Synthetic Metals 209 (2015) 68–73

Contents lists available at ScienceDirect

Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

A self-standing nanocomposite foam of polyaniline@reduced graphene

oxide for flexible super-capacitors
Hang Suna , Ping Shea , Kongliang Xua , Yinxing Shanga , Shengyan Yinb,* , Zhenning Liua,*
a
Key Laboratory of Bionic Engineering (Ministry of Education), College of Biological and Agricultural Engineering, Jilin University, Changchun, Jilin Province
130022, PR China
b
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Changchun, Jilin Province 130012, PR
China

A R T I C L E I N F O A B S T R A C T

Article history: Self-standing three-dimensional nanocomposite foam of polyaniline (PANI) and reduced graphene oxide
Received 27 March 2015 (rGO) has been fabricated by a convenient template-directed preparation of rGO and subsequent in situ
Received in revised form 19 June 2015 polymerization of aniline on pre-formed rGO foam, which can be directly used as electrodes for flexible
Accepted 1 July 2015
supercapacitors. The nanocomposite foam of PANI@rGO possesses the advantages of self-standing, foam-
Available online xxx
like high porosity, low density (
8.3 mg cm3), good flexibility and improved durability, which
collaboratively lead to superior electrochemical performance, as a result of enhanced charge-transfer and
Keywords:
mechanical support afforded by the rGO skeleton. The nanocomposite-based supercapacitor not only
Polyaniline
Graphene
displays a high specific capacitance of 701 F g1 at the current density of 1 A g1, but also demonstrates
Self-standing improved cycling stability, retaining 92% of its starting capacitance after 1000 charge–discharge cycles.
Nanocomposite foam Moreover, the bended symmetric pseudocapacitor based on the flexible nanocomposite foam of
Flexible supercapacitor PANI@rGO exhibits a high specific capacitance of 285 F g1 at 1 A g1, indicating excellent potential for
real energy storage in flexible supercapacitors. The approach presented here shows great promise for the
development of flexible low-density electrode materials with good potential for applications in portable
electronic devices.
ã 2015 Elsevier B.V. All rights reserved.

1. Introduction specific pseudocapacitance conferred by multiple redox states

Supercapacitors, also known as electrochemical capacitors,
have attracted tremendous attention in recent years due to their
high power density, fast charge–discharge process, and long
cycling life in general [1–11]. Electric double layer capacitors
(EDLCs) and pseudocapacitors are two major types of super-
capacitors. EDLCs are often made of carbon materials and possess
better cycling stability and mechanical strength, whereas pseu-
docapacitors, which are based on Faradaic mechanism, normally
demonstrate higher capacitance but limited durability [12,13].
Thus it has been envisioned that the combination of pseudoca-
pacitive material with carbon material would deliver a pseudo-
capacitive composite with both superior energy density and
excellent electrochemical stability [9,14,15].
Polyaniline (PANI) is one of the commonly investigated
pseudocapacitive materials, owing to its easy synthesis, good
conductivity, low cost, environmental friendliness and high
* Corresponding authors.
E-mail addresses: syyin@jlu.edu.cn (S. Yin), liu_zhenning@jlu.edu.cn (Z. Liu).
[16,17]. However, the practical application of PANI in super-
capacitors is still hindered by two challenges. First, the mechanical
degradation caused by swelling and shrinkage during doping and
dedoping process leads to limited cycling life of PANI-based
supercapacitors [18]. Second, the charge transfer of PANI during
the charging–discharging reactions is kinetically slow and thus
results in poor rate capability.
Recently, graphene, a two-dimensional carbon material with
outstanding electrical properties, good chemical stability, high
mechanical strength and large surface area, has been utilized to
form synergistic hybrid material with PANI to overcome its
constraints [5,12,19–26]. The resultant composite materials, such
as PANI nanowire arrays on graphene oxide (GO) and PANI nanorod
on graphene nanoribbons, have demonstrated enhanced rate
capability and cyclability [27,32–35]. Unfortunately, these nano-
composites were prepared as powders via a non-template-
directed approach and the nanocomposite electrodes were usually
prepared by the protocol of mixing the powder with binders and
pasting the mixture onto collector electrodes [35,36], which not
only limits the control over microstructure, but also reduces the
electrical and electrochemical properties of the resultant

http://dx.doi.org/10.1016/j.synthmet.2015.07.001
0379-6779/ ã 2015 Elsevier B.V. All rights reserved.
