J Mater Sci: Mater Electron
DOI 10.1007/s10854-017-7705-9
Facile and scalable synthesis of hierarchically porous graphene
architecture for hydrogen storage and high-rate supercapacitors
Zhiyuan Huang1 · Kaisheng Xia1   · Lin Zheng1 · Bo Han1 · Qiang Gao2 ·
Hongquan Wang2 · Zhen Li2 · Chenggang Zhou1 
Received: 18 April 2017 / Accepted: 12 August 2017
© Springer Science+Business Media, LLC 2017
Abstract  Porous graphene materials have been developed
for many energy applications. However, a facile and scalable
synthetic approach is still a challenge. Herein, we prepare
graphene-based carbons with hierarchically porous struc-
tures via a simple steam activation of oxygen-functionalized
graphene nanosheets. The as-prepared carbons show inter-
connected micro-meso-macroporous structures, high specific
surface areas up to 1238 m2 g−1 and ultra-large pore volumes
up to 4.28 cm3 g−1. The highest hydrogen storage on the
carbon sorbents is found to be 1.47 wt% at 77 K and 1 bar.
As electrode materials for supercapacitor, one of the carbons
delivers a specific capacitance of 121 F g−1 at 0.5 A g−1
with 85% retention at 20 A g−1. The enhanced surface area,
unique porous structure combined with the inherent prop-
erties of graphene are responsible for the excellent perfor-
mances in hydrogen storage and high-rate supercapacitors.
Electronic supplementary material  The online version of this
article (doi:10.1007/s10854-017-7705-9) contains supplementary
material, which is available to authorized users.
* Kaisheng Xia
xks_mail@126.com
Chenggang Zhou
cgzhou@cug.edu.cn
1
Sustainable Energy Laboratory, Faculty of Material
Science and Chemistry, China University of Geosciences,
Wuhan 430074, People’s Republic of China
2
Faculty of Material Science and Chemistry, China University
of Geosciences, Wuhan 430074, People’s Republic of China
1 Introduction
The growing energy crisis and environmental pollution
associated with fossil fuels has stimulated rapid research
on sustainable energy storage and conversion systems such
as lithium-ion batteries, supercapacitors, fuel cells and so
forth [1, 2]. Hydrogen fuel cells are fast emerging as an
alternative candidate for electric vehicles (EVs) and other
mobile applications, however, safe, efficient and revers-
ible hydrogen storage still remains a key challenge [3, 4].
Among the developed techniques to store hydrogen, phy-
sisorption on carbon adsorbents such as activated carbons,
carbon nanotubes and carbide derived carbons has attracted
considerable interest due to their lightweight, high surface
area, relatively low cost, excellent stability and fast kinetics
[5, 6]. Meanwhile, supercapacitors represent an important
energy storage device which possess high power density,
superior rate capability and long operation life. Electrode
materials are the key components that determine a superca-
pacitor’s performance. Over the past decades, carbon mate-
rials, including activated carbons and templated carbons,
have been widely investigated as the entity of supercapaci-
tor electrodes [6, 7]. Although carbon-based materials have
exhibited great potential for applications in hydrogen storage
and supercapacitors, however, the limited energy densities
of these materials have constrained the commercialization.
To resolve this problem, design and development of novel
carbon materials with more controlled structural and chemi-
cal characteristics is absolutely necessary.
Graphene as a dazzling carbon material has aroused much
attention in the field of hydrogen storage and supercapaci-
tors [6–8]. Unluckily, graphene sheets prefer restacking
or aggregating to form non-porous nanostructures during
preparation, leading to dramatic decrement of surface area
[9]. As a consequence, the hydrogen adsorption capacities
13
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and electrochemical capacitances of solely graphene are
far below expectations. Many attempts have been made in
recent years for tuning the textural properties of graphene
to improve its energy storage, where chemical or physical
activation have been demonstrated to be effective approaches
[10–16]. In general, chemical activation can be implemented
using different chemical reagents (typically KOH, ­H3PO4
or ­ZnCl2), while physical activation is conducted in C ­ O 2,
air or steam atmosphere. It is recognized that chemical
activation can greatly increase the microporosity and spe-
cific surface area and thus the energy density of graphene
material. Nevertheless, chemical activation is a complicated
process and may bring about secondary pollution, which
will heavily hinder its application in large-scale production.
In comparison, the physical activation (such as ­CO2, air or
