supporting Information
ABSTRACT: Graphene hydrogels prepared via hydrothermal
reduction of graphene oxide dispersions (GH-Hs) were further
reduced with hydrazine (Hz) or hydroiodic acid (HI) to
improve their conductivities. The chemically reduced graphene
hydrogels possess high conductivities of 1.3 3.2 S m 1, which
are 1 order of magnitude higher than that of a GH-H (0.3 S m 1).
The supercapacitor based on the Hz-reduced GH-H exhibited
a high specific capacitance of 220 F g 1 at 1 A g 1, and this
capacitance can be maintained for 74% as the discharging
current density was increased up to 100 A g 1. Furthermore, it
showed high power density and long cycle life. The high-
performances of this supercapacitor make it promising for high rate charge/discharge applications.
1. INTRODUCTION
Graphene, a one-atom thick graphite sheet, is recognized as a
promising carbon material for fabricating high-performance
supercapacitors because of its low mass density, excellent elec-
trical conductivity, and high specific surface area (SSA; ∼2630
m2 g 1, theoretical).1 6 Both surfaces of a graphene sheet are
exterior surfaces readily accessible by an electrolyte, and the
effective surface area of a practical graphene-based material
depends strongly on its layers of graphene nanosheets.5,6 To
date, a great deal of effort has been devoted to exploring
graphene-based electric double-layer capacitors (EDLCs).5 16
For example, graphene sheets prepared by chemical vapor
deposition can be used to fabricate ultrathin layer EDLCs with
high rate capability.14 On the other hand, chemically converted
graphene (CCG) materials can be prepared in large scale and at
low costs.1,2 Furthermore, EDLCs based on CCG sheets with
aqueous electrolytes exhibited high specific capacitances of 135
to 205 F g 1,7,8 which are comparable to or higher than those of
the EDLCs based on active carbon or carbon nanotubes.2,17
EDLCs fabricated from curved or surface-modified graphene
sheets and using ionic liquids as electrolytes showed ultrahigh
energy densities of 65 85 Wh kg 1 because of their high
operating voltages.18,19 However, in most of these studies, the
high specific capacitances and energy densities were only achiev-
able by charging/discharging at low current densities (<1 A g 1)
or cyclic voltammetry (CV) scanning at low potential scan rates
(<50 mV s 1), which defeats the primary purpose of using a
supercapacitor for high rate charge/discharge applications. This
phenomenon is partially attributed to the facile restack of
graphene sheets during material preparation and subsequent
electrode production processes. As a result, graphene-based
electrodes usually do not have sufficiently large pores for the
r 2011 American Chemical Society
facile access of electrolyte. 5,20 Furthermore, the formation of
a bulk electrode relies on multiple electrical contacts among
the graphene agglomerates, similar to the contacts existing in
all particulate electrode materials, contributing an additional
electronic resistance.10 Hence, it is crucial to prepare less-
agglomerated, self-supported, and binder-free graphene-
based electrodes for realizing the practical applications in
supercapacitors.21
Recently, a self-assembled graphene hydrogel prepared by a
one-step hydrothermal method (GH-H) was reported by our
group.22 This GH-H is characterized by a well-defined three-
dimensional (3D) porous network, which offers an opportunity
to optimize the ionic diffusion in graphene-based electrodes for
EDLCs. The unique 3D morphology of GH-H allows most of the
graphene sheets to be expose to electrolyte, and provides open
channels for unobstructed transportation of electrolyte. Actually,
the EDLC based on GH-H showed a high specific capacitance of
about 200 F g 1 at a low discharge current density (0.3 A g 1).22
However, its capacitance decreased greatly at a high discharge
rate because of the relatively low conductivity and large amount
of residual oxygenated groups of the hydrogel. In this work, we
treated GH-H by chemical reduction with Hz or HI to improve
its conductivity and further remove its residual oxygenated
groups. It was found that the EDLC based on Hz-reduced
GH-H could maintain a high specific capacitance of 165 F g 1
at an extraordinary fast discharge rate of 100 A g 1 in aqueous
KOH electrolyte. This value is 74% of that (222 F g 1) measured
at the discharge current density of 1 A g 1.