 H. Sun et al. / Synthetic Metals 209 (2015) 68–73
electrodes. In recent years, nanocomposite films of graphene and
PANI have been fabricated to achieve better control over the
microscopic structure, and have demonstrated improved pseudo-
capacitive performance, including PANI-embedded graphene
hydrogel film [16], three-dimensional (3D) porous graphene-PANI
film [37], etc [38,39]. Although these porous nanocomposite films
are self-standing and can be applied as binder-free electrodes,
most of them exhibit poor flexibility and are easy to crack and
collapse when bended without supporter, due to the hollow
internal structure and sparse skeleton.
The growing demand for portable and wearable energy storage
system has driven rapid development of flexible supercapacitors
over the past decade [7,40–42]. Thus it is desirable to develop a
flexible nanocomposite of PANI and graphene, particularly for
flexible supercapacitors. Recently, good mechanical flexibility has
been shown for graphene-PANI papers or films [43–45], and high-
performance flexible supercapacitors have been constructed based
on these nanocomposite electrode. Yet, an effective way to prepare
a nanocomposite material of PANI and graphene, which not only
has highly porous structure and excellent pseudocapacitance, but
also possesses good flexibility, remains to be explored.
Herein, a nickel (Ni) template-directed approach has been
developed to fabricate flexible self-standing nanocomposite foam
of PANI and reduced graphene oxide (rGO), which can be directly
applied as a working electrode without any binders, avoiding the
unwanted conductivity impairment and energy loss caused by the
resistance of binders. The PANI@rGO nanocomposite foam was
prepared by deposition of GO on Ni foam (NF), followed by
reduction, removal of NF, and a facile in situ polymerization of
aniline. The obtained 3D foam-like PANI@rGO nanocomposite
shows interconnected porous structure, which enables electrolyte
to access the internal surface and thus ensures high specific
capacitance (701 F g1 at the current density of 1 A g1). Good
cycling durability has also been observed with 92% of the starting
capacitance retained after 1000 charge–discharge cycles. More-
over, the PANI@rGO nanocomposite achieved exhibits good
flexibility and is able to deliver a high specific capacitance of
285 F g1 at 1 A g1 in a bended symmetric system, indicating
excellent potential for real energy storage in flexible super-
capacitors.
2. Materials and methods
2.1. Materials
Potassium persulfate (K2S2O8, A.R., Xilong Chemical Co., LTD.),
ammonium persulfate ((NH4)2S2O8, A.R., Xilong Chemical Co.,
LTD.), phosphorus pentoxide (P2O5, Tianjin Fuchen Chemical
Factory), ammonia (NH3H2O, A.R., Beijing Chemical Factory),
graphite (45 mm, A.R., Sigma,), aniline (C6H5NH2, A.R., Xilong
Chemical Co., LTD.), ethanol (C2H5OH, A.R., Beijing Chemical
Factory), hydrochloric acid (HCl, A.R., Beijing Chemical Factory),
ferric chloride (FeCl36H2O, A.R., Beijing Chemical Factory),
hydrazine hydrate (H2NNH2H2O, Tianjin Fuchen Chemical Facto-
ry), and concentrated sulfuric acid (H2SO4, A.R., Beijing Chemical
Factory) were used as received. Nickel foams (1.5 mm thick, 110 ppi,
99.8% purity) were purchased from Tianyuan Lizhiyuan Technology
Co. All solutions were prepared with ultrapure water (resistance
>18 MV cm1).
2.2. Preparation of rGO foam
Graphene oxide (GO) was prepared from graphite powder via a
modified Hummers method as previously described [46,47]. Nickel
foam (NF) was used as the template for the fabrication of GO foam.
Briefly, NF was sequentially washed with acetone, water, 1:10HCl,
69
water and alcohol under sonication for 15 min each, and dried
under vacuum for 4 h before use. Then, 0.9 mL GO suspension
(CGO = 3.75 mg mL1) was dropped onto NF (a square of
1.5  1.5 cm) and the NF filled with GO suspension was subse-
quently dried under room temperature to deposit GO sheets on the
NF surface (GO@NF). Next, GO@NF was transferred into an
autoclave with 10 mL hydrazine monohydrate and heated at
90  C for 16 h to obtain rGO@NF. The removal of NF from rGO@NF
was achieved by immersing rGO@NF in a solution containing
hydrochloric acid (2.0 M) and FeCl3 (0.8 M) overnight at room
temperature. The resultant rGO foam was rinsed with deionized
water several times to remove residual acid and metal ions.