steam activation) offers a more desirable option because the
process of activation involves a simple gas–solid reaction
without introducing any impurities [17–20]. Among the
commonly used physical activation methods, steam activa-
tion can be regarded as a facile and environmentally friendly
approach [21, 22]. A few recent studies have prepared steam
activated graphene materials with high specific surface area
(SSA) and porosity, which exhibited potential applications
in adsorption [13], sensing [14, 23] and lithium-ion battery
[24]. In particular, Huang and co-workers prepared steam
etched porous graphene oxide by hydrothermal steaming
of graphene oxide at 200 °C, and the products showed a
­ O2 detection [14]. Neverthe-
great increased sensitivity for N
less, the graphene oxide sheets was severely disrupted by
the steam activation because the graphene oxide contains
abundant defect sites, leading to a possible violent and fast
reaction between graphene oxide and steam. Alternatively,
Han and co-workers synthesized carbon-based porous mate-
rials through steam activation of graphene aerogel, and the
products exhibited high SSA (830–1230 m2 g−1) and large
pore volume (2.2–3.6 cm3 g−1) [13]. However, the synthesis
of graphene aerogel suffered from a lengthy and complicated
procedure (including hydrothermal treatment and freeze-
drying), which is unsuitable for large-scale preparation.
In order to simplify the synthesis procedure and
increase the productivity of steam activated porous gra-
phene materials, we employed our previously reported
ultra-fast thermal exfoliation technique [20] to prepare
thermally exfoliated graphene nanosheets (TEG), and
then used it as a precursor for steam activation in the
present work. The TEG possesses highly loose structure
and moderate defects, which could facilitate the steam
activation. The as-prepared carbons show interconnected
micro-meso-macroporous structures, high specific surface
areas up to 1238 m2 g−1 and ultra-large pore volumes up
to 4.28 cm 3 g −1. Furthermore, the effects of activation
temperature on the hydrogen adsorption and superca-
pacitive properties of the resulting carbon materials are
13
J Mater Sci: Mater Electron
investigated. This work would help to achieve a better
understanding on the structural change of the graphene
oxide subjected to steam activation, and may be further
extrapolated to benefit other applications of steam-acti-
vated graphene.
2 Experimental section
2.1 Materials synthesis
Graphite oxide (GO) was synthesized by the modi-
fied Hummer’s method [25]. The starting materials and
chemicals were analytical grade and without any further
purification. First, Graphite (5 g) was added to concen-
trated ­H2SO4 (20 mL) in which ­P2O5 (2.5 g) and ­K2S2O8
(2.5 g) were completely dissolved at 80 °C. The mixture
was kept at 80 °C for 6 h using an oil bath. After cool-
ing down and diluted with deionized water (400 mL), the
pre-oxidized graphite was filtered and washed until the
filtrate was neutral and dried at 65 °C for 24 h. Next, 2 g
of it was dispersed into chilled H­ 2SO4 (48 mL), and then
­KMnO4 (6 g) was slowly added with vigorous stirring. The
rate of addition was carefully controlled to keep the reac-
tion temperature below 5 °C. After stirring for 1.5 h, the
obtained dark green mixture was transferred to 35 °C oil
bath and stirred for another 1.5 h followed by addition of
100 mL deionized water. After additional stirring at 35 °C
for 1 h, the mixture was heated to 80 °C and stirred for 1 h,
and then a brown turbid liquid was obtained. Then, H ­ 2O 2
(30%, 20 mL) were added to get a bright yellow mixture.
The mixture was allowed to settle overnight. The superna-
tant was decanted, and the remaining product was further
washed with diluted HCl and deionized water until the pH
of the solution became neutral. The obtained product was
dried at 50 °C.
To prepare steam-activated exfoliated graphene (SAEG),
thermally exfoliated graphene oxide (TEG) needs to be pre-
pared beforehand. Typically, 1.0 g of dried GO was placed
in a quartz tube and purged with N ­ 2 for 30 min to remove
air, and then the tube was rapidly transferred to a vertical
furnace preheated to 800 °C. The TEG was obtained after
thermal exfoliation at 800 °C for 1 min followed by gradual
cooling to room temperature under ­N2 flow. Subsequently,
the TEG powder was placed in the centre of a tube fur-
nace and activated at different temperature (800, 850 and
900 °C, respectively) for 1 h under a flowing N ­ 2 and steam
−1
atmosphere, with a ­N2 flow of 40 mL min . The heating
rate of the tube furnace was set at 10 °C min−1. After cool-
ing to room temperature under N ­ 2, the obtained sample was
collected and denoted as SAEG-x, where x represents the