Received: May 1, 2011
Revised: July 9, 2011
Published: July 27, 2011
17206 dx.doi.org/10.1021/jp204036a | J. Phys. Chem. C 2011, 115, 17206–17212
The Journal of Physical Chemistry C
Figure 1. (a) Photographs of GH-H, GH-HI3, GH-HI8, GH-Hz3, and GH-Hz8 (from left to right); (b-d) SEM images of the interior microstructures
of freeze-dried GH-H (b), GH-HI8 (c), and GH-Hz8 (d), respectively; (e) XRD patterns of graphite, GO, and GHs; (f) N2 adsorption desorption
isotherms of freeze-dried GH-H, GH-HI8, and GH-Hz8.
2. EXPERIMENTAL SECTION
2.1. Preparation of Graphene Oxide (GO). GO was prepared
by oxidation of natural graphite powder (325 mesh) according to
a modified Hummers’ method.23,24 Briefly, graphite (3.0 g) was
added to concentrated sulfuric acid (70 mL) under stirring at
room temperature, then sodium nitrate (1.5 g) was added, and
the mixture was cooled to 0 °C. Under vigorous agitation,
potassium permanganate (9.0 g) was added slowly to keep the
temperature of the suspension lower than 20 °C. Successively,
the reaction system was transferred to a 35 40 °C water bath
for about 0.5 h, forming a thick paste. Then, 140 mL of water was
added, and the solution was stirred for another 15 min. An
additional 500 mL of water was added and followed by a slow
addition of 20 mL of H2O2 (30%), turning the color of the
solution from brown to yellow. The mixture was filtered and
washed with 1:10 HCl aqueous solution (250 mL) to remove
metal ions followed by repeated washing with water and cen-
trifugation to remove the acid. The resulting solid was dispersed
in water by ultrasonication for 1 h to make a GO aqueous
dispersion (0.5 wt %). The obtained brown dispersion was then
subjected to 30 min of centrifugation at 4000 rpm to remove any
aggregates. Finally, it was purified by dialysis for 1 week to
remove the remaining salt impurities. The thickness of the GO
sheets was measured to be around 1 nm as shown by their atomic
force microscopy (AFM) image (Figure S1, Supporting In-
formation), indicating that they are monolayers.25
2.2. Preparation and Purification of GH-H and Chemically
Reduced GH-Hs. GH-H was prepared by hydrothermal reduc-
tion of GO sheets in their aqueous dispersion.22 The procedures
are described briefly as follows. A 10 mL portion of 2 mg mL 1
homogeneous GO aqueous dispersion was sealed in a 16-mL
Teflon-lined autoclave and maintained at 180 °C for 12 h. Then,
17207
ARTICLE
the autoclave was naturally cooled to room temperature and
GH-H was obtained. The chemical reduction of GH-H was carried
out by immersing it into an aqueous solution of HI (55%) or
hydrazine monohydrate (50%) in a sealed cuvette. The reduction
was conducted for 3 or 8 h at 100 °C for HI and 95 °C for
hydrazine hydrate (Hz), respectively. Then, the resulting gra-
phene hydrogels (GHs) were purified by dialysis for 2 days in
ultrapure water to remove the residual reducing agents. The
chemically reduced hydrogels are defined as GH-HI3, GH-HI8,
GH-Hz3 and GH-Hz8, correspondingly, according to the type of
reducing agent and the time of reduction.
2.3. Fabrication of the Supercapacitors. The procedures of
fabricating the supercapacitors are described as follows. Two
slices of GH (each has a thickness of about 1 mm) were cut from
the as-prepared cylindrical GH sample. They were separated by a
filtrate paper soaked with electrolyte (5 M KOH) and used as the
supercapacitor electrode materials. Before electrochemical mea-
surements, the GH slices were immersed in 5 M KOH aqueous
electrolyte overnight to exchange their interior water with
electrolyte. Two Pt foils were used as the current collectors. All
the components were assembled into a layered structure and
sandwiched between two PTFE sheets (Figure S2, Supporting
Information).
2.4. Electrochemical Measurements. Electrochemical per-
formances of the supercapacitor cells were tested by CV,
galvanostatic charge/discharge (on a CHI 440 potentiostat,
CH Instruments, Inc.), and electrochemical impedance spectros-
copy (EIS, on a CHI 660 potentiostat, CH Instruments, Inc.). All
of the experiments were carried out in a two-electrode system.
