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Materials Chemistry
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Mechanically strong and highly conductive graphene aerogel and its use as
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electrodes for electrochemical power sources
Xuetong Zhang,*a Zhuyin Sui,a Bin Xu,b Shufang Yue,b Yunjun Luo,*a Wanchu Zhanc and Bin Liuc
Received 16th January 2011, Accepted 18th March 2011
DOI: 10.1039/c1jm10239g
Mechanically strong and electrically conductive graphene aerogels
can be prepared by either supercritical drying or freeze drying of
hydrogel precursors synthesized from reduction of graphene oxide
with L-ascorbic acid, and the resulting graphene aerogels possess the
specific capacitance of 128 F g 1 with superior rate performance.
Aerogels, generally prepared from molecular precursors by solgel
processing and subsequently by supercritical fluid drying or by freeze
drying to replace the solvents in the wet gels with air, are highly
porous solid nanomaterials with unique characteristics including
large pore volumes, high surface areas and tunable porosity, and thus
with potential applications in the fields of Cerenkov detectors,
catalysis, electronic devices and so on.1,2 Carbon aerogels, one kind of
the most important aerogels, are novel porous carbon materials that
have received considerable attention since they have great potential in
many fields.3,4 Basically, carbon aerogels made by pyrolysis of
resorcinol/formaldehyde or phenol/furfural aerogels under an inert
atmosphere have a network structure of zero-dimensional inter-
connected nanosized particles.5,6 Porous attributes of the carbon
aerogels can be regulated by simply adjusting the size and shape of
the primary nanoparticles as micropores are related to the intra-
particle structure, whereas mesopores and macropores are produced
by the inter-particle structure.7 Lately, one-dimensional carbon
nanotubes with exceptional mechanical properties, superior thermal
and electrical properties were designed as the building unit of the
network structure and the corresponding carbon nanotube aerogels
have been synthesized and found great potential in the field of
actuator, supercapacitors, polymer composites, etc.810 Two-dimen-
sional graphene with one atom thickness, a single layer of graphite,
has attracted a great deal of attention in recent years due to its more
excellent physical properties than those of carbon nanotubes to some
extent,1113 which drives scientists to design and synthesize novel
aerogels with graphenes as the building blocks of the three-
a
School of Materials Science & Engineering, Beijing Institute of
Technology, Beijing, 100081, P. R. China. E-mail: zhangxtchina@yahoo.
com; yjluo@bit.edu.cn; Tel: +86-10-68918591
b
Research Institute of Chemical Defence, Beijing, 100191, P. R. China
c
Aerospace Institute of Special Materials & Technology, China Aerospace
Science & Industry Corp, Beijing, 100074, P. R. China
Electronic supplementary information (ESI) available: experimental
procedures, AFM and SEM images, TGA curves and electrochemical
impedance spectrum. See DOI: 10.1039/c1jm10239g
6494 | J. Mater. Chem., 2011, 21, 64946497
COMMUNICATION
dimensional network structure. However it is a great challenge to
synthesize graphene aerogels due to lack of knowledge on solgel
chemistry of graphene. Only in a very recent Communication,14
virtually indistinguishable carbon cross-linked graphene aerogels
(namely carbon/graphene composite aerogels in essence), synthesized
by solgel polymerization of resorcinol (R) and formaldehyde (F) in
an aqueous suspension of graphene oxide, and followed by carbon-
ization of the organic cross-links and thermal reduction of the gra-
phene oxide to graphene occurred simultaneously during pyrolysis
after supercritical CO2 drying of graphene oxide-RF gels, were
reported by Worsley, et al., unfortunately, sacrificial RF gel
template and carbonization energy have to be used during their
synthesis.