2.3. In situ polymerization
In-situ polymerization of aniline on the pre-formed rGO foam
was carried out by using a protocol adopted from previous reports
to obtain the PANI@rGO nanocomposite foam [16,25]. The rGO
foam was immersed in 5 mL 1.0 M HCl aqueous solution containing
0.15 mL aniline. The mixture was stored at 4  C for 1 h. Then, 5 mL
1.0 M HCl aqueous solution containing 0.09 g ammonium
persulfate (pre-cooled to 4  C) was poured into the above mixture,
and the resultant mixture was left at 4  C for another 0.5 h. The
obtained nanocomposite foam was thoroughly rinsed with HCl
aqueous solution, ethanol, ammonia and water.
2.4. Electrochemical measurement
Electrochemical measurements were performed at room
temperature using a CHI 660E electrochemistry workstation. A
conventional three-electrode system was set up to characterize
electrochemical properties, including cyclic voltammetry (CV),
galvanostatic charge–discharge (GCD) cycling and electrochemical
impedance spectra (EIS). The PANI@rGO nanocomposite foam was
transferred onto Indium-Tin Oxide (ITO) glass to be used as the
working electrode. Platinum wire and AgCl/Ag electrode (saturated
with KCl) were adopted as the counter electrode and the reference
electrode, respectively. 1 M H2SO4 solution was used as the
electrolyte in all electrochemical measurements. CV tests were
carried out at a scan rate ranging from 5 mV s1 to 1000 mV s1
under the potential between 0.2 V and 0.8 V. The GCD cycling was
carried out within the same potential range at current densities
ranging from 0.5 A g1 to 10 A g1. The performance of symmetric
pseudocapacitor was measured in a two-electrode system,
composed of two identical working electrodes, which were
prepared by gluing the PANI@rGO nanocomposite foam onto
two slices of ITO-PET (polyethylene terephthalate) in same shape
and size with AB glue at four corners. A piece of filter paper soaked
with 1 M H2SO4 electrolyte was used as the separator. Rubber
bands were used to bend the prepared electrodes, during the
performance measurement for flexible symmetric pseudocapaci-
tor.
2.5. Material characterization
Scanning electron microscopy (SEM) images were collected on a
JEOL JSM-7500F field emission scanning electron microscope.
Fourier transform infrared (FT-IR) spectra were collected on an FT-
IR spectrometer (SHIMADZU IRAffinity-1) using KBr pellets (32
scans), and the spectra were recorded at a resolution of 4 cm1.
Atomic force microscopy (AFM) under tapping mode was carried
out with a commercial instrument (Digital Instrument, Nanoscope
III, and Dimension 3000) at room temperature in air. UV–vis
absorption spectra were taken in a quartz cell with light path of
1 cm on a SHIMADZU UV-2550 spectrophotometer (200–800 nm).
70 H. Sun et al. / Synthetic Metals 209 (2015) 68–73
3. Results and discussion
The fabrication of PANI@rGO nanocomposite foam is shown in
Fig. 1. First, GO was prepared from graphite via a modified
Hummers method, and characterized by UV–vis and Atomic Force
Microscopy (AFM), as shown in Figs. S1 and S2, respectively [48].
Then GO suspension (3.75 mg mL1) was dropped onto a piece of
Ni foam (NF), which was used as the template for the preparation
of graphene foam. Subsequently, the GO suspension was dried
under room temperature to deposit GO sheets on the NF surface.
Next, the resultant GO@NF was reduced by hydrazine vapor to
yield rGO@NF, which was then immersed in an aqueous solution of
HCl (2.0 M) and FeCl3 (0.8 M) for 10 h at room temperature to
remove NF. It is noted that the resultant rGO foam is self-standing
after the removal of NF, suggesting the p–p stacking force between
adjacent rGO sheets in the skeleton is strong enough to hold it from
self-collapsing [16,45]. Upon obtaining the self-standing rGO foam,
in situ polymerization of aniline was carried out on its surface (see
Section 2) to obtain self-standing PANI@rGO nanocomposite foam.