The potential range for CV measurements and galvanostatic
charge/discharge tests was 0 1 V. EIS tests were carried out in
the frequency range of 105 0.05 Hz at a10 mV amplitude
referring to open circuit potential. The mass specific capacitances
dx.doi.org/10.1021/jp204036a |J. Phys. Chem. C 2011, 115, 17206–17212
The Journal of Physical Chemistry C
Table 1. MB SSA, C/O and C/N Atomic Ratios, Electrical Conductivities (δ), Specific Capacitances (Csc) at Different Current
Densities, and Capacitance Retentions (Cr) of GHs
GH SSA (m2g 1) C/O (C/N) δ (S m 1)
GH-H 964 4.96 0.3
GH-HI3 778 6.56 1.8
GH-Hz3 911 5.85 (30.4) 1.3
GH-HI8 818 6.75 3.2
GH-Hz8 951 6.09 (36.7) 2.7
(Csc) were calculated by using the equations Csc = 2(IΔt/mΔV),
where I is the constant discharge current, Δt is the discharging
time, m is the mass of one electrode, and ΔV is the voltage drop
upon discharging (excluding the IR drop). The energy density
(E) and power density (P) of an EDLC electrode depicted in the
Ragone plot were calculated by using the equations E = (1/8)-
CscΔV2 and P = E/Δt, respectively.
2.5. Characterizations. Scanning electron micrographs
(SEMs) were recorded on a Hitachi S-4500 scanning electron
microscope operated at 2.0 kV. X-ray diffraction (XRD) mea-
surements were conducted using a D8 Advance (Bruker) X-ray
diffractometer with Cu Ka radiation (λ=1.5418 Å). Nitrogen
adsorption experiments and micropore analysis were conducted
at 77 K using a TriStar II 3020 (Micromeritics Instrument
Corporation) apparatus. Before adsorption measurements, the
samples were degassed in vacuum at 473 K for 12 h. The SSAs
of the freeze-dried hydrogels were calculated by Brunauer
Emmett Teller (BET) analyses of their adsorption isotherms.
The SSAs of the hydrogels were also measured by a methylene
blue (MB) adsorption method, where MB dye was employed as a
molecular probe, and UV vis spectroscopy was used to measure
the concentration change of MB before and after the adsorp-
tion.26 X-ray photoelectron microscopy (XPS) was performed
on a ESCALAB 250 photoelectron spectrometer (ThermoFisher
Scientific) with Al Ka (1486.6 eV) as the X-ray source set at
150 W and a pass energy of 30 eV for high-resolution scan.
Elemental analysis was conducted on a CE440 elemental ana-
lyzer. AFM image of GO sheets deposited on a freshly cleaved
mica surface was taken out by using a Nanoscope III MultiMode
SPM (Digital Instruments) with an AS-12 (“E”) scanner oper-
ated in tapping mode in conjunction with a V-shaped tapping tip.
Conductivities of the as-prepared GHs were measured by a
conventional four-probe technique.
3. RESULTS AND DISCUSSION
3.1. GH-H and Chemically Reduced GH-Hs. GH-H can be
easily prepared by one-step hydrothermal reduction of GO
aqueous dispersion (Figure 1a). According to our previous
report,22 the restored conjugated structure of GO sheets during
hydrothermal reduction can induce partial overlapping or coales-
cing of flexible graphene sheets via π π stacking interactions,
which forms the strong cross-links of the 3D graphene network.
As imaged by SEMs of freeze-dried GH-H (Figure 1b), the pore
structure was formed by physical cross-linking of graphene
sheets, and the pore sizes ranged from submicrometer to several
micrometers. This unique 3D morphology can effectively pre-
vent restacking of graphene sheets, which provides great promise
in preparing self-supported and binder-free graphene-based
EDLC electrodes. The further treatment of GH-H with reducing
agent has less impact on the microscopic pore structure of GH-H
17208
ARTICLE
Csc (F g 1) at 1 A g-1 Csc (F g 1) at 100 A g 1
Cr (%)
203 117 57
184 139 75
205 161 78
187 150 80
222 165 74
(Figure 1c, d); nevertheless, the HI-reduced GH-H became more
compact (the size of the gel became smaller) probably due to
enhanced π π stacking, while the hydrazine hydrate-reduced
GH-H showed a slight expansion caused by gas release during
reduction (Figure 1a).