Herein we report an easy method to create graphene aerogels from
aqueous gel precursors processed by supercritical CO2 drying or by
freeze drying. The resulting aerogels with densities in the range
1296 mg cm 3 show large BrunauerEmmettTeller (BET) surface
areas (512 m2 g 1) and pore volumes (2.48 cm3 g 1) with wide pore
size distribution revealed by scanning electron microscopy and
nitrogen adsorption investigation. Mechanical property tests indicate
that the graphene aerogels can support more than 14000 times their
own weight, nearly twice of the amount supported by the carbon
nanotube counterpart. The bulk electrical conductivity of the gra-
phene aerogel is approaching 1  102 S m 1, more than 2 orders of
magnitude greater than those reported for macroscopic three
dimensional graphene networks prepared without any chemical
cross-links. For comparison with those reported by Worsley, et al.,14
the graphene aerogels presented here have been fabricated without
the use of any sacrificial template during precursor synthesis and
without the need of carbonization after the drying. The electro-
chemical measurements indicate that the resulting graphene aerogels
at a constant current density of 50 mA g 1 possess the specific
capacitance of 128 F g 1 with superior rate performance.
Graphene aerogels were assembled through the formation of
physical cross-links between graphene sheets using solgel chemistry.
Solgel chemistry involves the reduction of graphene oxide to form
a highly cross-linked hydrogel, which can then be freeze-dried or
supercritical-CO2-dried to form a graphene aerogel. Graphene oxide
was synthesized according to the procedure reported elsewhere15 and
its aqueous suspension with 4.0 mg mL 1 graphene oxide as shown in
Fig. 1a was prepared by ultrasonication. The quantitative L-ascorbic
acid was mixed uniformly with above suspension for reduction of
graphene oxide into graphene,16 and then the graphene hydrogel
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Fig. 1 Digital photos of the aqueous suspension of graphene oxide (a), the
graphene hydrogel (b) in a vial prepared by heating the mixture of graphene
oxide and L-ascorbic acid without stirring, the supercritical CO2 dried (left)
and freeze-dried (right) graphene aerogel (c), and a 7.1 mg graphene aerogel
pillar with the diameter of 0.62 cm and the height of 0.83 cm supporting
a 100 g counterpoise, more than 14000 times its own weight (d).
precursor as shown in Fig. 1b was obtained by heating the mixture
without stirring for a couple of hours. The reason for choosing
L-ascrobic acid as the reducing agent in our case was that no gaseous
products were formed during the formation of the gel precurser. If
L-ascorbic acid is replaced with one of the frequently used reducing
agents, such as hydrazine, NaBH4, LiAIH4, etc., non-uniform gels
were formed on account of evolution of gaseous products in the
course of reducing GO. A detailed discussion on the nature of the
hydrogelation will be presented in a forthcoming paper, however in
brief, gradually restored strong pp interaction among these reduced
graphene oxide sheets is the main reason for such a gelation. Single-
layer sheets of both graphene oxide and graphene were observed
respectively from suspension and hydrogel by atomic force micros-
copy, transmission electron microscopy and O 1s XPS (see Sup-
porting Information: Fig. SI1). Fig. 1c shows the digital photos of
the resulting monolithic graphene aerogels from its purified hydrogel
precursors treated by supercritical CO2 drying or by freeze drying.
The apparent densities of the graphene aerogels with supercritical
CO2 drying are in the range 2396 mg cm 3, while those of graphene
aerogels with freeze drying are in the range 1238 mg cm 3. The
change in density from one sample to another has resulted from the
differences in the drying processing and synthetic parameters, e.g.,
concentration of GO, length of aging time after gelation, etc. The
aerogels with supercritical CO2 drying are darkish, the same as that of
graphene powder, while those with freeze drying shine with a metal
lustre. The aerogels with supercritical CO2 drying could support at
least 14000 times their own weight, as shown in Fig. 1d. In
comparison, it was reported that 1.0 wt % polyvinyl alcohol enhanced
carbon nanotube aerogels with supercritical CO2 drying could just
support 8000 times their own weight.9 Judged from this, our graphene
aerogels without any enhancements are much mechanically stronger
than carbon nanotube aerogels reported elsewhere.9 The compressive
stressstrain curves (see Fig. SI2) of graphene aerogels with density
in the range 3196 mg cm 3 show two regions: an elastic region and
a yield region. In the elastic region, the solid walls of various pores in
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the graphene aerogels have presented elastic bending, while in the
yield region, the pores in the graphene aerogels have gradually
collapsed when stress was slowly increased. Youngs moduli in the
elastic region are in the range of 1.26.2 MPa, while those in the yield
region are in the range of 0.32.2 MPa (see Table SI1). These values
are much higher than that of the graphene 3D assemblies reported by
Shi et al. (290 kPa)17 and that of the graphene 3D assemblies reported
by Wang et al. (260 kPa).18 To the best of our knowledge, the gra-
phene aerogel reported herein is the strongest 3D assembly for gra-
phenes so far. However, the graphene aerogels with freeze drying
could only support 3300 times their own weight.
