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The synthesis of highly corrugated graphene and

its polyaniline composite for supercapacitors
Cite this: DOI: 10.1039/c7nj00024c
Mohd. Khalid,a Luis T. Quispe,a Cristiani C. Pla Cid,a Alexandre Mello,b
Milton A. Tumeleroac and André A. Pasa *a

Received 3rd January 2017,
Accepted 27th April 2017
DOI: 10.1039/c7nj00024c
rsc.li/njc
Graphene based composites and blends are potential candidates for fast and highly dense energy
storage devices such as supercapacitors. Here is reported the preparation of highly corrugated graphene
(CG) thin films onto plastic sheets of polyvinyl chloride (PVC) through thermal treatment using hydroiodic acid
(HI) as the reducing agent. These films can be used as electrode materials for supercapacitors without the
need for binders or metal current collectors. The films show a specific gravimetric capacitance of 170 F g1 at
0.125 A g1 and retains over 81% of their initial capacitance after 10 000 repeating cycles of charging/
discharging. When the CG film is prepared in the presence of polyaniline (PANI), the resultant composite
electrode (CG–PANI) presents a high specific gravimetric capacitance of 1041 F g1, over 6 times greater than
CG electrodes. Further, a symmetrical solid-state supercapacitor with CG–PANI electrodes is assembled by
using a polyvinyl alcohol/sulfuric acid (PVA/H2SO4) gel electrolyte that shows an impressive volumetric energy
density of 3.1 mW h cm3 while maintaining a volumetric power density of 73.9 mW cm3. This simple and
costless effective preparation method of CG and its polyaniline composite can open up exciting opportunities
for supercapacitor applications.

Introduction A variety of techniques have demonstrated how to prevent the

It is known that supercapacitors are energy storage devices that
charge and discharge rapidly, often ten to hundred times faster
than batteries.1 Graphene has emerged as a potential candidate
for supercapacitors because of its unique structure and properties
such as large specific surface area (2630 m2 g1), outstanding
electrical conductivity (106 S cm1), high charge mobility
(200 000 cm2 V1 s1), great mechanical strength, unusual flex-
ibility, and high electrochemical stability.2–4 However, it is still
indispensable to boost the performance of graphene-based
supercapacitors to fulfil the requirements of emerging technologies.
Despite the above unique advantages, graphene has the main
drawback of sheet-to-sheet restacking due to the strong interactions
between p–p electrons, losing its high surface area.5,6 Retrieving this
considerable surface area is the most important key to improve the
capacitance of graphene electrodes. Traditional synthesis methods
like chemical reduction,7 thermal reduction,8 and electrochemical
reduction9 of graphene oxide are the most common ways to obtain
high yield of graphene, but restacking of the sheets is unavoidable.
a
Laboratório de Filmes Finos e Superfı́cies, Departamento de Fı́sica, Universidade
Federal de Santa Catarina, 88040-900-Florianopolis, Brazil.
E-mail: andre.pasa@ufsc.br
b
Centro Brasileiro de Pesquisas Fı́sicas, Xavier Sigaud, 150,
Rio de Janeiro 22.290-180, Brazil
c
Instituto de Fı́sica, Universidade Federal do Rio Grande do Sul, Avenida Bento
Gonçalves, 9500, P.O. Box 15051, 91501-970 Porto Alegre, RS, Brazil
restacking of graphene such as CVD growth of vertically oriented
graphene sheets,10 in plane graphene supercapacitors,11 holey
graphene,12 curved graphene,13 crumpled graphene,14 graphene
hydrogel (template assisted method),15 laser scribed graphene,16
and inkjet printing graphene.17 In another approach, Zhang et al.18
elaborated a free-standing activated reduced graphene oxide (GO)
film, which yields a specific surface area of up to 2400 m2 g1 and a
specific capacitance of 120 F g1 at 10 A g1 using 1 M TEABF4 in
acetonitrile. Recently, Ji et al.19 have fabricated a three-dimensional
free-standing nitrogen-doped porous graphene/graphite foam,
which delivers a high specific capacity of up to 1687 mA h g1.
Wang et al.20 reported carbon black nanoparticles used as spacers to
create flexible pillared-type graphene paper resulting in a significant
increase of the electrochemical performance showing specific capa-
citance of 138 F g1 in an aqueous electrolyte. Among all these
approaches, the incorporation of spacers like carbon nanotubes,
conducting polymers, and metal oxides is the most promising way
to avoid the agglomeration of graphene. Furthermore, these spacers
anchor on the surface of graphene avoiding restacking and working
as synergistic materials to improve the capacitance and energy
storage of the supercapacitor electrodes.
Polyaniline (PANI) is the most used conducting polymer in
composites and blends with graphene because of its conjugated
structure and the presence of electron rich nitrogen atoms,
which allows hydrogen bonding and p–p interactions with
graphene. Such interactions may improve the electrochemical