Figure 1e shows the XRD patterns of graphite, GO, and freeze-
dried GHs. The pattern of GH-H exhibits a broad peak centered
at 2θ = 23.5°, corresponding to the graphitic (002) profile with
an interlayer spacing of 3.77 Å. This value is much smaller than
that of the GO precursor (6.94 Å), while still being higher than
that of graphite (3.36 Å). This result suggests the recovery of
π-conjugated structure from GO sheets upon hydrothermal
reduction and also the presence of residual oxygenated functional
groups on reduced GO sheets.27 After chemical reductions, the
diffraction peaks of GH-HI and GH-Hz are slightly up-shifted
with an interlayer spacing of 3.68 Å because of further removing
the residual oxygenated groups of GH-H. By analyzing these
peaks through the Lorentzian fitting and Scherrer equation,28 the
average number of layers in the pore walls of the chemically
reduced GHs is about 4.
In order to characterize the exposed surface areas and micro-
structures of GHs, low-temperature nitrogen adsorption measure-
ments were conducted. Figure 1f shows the N2 adsorption
desorption isotherms of freeze-dried GH-H, GH-HI8, and GH-
Hz8, and all three curves are characterized by type II isotherms
with no hysteresis loops. These results reflect that no micropores
or mesopores exist in these hydrogels. The BET SSAs of GH-H,
GH-HI8, and GH-Hz8 were measured to be 166, 166, and
215 m2 g 1, respectively, indicating that chemical reductions
did not change or slightly increased the SSA of GH-H. Because
the large pore sizes of GHs lay beyond the range accessible to gas
adsorption29 and freeze-dried GHs would have less available
surfaces because of their slight volume shrinkages,26 MB dye
adsorption technique was also employed to measure the SSAs of
these GHs (Table 1). As can be seen from Table 1, the SSAs of
the chemically reduced GH-Hs are in the range of 780 to
950 m2 g 1, which is comparable to that of GH-H (960 m2 g 1).
It can be speculated that all these high SSAs based on MB dye
adsorption are associated with the open channels formed be-
tween ultrathin graphene sheets in GHs. These unique open-
channels can greatly reduce the dynamic resistance of electrolyte
ions within smaller pores, favoring the improvement of power or
rate capability of EDLC.
The surface chemistry of the GHs was analyzed by XPS, and
the C1s spectra of GH-H, GH-HI8, and GH-Hz8 are shown in
Figure 2. The C1s XPS spectra of these three samples exhibit the
same oxygen functionalities, C O (286.6 eV), CdO (288.0 eV),
and O CdO (289.2 eV) groups. However, the intensities of
these peaks in the spectra of GH-HI8 and GH-Hz8 are weaker
than those in the spectrum of GH-H, indicating further deoxy-
genation by chemical reductions. In addition, the C1s XPS
dx.doi.org/10.1021/jp204036a |J. Phys. Chem. C 2011, 115, 17206–17212
The Journal of Physical Chemistry C
spectrum of the Hz-reduced sample has an additional peak at
285.9 eV associated with CdN bonds of hydrazones.30 The XPS
survey scan also shows a N1s peak at 397 eV for the Hz-reduced
samples (Figure S3, Supporting Information). The C/O and
C/N atomic ratios of the GHs were calculated from the results of
elemental analysis (Table S1, Supporting Information) and the
data are listed in Table 1. According to this table, the residual
oxygenated groups of GH-H were partly removed by chemical
reductions. The chemical reduction of GH-H is also confirmed
by the improved conductivity of GH-HI and GH-Hz (Table 1).
The conductivity of as-prepared GH-HI8 hydrogel was measured
to be 3.2 S m 1, which is 1 order of magnitude higher than that of
GH-H (0.3 S m 1).