The morphology and porous attribute of the resulting graphene
aerogels were characterized by scanning electron microscopy and
nitrogen sorption tests. Fig. 2a and Fig. SI3 show typical SEM
images of the graphene aerogels with supercritical CO2 drying. It can
be seen that the morphology of the aerogels is quite uniform in the
large scale, and closer observations show that the aerogels exhibit
a three-dimensional network of randomly oriented sheet-like struc-
tures with wrinkled texture, and that the aerogels are rich in the
hierarchical pores with the wide size distribution: the macropores
(pore size of more than 50 nm) with the size of several micrometres
are closely stacked, and the solid walls of these macropores are
randomly self-assembled by the inter-twisted sheet-like graphene and
thus a lot of mesopores (pore size of 250 nm) are produced among
these sheet-like structures. Fig. 2b and Fig. SI4 show typical SEM
images of the graphene aerogels with freeze drying. It can be seen that
these aerogels, although they exhibit similar three-dimensional
network as observed for samples dried by supercritical CO2, present
different pore characteristics: plenty of larger macropores appeared
and many mesopores were barely produced. The porous properties of
the resulting graphene aerogels were also confirmed by the nitrogen
sorption tests. For the sample dried by supercritical CO2, a typical
Type IV isotherm characteristic with an adsorption hysteresis, as
shown in Fig. 2c, indicates that there are a lot of mesopores existing in
the aerogels. The pore size distribution as determined by the Barret-
Joyner-Halenda method, shows that much of the pore volume
(2.48 cm3 g 1) lies in the 2100 nm range, with a double-peak pore
diameter of 3.5 and 49 nm, respectively (Fig. 2d). The BET surface
Fig. 2 SEM images of supercritical CO2 dried (a) and freeze dried (b)
graphene aerogels, and typical nitrogen sorption isotherms (c), BJH
(BarretJoynerHalenda) desorption pore size distribution (d) of these
graphene aerogels.
J. Mater. Chem., 2011, 21, 64946497 | 6495

area for the sample dried by supercritical CO2 was 512 m2 g 1, much
lower than 2600 m2 g 1 of the theoretical value for a single graphene
sheet,19 indicating layering or overlapping of graphene sheets within
the aerogel. For the freeze-dried sample, the pore size distribution
shows that little of the pore volume (0.04 cm3 g 1) lies in the 1.5
55 nm range as shown in Fig. 2d, indicating that few of the mesopores
exist in the aerogels with freeze drying, consistent with the observa-
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tion given by SEM. It should be noted that, due to instrumentation
limitation, the macropores observed by SEM were not observed by
the nitrogen adsorption/desorption test. The BET surface area of the
freeze dried sample was 11.8 m2 g 1, much lower than that of the
supercritical dried one. This probably can be ascribed to the fact that
a lot of mesopores within the gel precursors were fused together to
form macropores impelled by gradual growth of ice crystals during
freeze drying.
The chemical attribute of the resulting graphene aerogels were
analyzed by X-ray photoelectron spectroscopy (XPS) and Raman
spectroscopy (see Fig. SI5). Fig. 3 shows the C1s XPS spectra of the
graphene aerogels with supercritical CO2 drying and freeze drying.