activation temperature.
J Mater Sci: Mater Electron
2.2 Materials characterizations
Powder X-ray diffraction (XRD) patterns of the prepared
samples were recorded on a Bruker AXS D8-FOCUS dif-
fractometer using monochromatized Cu-Kα radiation (40 kV,
20  mA; λ = 0.1540598  nm). Fourier transform infrared
(FT-IR) spectroscopy was carried on a Nicolet6700 system
using the KBr pellet method. The microscopic feature and
morphology of the samples were observed by field scanning
electron microscopy (FESEM, Hitachi SU8010) and trans-
mission electron microscopy (TEM, Philips CM12TEM/
STEM) operated at 120 kV. Specific surface area and pore
distribution measurements were carried out by ­N2 adsorp-
tion–desorption analysis at 77  K using a Micromeritics
ASAP 2020 HD88 system. All the samples were degassed
at 200 °C for 6 h before adsorption experiments. The Raman
spectra were recorded using a Horiba Jobin-Yvon LabRAM
HR800 Raman microspectrometer with an excitation laser
of 532 nm. The specific surface area (SSA) was calculated
from the adsorption data in the relative pressure range
between 0.05 and 0.35 using Brunauer–Emmett–Teller
(BET) method. The total pore volume was determined from
the amount of ­N2 adsorbed at a relative pressure of 0.995.
The micropore volume (­ VMicro) and micropore surface area
­(SMicro) were estimated using a t-plot method. The pore size
distribution was analysed by Barrett-Joyner-Halenda (BJH)
method using the data of the adsorption branch.
2.3 Performance measurements
The hydrogen adsorption capacities of the samples were
measured by the volumetric method at 77 K in the pressure
range of 0–1 bar using the Micromeritics ASAP 2020 HD88
system. Before the adsorption measurements, samples were
degassed at 350 °C for 6 h.
The electrochemical capacitive properties of the samples
were tested in an electrochemical workstation (VMP3, Bio-
logic) using a conventional three-electrode configuration
with 6.0 M aqueous KOH solution as electrolyte. A Pt wire
and an Hg/HgO electrode were used as counter and reference
electrodes, respectively. The active materials were prepared
by mixing the SAEG, acetylene black and polytetrafluoroeth-
ylene (PTFE) in a weight ratio of 80:10:10 with ethanol. And
then the pastes were pressed into Ni foam and then dried
overnight at 80 °C. The dried electrode was then pressed at
Fig. 1  Schematic diagram
of the preparation process of
SAEGs via steam activation of
TEG
10 MPa for 1 min. Approximately, 1.5 mg of active materials
was loaded in each electrode. The electrochemical meas-
urements were carried out by cyclic voltammetry (CV),
galvanostatic charge–discharge (GCD) and electrochemical
impedance spectroscopy (EIS) methods. The CV and GCD
were recorded in the −1.0 to 0 V potential window. EIS
measurements were carried out in the frequency range of
10 kHz to 10 mHz. The specific capacitance was calculated
from the GCD measurement using the following equation:
i⋅t
C=
m⋅V
where i is the current, t is the time of discharge, m is the
mass of the active material, and V is the potential window.
3 Results and discussion
The strategy to prepare SAEGs is schematically shown in
Fig. 1. First, TEG was obtained by rapid thermal exfoliation
of GO at 800 °C. During this process, the gas ­(CO2 or O ­ 2)
escaping can exfoliate GO into numerous curved graphene
nanosheets, which may stack together to form mesopores and
macropores [26]. Due to the rapid thermal exfoliation, abun-
dant oxygen-containing groups are still preserved on the gra-
phene nanosheets, which endows the TEG with high reactiv-
ity. In the following activation procedure, active carbon atoms
in graphene layer would react with ­H2O to produce CO and
­H2, leaving behind carbon vacancies that gradually grow into
micropores or mesopores [14, 27]. Thus, the SAEGs with large
specific surface area and hierarchical porosity were obtained.
The SEM and TEM measurements were first performed to
examine the morphology and porous structure of the prepared
samples. It is seen that the TEG (Fig. 2a) is composed of thin
sheets with curly and wrinkly morphology. In contrast, there
are a number of nanopores on the surface of the SAEG-850 as
highlighted by the dashed boxes in Fig. 2b, which are believed
to be created by steam activation. Figure 2c, d show the TEM
images of SAEG-850, which display a typical wrinkled layer-
like structure and numerous nanopores in the graphene sheets.
It is anticipated that the SAEGs with such architecture might
have large surface area and high porosity, which are beneficial
for both hydrogen storage and supercapacitive applications.
The XRD patterns of the samples are exhibited in Fig. 3a.
It is observed that the TEG and SAEGs show a very weak
13

