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Electrochemically Synthesized Polypyrrole/Graphene
FULL PAPER
Composite Film for Lithium Batteries
Yang Yang, Caiyun Wang, Binbin Yue, Sanjeev Gambhir, Chee O. Too,
and Gordon G. Wallace*
A polypyrrole/reduced graphene oxide (PPy/r-GO) composite film is pre-
pared by inducing electrochemical reduction of graphene oxide incorporated
into PPy as the dopant. This film has a wrinkled surface morphology with
a porous structure as revealed by scanning electron microscopy. Its porous
structure is attributed to the physical nature of the GO sheets, providing a
templating effect during PPy deposition. This PPy/r-GO composite is char-
acterized using in-situ UV–visible spectroelectrochemistry as well as Raman
and Fourier-transform IR spectroscopy. The PPy/r-GO material shows greatly
improved electrochemical properties, i.e., a high rate capability and excellent
cycling stability when used as a cathode material in a lithium ion battery. It
also delivers a large reversible capacity when used as an anode material, and
this is mainly attributed to the reduced graphene oxide (r-GO) component.
1. Introduction
There is a great demand for the development of flexible or bend­
able energy storage devices for soft portable equipment. Inher­
ently conducting polymers (ICPs) are particularly interesting
candidates for use as electrode materials in such devices.[1]
Apart from their inherent redox properties,[2] these materials are
light weight and possess useful mechanical properties in terms
of tensile strength and flexibility.[3] However, a poor charge/dis­
charge rate capability and a limited cycle stability has mitigated
against the practical application of ICPs in battery technologies.
One commonly applied strategy used to overcome these draw­
backs is the formation of composites with other materials such
as metal oxides or carbons.[4]
The introduction of carbon nanotubes into conducting poly­
mers provides mechanical reinforcement that accommodates
the volumetric changes associated with the charge/discharge
process. In addition, the enhanced conductivity provided by
the carbon nanotube network enables a more rapid charge/
discharge.[5] Graphene, a monolayer of sp2 bonded carbon
Y. Yang, Dr. C. Wang, B. Yue, Dr. S. Gambhir, Prof. C. O. Too,
Prof. G. G. Wallace
ARC Centre of Excellence for Electromaterials Science
Intelligent Polymer Research Institute
AIIM Facility, Innovation Campus
University of Wollongong
NSW 2522, Australia
E-mail: gwallace@uow.edu.au
DOI: 10.1002/aenm.201100449
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atoms, is the most recently uncovered
carbon nanocomponent and has aroused
great interest in those involved in energy
storage.[6] Graphene provides high con­
ductivity, a large surface area, excellent
mechanical properties, and rich chemistry.
The effective integration of graphene into
ICPs is expected to provide unprecedented
properties. For example, a large specific
capacitance and greatly improved electro­
chemical stability have been demonstrated
for polyaniline containing graphene.[7]
Polypyrrole/graphene composites have
been prepared via the chemical poly­
merization of pyrrole in the presence of
graphite oxide followed by chemical reduc­
tion using hydrazine monohydrate.[8] The
composite produced exhibited a conductivity of approximately
8 S cm−1, some 40 times greater than the PPy without graphene
present.[8a] This composite displayed a highly selective Hg2+
removal capacity with an adsorption capacity of 980 mg g−1
and desorption capacity of up to 92.3%.[8b] In other work, a
multilayer-structure consisting of graphene and PPy exhibited a
high specific capacitance of ∼165 F g−1 at the end of 1000 cycles
using a 1 A g−1 discharge current density.[9] Sulfonated graphene
(SG) sheets and polypyrrole have been electrodeposited to form
a porous composite film.[10] This composite film showed a high
specific capacitance of 285 F g−1 at a discharge rate of 0.5 A g−1,
in addition to the greatly improved electrochemical stability and
rate performance compared to PPy.
Graphene oxide (GO), an inexpensive precursor, is cur­
rently used to prepare chemically or electrochemically reduced
graphene and chemically functionalized graphene oxide such
as sulfonated graphene.[11] It consists of a number of oxygen
containing functional groups including epoxy, hydroxyl, and
carboxyl groups. These functional groups make it possible for
GO to function as the dopant when incorporated into con­
ducting polymers. For example, polyaniline doped with GO was
chemically synthesized and characterized but no application
was mentioned in that report.[12] A layer-structured polypyrrole/
graphene oxide composite (PPy/GO) was chemically prepared
with ammonium persulfate (APS) as oxidant. This composite
exhibited a high specific capacitance of 510 F g−1 at a current
density of 0.3 A g−1.[13]
In this work, GO was electrodeposited with pyrrole
monomer from aqueous solution to form a polypyrrole/
graphene oxide film (PPy/GO). This film was subjected to elec­
trochemical reduction to form polypyrrole/reduced graphene
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oxide (PPy/r-GO). It has been shown previously that GO can