For comparison, the C1s XPS spectrum of the graphene oxide
powder is presented in Fig. 3 as well. Elemental O contents (atomic
%) were 32.44 for graphene oxide, 13.49 for graphene aerogel with
supercritical drying and 14.72 for graphene aerogel with freeze
drying, respectively, indicating removal of O happened. For the
graphene oxide powder, four different peaks centered at 284.5, 286.5,
287.8, and 289.0 eV, corresponding to C]C/CC in aromatic rings,
CO (epoxy and alkoxy), carbonyl, and carboxyl groups, respec-
tively,20 were detected and shown in Fig. 3a. Although the C1s XPS
spectra of graphene aerogels exhibit these same oxygen functionalities
shown in Fig. 3b, c, the peak intensities centered at 286.2, 287.8 and
289.0 eV, especially for the intensities of the peaks centered at
286.2 eV, are much smaller, and the intensities of the peaks centered
at 284.8 eV are much bigger, than those observed for the graphene
oxide. This reveals that, during hydrogelation of the aerogel
Fig. 3 C1s XPS spectra of graphene oxide (a), graphene aerogel with
supercritical drying (b) and freeze drying (c).
6496 | J. Mater. Chem., 2011, 21, 64946497
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precursors, most of the oxygen-containing functional groups in gra-
phene oxide, especially for the epoxy and alkoxy groups, were
removed by L-ascorbic acid16 and most of the conjugated bonds were
restored, namely, fewer defects in structure existed, in graphene sheets
of the aerogels.21 The removal of the thermally labile oxygen func-
tional groups by chemical reduction results in much increased
thermal stability22 for the graphene aerogels, which can be clearly seen
from thermal gravimetric analysis curves (see Fig. SI5).
The resulting bulk graphene aerogels with either supercritical CO2
drying or freeze drying present linear IV curves as shown in Fig. 4a,
indicating that these aerogels are highly conductive. This is ascribed
to the recovery of p-conjugated systems from graphene sheets upon
L-ascorbic acid reduction, as confirmed by XPS analysis as shown in
Fig. 3. However the dI/dV values are dependent on the drying
method of the graphene aerogels. The sample dried by supercritical
CO2 has the appreciably higher dI/dV value than the sample with
freeze drying, which indicates that the former has the slightly higher
conductivity than the latter. This tendency can be further confirmed
by the X-ray diffraction (XRD) patterns shown in Fig. 4b. The broad
XRD peaks of the resulting graphene aerogels with either supercrit-
ical CO2 drying or freeze drying indicate the poor ordering of gra-
phene sheets along their stacking direction and reflect that the
frameworks of the aerogels are composed of few-layer stacked gra-
phene sheets. The interlayer spaces of the aerogels are calculated to be
3.74 A
for the sample dried by supercritical CO2, and 3.80 A
for the
sample with freeze drying. These values are much lower than that of
graphene oxide precursor (8.63 A)
while slightly higher than that of


natural graphite (3.37 A). These results suggest the existence of pp
stacking between graphene sheets in the aerogels. The shorter inter-
layer spacing of the sample dried by supercritical CO2 than the
sample with freeze drying indicates that the former has the lower
resistance than the latter when the electrons transfer among the
grapene sheets in the aerogels. The difference between the supercrit-
ical CO2 dried sample and the freeze-dried one in conductivity, as well
as in color and mechanical properties mentioned above, probably
attributes to disruptions of the graphene network caused by ice
crystals that occur during the freezing process.9 Via the four-probe
method, the bulk electrical conductivity of the graphene aerogel dried
by supercritical CO2 with apparent density of 86 mg cm 3 was
determined to be 63 S m 1, more than 2 orders of magnitude greater
than those reported for macroscopic three dimensional graphene
networks prepared with similar physical cross-links17,18 as in our case,
and comparable with the value reported for carbon jointed graphene
aerogels with chemical cross-links.14
The large BET surface areas and pore volumes, together with their
excellent mechanical properties and high conductivity, can make these
graphene aerogels viable candidates for use in many fields including
Fig. 4 IV curves (a) and XRD patterns (b) of the resulting graphene
aerogels with either supercritical CO2 drying or freeze drying.
