Nano Energy (2015) 15, 9–23

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/nanoenergy

RAPID COMMUNICATION

Graphene-based nitrogen self-doped

hierarchical porous carbon aerogels
derived from chitosan for high
performance supercapacitors
Pin Haoa,b, Zhenhuan Zhaoa, Yanhua Lenga, Jian Tiana,
Yuanhua Sanga, Robert I. Boughtonc, C.P. Wongb,n,
Hong Liua,d,n, Bin Yange,*
a
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
b
School of Materials Science and Engineering, Georgia Tech, Atlanta, GA 30032, USA
c
Department of Physics and Astronomy, Green State University, Bowling Green, OH 43403, USA
d
Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences, Beijing 100864, PR China
e
Division of Advanced Materials, High Technology R&D Center, Ministry of Science & Technology,
Beijing 100044, PR China

Received 24 February 2015; accepted 28 February 2015

Available online 9 April 2015

KEYWORDS Abstract
Graphene-based car- Graphene-based nitrogen self-doped hierarchical porous carbon aerogels were synthesized for
bon aerogel; supercapacitor electrode application by using chitosan as a raw material through a carefully
N-self doping; controlled aerogel formation–carbonization–activation process. The as-synthesized N-doped
Hierarchical porous graphene-based carbon aerogels contained both macropores and mesopores from the aerogel
structure;
preparation and carbonization process, and micropores from the chemical activation, con-
Chitosan;
firmed by TEM, SEM, BET, etc. Because chitosan is a nitrogen-containing renewable biopolymer,
Supercapacitor
the carbon aerogel derived from chitosan in this work was N-self-doped. The carbonized carbon
aerogel was composed of a graphene framework and amorphous carbon, and the ratio between
these two components was controlled by the activation temperature. With an increase in
activation temperature, the amorphous carbon was etched away gradually, and a stable
graphene portion remained to form a framework. Accordingly, the performance of the
graphene-based carbon aerogel as a supercapacitor varied with increasing activation tempera-
ture. Electrochemical investigation measurements showed that the N-doped graphene-based
hierarchical porous carbon aerogel represents a good electrode candidate for construction of a
solid symmetric supercapacitor, which displays a high specific capacitance of about 197 F g 1 at
a current density of 0.2 A g 1. In addition, the solid state supercapacitor displayed excellent

n
Corresponding authors.
E-mail addresses: cpwong@cuhk.edu.hk (C.P. Wong), hongliu@sdu.edu.cn (H. Liu), yangb@htrdc.com (B. Yang).