3.2. Electrochemical Studies on GH Based Supercapaci-
tors. GH-H and its chemically reduced counterparts can be
directly used as the electrodes of supercapacitors without using a
binding agent and/or conducting additive, and their perfor-
mances were evaluated by CV, galvanostatic charge/discharge,
and EIS tests. Two-electrode capacitor configuration (Figure 3a)
was used for these measurements to provide the most reliable
results.31 Panels b and c of Figure 3 are the CV curves of the
supercapacitor cells based on GH-H, GH-HI8, and GH-Hz8 at
potential scan rates of 50 and 800 mV s 1, respectively. At a
Figure 2. C1s XPS spectra of GH-H (a), GH-HI8 (b), and
GH-Hz8 (c).
Figure 3. (a) Schematic illustration of GH-based supercapacitor devices; (b,c) cyclic voltammograms of the supercapacitor cells based on GH-H,
GH-HI8, and GH-Hz8 at scan rates of 50 (b) and 800 mV s 1 (c).
17209
ARTICLE
relatively low scan rate of 50 mV s 1, the CV curves are in typical
rectangular shape, indicating good charge propagations at the
electrode interfaces following the EDLC mechanism. When the
scan rate increased up to 800 mV s 1, the CV curves of GH-HI8
and GH-Hz8 still keep a quasi-rectangular shape with small
distortion, while the shape of the CV loop of GH-H electrode
became narrower and more oblique. These results imply that
the chemically reduced GHs possess better rate capabilities and
lower internal resistances.32
Figure 4 demonstrates the representative galvanostatic
charge/discharge curves of GH-H, GH-Hz3, and GH-Hz8 tested
at a charging/discharging current density (id) of 20 or 100 A g 1.
GH-Hz3 and GH-Hz8 can retain nearly linear and symmetric
charge/discharge profiles even at an ultrahigh id of 100 A g 1,
while the charge/discharge curve of GH-H became asymmetric,
probably because of some irreversible faradic processes. These
observations are consistent with the results of CV measurements,
further indicating a rapid current response and excellent capaci-
tive behavior of Hz-reduced GHs. Moreover, at the same current
density, GH-Hz8 displayed a much lower IR drop at the very
beginning of the discharge process. This potential drop was
caused by the overall internal resistance of the electrode. Low
internal resistance is of great importance in energy-storing
devices, as less energy will be wasted to produce unwanted heat
during charging/discharging processes. Thus, GH-Hz8 is more
suitable for fabricating safe and power-saving supercapacitors
compared with GH-H electrodes.
The specific capacitances were calculated from the slopes of
the charge discharge curves, and the results obtained at id of 1 and
100 A g 1 are listed in Table 1. The rate performance of these
GH electrodes was also evaluated by charging/discharging at
different id's (Figure 5). Accordingly, the specific capacitances
of chemically reduced GH electrodes were measured to be
184 222 F g 1 at id =1 A g 1, and these values are comparable
to that of the GH-H electrode (203 F g 1). However, the GH-H
electrode lost its 47% capacitance as id was increased from 1 to
100 A g 1, while the chemically reduced GH electrodes main-
tained their 74 80% specific capacitances in the same id range.
This is possibly due to the improved conductivity of reduced
hydrogels accelerating its charge-transfer during the discharge
processes at high current densities. Furthermore, Hz-reduced
hydrogels exhibited better capacitive performance than that of
HI-reduced hydrogels. This phenomenon is possibly attributed
to the following two factors. First, Hz-reduced hydrogels possess
a slightly larger SSA than that of HI-reduced hydrogels. Second,
some nitrogen atoms were incorporated into the hydrogels
through hydrazine reduction, as indicated by XPS and elemental
analysis results described above. It was reported that the
dx.doi.org/10.1021/jp204036a |J. Phys. Chem. C 2011, 115, 17206–17212
The Journal of Physical Chemistry C
Figure 4. Galvanostatic charge/discharge curves of GH-H, GH-Hz3, and GH-Hz8 at a charging/discharging current density of 20 (a) and
100 A g 1 (b).
Figure 5. Plots of specific capacitance versus discharging current density for GH-HI (a) and GH-Hz (b) compared with GH-H.