This journal is The Royal Society of Chemistry 2011

energy storage, catalysis, sensors, actuators, polymeric composites,
etc. In the first instance, preliminary investigation to evaluate the
potential of these supercritical CO2 dried graphene aerogels for
supercapacitors was carried out in 6 mol L 1 KOH electrolyte. The CV
curve of the graphene aerogel with apparent density of 46 mg cm 3 at
a scan rate of 2 mV s 1 presents a typical rectangular shape as shown in
Fig. 5a, implying pure electric double layer capacitance, consistent
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with the behavior of the conventional carbon aerogels3,4 and the novel
carbon nanotube aerogels.10 The double layer capacitive behavior was
further confirmed by a galvanostatic charge/discharge experiment at
a constant current density 50 mA g 1 shown in Fig. 5b. From the slope
of discharge curve, the specific capacitance of the graphene aerogel
electrode was evaluated to be about 128 F g 1, which is higher than the
result17,23 obtained at the same current density. Whats more, our
graphene aerogels show superior rate capacity. As shown in Fig. 5c,
even when the scan rate increases to 200 mV s 1, the cyclic voltam-
mogram of the graphene aerogels basically remains a rectangular
shape with a slight deviation at lower potentials, implying a quick
charge propagation capability of double layer capacitance. The rate
performance of the graphene aerogel was also evaluated by galvano-
static charge/discharge under enhanced current density as shown in
Fig. 5d. With the increase of the current density, the capacitance of the
graphene aerogel decreases very slowly. As the current density
increases to 20 A g 1, the specific capacitance of the graphene aerogel
remains at 76 F g 1. These results indicate the good rate performance
of the investigated graphene aerogels, which probably is ascribed to its
robust physical cross-links confirmed by the mechanical tests, hierar-
chically porous structure confirmed by the SEM observation and
nitrogen sorption tests, and the low internal resistance confirmed by
the electrochemical impedance spectroscopy analysis (see Fig. SI6).
We believe that the graphene aerogel based supercapacitor can be
further optimized for best performance by synthetic parameter
adjusting, CO2 activation,10 KOH treatment,24 etc.
In conclusion, the graphene aerogels can be prepared by either
supercritical CO2 drying or freeze drying of graphene hydrogel
precursors obtained from heating the aqueous mixture of graphene
Fig. 5 Electrochemical characterization of graphene aerogel electrodes:
(a) cyclic voltammetry at a scan rate of 2 mV s 1, (b) chargedischarge
curves in 6 mol L 1 KOH at a current load of 50 mA g 1, (c) cyclic vol-
tammetry at enhanced scan rate, and (d) the dependence of specific
capacitance of the electrode on the current density.
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oxide with L-ascorbic acid without stirring. The resulting graphene
aerogels show light weight (1296 mg cm 3), high conductivity
(approaching to 102 S m 1), large BET surface area (512 m2 g 1), and
ample volume (2.48 cm3 g 1) with hierarchically porous structure.
The electrochemical investigation shows that the resulting graphene
aerogels with a specific capacitance 128 F g 1 (at a constant current
density 50 mA g 1) can be used as electrodes with superior rate
performance for electrochemical power sources. The mechanical
study shows that the graphene aerogel can support more than 14000
times their own weight, nearly twice of the amount supported by the
carbon nanotube counterpart. The light weight and large surface
area, together with their excellent electrical and mechanical proper-
ties, would allow these graphene aerogels to be applied in many fields
with unexpected performance.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (Grant No. 20903009, 21073233) and the
Science Foundation for the Excellent Youth Scholars of Beijing
Institute of Technology (Grant No. 2010YS0903).
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