http://dx.doi.org/10.1016/j.nanoen.2015.02.035
2211-2855/& 2015 Elsevier Ltd. All rights reserved.
10
cyclability with a capacitance retention of about 92.1% over 10,000 cycles. The excellent
energy storage ability of the chitosan-derived hierarchical graphene-based carbon aerogels is
ascribed to the high conductivity of the graphene framework with nitrogen doping and the high
storage ability of amorphous carbon with variable pore size and distribution.
& 2015 Elsevier Ltd. All rights reserved.
Introduction
Supercapacitors, possessing a high power density, long life-
time and excellent safety properties, have been widely used
in various areas, such as memory back-up, electric vehicles,
power quality management, battery improvement and
renewable energy applications [1]. A number of different
materials have been selected to build high-performance
supercapacitors to obtain high energy storage capability,
such as porous carbon, transition metal oxides, and conduct-
ing polymers [2–6]. However, supercapacitors using metal
oxides and conducting polymers exhibit poor stability and
rate capability, despite their high energy density and specific
capacitance. As an alternative, activated carbon has been
commercially applied as a supercapacitor electrode material
because of its well-developed microstructure, high specific
surface area and relatively high packing density [7,8]. At
present, commercial porous activated carbon-based super-
capacitors have two main bottlenecks: a low energy density
and high cost, which significantly limit its broad application.
To enhance the energy density, many carbon materials, such
as activated carbon, carbon fibers, carbon nanotubes and
graphene, are usually coupled with transition metal oxides
and conducting polymers, or used as the anode material to
assemble asymmetric supercapacitors such as battery-like
supercapacitors [9–19]. However, the comparatively poor
electrochemical performance of carbon limits the develop-
ment of carbon-based supercapacitors. Another disadvantage
for the carbon-based electrode materials is that most of
them are derived from petroleum-based chemical products,
which introduces the high cost associated with a limited
resource because of the fossil fuel crisis looming in the very
near future.
Graphene, a single layer of carbon atoms in a hexagonal
lattice, which can be derived from graphite formation or
obtained by a synthesis process, has been considered to be an
outstanding candidate for supercapacitor fabrication due to
its stable thermal and mechanical properties, high specific
surface area, high electrical conductivity and stable chemical
properties [7,20–24]. More importantly, the theoretical spe-
cific capacitance of graphene is calculated to be 550 F g 1
with the entire utilization of the surface [25]. In fact,
graphene has already exhibited its superiority as a super-
capacitor electrode material. Because of its unique layered
structure, various materials have been coupled with gra-
phene to form a layer-by-layer structure, leading to the
enhancement of both the specific capacitance and energy
density [26]. Recently, much research has been focused on
enhancement of the electronic properties of graphene
materials through doping hetero-atoms, such as N and B
[27–31]. For instance, nitrogen-doped graphene (NG) can be
P. Hao et al.
synthesized through the thermal annealing of GO in a NH3
atmosphere, and the obtained NG showed improved excellent
electrochemical performance [22]. Unfortunately, most gra-
phene nanostrucutres for supercapacitor applications are
prepared from the chemical vapor deposition (CVD) method
or chemical oxidation/exfoliation from graphite. The synthesis
of graphene using CVD is typically a high energy-consumption
process and the chemical method usually involves highly toxic
materials. Neither of these methods can produce graphene
with a specially designed microstructure on a large-scale. In
addition, it is difficult to prepare nitrogen-doped graphene
with uniform and high-concentration nitrogen doping when
using NH3 as the N source. The high cost of raw materials,
environmental destructiveness of preparation, complicated
manufacturing and difficulty in obtaining graphene by the
ton level, largely limit its further applications in the market
[32–34]. Therefore, researchers have turned their attention to
using green, reproducible biomass or its derivatives, and the
use of renewable materials to produce porous carbon and
graphene materials is critical to sustainable development and
environmental protection [27,35–38].
Chitosan, a material derived from the chitin in crustacean
cells, insect exoskeletons, and fungus cell walls, is the second
most abundant and renewable biopolymer after cellulose [39].
Because of good bio-compatibility and non-toxicity, chitosan has
been widely used in the field of biology and medicine. However,
its application in electrochemistry is currently limited to the
preparation of solid polymer electrolytes. Because chitosan can
easily form a 3D hierarchical porous scaffold, chitosan-based
solid polymer electrolytes are expected to enhance electro-
chemical cyclability and rate capability [39–43]. For example,
chitosan can easily be used to form gels with LiClO4 or ionic
liquids in order to prepare solid electrolytes [44,45]. Because
chitosan molecules are easy to connect together to form a large
area polymer, it can form graphene-like materials during the
carbonization process. To the best of our knowledge, the only
report on the synthesis of chitosan-derived graphene-based
materials is by García and coworkers [27]. In their study, an
ultrathin chitosan film of 100 nm thickness was first prepared on
a substrate and then carbonized at a high temperature to
obtain a graphene film. However, this method is difficult to
scale up, and the product film cannot be used as a super-
capacitor electrode. Up to now, there are few reports on the
synthesis of chitosan-derived graphene-based aerogels for
supercapacitor electrode applications. In addition, chitosan
consists of a large number of amino-groups that can be used
to synthesize N-doped carbon aerogels with excellent super-
capacitor performance.
In this report, we present a method of fabrication of
graphene-based nitrogen self-doped hierarchical porous car-
bon aerogels using the abundant natural biopolymer chitosan
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high
as a raw material. The obtained hierarchical porous carbon
aerogels consist of a graphene framework and nanoporous
amorphous carbon. At a high activation temperature, a single
phase graphene framework built with a few layered graphene
flakes can be obtained. The optimized graphene-based
carbon aerogels exhibit a high specific capacitance and
outstanding cyclability due to the high degree of graphitiza-
tion, the high specific surface area, reasonable pore size and
distribution, and uniform nitrogen doping.
Experimental
Materials
Chitosan was purchased from Aladdin (deacetylation Z95%,
viscosity 100–200 mPa·s). All other chemicals were reagent
grade and used without further purification. Deionized water
was used throughout the experiments.
Material preparation
Chitosan-derived carbon aerogels with a hierarchical porous
structure were prepared by the following steps in sequence:
(i) preparation of chitosan aerogels, (ii) carbonization of
chitosan aerogels, and (iii) activation of the carbon aerogels.
(i) Chitosan aerogels were prepared by the freeze–drying
method. Here, 1 g of chitosan powder was dispersed in
40 mL of deionized water, 1–2 v% of acetic acid solution
was dropped into the system with vigorous stirring until
a transparent chitosan solution with high viscosity was
obtained. After standing for 2 h, the obtained chitosan