FULL PAPER
be reduced to graphene by electrochemical methods.[14] How­
A)
ever, to the best of our knowledge, this is the first report of
+0.5 V
electrochemical reduction of GO being used as a dopant in a
conducting polymer. Moreover, the method reported here is an

Absorbance (a.u.)
environmentally benign approach to produce PPy/r-GO. No oxi­
dant or toxic reducing agent (e.g., hydrazine monohydrate) is
required. Also this green electrochemical synthesis method can -1.1 V
produce PPy/r-GO on conductive complex shaped substrates.
-1.0 V
The PPy/r-GO film obtained exhibited impressive electrochem­
ical properties including a high charge/discharge rate capability -0.8 V
and cycling stability when used as a cathode material in lithium -0.5 V
ion batteries. A specific capacity of 55 mAh g−1 was delivered at
20 C rate, which was 74% of the capacity obtained at 1 C rate.
No capacity fade was observed during 200 consecutive charge/ as-synthesized
discharge cycles at 10 C rate. The material also provided a large 200 400 600 800 1000
reversible capacity when used as an anode material in lithium
Wavelength (nm)
ion batteries.
B)
+0.5 V
Absorbance (a.u.)
2. Results and Discussion
*
2.1. Characterization
-1.1 V

After galvanostatic electrodeposition, a black uniform polypyr­ -1.0 V

role film was obtained on the stainless steel mesh working -0.9 V
electrode. A solution containing pyrrole and either GO
or sodium p-toluenesulfonate (pTS) was used to produce -0.8 V
the polymer. To characterize the films produced spectro­ -0.5 V
electrochemical measurements were performed (Figure 1).
As-synthesized PPy/pTS film demonstrated the typical char­
acteristics of ICPs, i.e., an absorption peak at 420 nm and free as-synthesized
carrier tail beyond 600 nm (Figure 1A). This absorption peak 200 400 600 800 1000
is related to the electron transition from valence band to anti­
bipolaron band and the tail is due to electron transition from
Wavelength (nm)
the valence band to the bipolaron band.[15] The absorption
peak became pronounced and moved to low wavelength for C) 285
the reduced PPy. The free carrier tail was being diminished at
280
the applied negative potentials and restored at the reapplied
Absorbance (a.u.)

positive potential (+0.5 V) demonstrating the reversible redox 274

properties of PPy/pTS.
The as-synthesized PPy/GO film displayed a strong absorp­
tion band at 219 nm, and this is attributed to the π–π* transition 30 mins
of aromatic C–C bonds for GO (Figure 1B).[16] The free carrier
tail observed at wavelengths greater than 600 nm is indicative 15 mins
of polypyrrole being in the oxidized and doped state. When a 5 mins
potential of -0.5 V was applied to the PPy/GO film, an absorp­
tion band attributed to the PPy π–π* transition appeared at
387 nm. The diminishing absorption beyond 600 nm confirmed
as-synthesized
reduction of the PPy backbone.[16] A new absorption peak at
271 nm (denoted *), typical of absorption bands observed for 200 400 600 800 1000
reduced graphene oxide (r-GO), appeared when the potential Wavelength (nm)
applied was -1.0 V. The absorption band at 219 nm almost dis­
appeared with an applied potential of -1.1 V, which indicates Figure 1.  Spectroelectrochemistry of PPy/GO during the electrochemical
that graphene oxide entrapped within PPy could be effectively reduction process. A,B) Different potentials (versus Ag/AgCl) were applied
consecutively at the as-synthesized PPy/pTS (A) and PPy/GO (B): -0.5 V,
reduced at this potential. When a potential of +0.5 V was subse­ -0.8 V, -0.9 V, -1.0 V, -1.1 V, and +0.5 V. C) Different reduction times
quently applied, the peak assigned to reduced r-GO still existed were applied to the as-synthesized PPy/GO at -1.1 V (versus Ag/AgCl):
and no peak corresponding to GO could be found, confirming 5 min, 15 min, and 30 min.