The morphologies of rGO foam and PANI@rGO nanocomposite
foam were observed by scanning electron microscopy (SEM)
(Fig. 2). The rGO foam clearly shows an interlinked 3D porous
structure with an averaged pore size around 500 mm (Fig. 2a),
preserving a foam structure dictated by NF. The thickness of the
wall is relatively uniform and approximately of 50 mm, which
provides the rGO skeleton adequate mechanical strength to protect
the pores from collapsing. The highly porous feature of rGO foam
has been maintained in the PANI@rGO nanocomposite (Fig. 2c)
indicating that the in situ polymerization has not altered the
overall structure of rGO foam. However, the comparison of high-
magnification SEM images of rGO and PANI@rGO nanocomposite
foam (Fig. 2b and d, respectively) revealed different surface
morphologies. While the micro-surface of rGO is relatively smooth
(Fig. 2b), the surface of the PANI@rGO nanocomposite is rough,
covered with densely packed PANI flakes (Fig. 2d). More
importantly, it has been found that the distribution of PANI layer
is quite even, which neatly conceals the surface of rGO foam
without clogging the pores and thus preserves the large surface
area nature of rGO foam. Transmission electron microscopy (TEM)
images (Fig. S3) further confirm that the rGO foam in the
nanocomposite has been evenly covered by PANI flakes after in
situ growth of PANI on the rGO foam. The density of PANI@rGO
nanocomposite foam is estimated as low as
8.3 mg cm3,
suggesting a light-weight property that can be a potential
advantage for applications such as portable supercapacitors. The
density was calculated by dividing the mass (2.1 mg) of the
PANI@rGO foam by its volume, which was estimated by multiply-
ing the area (1.30  1.30 cm) with the thickness of the PANI@rGO
foam (1.5 mm).
Fig. 1. The schematic illustration for the fabrication of PANI@rGO nanocomposite foam: (a) fill GO suspension into NF template and dry the suspension to deposit GO sheets on
NF; (b) reduce GO to yield rGO@NF; (c) remove NF to obtain rGO foam; (d) in situ polymerization of aniline on rGO foam to obtain PANI@rGO foam.
Fourier transform infrared spectroscopy (FT-IR) was used to
identify the functional groups of PANI@rGO nanocomposite foam
(Fig. S4). The spectrum of rGO alone displays two prominent bands
at 1563 and 1189 cm1, corresponding to the vibrations of C¼C and
CC, respectively [32], and no observable bands representing
oxygen-containing groups, suggesting complete reduction of GO to
rGO. In comparison, the spectrum of PANI@rGO nanocomposite
exhibits a set of characteristic bands of PANI in addition to the
bands of rGO, as evidenced by the reference spectrum of PANI
alone, indicating the formation of PANI on rGO foam. The bands at
1562 and 1490 cm1 can be attributed to C¼C stretching of the
quinonoid ring and benzenoid ring, respectively, whereas the
bands at 1235 and 1124 cm1 can be assigned to C H bending of
the benzenoid ring and quinonoid ring, respectively [25,27]. C N
stretching of secondary aromatic amines has also been found at
1294 cm1. It is noted that the “electronic-like band” at 1124 cm1,
related to PANI conductivity [27], has been enhanced in the
PANI@rGO nanocomposite, which can be explained by the p–p
interactions between the rGO sheets and conjugated PANI. In
addition, Raman spectra were obtained to confirm the successful
formation of PANI on rGO foam (Fig. S5). The bands at 1160, 1254,
1325, 1480, and 1572 cm1 can be assigned to C H bending of
quinoid ring, CH bending of the benzenoid ring, C N+ stretching
vibration, C¼C vibration of the quinoid rings and CC stretching of
the benzenoid ring, respectively, indicating the presence of a
conductive PANI structure [28,29]. The PANI formed on rGO by
oxidation of aniline with ammonium persulfate has been
confirmed as emeraldine salt phase, evidenced by UV–vis
measurement (Fig. S6), which exhibits absorption peaks at 362,
441, and 789 nm consistent with reported characteristic peaks of
emeraldine salt phase [30,31].