solution was then frozen to 80 1C for 12 h and dried
using a lyophilizer to form chitosan aerogels.
(ii) The carbonization of the chitosan aerogels proceeded
in a tube furnace. The as-formed chitosan aerogels
were pyrolyzed at 800 1C for 3 h in flowing N2 at a rate
of 3 1C min 1 to obtain carbonized aerogels.
(iii) The KOH activation process is similar to the procedure
described in previous work [46]. Briefly, the obtained
carbonized carbon aerogels were mixed with a KOH solution
with a KOH/carbon aerogel weight ratio of 3:1. The mixture
was then dried at 110 1C to evaporate the water. The
impregnated sample was heated up to a pre-designated
temperature under N2 flow at a rate of 5 1C min 1 and held
for 2 h. The activation temperature was selected as: 700 1C,
800 1C, 900 1C and 1000 1C (samples were denoted as K700,
K800, K900 and K1000, respectively). After activation, the
sample was washed thoroughly with 1 M HCl solution and
deionized water. Finally, hierarchical porous carbon was
obtained by drying the sample at 70 1C overnight.
Structural characterization
A HITACHI S-4800 field-emission scanning electron micro-
scope (FE-SEM) was used to characterize the morphology of
the carbon aerogels. High-resolution transmission electron
microscopic (HRTEM) images were obtained with a JEOL
11
JEM2100F microscope. Atomic force microscopy (AFM) was
carried out using a Bruker Dimension Icon with ScanAsyst.
The chemical structure was characterized using a PHI 5000
Versa Probe X-ray photoelectron spectroscope (XPS). Raman
spectra were acquired with a Jobin-Yvon HR 800 spectro-
meter. The porosity characteristics of the porous carbon
aerogels were obtained by N2 adsorption/desorption experi-
ments at 77 K using ASAP 2020 V3.02 H. The specific surface
area was measured using the Brunauer–Emmett–Teller (BET)
method and the pore size distribution was calculated using
the classical Barrett–Joyner–Halenda (BJH) model.
Electrochemical measurements
To obtain the electrochemical properties of the samples, both a
three-electrode configuration and a two-electrode configura-
tion were used. To prepare the electrodes used in the three
electrode set-up following conventional optimization methods,
the supercapacitor electrodes were made of activated carbon
aerogel, acetylene black and poly-vinylidenefluoride (PVDF)
[47]. Prior to preparation of the electrode, PVDF was added
into an N-methyl pyrrolidinone (NMP) solution (0.01 g mL 1),
and then carbon aerogel and acetylene black were added to the
above solution with a carbon aerogel/acetylene black/PVDF
weight ratio of 8:1:1 to form the slurry. After stirring for 12 h,
the mixture was pressed onto a nickel foil with a size of
1 cm  1 cm, and the prepared electrodes were dried at 60 1C
overnight to remove NMP. The mass loading of the sample
without activation, K700, K800 and K900 is 3.0, 2.2, 2.4 and
2.7 mg, respectively. In a conventional three-electrode cell, a
Pt wire and a Ag/AgCl (saturated with KCl (aq)) were used as
the counter electrode and the reference electrode, respec-
tively, and an aqueous solution of 6 M KOH was used as the
electrolyte. The performance evaluation of activated carbon
aerogel as two symmetrical electrodes was carried out in a two-
electrode configuration. Two-electrode set-up was built in a
stainless cell with a glassy fibrous paper as separator and carbon
fiber paper as current collectors. The electrode can be obtained
through drying the above slurry in 55 1C for 20 min and then
rolling to the thin slice. After drying at 60 1C for 12 h to remove
NMP, the slice was cut into circular films with the diameter
about 6 mm. The mass loading of the electrode is 2.8 mg.
TEABF4 and 6 M KOH solution are used as the electrolyte. To
prepare the KOH/PVA gel electrolyte, 4.5 g of KOH was added
to 60 mL of deionized water, into which was added 6 g of PVA
powder. The mixture was heated to 85 1C under stirring until
the solution became clear. Two electrodes made by the above
method were immersed in the KOH/PVA solution for 5 min,
keeping the foil without carbon materials above the solution,
and then overlaying the two electrodes head-to-head until the
gel solidified at room temperature. The mass loading of the
electrode is 2.0 mg.
Cyclic voltammetric measurements (CV), galvanostatic char-
ging/discharging measurements (GCD) and electrochemical
impedance spectroscopy (EIS) were performed by using a CHI
660C Electrochemical Workstation (CH Instruments, China). The
specific capacitance was calculated from CV curves collected
fromR three electrodes testing according to the equation
C= Idt/mV, where I is the current, V is the working voltage
window, and m is the mass of the working electrode
active material. The specific capacitance from galvanostatic
12
charging/discharging curves was calculated via C=It/mV.
Where I is the discharge current, t is the discharge time, V is
the working voltage window, and m is the mass of the active
material at each electrode. The specific capacitance derived
from the CV curve and galvanostatic testing Rthrough two
electrodes testing was determined via C=4 Idt/MV and
C=4It/MV, respectively, where M is the total mass of the
active material at the two electrodes. The energy density (E)
and the power density (P) were calculated from galvanostatic
charge/discharge testing via E=(CV2)/2 and P=E/t, respec-
tively. Where C is the specific capacitance from the two
electrodes testing and t is the discharge time.
Results and discussion
The microstructure of the as-synthesized carbon aerogels at
different synthesis steps was characterized by SEM. Figure 1
shows SEM images of the hierarchical porous carbon aerogels
after chemical activation at 700–900 1C. For comparison, the
microstructures of the as-formed chitosan aerogel and the
carbon aerogel without activation were also observed by SEM
(Figure S1). Before carbonization, the as-synthesized cylindri-
cal chitosan aerogel possessed a porous structure with uniform
Figure. 1 Representative SEM images of N-doped carbon aerogels activated at different temperatures: (a–c) K700, (d–f) K800, (g–i)
K900. Inset in (a) is magnified image of (a).
P. Hao et al.
3-dimensional connected channels (Figure S1a). Interestingly,
after carbonization, the uniform 3-D connected channels in the
chitosan aerogel were broken, and re-assembled into a porous
scaffold with a new morphology. Most channel walls became flat
nanosheets oriented along a certain direction that were stacked
together, to form a squashed 3-D porous microstructure
(Figure S1b). After activation at different temperatures, as
shown in Figure 1a, d and g, the carbon aerogels still maintain
the 3-D network morphology. From the inset of Figure 1a, one
can see that carbon aerogel activated at 700 1C consists of a 3-D
porous structure, which is similar to the morphology of the as-
carbonated carbon aerogel. However, the wall surfaces of the
porous structure are reassembled with some small carbon flakes.
The surface of the carbon flakes is relatively smooth without
macro- or meso-pores (Figure 1b). It is difficult to observe the
micropores on the flake surface in the carbon aerogel because of
resolution limitations of the SEM (Figure 1c). With increase in
activation temperature, the surfaces of the channel walls
throughout the porous carbon aerogels became very rough
(Figure 1e and h). From fractured surfaces taken from samples
K800 and K900, one can see that the nanoflake surfaces and the
walls of the 3-D porous network are full of open and inter-
connected pores (Figure 1f and i). The reason can be ascribed to
the more violent reaction between carbon and KOH at higher
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high
activation temperatures. Therefore, with chemical activation,