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the irreversible nature of the electrochemical reduction of the
FULL PAPER
GO as described previously.[14a,c,f ]
The effect of the reduction time on this electrochemical
reduction process at the applied potential of -1.1 V was also
investigated (Figure 1C). As the reduction time increased
the absorption intensity relating to r-GO increased and the
absorption relating to GO diminished accordingly. The absorp­
tion intensity from GO could barely be detected after 30 min
reduction. The absorption band corresponding to r-GO was
red-shifted during this process. It appeared at 274 nm after
5 min reduction, and it shifted to 280 and 285 nm as the reduc­
tion time increased to 15 and 30 min, respectively. This red-
shift can be explained by the increased electronic conjugation
within the reduced graphene oxide sheets as the reduction
progresses.[16a]
Field-emission scanning electron microscope (FESEM)
images were obtained for the PPy/pTS and the PPy/r-GO mate­
rials deposited on the stainless steel mesh (Figure 2). PPy/pTS
exhibited a cauliflower morphology composed of large nodules
as reported previously,[17] while a wrinkled or crumpled mor­
phology was observed for the PPy/r-GO (Figure 2A,D). The
morphology observed for the PPy/GO was similar to PPy/r-GO
Figure 2.  FESEM images of surface morphology and cross-section views of PPy/pTS (A,B,C) graphene oxide entrapped in the PPy matrix
and PPy/r-GO films (D,E,F).
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and is not shown here. Cross sectional micrographs revealed a
porous structure for PPy/r-GO (Figure 2E,F) in contrast to the
solid, compact structure observed for PPy/pTS (Figure 2B,C).
This porous structure is attributed to the physical nature
of the GO sheets providing a templating effect during PPy
deposition.
The Raman spectra obtained for PPy/pTS, PPy/GO and
PPy/r-GO are shown in Figure 3A. In the spectrum obtained
for PPy/pTS, bands located at 933, 983, and 1052 cm−1 can
be assigned to C–H out-of-plane deformation, ring deforma­
tion and C–H in-plane deformation of PPy, respectively.[18]
The double bands at 1335 and 1372 cm−1 and the band at
1580 cm−1 are attributed to ring-stretching and C=C back­
bone stretching.[19] These characteristic bands for PPy were
also observed in the Raman spectra obtained for PPy/GO and
PPy/r-GO film. Nevertheless, a significant increase in inten­
sity was observed for bands around 1580 cm−1 and 1335 cm−1
after the introduction of GO and subsequently r-GO into the
PPy matrix. These two bands could be assigned to the D and
G bands for carbon materials.[16b] The D band corresponds
to the first-order scattering of the E2g mode and the G band
is attributed to the in-plane A1g zone-edge mode. The inten­
sity ratio of the D and G band (ID/IG) pro­
vides an estimate of the amounts of defects
in the carbon material under investiga­
tion. It was 1.03 for as-synthesized PPy/
GO and increased to 1.24 after the elec­
trochemical reduction to form PPy/r-GO.
Such intensity ratio increases, indicating
an increase in the number of defects, have
been reported for graphene obtained chem­
ically or electrochemically from graphene
oxide.[14a,c,e,f,16b] This phenomenon may
be attributed to the increased number of
new sp2 domains being formed during the
reduction process.[14e,16b]
To further characterize the PPy/GO reduc­
tion process, Fourier-transform (FT)-IR spec­
troscopy was performed (Figure 3B). PPy/GO
and PPy/r-GO films all exhibited the charac­
teristic absorption bands of PPy in the FTIR
spectra. The peaks at 1198 and 1554 cm−1 are
assigned to C–N stretching and C=C back­
bone stretching of PPy, suggesting that PPy
was successfully polymerized in the pres­
ence of GO. In the FT-IR spectrum of PPy/
GO, the peaks around 1049, 1392, 1710, and
3222 cm−1 are attributed to the C–O (v(epoxy
or alkoxy)), O–H (v(carboxyl)), C=O in carbox­
ylic acid and carbonyl moieties (v(carboxyl)),
and O–H (broad coupling v(O–H)), respec­
tively. These absorption bands are typical of
graphene oxide as reported previously.[8,14a,20]
As the PPy/GO was electrochemically
reduced, the absorption bands related to
oxygen containing groups on GO diminished
considerably or disappeared, proving that
had been effectively reduced.
Adv. Energy Mater. 2012, 2, 266–272