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stability of the composite and the mechanical strength of the
electrode.21–24 In previous reports, graphene-PANI composites
were made either by powder alloying, electrodeposition or by
vacuum filtration of the mixture of graphene and PANI, which
lacks a synergistic effect between PANI and graphene sheets.
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Metal oxides such as MnO2, Fe3O4, NiO, RuO2, Co3O4,
Ni(OH)2, TiO2, and V2O5 have also been investigated in compo-
sites with graphene.25–32 Shi et al.26 developed a solvothermal
approach for decorating reduced GO (rGO) with Fe3O4 showing
much higher capacitance than pure rGO. Chen et al.33 fabri-
cated GO/MnO2 nanocomposites via a simple chemical route in
water–isopropyl alcohol, for use as electrodes in supercapacitors
with improved capacitance. Cheng et al.34 fabricated rGO/MnO2
composite electrodes by in situ anodic electrodeposition. Other
than the utilization of spacers, different new techniques have
been reported on the fabrication of high surface area graphene
such as tap casting,35 leavening,36 and chemical activation.37
Here, we demonstrate the rapid heat treatment of the
mixture of GO and hydroiodic acid (HI) (57%) resulting in the
formation of reduced highly corrugated graphene (CG) films
onto polyvinyl chloride (PVC) sheets. HI reduces the GO under
thermal treatment and makes the graphene films conductive.
The films were electrochemically characterized as supercapacitor
electrodes resulting in a high specific capacitance of 170 F g1.
When CG is mixed with PANI (CG–PANI), the composite capaci-
tance increases to 1041 F g1, about 6 times higher than pure
CG. Further, we assembled a symmetrical solid-state super-
capacitor using CG–PANI electrodes that shows an impressive
specific energy of 3.1 mW h cm3 at a specific power of
73.9 mW cm3. These results demonstrate that the preparation
process of CG and CG–PANI would offer an easy and effective
way to fabricate graphene-based supercapacitors.
Experimental
Aniline was distilled twice before use. All the other reagents
were of analytical grade and used as received. All solutions
were prepared using Milli-Q grade water (18.2 MO cm) and GO
(2 mg mL1) was purchased from Sigma-Aldrich. PANI was
synthesized by oxidative polymerization of aniline in the
presence of H2SO4 using ammonium peroxydisulphate (as an
oxidizing agent). For the synthesis, a solution of 1% aniline
with 100 mL of 1 M H2SO4 in water was taken and stirred at
room temperature for 30 min. The precooled solution (100 mL) of
ammonium peroxydisulphate (0.5 g) in 1 M H2SO4 was rapidly
mixed into the above solution of aniline and left overnight under
continuous stirring at room temperature (251). Then, the product
was filtered and washed several times with water and finally with
methanol. The green colored precipitate was collected and kept
in an oven at 50 1C for 24 h to obtain dried PANI. The CG and
CG–PANI synthesis will be described in the next section. A PVC
sheet was used as a flexible and transparent substrate; prior to
casting of the films, the substrate was cleaned by sonicating in
water for 10 min. The thickness of the films was measured with a
profilometer (Bruker Dektak). Electrical contacts to the samples
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were made by using copper wire with silver paint, while Kapton
tape was used to protect the copper wire and silver paint from
exposure to electrolytes.
The morphologies of the materials were investigated using a
JEOL JSM-6701F field-emission scanning electron microscope
(SEM) and JEOL JSM-2100 transmission electron microscope
(TEM). X-ray diffraction (XRD) patterns of the samples were
recorded with Cu-Ka radiation at the scan rate of 21 (2y) min1.
XPS analysis was done using a SPECS PHOIBOS 100/150 spectro-
meter with a 150 mm hemispherical analyzer at an X-ray energy
of 1486.6 eV from polychromatic Al-Ka radiation in 301 of take-off
angle, Epass of 15.5 eV. An energy step of 0.5 eV for the survey
scans and energy step of 0.02 eV for the high-resolution spectra
over each element peak were used. For energy calibration, the C
1s peak with binding energy at 284.6 eV was used. The curve
fittings were done using CASA-XPS software.
Electrochemical analyses were carried out using a potentiostat
(Autolab PGSTAT 302N) electrochemical workstation at room
temperature (25 1C). A three-electrode cell was used for capaci-
tance measurements in a 1 M H2SO4 electrolyte, consisting of a
SCE reference electrode, a platinum foil (area 2 cm2) as the
counter electrode and graphene composite films as the working
electrode. The gravimetric (CSM), volumetric (CSO) and areal (CSA)
specific capacitances of the films in the three-electrode measure-
ments were calculated from discharge measurements by applying
the following equations:
I I I
CSM ¼  ; CSO ¼  ; and CSA ¼   (1)
dV dV dV
M
dt
O
dt
A
dt
where I is the discharge current in amperes, M is the mass (g), O is
the volume (cm3), and A is the area (cm2) of the active material on
the PVC sheet, and dt is the discharge time (in seconds) corres-
ponding to the voltage drop of dV (in volts). dV/dt is simply the
slope of the discharge curve and can be calculated by the equation
dV/dt = (V2 V1/2)/(t2  t1), where V2 and V1 are the voltage and
half voltage of the discharge curve, respectively, t2 and t1 are the
corresponding discharge times of V2 and V1.38
The electrochemical impedance spectroscopy (EIS) analysis
of the samples were done by applying a sinusoid perturbation
of 5 mV at zero biased voltage and measuring the in- and out-
phase current components for frequencies ranging from 10 mHz
to 100 kHz. Two consecutive experiments were performed for
each sample, whereas the first experiment was discarded to
avoid charging effects. The equipment employed was a FRA2
model in the Autolab potentiostat. The proton conducting gel
polymer electrolyte was prepared using 3 g PVA powder (mole-
cular weight 89 000–98 000, 99% hydrolyzed, Sigma-Aldrich) and
3 g H2SO4, both mixed in 30 mL of distilled water. The mixture
was heated at B85 1C under constant stirring until the solution
become transparent. The symmetrical solid-state supercapacitor
device was constructed by sandwiching a gel electrolyte between
two identical active areas of CG–PANI electrodes (2 cm2 of each
electrode). The two electrodes were uniformly coated with
gel electrolyte and air-dried under ambient conditions for
30 min to evaporate the excess of water and then were gently
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laminated together. The polymer gel acts as a kind of glue and
host for ionic conduction. The electrochemical performance
of the device was tested after the gel electrolyte dried and all of
the measurements were based on the total volume of the two
electrodes active materials.
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assumed that the partial reduction of GO layers during this
period of time tends to form disorder clusters of layers and upon
heat treatment at 80 1C, the disorder solid clusters turned into a
fluffy and heavily corrugated graphene structure. In contrast, in
a freshly prepared mixture of GO and HI without standing,