a high specific surface area and a hierarchical porous
structure in the carbon aerogel are expected.
To further investigate the microporous structure of the
samples activated at different temperatures, TEM images were
taken on ground fragments of carbon aerogel samples activated
at different temperatures (Figure 2). As shown in Figure 2, with
an increase in the activation temperature from 700 1C to
900 1C, the aerogel samples show distinctively different
morphologies. At 700 1C, the carbon aerogel shows a sheet-
like microstructure (Figure 2a), and is less transparent under
electron beam irradiation, which indicates that the nanosheet
thickness is quite large. In a high-resolution image (Figure 2b),
the nanosheet exhibits the typical morphology of amorphous
carbon with numerous nanopores about 2–3 nm in size. When
the temperature is increased to 800 1C, most parts of the
carbon aerogel walls become much more thinly layered and are
connected with each other. Among the connected thin layers,
some amorphous carbon particles of 20–30 nm in diameter
distribute themselves and become tightly attached to the
connected transparent carbon layers to form a carbon parti-
cle–carbon layer hybrid structure (Figure 2c). The amorphous
Figure 2 TEM images of N-doped carbon aerogels activated at different temperatures: (a and b) K700, (c and d) K800, (e–g) K900.
Inset in (g) is the corresponding SAED pattern.
13
nanoparticles also possess nanopores of 2–3 nm in diameter
(Figure 2d). Further increasing the activation temperature to
900 1C, only a few of the nanoporous amorphous nanoparticles
can be found (Figure 2e and f). Figure 2g is the HRTEM image of
carbon layers in Figure 2e. It is nice to see the lattice fringes of
carbon layers. And from selected area electron diffraction
(SAED) pattern (inset in Figure 2g), we can find that carbon
atoms are in a hexagonal lattice, indicating the formation of
graphene. When the activated temperature was raised to
1000 1C, there is no carbon particle in the image (Figure S2).
Based on the above observations, we propose that the con-
nected transparent thin walls of the carbon aerogel activated
at temperatures above 800 1C are graphene layers. To confirm
this suggestion, the pieces of wall fragment ground from the
carbon aerogel activated at 800 and 900 1C were used to
determine the phase composition by using Raman spectrum
analysis and AFM methods, and the corresponding results are
shown in Figure 3.
The Raman spectra of the samples prepared at various
activation temperatures are shown in Figure 3. For compar-
ison, the Raman results on carbon aerogel without activation
are also displayed in Figure 3. It can be seen that all the
14
Figure. 3 (a) Raman spectra of pristine and activated samples, (b) ratio of integrated intensities of D- and G-bands (ID/IG), (c) full
width at half maximum (FWHM) of D- and G-band peaks, AFM images of (d) K800 and (e) K900, (f) thickness of the samples vs. length.
samples display two distinct bands, indexed to the D band at
about 1350 cm 1 and the G band at about 1580 cm 1.
Generally, the height of the D band represents the concen-
tration of disordered carbon in the sample, while the
intensity of the G peak indicates the concentration of
graphitized carbon [48,49]. The intensity of the D band is
obviously lower than that of the G peak for all the samples,
indicating a high graphitization concentration in the carbon
aerogels. This can be demonstrated by the intensity ratio
(ID/IG) of the D and G bands, which reflects the ratio of
disordered carbon and ordered graphitized carbon in the
carbon aerogels. The intensity ratio of disordered carbon to
ordered carbon (ID/IG) can be used to make an estimate of
disordered carbon content in the carbon aerogel samples. As
shown in Figure 3b, the ID/IG ratio of the carbon aerogel
without activation is about 0.83. With increase in the
activation temperature, the ID/IG ratio decreases. When the
activation temperature reaches 900 1C, the graphitization
ratio decreases to 0.74, indicating a very high concentration
of ordered carbon in the activated carbon aerogel samples.
The enhanced degree of graphitization indicates that the
activation process not only can be expected to create pores,
as discussed above, but also can enhance the concentration
of graphitized carbon in the carbon aerogel. This structural
change is also demonstrated by a drastic decrease in peak
width (full-width at half maximum, FWHM) when comparing
the sample without activation to sample K900 (Figure 3c). As
shown in Figure 3c, with an increase in activation tempera-
ture, the FWHM of both bands becomes smaller, indicating an
increased sharpness of the peaks due to the high degree of
graphitization. Impressively, samples K800 and K900 not only
show the D band and the G band, but also display the 2D peak
P. Hao et al.
at about 2700 cm 1, which is thought to be the character-
istic peak of graphene [50,51]. The AFM results of K800 and
K900 are showed in Figure 3d–f. As shown in Figure 3d,
different brightness is displayed in the sample of K800,
indicating different thickness. This is because that at the
activation temperature of 800 1C, the reaction between KOH
and amorphous carbon became violent and most of amor-
phous carbon was etched away, leaving some carbon particles
or small carbon pieces between the layers of graphene, and
resulting in the different thickness. However, further increas-
ing the activation temperature to 900 1C, the reaction was
more violent, almost all the amorphous carbon was etched
away and the major remaining component of the carbon
aerogel is the graphene framework, resulting in the uniform
brightness in Figure 3e. From Figure 3f we can see that K800
exhibits different thickness and the thickest is 13 nm. The
thickness of K900 is less than 1.5 nm, indicating about four
layers of graphene. Therefore, in this study we conclude that
when the chitosan aerogel precursor was carbonized at
800 1C, a part of the aerogel precursor in the walls of the
aerogel was graphitized to become layered graphene, and
other parts were carbonized to become amorphous carbon.
These two carbon portions comprise the thick wall of the
carbon aerogel, in which the graphene nanosheets connect
together, but are buried in solid amorphous carbon to form a
graphene-based carbon aerogel. After activation by KOH at
high temperature, the solid amorphous carbon was etched to
form a nanoporous structure, and the wall thickness
decreased. With an increase in activation temperature, the
amorphous carbon layer on the graphene-based carbon
aerogel wall decreases, and the relative graphene content
increases. This is why the samples activated at 800 and
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high
900 1C look transparent under HRTEM, and the amorphous
carbon particles become fewer. When the activation tem-
perature reached 1000 1C, most of the amorphous carbon was
etched away by KOH during the high temperature activation
process, and the remaining part of the carbon aerogel was
mainly composed of graphene nanosheets. It should be
pointed out that the formation temperature of graphene is
much lower than the pyrolysis temperature of graphite or the
epitaxial growth temperature on single crystal silicon carbide
[52,53].
XPS was carried out to examine the chemical nature of the
carbon and the presence and types of nitrogen in the graphene-
based carbon aerogels after activation. From the XPS results
(Figure 4a), there are three peaks, C1s, N1s and O1s exhibited
by all the samples after activation. Thus, the XPS data give
strong evidence for the existence of nitrogen in the graphene-
based carbon aerogels, which is expected when using chitosan