Figure 6. Ragone plot of the supercapacitor based on GH-Hz8. Scatter
dots refer to the largest power densities and the corresponding energy
densities reported in the literature (the reference numbers are indicated
in the figure).
heteroatoms and functional groups on graphene sheets could
increase the wettability of the electrode33,34 and improve the
overall performance of the capacitor. In comparison, most of the
graphene-based EDLC electrodes reported previously can
achieve high specific capacitances only at very low id (<1 A g 1)
or CV scan rate (<50 mV s 1). However, the GH-Hz8 electrode
has a high specific capacitance of 165 F g 1 even at id = 100 A g 1,
indicating its superior rate capability. The power density of
the supercapacitor with GH-Hz8 electrodes can reach up to
30 kW kg 1 at 100 A g 1 without sacrificing its energy storage
capability (energy density = 5.7 Wh kg 1, Figure 6), which
is much higher than the largest power densities of graphene-
based EDLC electrodes declared in the literature (also illus-
trated in Figure 6).7 11,35 This result is also comparable
to that of a pseudo-two-dimensional hydrated graphene film
electrode in aqueous electrolyte (power density = 24 kW kg 1,
17210
ARTICLE
energy density = 5.5 Wh kg 1).21 Given that supercapacitors are
usually operated at high current densities,36,37 these improvements
are of significance for practical applications.
Figure 7 shows the Nyquist plots of the GH-based super-
capacitors in the frequency range of 0.05 to 1 MHz. Each plot is
characterized by an inconspicuous arc in the high frequency
region and a straight line in the low frequency region. The
depressed high frequency loop is related to the electronic
resistance. It is clear from these plots that the resistances of the
electrodes based on chemically reduced GH-Hs are lower than
that of GH-H. The 45° region in the plot of chemically reduced
GH-H is short (82 12 Hz for GH-HI8 or 112 38 Hz for GH-
Hz8, inset of Figure 7), indicating a typical Warburg impedance.
This result is in accord with the “transmission line” behavior,
reflecting that the hydrogels have a porous structure as confirmed
by its SEM images. The vertical lines at lower frequencies indi-
cate a pure capacitive behavior. The more vertical the curve, the
more closely the supercapacitor behaves as an ideal capacitor.8
The transition point between the Warburg region and the vertical
region is referred to as the “knee”.38,39 The knee frequency
denotes the maximum frequency at which capacitive behavior is
dominant, and it is an indication of the power capability of a
supercapacitor. Note that the knee frequencies of chemically
reduced hydrogels (e.g., 38 Hz for GH-Hz8, 12 Hz for GH-HI8)
are much higher than that of GH-H (3 Hz), while the knee
frequency for most commercially available supercapacitors in-
cluding those specially designed for high power applications is
lower than 1 Hz.40 The superior frequency responses of our
supercapacitors based on reduced GHs are mainly due to their
small internal resistances and the excellent electrolyte accesses to
the hydrogel electrodes through their unique porous networks.
The cycle life of the supercapacitor cell based on a GH-Hz8
electrode was tested between 0 and 1 V at a moderate constant
dx.doi.org/10.1021/jp204036a |J. Phys. Chem. C 2011, 115, 17206–17212
The Journal of Physical Chemistry C
Figure 7. Nyquist plots of GH-HI (a) and GH-Hz (b) compared with GH-H. Inset shows the magnified high-frequency regions.
Figure 8. Cycling stability of GH-Hz8 electrode upon charging/
discharging at a current density of 4 A g 1.
current density of 4 A g 1 as shown in Figure 8. As can be seen,
the specific capacitance of the supercapacitor still remained at
182 F g 1 (∼92%) after 2000 charge/discharge cycles, reflecting
that the electrode has good electrochemical stability and a
high degree of reversibility in the repetitive charge/discharge
cycling test.
4. CONCLUSION
We prepared highly conductive GHs by chemical reduction of
GH-H with hydrazine or hydroiodic acid. The GH-H reduced by
50% hydrazine at 100 °C for 8 h (GH-Hz8) was tested to be the
best electrode material among the GHs for supercapacitors. The
GH-Hz8-based supercapacitor has a high specific capacitance of
220 F g 1 at id =1 A g 1, and this capacitance can be maintained
for about 74% as id was increased up to 100 A g 1. Furthermore,
the capacitor exhibited a high power density of 30 kW kg 1 and
energy density of 5.7 Wh kg 1 at id = 100 A g 1. It also showed
long cycle life along with ∼92% capacitance retention after 2000
cycle tests at a moderate id = 4 A g 1. The rate capability or power
density of this supercapacitor is much higher than those of the
supercapacitors based on pure CCGs reported in literature,
mainly due to its high conductivity and unique 3D macroporous
structure.