The electrochemical properties of PANI@rGO nanocomposite
foam were investigated by cyclic voltammetry (CV), electrochemi-
cal impedance spectra (EIS) and galvanostatic charge–discharge
(GCD) measurements (Fig. 3). Fig. 3a shows the CV curves of
PANI@rGO nanocomposite foam, rGO alone foam and PANI alone
film at the scan rate of 20 mV s1. The CV curve of PANI@rGO
nanocomposite not only shows peak current higher than those of
rGO and PANI alone, but also exhibits a much larger integrated area
than those of the other two materials, indicating a better capacitive
performance. Moreover, the CV curve of PANI@rGO displays two
pairs of redox peaks representing reversible charge–discharge
behavior. The pair of peaks observed between 0.3 V and 0.4 V can
be accredited to the redox transition of PANI between leucoemer-
aldine and emeraldine, while the other pair of peaks around 0.6 V
can be derived from the emeraldine–pernigraniline transforma-
tion [27,39]. The CV curves of PANI@rGO within the scan rate range
of 5 to 1000 mV s1 have been shown in Fig. S7. The PANI@rGO
nanocomposite electrode is able to maintain a wide-opened CV
 H. Sun et al. / Synthetic Metals 209 (2015) 68–73 71

Fig. 2. SEM images of rGO foam and PANI@rGO nanocomposite foam. (a) SEM image of rGO foam, inset is the photograph of self-standing rGO foam; (b) the high-
magnification image of (a); (c) SEM image of PANI@rGO nanocomposite foam, inset is the photograph of self-standing PANI@rGO foam; (d) the high-magnification image of
(c).

Fig. 3. Electrochemical performance of PANI@rGO nanocomposite foam, rGO foam and PANI film in 1 M H2SO4. (a) CV curves of PANI@rGO nanocomposite foam, PANI film and
rGO foam at the scan rate of 20 mV s1; (b) GCD curves of PANI@rGO nanocomposite foam, rGO foam and PANI film at 1 A g1; (c) calculated specific capacitances for
PANI@rGO nanocomposite foam, rGO foam and PANI film at different current densities, inset is the relative specific capacitance (normalized to the specific capacitance at
0.5 A g1); (d) Nyquist plots of PANI@rGO nanocomposite foam, rGO foam and PANI film.

curve up to a scan rate of 100 mV s1, implying a good rate
capability.
Fig. 3b shows the GCD curves of PANI@rGO nanocomposite
foam, rGO foam and PANI film at the same current density of
1 A g1. The rGO foam yielded a linear charge–discharge curve,
consistent with its nature of EDLC. In contrast, the PANI@rGO
nanocomposite foam and PANI film displayed non-linear GCD
curves, representing an evident pseudocapacitive characteristic
conferred by the transition between the redox states of leucoe-
meraldine, emeraldine, and pernigraniline. It has been found that
the PANI@rGO nanocomposite foam exhibits a longer charge and
discharge time than either rGO or PANI alone, demonstrating an
enhanced capacitive performance. Subsequently, the correspond-
ing specific capacitances (Cs) have been calculated from the
discharging curves according to the following equation:
I  Dt
Cs¼ (1)
DV  m
where I is the constant discharge current (A), Dt is the discharge
time (s), DV is the potential change during discharge process (V),
and m is the mass of the whole electrode including both rGO and
PANI (g).
The calculated Cs of PANI@rGO nanocomposite foam is 701 F
g1 at the current density of 1 A g1, significantly higher than those
of rGO foam and PANI film (59 and 99 F g1, respectively), implying
that the foam feature of the nanocomposite can efficiently boost
the capacitance of PANI by providing more accessibility.
72 H. Sun et al. / Synthetic Metals 209 (2015) 68–73
As aforementioned, the poor rate capability of PANI has been a
constraint for its application. In order to assess whether the rGO
foam skeleton could enhance the rate capability of PANI, the Cs
values of PANI@rGO nanocomposite foam, rGO foam and PANI film
were measured at different current densities (Fig. 3c). As the
current density increased from 0.5 to 1.5 A g1, the Cs of PANI@rGO
nanocomposite foam declined by 13%, significantly less than those
of rGO foam and PANI film, which dropped by 65% and 85%,
respectively (inset of Fig. 3c). More importantly, even at the current
density of 10 A g1, the nanocomposite electrode can still maintain
a Cs of 137 F g1 (Fig. S8). Thus the rate capability of PANI can
indeed be improved by forming nanocomposite with 3D rGO foam,
which extends the surface of PANI exposed to electrolyte and
enables faster charge transfer.