as the carbon source. The high resolution C1s spectrum of K800
was deconvolved and is shown in Figure 4b. The line represent-
ing sp2 hybridized carbon was recorded at around 284.5 eV,
whereas the sp3 hybridized state has a slightly higher binding
energy at around 285.0 eV [54]. For comparison, the high
resolution C1s spectra of the other samples are displayed in
Figure S3. As shown in Figure S3a, the sample without
activation displays a broad sp2 shape, indicating a much lower
relative content of sp2-hybridized carbon. After activation at
700 1C and 800 1C, the sp2 peak displays a sharper shape and
increased intensity. Until activation at 900 1C, the sp3 peak is
very weak, but then the sp2 peak becomes very strong at
900 1C, hence there is a high degree of graphitization, further
demonstrating the existence of the graphene structure. Table
S1 displays the sp2/sp3 ratio of the samples. As shown in this
table, the ratio increases from 3.5 for the sample without
activation to 10.81 for sample K900, showing a much higher
degree of graphitization, in agreement with the Raman results.
Figure. 4 (a) XPS spectra of the samples, (b) high-resolution C1s and (c) N1s XPS spectra of K800, (d) nitrogen adsorption/
desorption isotherms of the samples, (e) pore size distribution (calculated by using BJH model), (f) detailed view of (e).
15
The peaks around 286.2, 286.6 and 288.1 eV correspond to C–N,
C–O and C=O, respectively. The N1s XPS spectra of sample K800
are shown in Figure 4c. The N1s peak can be deconvolved into
three components, indicating that the N atoms exist in three
different bonding situations in the graphene-based carbon
aerogels. The peaks at binding energies of 398.4, 400.4 and
402.2 eV correspond to pyridine nitrogen, pyridinium nitrogen
in condensed polycycles and pyridine N-oxide, respectively
[27,55–57]. Furthermore, the proportion of pyridine nitrogen,
pyridinium nitrogen in condensed polycycles and pyridine N-
oxide are quantified as 15.0, 72.3 and 12.6%, respectively.
Overall, the XPS results agree with the Raman data, and
confirm the proposed structure of nitrogen-doped graphene-
based carbon aerogels, which is favorable for the enhancement
of supercapacitor performance.
N2 adsorption/desorption isotherms are used to examine
the specific surface area and the variation of pore size and
the pore distribution in the samples. As illustrated in
Figure 4d, all the activated samples display type IV nitrogen
adsorption isotherms, indicating different pore sizes from
micro- to meso-pores. Major adsorption by the samples
occurs at a low relative pressure of less than 0.1 and gives
rise to an almost horizontal plateau at higher relative
pressures, indicating high microporosity in the samples
[58]. Sample K900 exhibits a small rise at 0.5–1.0 P/P0,
showing the existence of mesopores. This result can be
further demonstrated by the pore size distribution calculated
from the BJH model. As shown in Figure 4e and f, all three
samples have both mesopores (2–50 nm) and micropores
(o2 nm). The mesopores have a pore size of  2 nm,
consistent with the HRTEM images, while the size of the
micropores is typically centered at 0.6 nm. In fact, the ideal
EC electrode materials should have a hierarchical porous
structure containing macropores (larger than 50 nm) for ion-
buffering reservoir, mesopores (2–50 nm) for ion transport
16
and micropores (less than 2 nm) for enhancement of charge
storage. Moreover, it is also desirable that the porous
structure have an optimal variation in pore size and pore
size distribution [59]. However, from Figure 4f, it is seen that
sample K700 has a large number of micropores with very few
mesopores, while sample K900 has a large number of
mesopores with relatively fewer micropores. Impressively,
sample K800 has the ideal pore size and size distribution. The
data on specific surface area and pore volume are listed in
Table S2. After activation, the specific surface area is
enhanced to 2435.2 m2 g 1. The specific surface area of
sample K800 is the highest with ideal pore volumes of micro-
and meso-pores. However, samples K700 and K900 have the
lowest pore volume of mesopores and micropores, respec-
tively. From the above results, it is seen that the activation
process and the activation temperature can greatly influence
the specific surface area and pore volume. Sample K800 has
the most suitable pore size and size distribution, which is
expected to enhance its behavior as a capacitor.
In order to demonstrate the high specific surface area and
the hierarchical porous structure of the graphene-based
carbon aerogels, an organic solvent adsorption experiment
was performed on sample K800. Figure S4a reveals the
rapidity of the process of cyclohexane adsorption labeled
with Sudan III dye on the water surface. Furthermore,
sample K800 has an outstanding regeneration capacity after
being dried 10 h at 100 1C. As shown in Figure S4b, the
sample maintained good adsorption after six adsorbing and
drying cycles due to the high specific surface area, open and
interconnected network, and stable hierarchical porous
structure. In addition, as shown in Figure S4c, we put
sample K800 on a flower to illustrate the high ratio of
surface area/weight that arises from the porous structure.
Based on the above experimental results, a formation
mechanism of graphene-based carbon aerogels is proposed.
Scheme 1 Structure evolution in the preparation process: (a) chitosan, (b) 3D chitosan network when dissolved in acetic acid,
(c) carbon products from carbonization, (d) and (e) porous carbon networks activated at 800 1C and 1000 1C, respectively.
P. Hao et al.
Scheme 1 illustrates the formation of the chitosan aerogel
precursor and the structure evolution of the carbon aerogel
during the carbonization and activation process. As shown in
Scheme 1a, chitosan, poly(2-amino-2-deoxy-D-glucose), pos-
sesses a chain structure with β(1-4) linkage [60]. When
chitosan is dissolved in acetic acid, the chitosan molecule is
surrounded by acetate molecules, which significantly prohibit
the formation of hydrogen bonds between the chitosan mole-
cules, thus reducing the possibility of crystallization. In addi-
tion, as shown in Scheme 1b, ketonic oxygen from the acetate
molecule can form a hydrogen bond with other chitosan
molecules, which helps to form a planar network consisting of
chitosan molecules and acetate molecules. During the quick-
freezing and lyophilization process, the surface tension of the
chitosan solution forces the chitosan molecules to arrange
themselves into film structures that connect together to form
a 3-D structure. This is the reason why a 3-D chitosan aerogel
with smooth channel surfaces can easily be obtained. During
carbonization, the chitosan planar network decomposes to form
carbon, carbon dioxide and water. Some of the carbon atoms
decomposed from the chitosan planar networks connect
together in situ to form graphene nanosheets, and the atoms
decomposed from disordered connected chitosan molecules
form amorphous carbon (Scheme 1c), to complete the forma-
tion of the graphene-based carbon aerogel. The –NH2 group
decomposes into elemental N and H. The H atoms react with
the OH atoms decomposed from –C–OH to form H2O. The N
atoms remain in the carbon aerogel to form the N self-doped
carbon aerogel. During the high temperature activation pro-
cess, KOH molecules react with amorphous carbon, to form
H2O, K2O and K2CO3, which can be removed during the post
washing process, leaving some pores in the amorphous carbon
portion of the carbon aerogel wall [46,61]. KOH is thought to
react with amorphous carbon first, because the amorphous
carbon possesses higher energy compared with well crystalline
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high 17