’ ASSOCIATED CONTENT
bS Supporting Information. Photograph of a two-electrode
test cell, AFM image of GO sheets, survey scanned XPS, and
17211
ARTICLE
element analyst results of GHs. This information is available free
of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*To whom correspondence should be addressed. Phone: +86-10-
6277-3743. Fax: +86-10-6277-1149. E-mail: gshi@tsinghua.edu.cn.
’ ACKNOWLEDGMENT
This work was supported by the Natural Science Foundation
of China (91027028, 50873052, 50973054) and the China
Postdoctoral Science Foundation.
’ REFERENCES
(1) Allen, M. J.; Tung, V. C.; Kaner, R. B. Chem. Rev. 2009, 110,
132–145.
(2) Sun, Y.; Wu, Q.; Shi, G. Energy Environ. Sci. 2011, 4, 1113–1132.
(3) Rao, C. N. R.; Sood, A. K.; Subrahmanyam, K. S.; Govindaraj, A.
Angew. Chem., Int. Ed. 2009, 48, 7752–7777.
(4) Hall, P. J.; Mirzaeian, M.; Fletcher, S. I.; Sillars, F. B.; Rennie,
A. J. R.; Shitta-Bey, G. O.; Wilson, G.; Cruden, A.; Carter, R. Energy
Environ. Sci. 2010, 3, 1238–1251.
(5) Zhang, L. L.; Zhou, R.; Zhao, X. S. J. Mater. Chem. 2010, 20,
5983–5992.
(6) Zhu, Y.; Murali, S.; Cai, W.; Li, X.; Suk, J. W.; Potts, J. R.; Ruoff,
R. S. Adv. Mater. 2010, 22, 3906–3924.
(7) Stoller, M. D.; Park, S.; Zhu, Y.; An, J.; Ruoff, R. S. Nano Lett.
2008, 8, 3498–3502.
(8) Wang, Y.; Shi, Z.; Huang, Y.; Ma, Y.; Wang, C.; Chen, M.; Chen,
Y. J. Phys. Chem. C 2009, 113, 13103–13107.
(9) Zhu, Y.; Murali, S.; Stoller, M. D.; Velamakanni, A.; Piner, R. D.;
Ruoff, R. S. Carbon 2010, 48, 2118–2122.
(10) Biswas, S.; Drzal, L. T. ACS Appl. Mater. Interfaces 2010,
2, 2293–2300.
(11) Du, Q. L.; Zheng, M. B.; Zhang, L. F.; Wang, Y. W.; Chen, J. H.;
Xue, L. P.; Dai, W. J.; Ji, G. B.; Cao, J. M. Electrochim. Acta 2010,
55, 3897–3903.
(12) Lv, W.; Tang, D. M.; He, Y. B.; You, C. H.; Shi, Z. Q.; Chen,
X. C.; Chen, C. M.; Hou, P. X.; Liu, C.; Yang, Q. H. ACS Nano 2009,
3, 3730–3736.
(13) Zhu, Y.; Stoller, M. D.; Cai, W.; Velamakanni, A.; Piner, R. D.;
Chen, D.; Ruoff, R. S. ACS Nano 2010, 4, 1227–1233.
(14) Miller, J. R.; Outlaw, R. A.; Holloway, B. C. Science 2010,
329, 1637–1639.
dx.doi.org/10.1021/jp204036a |J. Phys. Chem. C 2011, 115, 17206–17212
The Journal of Physical Chemistry C ARTICLE

(15) Vivekchand, S. R. C.; Rout, C. S.; Subrahmanyam, K. S.;

Govindaraj, A.; Rao, C. N. R. J. Chem. Sci. 2008, 120, 9–13.