We then investigated the charge transfer resistance, internal
resistance, and ion diffusion process of these electrodes by EIS
measurement within a frequency range of 100 kHz–0.01 Hz
(Fig. 3d), which displayed a typical Nyquist plot consisting of a
semicircle in the high frequency region and a linear part in the low
frequency area [32,49]. The diameter of the semicircle correlates
with the interfacial charge-transfer resistance, which usually
accounts for the resistance of the electrochemical reaction on the
electrode (Faradaic resistance). The PANI@rGO nanocomposite
foam exhibits a semicircle smaller than those of rGO foam and PANI
film, suggesting better conductivity and lower charge-transfer
resistance, in line with its hybrid composition. The intercept of the
curve on the Z’-axis of Z” = 0 represents the contributions from the
inherent resistance of electrode material, bulk resistance of the
electrolyte and contact resistance at the active material/current
collector interface. As shown in Fig. 3d, the intercept of the
PANI@rGO curve on the Z’-axis (
1.5 Ohm) is smaller than those of
rGO alone and PANI alone (3.5 and 8.6 Ohm, respectively). Since the
same electrolyte was used for all EIS measurements, these data
implies that the internal resistance and/or the contact resistance of
PANI@rGO nanocomposite foam are lower than those of rGO foam
and PANI film. The EIS spectrum in the low frequency region
mainly corresponds to the magnitude of Warburg resistance,
which reflects the diffusion of redox species in the electrolyte, and
a steeper plot usually indicates faster ion diffusion. The slope of
PANI@rGO nanocomposite foam is larger than that of PANI film,
suggesting the high porosity of the nanocomposite afforded by the
rGO skeleton can indeed enable faster ion diffusion. In addition, the
PANI@rGO nanocomposite also exhibits a steeper plot than rGO
alone implying a synergistic effect of PANI and rGO. Together, these
electrochemical characterizations corroboratively demonstrate
that the PANI@rGO nanocomposite possesses better capacitive
properties than PANI or rGO alone.
As previously discussed, another constraint of PANI is its limited
cyclability. In order to determine whether the rGO foam skeleton
could improve the cyclability of PANI, a supercapacitor based on
the PANI@rGO nanocomposite foam was tested for 1000 GCD
Fig. 4. Electrochemical performance of bended symmetric PANI@rGO nanocomposite foam pseudocapacitor. (a) CV curve of bended symmetric pseudocapacitor at the scan
rate of 20 mV s1, inset is the photograph of the bended nanocomposite foam; (b) galvanostatic charge-discharge curves of bended symmetric pseudocapacitor at 1 A g1.
cycles at 1.5 A g1, which exhibited an excellent cycling perfor-
mance (Fig. S9). The relative specific capacitance of the nano-
composite electrode shows a gradual decrease in the first 500
cycles and an interesting increase from 500 to 800 cycles. This
phenomenon is probably due to the activation of the electrode,
similar to the observations made by other groups [33,37]. It has
also been found that the PANI@rGO electrode can retain 92% of its
starting capacitance even after 1000 cycles, confirming a good
cycling durability. The loss of the capacitance can be explained by
the decomposition, corrosion or detachment of PANI during the
charge–discharge cycles [45].
To our delight, the obtained PANI@rGO nanocomposite foam
also shows good flexibility and can be bended without
detectable damage (inset of Fig. 4a). Thus flexible symmetric
pseudocapacitor based on the PANI@rGO nanocomposite foam
was set up to investigate the behavior of the nanocomposite in
real energy storage. The CV curve of the two-electrode system
displays a large window with two pairs of redox peaks, similar to
the findings of 3-electrode system. The redox peaks are in line
with transitions of PANI between multiple redox states (i.e., the
leucoemeraldine–emeraldine transition and the emeradine–
pernigraniline transition) [16,27], indicating that Faradaic reac-
tions of PANI contribute a lot to this symmetric configuration
(Fig. 4a). The corresponding capacitance of PANI@rGO nano-
composite foam in two-electrode system is calculated as 285 F g1
by GCD cycling at 1 A g1 (Fig. 4b), suggesting a good promise for
real-world applications.
Together, the observed excellent pseudocapacitive performance
indicates that the PANI@rGO nanocomposite foam combines the
advantages of EDLCs and pseudocapacitors, expressing the
synergistic effect of PANI and rGO, which can be rationalized by
following reasons: (1) Large-scale p–p interaction between PANI
and rGO can facilitate charge transfer and as a consequence,
significantly improves charge–discharge rate. (2) The PANI@rGO
nanocomposite foam shows interconnected porous structure,
which enables electrolyte to access the internal surface, making
full use of the active material, and thus ensures a high capacitance.