Figure. 5 (a–d) CV curves of porous N-doped graphene-based carbon aerogel electrodes at various scan rates in 6 M KOH aqueous
solution ((a) without activation; (b) K700; (c) K800; (d) K900), (e) CV curves of the four electrodes at potential scan rates of
100 mV s 1, (f) specific capacitance of the four electrodes as a function of scan rate derived from (a–d).

grapheme parts. In fact, the obtained carbon samples at
different activation temperatures contain different content
of amorphous carbon. According to Raman and XPS results,
K700 sample has the highest content of amorphous carbon,
which is followed by K800 and K900 sample. At the lower
activation temperature at 700 1C, the reaction between KOH
and amorphous carbon is slight, leaving more amorphous
carbon on the surface of graphene. At the optimum activation
temperature, most of amorphous carbon is etched away,
leaving the highly graphitized graphene layer and nanoporous
amorphous carbon particles between or on the graphene layers
(Scheme 1d). This hybrid graphene-based carbon aerogel,
possessing the high charge storability of nanoporous carbon,
and the high conductivity of a graphene network, is expected
to display superior supercapacitor performance. When the
activation temperature is increased further, almost all the
amorphous carbon is etched away, and the major remaining
component of the carbon aerogel is the graphene framework
(Scheme 1e).
To evaluate the electrochemical performance of porous
graphene-based carbon aerogels, cyclic voltammetric (CV) tests
were carried out using a three-electrode configuration in an
18
aqueous solution of 6 M KOH, and the results are depicted in
Figure 5. The CV scanning was performed in the voltage window
of 1 to 0 V for all the electrodes. As shown in Figure 5a, the
CV curves of the carbon aerogels without activation exhibit a
triangular shape, indicating poor supercapacitive behavior.
After activation at different temperatures, the CV curves of
the three samples exhibit an approximately rectangular shape
even at a scan rate of 200 mV s 1, indicating near-ideal
capacitive behavior (Figure 5b–d). Figure 5e displays the CV
curves of the four electrodes at a scan rate of 100 mV s 1. In
Figure 5e, one can see that the current density of sample K800
is the highest compared with the values exhibited by the other
samples. Figure 5f summarizes the gravimetric specific capaci-
tance of the samples as a result of CV testing. It is found that
the unactivated carbon aerogels and sample K700 had a very
low specific capacitance, and the specific capacitance
decreased to less than 100 F g 1 when the scan rate was
increased to 200 mV s 1, indicating that the unactivated
carbon aerogel and sample K700 not only have poor electro-
chemical performance, but also exhibit undesirable rate
capability. Sample K800 has the highest capacitance among
all samples at the same scan rate. For instance, sample K800
possesses a specific capacitance of about 291.8 F g 1 at
2 mV s 1, far higher than the specific capacitance of samples
K700 (245.5 F g 1) and K900 (204.8 F g 1). Moreover, the
capacitance showed only a slight decrease to 214.5 F g 1
when the scan rate was increased to 200 mV s 1, suggesting
good rate capability for a K800-based supercapacitor. Nota-
bly, the specific capacitance value of 291.8 F g 1 for K800 is
higher than the reported values for pure graphene electrodes
in aqueous electrolyte (about 70–250 F g 1), [62–64]
graphene-based frameworks (166 F g 1), [65] graphene/car-
bon composites (150–210 F g 1), [7,66] and N-doped gra-
phene (150–250 F g 1) [22,67] electrodes used in
supercapacitors. In addition, sample K800 also shows better
supercapacitive performance compared to electrodes made
from various other carbon-based materials using other bio-
polymers as reported in the literature. Bichat et al., reported
obtaining high oxygen content nanotextured carbon using
seaweed as the raw material, and the optimal specific
capacitance of the obtained carbon electrodes was 206 F g 1
in 6 M KOH solution [35]. Subramanian et al., also obtained
porous carbon after KOH activation using banana fiber as the
raw material [6]. However, the electrochemical performance
was so poor that its specific capacitance was only 66 F g 1 at
5 mV s 1, which is 4 times lower than that of sample K800.
The electrochemical impedance spectrum (EIS) was also
used to compare the electrochemical properties of the
samples, and is shown in Figure 6. The series resistance
and charge transfer resistance of the electrodes can be
derived from the Nyquist plot. Figure 6 shows the impe-
dance curves obtained for different samples at different
frequencies ranging from 0.01 Hz to 100 kHz. For an ideal
supercapacitor electrode, the series resistance and charge
transfer resistance should be as small as possible. It is found
that the sample K800 electrode displayed a relatively low
equivalent series resistance (ESR) of about 0.71 Ω, which is
lower than the as-synthesized carbon aerogels (0.78 Ω,) and
sample K700 (0.72 Ω,), but higher than that of sample K900
(0.59 Ω,). This result can be explained by examining the
disordered carbon content in graphene-based carbon aero-
gel samples. When they are carbonized at 700 1C, there is a
P. Hao et al.
large amount of amorphous carbon that can bury the
graphene layers, indicated by a high amorphous carbon
content. After activation by KOH, part of the amorphous
carbon was etched away, while the other part of the
amorphous carbon and highly graphitized graphene layers
remain in the aerogel. With an increase in activation
temperature, the relative content of graphene increases,
leading to good conductivity after activation, which is
consistent with the Raman and XPS results. Compared with
the other samples, the K800 electrode displayed the
smallest charge transfer resistance of about 0.68 Ω because
of the optimized manipulation of pore size and distribution.
This result is in accordance with the results of the CV scans
in which the sample K800 electrode shows the best super-
capacitor performance. Hence, it is believed that the
electrochemical performance of as-prepared carbon aero-
gels can be improved dramatically by the activation
process.
The above results clearly reveal that sample K800 exhibits
significantly improved electrochemical performance compared
with samples K700 and K900. We summarize the significant
factors in order to elucidate the important aspects of high
capacitance, excellent rate capability and cycling performance
achieved in sample K800 as the following. First, K800 has a high
degree of graphitization, indicating high conductivity, which
ensures rapid charge transport. Second, K800 possesses an
ultrahigh pore volume of 1.1 cm3 g 1 while maintaining the
3D hierarchical porous nanostructure of graphene with a con-
siderably large specific surface area of 2435.2 m2 g 1. It is
known that the capacitive behavior of graphene-based nanos-
tructures used in supercapacitors is highly dependent on both
the accessible specific surface area and the pore structure. The
graphene network ensures good conductivity. At the same time,
the porous amorphous carbon enhances charge transport and
storage. However, samples K700 and K900 have a lower
graphene content and amorphous carbon content, respectively,
leading to inferior electrochemical performance when compared
to sample K800. Impressively, sample K800 has the optimum
content of both graphene and amorphous porous carbon, leading
to outstanding capacitive behavior. Additionally, sample K800
Figure. 6 Nyquist plots showing imaginary part versus real
part of impedance in 6 M KOH aqueous solution. Inset magnifies
the data in high-frequency region showing series resistance in
high frequency region and charge transfer resistance in medium
frequency region.
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high 19