(16) Zhu, Y.; Murali, S.; Stoller, M. D.; Ganesh, K. J.; Cai, W.;
Ferreira, P. J.; Pirkle, A.; Wallace, R. M.; Cychosz, K. A.; Thommes, M.;
et al. Science 2011, 332, 1537–1541.
(17) Simon, P.; Gogotsi, Y. Nat. Mater. 2008, 7, 845–854.
(18) Liu, C. G.; Yu, Z. N.; Neff, D.; Zhamu, A.; Jang, B. Z. Nano Lett.
2010, 10, 4863–4868.
(19) Kim, T. Y.; Lee, H. W.; Stoller, M.; Dreyer, D. R.; Bielawski,
C. W.; Ruoff, R. S.; Suh, K. S. ACS Nano 2011, 5, 436–442.
(20) Kotz, R.; Carlen, M. Electrochim. Acta 2000, 45, 2483–2498.
(21) Yang, X.; Zhu, J.; Qiu, L.; Li, D. Adv. Mater. 2011, 23, 2833–
2838.
(22) Xu, Y. X.; Sheng, K. X.; Li, C.; Shi, G. Q. ACS Nano 2010, 4,
4324–4330.
(23) Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80,
1339–1339.
(24) Xu, Y. X.; Zhao, L.; Bai, H.; Hong, W. J.; Li, C.; Shi, G. Q. J. Am.
Chem. Soc. 2009, 131, 13490–13497.
(25) Xu, Y. X.; Bai, H.; Lu, G. W.; Li, C.; Shi, G. Q. J. Am. Chem. Soc.
2008, 130, 5856–5857.
(26) McAllister, M. J.; Li, J. L.; Adamson, D. H.; Schniepp, H. C.;
Abdala, A. A.; Liu, J.; Herrera-Alonso, M.; Milius, D. L.; Car, R.;
Prud’homme, R. K.; et al. Chem. Mater. 2007, 19, 4396–4404.
(27) Murugan, A. V.; Muraliganth, T.; Manthiram, A. Chem. Mater.
2009, 21, 5004–5006.
(28) Yang, S. Y.; Chang, K. H.; Tien, H. W.; Lee, Y. F.; Li, S. M.;
Wang, Y. S.; Wang, J. Y.; Ma, C. C. M.; Hu, C. C. J. Mater. Chem. 2011,
21, 2374–2380.
(29) Branchaud, B. P. J. Am. Chem. Soc. 2005, 127, 14117–14118.
(30) Stankovich, S.; Dikin, D. A.; Piner, R. D.; Kohlhaas, K. A.;
Kleinhammes, A.; Jia, Y.; Wu, Y.; Nguyen, S. T.; Ruoff, R. S. Carbon
2007, 45, 1558–1565.
(31) Stoller, M. D.; Ruoff, R. S. Energy Environ. Sci. 2010, 3, 1294–
1301.
(32) Yoon, B. J.; Jeong, S. H.; Lee, K. H.; Kim, H. S.; Park, C. G.;
Han, J. H. Chem. Phys. Lett. 2004, 388, 170–174.
(33) Hulicova, D.; Kodama, M.; Hatori, H. Chem. Mater. 2006, 18,
2318–2326.
(34) Lota, G.; Lota, K.; Frackowiak, E. Electrochem. Commun. 2007,
9, 1828–1832.
(35) For comparison, we recalculated the energy and power den-
sities using the original experimental data reported in the literature by
the method described in the Experimental Section.
(36) Burke, A. Electrochim. Acta 2007, 53, 1083–1091.
(37) Miller, J. R.; Simon, P. Science 2008, 321, 651–652.
(38) Hughes, M.; Shaffer, M. S. P.; Renouf, A. C.; Singh, C.; Chen,
G. Z.; Fray, J.; Windle, A. H. Adv. Mater. 2002, 14, 382–385.
(39) Niu, C. M.; Sichel, E. K.; Hoch, R.; Moy, D.; Tennent, H. Appl.
Phys. Lett. 1997, 70, 1480–1482.
(40) Du, C. S.; Pan, N. Nanotechnology 2006, 17, 5314–5318.

17212 dx.doi.org/10.1021/jp204036a |J. Phys. Chem. C 2011, 115, 17206–17212