Fig. 2  SEM images of TEG (a) and SAEG-850 (b); TEM images of the SAEG-850 (c and d)
broad (002) graphitic peak, while GO exhibits a sharp (001)
peak at 2θ of 11.4°. It indicates that the GO was converted
into many single- and several-layer nanosheets during the
exfoliation process and the exfoliated structure is main-
tained after steam activation. The FT-IR spectra shown in
Fig. 3b demonstrate the weakening of bands attributed to
C–O and C=O. It suggests the reduction of GO after exfolia-
tion and steam activation. The textural properties of SAEGs
are investigated by nitrogen adsorption–desorption analy-
ses. As shown in Fig. 3c, the SAEGs show increased N ­ 2
adsorption after steam activation and exhibit a combination
of type IV and type II isotherms, indicating the presence of
mesopores and macropores. Moreover, the SAEGs exhibit
distinct ­N2 adsorption at very low relative pressure, which
implies the existence of abundant micropores. The results
are consistent with the SEM and TEM measurements and
clearly show the hierarchically micro-meso-macroporous
structures in the SAEGs. The pore size distributions based
on the BJH method (Fig. 3d) show a narrow distribution of
small mesopores centered at about 2.5 nm and a broad dis-
tribution of pores in the range of 5–50 nm. As summarized
in Table 1, the calculated SSAs and pore volumes increase
13
J Mater Sci: Mater Electron
from 432 m2 g−1 and 1.45 cm3 g−1 for TEG to 1238 m2 g−1
and 4.28 cm3 g−1 for SAEG-850, respectively. The remark-
able increments are ascribed to the porosity developments
of SAEGs caused by steam activation. In our experiments,
850 °C seems to be the optimal activation temperature. A
higher temperature such as 900 °C may lead to overreact
between graphene and steam, which may results in the
destruction of the porous structure and low yield [13]. Sig-
nificantly, the high SSA of 1238 m2 g−1 and the ultra-large
pore volume of 4.28 cm3 g−1 in SAEG-850 are higher than
that of most physical activated graphene-based carbons,
such as ­CO2 activated graphene framework (829 m2 g−1 and
2.83 cm3 g−1) [15], air activated graphene (646 m2 g−1 and
2.39 cm3 g−1) [12] and steam activated graphene aerogels
(1230 m2 g−1 and 3.6 cm3 g−1) [13].
To determine the quality and layer number of the as-
prepared graphene, Raman measurement was performed
as shown in Fig. 4. All the samples have two pronounced
peaks at around 1350 and 1580 cm−1, which corresponds
to the D and G bands of graphene, respectively. It is known
that the intensity ratio of D to G peak ­(ID/IG) is related to
the crystalline quality of graphene layers: the smaller the
J Mater Sci: Mater Electron