has a homogeneous nitrogen distribution using chitosan in the
role of both the carbon and nitrogen sources, which differs from
nitrogen-doped graphene prepared using NH3 gas as the nitrogen
source, in which the reaction mainly occurs on the exposed
surfaces of the carbon nanostructures, thereby resulting in
inhomogeneous and comparatively low nitrogen doping
[22,68,69]. As is well known, nitrogen doping can enhance the
electrochemical performance of a supercapacitor. According to
the calculation of the binding energy between the potassium
ion and nitrogen configurations at different positions of
nitrogen-doped graphene, the pyridine N and pyridinium N,
which constitute major parts of the graphene-based carbon
aerogel have a larger binding energy with the potassium ion.
This larger binding energy results in a larger number of ions
that can be accommodated on the electrode surface even for
a given electrode surface area, leading to an increase in
capacitance [26,31]. Moreover, N species on the carbon
surface could lead to the pseudocapacitive interaction

Figure. 7 (a) CV curves of K800 in a KOH/PVA solid electrolyte, (b) specific capacitance of K800 as a function of scan rate derived
from (a), (c) charge–discharge curves of K800 at different current densities, and (d) specific capacitance of K800 as a function of
current density derived from (c), (e) cycling performance and capacitance retention at 1 A g 1 over 10,000 cycles and (f) Ragone
plots of K800.
20
between the ions of electrolytes and the N-containing
functional groups, and then generate high pseudocapacitance
[70,71]. In addition, the oxygen functional groups in carbon
materials have been reported that can also improve the
capacitive behavior [72–74]. It is well accepted that there are
mainly two roles of the oxygen groups in carbon materials.
The first one is to provide more available sites for ion
adsorption in the micropores of carbon aerogels because of
the iondipole attraction, which can generate an excess
specific double layer capacitance due to the local changes
of electronic charge density [74]. The second role of oxygen
is to provide redox activity, which is responsible for the
enhancement of the overall capacitance for supecapacitors
[72,73].
In order to further identify the eletrochemical perfor-
mance of the K800 sample, CV tests were carried out using a
two-electrode configuration both in organic and 6 M KOH
aqueous electrolytes and the results are depicted in Figure
S5. As shown in Figure S5, K800 possesses a specific
capacitance of about 233.8 F g 1 at 2 mV s 1, lower than
the specific capacitance of K800 in the three-electrode set-
up. This can be explained that in a three-electrode set-up,
the potential value that shown on the X-axis of the CV
curves is equal to the potential applied to the working
electrode. However, for a symmetrical two-electrode cell,
the sum of the potential differences applied to each
electrode is equal to the value shown on the X-axis of the
CV curves. Therefore, for a given potential range on the X-
axis of the CV, the potential applied to the working
electrode in a three-electrode cell is much higher than
the one applied to the each electrode in a two electrode
cell, and this results in an increase of the specific capaci-
tance [75]. In addition, taking into account the equivalent
circuit of a two-electrode supercapacitor, the two electro-
des are in series, the total capacitance of the supercapa-
citor will be determined by the smaller of the two electrode
[76]. When using TEABF4 as the electrolyte, the specific
capacitance of K800 at 2 mV s 1 decreases to 135.9 F g 1. It
is found that the specific capacitance of the symmetric
supercapacitor in aqueous electrolyte is much higher than
that in organic electrolyte.
As is well known, the potential range and ionic conductiv-
ity of the electrolyte play important roles in supercapacitor
behavior. Liquid electrolytes are widely used in many
researches because of their higher ionic conductivity com-
pared with organic electrolytes. However, there are also
many existing shortcomings in the liquid electrolytes such as
low potential range, corrosion, leakage and explosions.
Therefore, many studies have replaced liquid electrolytes
with solid electrolytes in the supercapacitor. The solid
electrolytes have several advantages over liquid ones, which
include easy handling, increased safety, flexibility in packing,
etc. Therefore, a two-electrode symmetrical supercapacitor
device was assembled to characterize the electrochemical
storage capability of sample K800 in a KOH/PVA solid
electrolyte. As shown in Figure 7a, cyclic voltammetry shows
rectangular and symmetric curves from 0 to 1 V at various
scan rates ranging from 2 to 200 mV s 1, which is character-
istic of ideal supercapacitor behavior with good rate perfor-
mance. Even at a fast scan rate of 200 mV s 1, only a little
distortion can be observed, and the highest specific capaci-
tance reaches a value of 192 F g 1 at 2 mV s 1 (Figure 7b),
P. Hao et al.
which is slightly lower than the value obtained by using 6 M
KOH liquid electrolyte because of the slower ion diffusion in
KOH/PVA solid state electrolyte. The galvanostatic charge–
discharge curves at various current densities are shown in
Figure 7c. All the curves are nearly-isosceles triangles and
show good symmetry, quick current–voltage response and
nearly linear slope, indicating high coulombic efficiency and
standard double layer capacitor behavior [77]. Outstanding
specific capacitance values calculated from the charge/
discharge curves are shown in Figure 7d. The specific
capacitance at 0.2 A g 1 is about 197 F g 1 and still remains
at about 108 F g 1 even with a discharge current density as
high as 10 A g 1. The specific capacitance of the sample
decreases slightly with an increase in the charge/discharge
rate, additionally suggesting good rate capability. The vol-
tage drop at the initiation of the discharge is extremely small
(0.005 V) even at the high current density of 10 A g 1,
indicating a very low equivalent series resistance (ESR) in
the symmetric supercapacitor. Stability testing was con-
ducted under a constant charge and discharge current
density of 1 A g 1 for 10,000 cycles. Figure 7e shows the
cycling stability of the symmetric electrodes. The capaci-
tance retention was about 92.1% with a small decrease from
165.2 to 152.1 F g 1 after 10,000 cycles, indicating the
excellent cycling stability of K800. For comparison, the
cycling performance of graphene without nitrogen doping is
also displayed in Figure S6. As shown in Figure S6, the
capacitance retention was about 82.3% after 10,000 cycles,
which is much lower than K800. This is because that the
nitrogen groups in chitosan molecules are uniformly dis-
persed and bound to graphene planes, so they are highly
reversible and provide considerable stability during the