smooth surface of graphene film was observed on the plastic

sheet. This may be because of the GO shows little tendency to
Results and discussion form clusters of disorder solid into the freshly prepared mixture.
Thus, the obtained films were directly adopted as working
The preparation procedure of the CG film is illustrated in electrodes acting as both active material and current collector.
Fig. 1a. The uniform mixture of GO suspension (2 mg mL1) The widened spatial gaps between the layers at the edges of
and HI (57%) with a volume ratio of 2 : 0.5 was dropcast onto the film are presented in Fig. 2c, this type of morphology
the PVC sheet. At first, the mixture of GO and HI was shaken for facilitates the access of ions to the inner region of the electrode.
a few minutes and left to stand for 16 h before casting and a
dark brown dispersion was obtained. Additionally, a few drops
of fresh GO was added into the above dispersion, then the
mixture was agitated for 10 min, drop cast onto the PVC sheet
and directly placed onto the hot plate at 80 1C in a suction
chamber for three hours. The obtained films were washed
several times with distilled water and ethanol to remove the
residual iodine. The area of casting can be adjusted by choice
and the thickness of the film can be tailored in a wide range by
using different volumes and concentrations of GO suspension.
Chemical reduction of GO by HI acid was carried out through
the procedure reported by Pei and co-workers.39 The digital
image (Fig. 1b) shows that the CG film is firmly adhered onto
the surface of PVC sheet with a thickness of B3 mm (Fig. 1c).
Fig. 1d displays the scheme used for the symmetrical mounting
of the supercapacitor device. In Fig. 1e is proposed some
possible chemical interactions between graphene and PANI.
After heat treatment, an intermittent corrugated structure of
graphene layers was obtained, as can be seen in SEM micro-
graphs of Fig. 2a and b for as-prepared CG films at low and high
magnification, respectively. The reason behind the formation of
the corrugated structure of graphene after allowing the mixture
of GO and HI to stand for 16 hours, is not clear. However, we

Fig. 1 (a) Schematic illustration of film fabrication onto PVC sheets,

(b) digital photograph of CG films, (c) thickness measurements, (d) scheme
of the supercapacitor using two symmetrical electrodes of CG–PANI with a Fig. 2 SEM images of (a–c) CG films at different magnifications, (d) SG films,
polymer gel electrolyte (PVA/H2SO4), and (e) possible interactions between (e) CG–PANI films, (f) PANI, (g) and (h) TEM images of CG and CG–PANI, and
graphene and PANI. (i) SAED patterns of CG–PANI.

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Therefore, a high amount of graphene surface may be exposed

to the electrolyte leading to enhanced capacitance. For comparison
purpose, a smooth surface graphene (SG) film was prepared by
using the procedure described above, but without allowing the
mixture of GO and HI to stand. The resulting film surface was
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almost smooth with some wrinkles, as shown in Fig. 2d.