(3) The skeleton of rGO foam can easily relieve the internal stress
incurred during charging and discharging, protecting the electrode
from physical damage caused by swelling and shrinkage, which
seriously reduces the cyclability of PANI and hinders its application
in supercapacitors [43]. (4) The rGO foam skeleton can provide
adequate mechanical support, delivering a nanocomposite that can
be bended and used as flexible supercapacitor. (5) The use of as-
synthesized self-standing nanocomposite foam as electrode avoids
the unwanted conductivity impairment and energy loss caused by
the resistance of binders.
 H. Sun et al. / Synthetic Metals 209 (2015) 68–73
4. Conclusion
In summary, flexible self-standing PANI@rGO nanocomposite
foam has been delicately synthesized by a template-directed in situ
polymerization method, which can be directly used as electrodes
for flexible supercapacitors. The as-synthesized PANI@rGO nano-
composite foam shows highly porous 3D structure with PANI
evenly coated on rGO skeleton as revealed by SEM. More
importantly, the resultant nanocomposite combines the advan-
tages of both PANI and rGO, which synergistically leads to
enhanced electrochemical performance, such as high specific
capacitance, excellent rate capability and good durability. Further-
more, the bended symmetric pseudocapacitor based on the
PANI@rGO nanocomposite foam exhibits a high specific capaci-
tance of 285 F g1 at 1 A g1, indicating excellent potential for real
energy storage in flexible supercapacitors. Therefore, the approach
presented here not only provides a facile method for binder-free
electrode preparation, but also offers great promise for the
development of flexible low-density electrode materials with
good potential for applications in portable electronic devices.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (NSFC, 21471067, 51402121, 51302103, and
51375204), and Jilin Provincial Science & Technology Department
(20140520101JH, 20140520163JH, and 20140101056JC).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.
synthmet.2015.07.001.
References
[1] L. Mao, K. Zhang, H.S.O. Chan, J.S. Wu, J. Mater. Chem. 22 (2012) 80.
[2] P. Simon, Y. Gogotsi, Nat. Mater. 7 (2008) 845.
[3] K. Wang, H.P. Wu, Y.N. Meng, Z.X. Wei, Small 10 (2014) 14.
[4] E. Frackowiak, F. Beguin, Carbon 39 (2001) 937.
[5] Y. Zhai, Y. Dou, D. Zhao, P.F. Fulvio, R.T. Mayes, S. Dai, Adv. Mater. 23 (2011)
4828.
[6] L.L. Zhang, X.S. Zhao, Chem. Soc. Rev. 38 (2009) 2520.
[7] J.R. Miller, P. Simon, Science 321 (2008) 651.
[8] L.L. Zhang, R. Zhou, X.S. Zhao, J. Mater. Chem. 20 (2010) 5983.
73
[9] Z.Q. Niu, P.S. Luan, Q. Shao, H.B. Dong, J.Z. Li, J. Chen, D. Zhao, L. Cai, W.Y. Zhou,
X.D. Chen, S.S. Xie, Energy Environ. Sci. 5 (2012) 8726.
[10] J.T. Zhang, J.W. Jiang, H.L. Li, X.S. Zhao, Energy Environ. Sci. 4 (2011) 4009.
[11] S. Chen, W. Xing, J.J. Duan, X.J. Hu, S.Z. Qiao, J. Mater. Chem. A 1 (2013) 2941.
[12] G.P. Wang, L. Zhang, J. Zhang, J. Chem. Soc. Rev. 41 (2012) 797.
[13] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V.
Grigorieva, A.A. Firsov, Science 306 (2004) 666.
[14] Y. Zhao, H. Bai, Y. Hu, Y. Li, L.T. Qu, S.W. Zhang, G.Q. Shi, J. Mater. Chem. 21 (2011)
13978.
[15] T. Kuilla, S. Bhadra, D.H. Yao, N.H. Kim, S. Bose, J.H. Lee, Prog. Polym. Sci. 35
(2010) 1350.
[16] Y.F. Wang, X.W. Yang, L. Qiu, D. Li, Energy Environ. Sci. 6 (2013) 477.
[17] S.Q. Jiao, J.G. Tu, C.Y. Fan, J.G. Hou, D.J. Fray, J. Mater. Chem. 21 (2011) 9027.
[18] E. Frackowiak, V. Khomenko, K. Jurewicz, K. Lota, F. Beguin, J. Power Sources
153 (2006) 413.
[19] R. Kotz, M. Carlen, Electochim. Acta 45 (2000) 2483.
[20] Y. Zhou, Z.Y. Qin, L. Li, Y. Zhang, Y.L. Wei, L.F. Wang, M.F. Zhu, Electrochim. Acta
55 (2010) 3904.