Fig. 3  XRD patterns (a), FT-IR spectra (b), nitrogen adsorption–desorption isotherms (c) and BJH pore size distributions (d) of the prepared
samples

Table 1  The textural parameters and hydrogen uptake capacities of

the TEG and SAEGs

Samples SBET ­(m2 g−1) VTotal SMicro ­(m2 g−1) H2

­(cm3 g−1) ­uptakea
(wt%)

TEG 432 1.45 70 0.58

SAEG-800 838 2.34 262 0.96
SAEG-850 1238 4.28 184 1.47
SAEG-900 996 3.31 172 1.25
a
 H2 uptake at 77 K and 1 bar

value, the better the crystalline quality. TEG has an ­ID/

IG value of 0.92, indicating the presence of defects due
to rapid heating. After steam activation, the value of ­ID/
IG increases to 1.04 for SAEG-800, and 1.31 for SAEG-
850, and then drops to 1.14 for SAEG-900, respectively.
This illustrates that steam activation bring more defects
and edges to the as-prepared samples. The 2D band
(∼2750 cm−1) has been used to estimate the layer num-
ber of the graphene because the shape and intensity of
the 2D band changes with number of layers [28]. How-
ever, traditional method is often carried out on very few
nanosheets of micromechanically-cleaved graphene or
Fig. 4  Raman spectra of TEG, SAEG-800, SAEG-850 and SAEG-
900
CVD grown graphene, which is different from bulk-pro-
duced graphene materials. Therefore, we choose another
calculating method, which is based on the value of I­ 2D/
IG and empirical fitting, to estimate the mean number of
layers of the as-prepared graphene: Layer number = 1.04
­(I2D/IG)−2.32 [29, 30]. The calculated layer number of TEG