CG–PANI composite films were prepared by adding PANI
powder in the mixture of GO and HI, following the same
procedure described above. The obtained film (Fig. 2e) reveals
that the PANI coating is likely to be adsorbed onto the surface
of graphene by p–p stacking.40 Fig. 2f shows the nanogranular
character of the as-synthesized PANI powder, i.e., before being
mixed with graphene. Fig. 2g displays the TEM image of the
CG sample, where a few stacked layers of graphene are seen. In
Fig. 2h, the TEM image of the CG–PANI shows a PANI covered
single graphene layer. The in-plane crystallographic structure
of the CG–PANI sample was analyzed by electron diffraction
and is displayed in Fig. 2i. The pattern obtained for a few layers
of graphene shows diffraction rings, which could indicate some
stacking disorder, and some bright spots with six-fold rotation
symmetry. The bright spots are probably from CG regions that
were not fully covered by the PANI, maintaining its graphitic
structure. Through the interplanar distance of (1010) planes,
of about 2.08 Å, a lattice parameter for the graphene structure
of 2.4 Å was obtained, close to the expected value of 2.46 Å.41
The XRD patterns of pure GO, CG and CG–PANI samples are
presented in Fig. 3a. For GO, the intense and sharp peak
located at about 101 is ascribed to GO interlayer distances.
After reduction, the peak of GO disappeared and two new peaks
arise, a minor peak and a major centered at 12.91 and 24.71,
respectively, confirming the reduction of GO to rGO and the
existence of week p–p stacking between graphene layers.42
Similarly, the minor peak disappeared from the CG–PANI Fig. 3 (a) XRD patterns of GO, CG, CG–PANI and PANI. In (b) survey and
composite and two broad peaks appeared near at 161 and 221 (c) high-resolution XPS spectra of samples CG and CG–PANI.
which correspond to the PANI diffraction position, implying
that PANI has well covered the graphene layers.42,43 The peak at
about 251 for CG–PANI is much intense in comparison to the the presence of PANI. A peak located at low binding energy
one in the same position found for pure PANI and get broader for both samples may be due to surface contaminants and
in comparison to CG, showing that PANI does not destroy the adsorbates. For the sample CG–PANI (Fig. 3c, inset) a weak
graphene stacking (in agreement with Fig. 2i) but changes the peak was also observed at the position of 290.8 eV, this is the
interlayer distances. The pure PANI powder showed broad transition of p–p* which is a characteristic shake-up line
peaks at 251, 201, 161, and 81, these reflections belong to the (satellite peak) of carbon coming from the ring excited by
emeraldine salt form of PANI.43,44 photoelectrons.46
The XPS analysis of the samples CG and CG–PANI is The electrochemical properties of the CG, SG and CG–PANI
presented in Fig. 3b and c. The XPS survey spectra in Fig. 3b are presented in Fig. 4. Fig. 4a displays the cyclic voltammetry
show the presence of C, O, N, and I elements, where N confirms (CV) curves of CG electrodes at different scan rates using a
the PANI in the composite, while I comes from the reducing 1 M H2SO4 electrolyte. All the CV measurements retain a quasi-
agent hydroiodic acid. Fig. 3c displays the C 1s core level high- rectangular shape in whole range of scan rates, i.e., from 10 to
resolution XPS spectrum of CG and CG–PANI, in which both 100 mV s1, which is a good indication of non-faradaic capa-
samples show similar aspects with five prominent peaks at 284.0, citive behavior of CG electrodes. Fig. 4b depicts the difference
284.7, 285.8, 287.2, and 289.0 eV for –CQC– (sp2), –C–C– (sp3), in CV curves of CG and SG electrodes at 50 mV s1 showing the
–C–O–, –CQO, and –O–CQO bonds, respectively. The signals for lower capacitance of SG electrodes in comparison to CG, clearly
–C–O, –CQO, and –O–CQO bonds confirm the oxygen function- due to the flat surface of SG electrodes. In Fig. 4c is presented
alities on the surface of CG.45 The ratio between sp3 and sp2 the galvanostatic charge/discharge (GCD) response for the CG
carbons for CG and CG–PANI were calculated to be about 3.7 and electrode at different current densities. During GCD measure-
3.1. The increase of sp2 carbons in the composite is ascribed to ments, the charge and counterpart discharge curves are almost