cycling process [78]. In addition, as shown in Figure 7f, the
all solid-state supercapacitor displayed excellent electroche-
mical performance with both very high energy and power
densities. The energy density can reach as high as 27.4 W h
kg 1 at a power density of 0.4 kW kg 1 and 15 W h kg 1 at a
power density of 20 kW kg 1. Although the electrochemical
performance of the K800 sample was not the most out-
standing compared with a few individual cases prepared from
mineral materials, petroleum or organic reagents, the
requirement of highly toxic organic reagents and mineral
materials which are expected to be depleted in the near
future in these other cases can discourage their use in
electrode preparation. Thus, the presented work is highly
promising if one can consider the availability of chitosan as a
biopolymer and the ease of the preparation method.
Nyquist plots of the all solid-state supercapacitor were
obtained over the range of 0.01 Hz to 100 kHz, as shown in
Figure S7 with an expanded view provided in the inset. The
ERS of sample K700 is 0.74 Ω, and a more vertical straight
line is a typical response for a hierarchical porous structure
in the low frequency region, indicating faster ion diffusion
in sample K800.
Conclusion
In summary, graphene-based hierarchical porous nitrogen self-
doped carbon aerogels with outstanding performance have
been produced by the carbonization of chitosan aerogel
and activation with KOH. The resulting graphene-based
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high
carbon aerogels have macro-, meso-, and micro-hierarchical
porous structures and possess an extremely high specific
surface area of 2435.2 m2 g 1. The specific capacitance
calculated from charge–discharge measurements using an all
solid-state symmetric supercapacitor was about 197 F g 1 at
0.2 A g 1 with excellent capacitance retention of 92.1% over
10,000 cycles. The energy density reached as high as 27.4 W
h kg 1 at a power density of 0.4 kW kg 1 and 15 W h kg 1 at a
power density of 20 kW kg 1. The outstanding capacitive
behavior is attributed to the unique features of graphene-
based carbon aerogels, including a high degree of graphitiza-
tion, high specific surface area and pore volume, reasonable
pore size and pore size distribution, and uniform nitrogen
doping. The results obtained demonstrate the possibility for
large-scale production of hierarchical porous carbon and
graphene materials by choosing a low-cost biopolymer, i.e.
chitosan, as the raw material.
Acknowledgements
The authors are thankful for funding from the National
Natural Science Foundation of China (Grant no. 51372142),
Innovation Research Group (IRG: 51321091) and the “100
Talents Program” of the Chinese Academy of Sciences.
Thanks for the support from the “thousands talents“ program
for pioneer researcher and his innovation team, China.
Appendix A. Supporting information
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/
j.nanoen.2015.02.035.
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Pin Hao She received her B.S. and Master
degree in the department of Materials
Science and Engineering in 2008 and 2011
from the Shaanxi University of Science and
Technology, China. She is now pursuing the
Ph.D. degree in the department of State
Key Laboratory of Crystal Materials at
Shandong University (China). She is now
united training by Georgia Institute of Tech-
nology. Her research interests include
energy storage and conversion, photocatalysis, etc.
P. Hao et al.
Zhenhuan Zhao He is currently pursuing his
PhD at State Key Laboratory of Crystal
Materials in Shandong University. His
research is focused on nanostructured semi-
conductors for photocatalytical application
and porous carbon materials for electroche-
mical energy storage using renewable nat-
ural sources.
Yanhua Leng He obtained his B.Sc. degree
from Shandong University in 2012. Cur-
rently, he is pursuing his M.Sc. degree in
State Key Laboratory of Crystal Materials,
Shandong University, China. His research is
mainly focused on the first-principle calcu-
lation and crystal growth simulation.
Dr. Jian Tian He obtained his B.Sc. degree
from Beijing University of Chemical Technol-
ogy in 2008. He received his doctor degree in
the department of State Key Laboratory of
Crystal Materials at Shandong University in
2014. His research interest in his Ph.D. study
is mainly focused on preparation and modifi-
cations of one-dimensional TiO2 nanostruc-
tured surface heterostructures for photo-
catalysis applications.
Dr. Yuanhua Sang He obtained his
B.S. degrees at Shandong University in
China in 2007 and completed his Ph.D. with
Prof. Hong Liu at Shandong University in
July 2012. Now, he works as a lecturer in
State Key Laboratory of Crystal Materials,
Shandong University, China. His research
interests are structure and property inves-
tigation of inorganic crystal materials with
neutron and X-ray diffraction, functional
materials, and materials for solar light conversion.
Robert I. Boughton He is a professor in the
department of Physics and Astronomy at
Green State University, His research inter-
ests mainly focus on the measurement of
electron transport properties at LHe temps,
Nanomaterials.
Prof. C. P. Wong, the Dean of Engineering
of the Chinese University of Hong Kong, is a
world-renowned scholar in Electronic Engi-
neering and a member of the US National
Academy of Engineering. He is on a no-pay
leave from the Georgia Institute of Technol-
ogy where he is a Regents’ Professor and
Charles Smithgall Institute Endowed Chair in
the School of Materials Science and Engi-
neering. Professor Wong has published
Graphene-based nitrogen self-doped hierarchical porous carbon aerogels derived from chitosan for high 23

widely with over 900 technical papers. He has yielded fruitful

research results and holds over 50 US patents. Professor Wong is
considered an industry legend and has made significant contribu-
tions to the industry by pioneering new materials, which funda-
mentally changed the semiconductor packaging technology.

Prof. Hong Liu is a professor in State Key

Laboratory of Crystal Materials, Shandong
University, and adjunct professor in Beijing
Institute of Nanoenergy and Nanosystem,
Chinese Academy of Science. He received
his PhD degree in 2001 from Shandong
University. He has published over 200 refer-
eed papers, and over 30 patents. In 2009,
he was awarded as Distinguished Young
Scholar by National Natural Science Founda-
tion of China. In 2012, he is awarded as Professor of Hundred
Talents Program of CAS at Beijing Institute of Nanoenergy and
Nanosystem. His current research is focused mainly on nonlinear
crystal growth, chemical processing of nanomaterials for energy
related applications including photocatalysis, energy storage and
conversion, tissue engineering, especially the interaction between
stem cell and nanostrucuture of biomaterials.