13

is about 6.6, which is consistent with its specific surface
area (432 m2 g−1), ∼1/6 of the theoretical surface area of
graphene [31]. In contrast, the calculated layer numbers of
the SAEGs are all greater than 10, which may be ascribed
to the irreversible stacking of graphene during thermal
annealing process. Although the graphene nanosheets
stack to some extent, the steam activation can introduce
a lot of micro- and mesopores into the graphene-based
carbon, and thus increase its SSA greatly.
Figure 5a shows the hydrogen adsorption isotherms of
TEG and SAEGs at 77 K, which display broad knees and
gradually increased H­ 2 uptake with the increment of pres-
sure. The highest hydrogen adsorption capacity of 1.47 wt%
at 77 K and 1 bar is found in sample SAEG-850 (Table 1).
The value is higher than those of ­CO2-activated graphene
(0.75 wt%) [25], GO-based frameworks (1.2 wt%) [32], GO-
based network materials (1.24 wt%) [33] and many other
carbon materials under the same testing conditions as shown
in Table S1. Besides, there is a linear relationship between
the SSAs and hydrogen adsorption capacities as illustrated
in Fig. S1, which indicates that the ­H2 uptake in SAEGs is
mainly physisorption mode [34]. Thus, the obvious higher
SSA of SAEG-850 could be used to explain its superior
hydrogen adsorption performance.
Fig.  5  a Hydrogen adsorption isotherms of TEG and SAEGs; b CV curves of SAEGs in 6 M KOH at scan rate of 50 mV s−1; c specific capaci-
tance change of SAEGs at different current densities; d Nyquist plots impedance of SAEGs
13
J Mater Sci: Mater Electron
The supercapacitive performance of SAEGs are shown
in Fig. 5b, c. It can be found that all the cyclic voltammetry
(CV) curves exhibit the nearly rectangular shape (Fig. 5b),
showing the standard electrochemical double layer capaci-
tive behavior. The specific capacitances of SAEG-800,
SAEG-850 and SAEG-900 calculated under the current
density of 0.5 A g−1 are 121, 111 and 96 F g−1, respectively.
Although this value is higher than air activated graphene
(102 F g−1 at 0.1 A g−1) [12], it is still moderate compared
with other physical activated carbons such as steam activated
carbon nanofibers [35] and ­CO2 activated graphene frame-
works [15] as shown in Table S2. The possible reason is that
the functional groups introduced by steam activation could
degrade the supercapacitive performance of SAEGs because
of their instability or polarity mismatch with the electrolyte
[35]. Remarkably, all the SAEGs display an excellent capac-
ity retention rate up to 85% at 20 A g−1 (compared with
0.5 A g−1), indicating their potential in high-rate superca-
pacitors (Fig. 5c). The high-rate capability is attributed to
the hierarchical porous structure of the SAEGs, in which
macropores and large mesopores can minimize the distances
between electrolytes and the interior surfaces of the pores
and thus enable rapid ion transport, and small mesopores
and micropores can facilitate the charge storage [36–39].
J Mater Sci: Mater Electron
The electrochemical impedance spectroscopy (EIS) were
performed in a frequency range from 100 kHz to 10 mHz,
and the corresponding Nyquist impedance plots of the
SAEGs electrodes are shown in Fig. 5d. All EIS curves show
straight line in low-frequency region and small semicircle in
the high-frequency region. It suggests the fast formation of
electric double layer capacitance and small charge transfer
resistance in SAEGs, which is also in consistent with the CV
results. By comparing the patterns in the insets of Fig. 5d,
SAEG-800 exhibits the smallest Z′-axis intercept and semi-
circle at high frequency, indicating the lowest charge transfer
resistance and internal resistance in it. This may explain why
the SAEG-800 has the best supercapacitive performance.
4 Conclusions
A facile and scalable steam activation was employed to
treat oxygen-functionalized graphene nanosheets for super-
capacitors and hydrogen storage. As a result, the obtained
graphene-based carbons exhibited a hierarchically micro-
meso-macroporous architecture built by holey graphene
sheets. The specific surface area and pore volume of the
graphene-based carbons could be tuned in the range of
838–1238 m2 g−1 and 2.34–4.28 cm3 g−1, respectively, by
varying the steam activation temperature. The carbons were
25. K. Xia, X. Tian, S. Fei, K. You, Int. J. Hydrog. Energy 39, 11047–
found to have impressive hydrogen adsorption capacities as
high as 1.47 wt% at 77K and 1 bar and high capacitance
retentions up to 85% from 0.5 to 20 A g−1 using as super-
capacitor electrodes. Our results demonstrated the potential
applications of steam-activated graphene materials in hydro-
gen storage and high-rate supercapacitors.
Acknowledgements  This work was supported by the Natural Sci-
ence Foundation of Hubei Province (No. 2015CFB187), National
Natural Science Foundation of China (No. 21303170), and the Fun-
damental Research Funds for the Central Universities, China Univer-
sity of Geosciences (Wuhan) (No. CUGL150414, CUGL140413 and
CUG120115).
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