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Fig. 4 (a) CV curves of CG electrodes at different scan rates, (b) CV of CG
and SG electrodes at 50 mV s1, (c) GCD curves of CG electrodes at
different current densities, (d) specific capacitance of CG and SG electro-
des at different current, (e) volumetric and areal capacitance of CG
electrodes at different current densities, (f) charge/discharge cyclic per-
formance of CG electrodes at 1.6 A cm3, (g) CV curves after different
cycles, and (h) Nyquist plot of CG electrodes in the beginning and after
10 000 cycles.
symmetric, given the good efficiency of the electrodes. Addi-
tionally, the lower voltage drops (IR drop) of 0.02 V, 0.04 V, and
0.08 V were noticed in the beginning of discharge curves at
0.125, 0.250, and 0.625 A g1, respectively. The mass specific
(gravimetric) capacitances of CG and SG electrodes at different
current densities are illustrated in Fig. 4d. The highest capacitance
of 170 F g1 was calculated for the CG electrode at 0.125 A g1 and
the lowest was 36 F g1 at 5 A g1. The highest capacitance of
94 F g1 and the lowest capacitance of 33 F g1 were calculated
for SG electrodes at 0.250 A g1 and 3.7 A g1 current densities,
smaller than CG, due to less active surface area. The CG
electrode not only shows the high capacitance than the SG
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electrode but also maintains a wide range of current densities
compared to the SG electrode. Notably, the CG electrode
simultaneously delivers a volumetric capacitance of 227 F cm3
and areal capacitance of 88 mF cm2 at 0.125 A g1, as displayed
in Fig. 4e.
The long term cyclic stability of CG electrodes was tested by
the GCD process at a fixed current density of 1.6 A cm3 and
0 to 1 V potential window. The electrode exhibits 81% of
capacitance retention of its initial state after 10 000 repeated
cycles, as shown in Fig. 4f. Initially, up to 1000 cycles, the
capacitance increases, but starts to decrease after 2000 cycles.
Initial increase in capacitance is also observed by other
research groups,47,48 and this increment in capacitance was
observed due to the activation of graphene layers that may flip
during the charge/discharge cycling process and let the trapped
electrolyte ions diffuse out.49 In the CV curves (Fig. 4g) obtained
after 1000 and 2000 cycles, two small humps appeared at 0.25
and 0.4 V, likely to be related to the redox reaction originating
from oxygen functionalities of CG layers, which might be intro-
duced by the H2SO4 electrolyte during long GCD experiment.50,51
The degradation in capacitance of the CG electrode upon
repeating cycles may be understood as a sum of two different
effects: first, the collapse of the layered graphene structure,
reducing the effective surface area and reducing the double-
layer capacitance and second is likely to be diminished pseudo-
capacitance due to oxygen functionalities of CG layers. Both
degradation effects proposed above should make electrical
resistance of CG increase, which was confirmed by the EIS
measurements presented in Fig. 4h taken just before and after
10 000 cycles. The charge transfer resistance increases as
indicated by the larger semi-circle.
Fig. 5a and b show the CV and GCD analysis, respectively,
for the CG–PANI composite film (thickness B12 mm) under a
mass loading of 0.6 mg cm2, from where the capacitance of
the electrodes can be obtained. A significant improvement was
observed in the capacitive performance of CG–PANI composite
electrodes compared to CG only, attributed to a synergistic
combination of CG and PANI. The highest specific capacitance
measured for CG–PANI was about 1041 F g1 at about 0.6 A g1,
which is much larger than the capacitance of CG electrodes
(about 145 F g1 for the same current density). Furthermore,
the CG–PANI possessed a remarkable areal capacitance of
625 F cm2 and a volumetric capacitance of 520 mF cm3 at
0.6 A g1, displayed as a function of current in Fig. 5c. The
gravimetric capacitance is displayed in Fig. 5d. The capacitance
values found here are higher than reported for electrodeposited