[21] A.K. Geim, Science 324 (2009) 1530.
[22] A.K. Geim, K.S. Novoselov, Nat. Mater. 6 (2007) 183.
[23] M. Pumera, Energy Environ. Sci. 4 (2011) 668.
[24] L. Wang, X.P. Lu, S.B. Lei, Y.H. Song, J. Mater. Chem. A 2 (2014) 4491.
[25] W. Chen, R.B. Rakhi, H.N. Alshareef, Nanoscale 5 (2013) 4134.
[26] X. Huang, Z.Y. Zeng, Z.X. Fan, J.Q. Liu, H. Zhang, Adv. Mater. 24 (2012) 5979.
[27] J.J. Xu, K. Wang, S.Z. Zu, B.H. Han, Z.X. Wei, ACS Nano 4 (2010) 5019.
[28] H. Fan, H. Wang, N. Zhao, X. Zhang, J. Xu, J. Mater. Chem. 22 (2012) 2774.
[29] X. Yan, Z. Tai, J. Chen, Q. Xue, Nanoscale 3 (2011) 212.
[30] J. Yue, A.J. Epstein, J. Am. Chem. Soc. 112 (1990) 2800.
[31] S. Xing, L.H. Tan, M. Yang, M. Pan, Y. Lv, Q. Tang, Y. Yang, H. Chen, J. Mater. Chem.
19 (2009) 3286.
[32] L. Wang, Y.J. Ye, X.P. Lu, Z.B. Wen, Z. Li, H.Q. Hou, Y.H. Song, Sci. Rep. 3 (2013) .
[33] L. Li, A.R.O. Raji, H.L. Fei, Y. Yang, E.L.G. Samuel, J.M. Tour, ACS Appl. Mater.
Interfaces 5 (2013) 6622.
[34] Y. Liu, Y. Ma, S.Y. Guang, H.Y. Xu, X.Y. Su, J. Mater. Chem. A 2 (2014) 813.
[35] N.A. Kumar, H.J. Choi, Y.R. Shin, D.W. Chang, L.M. Dai, J.B. Baek, ACS Nano 6
(2012) 1715.
[36] J.T. Zhang, X.S. Zhao, J. Phys. Chem. C 116 (2012) 5420.
[37] Q.Q. Zhou, Y.R. Li, L. Huang, C. Li, G.Q. Shi, J. Mater. Chem. A 2 (2014) 17489.
[38] Z. Tong, Y. Yang, J. Wang, J. Zhao, B.L. Su, Y. Li, J. Mater. Chem. A 2 (2014) 4642.
[39] T. Lee, T. Yun, B. Park, B. Sharma, H.K. Song, B.S. Kim, J. Mater. Chem. 22 (2012)
21092.
[40] H. Nishide, K. Oyaizu, Science 319 (2008) 737.
[41] X.M. Lu, Y.N. Xia, Nat. Nanotechnol. 1 (2006) 163.
[42] A. Rogers, Y.G. Huang, Proc. Natl. Acad. Sci. U. S. A. 106 (2009) 10,875.
[43] H.P. Cong, X.C. Ren, P. Wang, S.H. Yu, Energy Environ. Sci. 6 (2013) 1185.
[44] D.W. Wang, F. Li, J.P. Zhao, W.C. Ren, Z.G. Chen, J. Tan, Z.S. Wu, I. Gentle, G.Q. Lu,
H.M. Cheng, ACS Nano 3 (2009) 1745.
[45] Y.N. Meng, K. Wang, Y.J. Zhang, Z.X. Wei, Adv. Mater. 25 (2013) 6985.
[46] S.Y. Yin, Y. Goldovsky, M. Herzberg, L. Liu, H. Sun, Y.Y. Zhang, F.B. Meng, X.B. Cao,
D.D. Sun, H.Y. Chen, A. Kushmaro, X.D. Chen, Adv. Funct. Mater. 23 (2013) 2972.
[47] S. Yin, Y.-L. Wu, B. Hu, Y. Wang, P. Cai, C.K. Tan, D. Qi, L. Zheng, W.R. Leow, N.S.
Tan, S. Wang, X. Chen, Adv. Mater. Interfaces 1 (2014) 1,300,043.
[48] S. Park, R.S. Ruoff, Nat. Nanotechnol. 4 (2009) 217.
[49] Z. Liu, K. Xu, H. Sun, S. Yin, Small 11 (2015) 2182.