PANI over graphene paper and for the in situ polymerization of
aniline with graphene composite in three-electrode cells.43,52–56
The shape of the CV curves for CG–PANI electrodes (Fig. 5a)
indicates higher series resistance than CG only electrodes,
probably due to the poor conductivity of PANI (in relation to
graphene). A closer inspection of GCD measurements, in
Fig. 5b, reveal that the curves do not show a single linear
behavior, but two distinct stages; one in the voltage range of
0.8 to 0.5 V corresponds to a fast discharge, which is originated
from the electrical double-layer capacitance. Another in the
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Fig. 5 (a) CV curves of CG–PANI electrodes at different scan rates,
(b) GCD curves of CG–PANI electrodes at different current densities,
(c) volumetric and areal capacitance of CG–PANI electrodes, (d) gravimetric
specific capacitance of CG–PANI electrodes at different current, (e) charge/
discharge cyclic performance of CG–PANI electrodes at 1 A g1 and
the inset shows CV curves after each 1000 cycles, and (f) Nyquist plot of
CG–PANI electrodes in the beginning and after 10 000 cycles.
range of 0.5–0 V corresponds to a slow rate of discharge, which
is ascribed to both double-layer and pseudocapacitance. The
enhancement in the discharge time for CG–PANI samples
confirms the synergistic combination of both components to
achieve the high capacitance. In Fig. 5d the specific capacitance
falls sharply as the current density rate of GCD increases,
Fig. 6 (a) CV curves of the symmetric solid-state supercapacitor, (b) GCD curves of the symmetric solid-state supercapacitor and (c) Ragone plot with
the data obtained here.
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suggesting the crucial effect of conductivity of the composite
CG–PANI, in this case higher conductivities are desired to
improve the electrochemical performance, especially the rate
performance of the electrode materials.57–59 Another reason for
the low rate performance of the CG–PANI electrodes is the low
ionic mobility of PANI which leads to a decrease in pseudo-
capacitance at high current densities.
The improvement in capacitance of CG–PANI could be
correlated with the fast ionic transport within the electrode,
induced by the large separation between layers in the presence
of PANI. The graphene may also enhance the stability of PANI
during numerous charge/discharge cycles, though, PANI by
nature has poor cyclic stability caused by the degradation of
polymer chains along the charge/discharge process.60 A 60%
retention in capacitance was achieved after 10 000 cycles for
CG–PANI electrodes at 3.3 A g1 (Fig. 5e). This loss in capaci-
tance may be attributed to the degradation of PANI chains that
had not anchored tightly over the graphene layers. The decrease
of the capacitance after cycling can also be seen in CV curves as
presented in the inset of Fig. 5e. The EIS spectra taken before
and after 10 000 cycles of the CG–PANI electrode are displayed
in Fig. 5f. The charge transfer resistance increases after cycling
test, as observed by the larger semi-circle.
Aqueous electrolyte based supercapacitor devices generally
suffer from electrolyte leakage and lack of flexibility, problems
that can be solved by considering solid-state supercapacitors.
For this purpose, a two-electrode symmetrical solid-state super-
capacitor was assembled and tested using CG–PANI electrodes
and a PVA/H2SO4 gel electrolyte as described above in the
Experimental section. The CV and GCD curves of the device
are plotted in Fig. 6a and b, respectively, with an operating
potential range of 0 to 0.8 V.
Similar behavior to CG–PANI electrodes in three-electrode
cells was found (Fig. 5a), but with smaller capacitance, as
expected since a serial connection of capacitors is present.
A maximum volumetric specific capacitance of 32.7 F cm3
was achieved for solid-state supercapacitors at the current
density of 0.10 A cm3, which is higher than reported values
for solid state graphene (9.6 F cm3)16 and comparable to

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graphene hydrogel (31 F cm3)61 and PEDOT paper (35 F cm3).62
The maximum volumetric specific capacitance of 32.7 F cm3
corresponds to the specific energy of 3.1 mW h cm3 while main-
taining the specific power of 73.9 mW cm3. The minimum specific
capacitance value of 3.12 F cm3 was calculated at 0.62 A cm3,
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corresponding to the specific energy of 0.27 mW h cm3 and
specific power of 486 mW cm3. The values of specific capaci-
tance, energy and power were calculated with respect to the total
volume of two electrode materials. The specific energies and
power for different current densities are presented in the Ragone
plot of Fig. 6c, showing values higher than those observed
previously in laser-scribed graphene (1.36 mW h cm3 in ionic
liquid),16 PPy/nanoporous gold solid-state supercapacitors
(2.8 mW h cm3 in PVA/LiClO4 gel),63 ZnO@C@MnO2 solid-
state supercapacitors (0.04 mW h cm3 in PVA/LiCl gel),64
TiO2@C solid-state supercapacitors (0.011 mW h cm3 in
PVA/H2SO4),65 and WO3x/MoO3x//PANI/ solid-state superca-
pacitors (1.9 mW h cm3 in PVA/H3PO4 gel).66 Energy density of
the device reported here (3.1 mW h cm3) is about three times
higher than commercially available supercapacitors (2.75 V/44 mF
and 5.5 V/100 mF, o1 mW h cm3).16,67 Evaluating the specific
energy and power in terms of volume is considered more mean-
ingful than gravimetric energy and power densities based on the
mass of active materials. The volumetric energy density and power
density of solid-state supercapacitors were obtained from the
equations: Ecell = Ccell  V2/(2  3600), where V is the operating
potential window in volts; Pcell = 3600  Ecell/tdischarge, where
tdischarge is the discharge time.
Conclusions
Our study has demonstrated a simple technique to prepare
interconnected corrugated layers of graphene. This unique
structure electrode material ensures efficient electron and ion
transport to enable the high-performance supercapacitor with
high gravimetric, volumetric and areal capacitances. Apart from
high specific capacitances, the composite of CG and PANI
showed high energy density with high power density in symmetrical
solid-state cells, which is three times greater than those of commer-
cially available supercapacitors.
Acknowledgements
The authors thank the agencies CAPES, FINEP, FAPESC and
CNPQ for financial support of this work and LCME/UFSC for
the electron microscopy facilities.
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