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A)
Intensity (a.u.)
600 800 1000 1200 1400 1600 1800 2000 2200
-1
Raman Shift (cm )
B)
PPy/r-GO
Transmittance (%)
PPy/GO 1710
3222
4000 3500 3000 2500 2000
-1
Wavenumber (cm )
Figure 3.  A) Raman spectra of PPy/p TS,PPy/GO and PPy/r-GO; B) FT-IR
spectra of PPy/GO and PPy/r-GO.
2.2. Electrochemical Performance
The electrochemical data obtained using either PPy/r-GO or the
PPy/pTS film in a lithium ion battery are shown in Figure 4.
The current density of 70 mA g−1 was taken as 1 C rate based on
the theoretical capacity of PPy/pTS (∼73 mAh g−1), and the spe­
cific capacities of all the samples were calculated based on the
mass of active material (e.g., PPy/pTS and PPy/r-GO film only).
These two samples displayed the charge/discharge character­
istic of a polypyrrole/Li battery, no obvious potential plateau was
observed. A pair of redox peaks related to the doping/dedoping
process was observed in the potential range of ∼2.3–3.1 V (inset
of Figure 4A). The rate capability of PPy/r-GO was superior to
PPy/pTS as clearly demonstrated in Figure 4A,B. PPy/r-GO film
exhibited a slightly higher discharge capacity than PPy/pTS at
low current rate of 1 C and 2 C, 74 compared to 62 mAh g−1 at
1 C and 70 compared to 57 mAh g−1 at 2 C. A specific capacity
of 55 mAh g−1 could be delivered by PPy/r-GO at 20 C rate,
which was 74% of the capacity obtained at 1 C rate. The cor­
responding energy density and power density at 20 C rate were
158 Wh Kg−1 and 4032 W Kg−1, respectively. However, only
50% or 25% of the capacity obtained at 1 C was retained for
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PPy/pTS film at the 5 C and 10 C rate, respectively. PPy/r-GO
FULL PAPER
also displayed an excellent cycling performance. The capacity
maintained a steady value around 61 mAh g−1 and no capacity
fade was observed during 200 consecutive charge/discharge
cycles at 10 C rate (Figure 4C). These greatly improved electro­
chemical properties of PPy/r-GO are attributed to the porous
structure and the high surface area induced by graphene oxide
PPy/r-GO
incorporation. The electrically conducting network created by
the introduction of the highly conductive r-GO sheets improved
the composite conductivity, particularly when the polymer was
reduced and in its insulating state. Consequently a high rate
PPy/GO capability was achieved. The robust, flexible and mechanically
PPy/pTS strong r-GO sheets could also accommodate the volume change
occurring in the PPy components during oxidation-reduction
leading to good cycling stability.
PPy/r-GO demonstrated a supercapacitor characteristic, an
ability to undergo rapid oxidation and reduction (i.e., charge/
discharge within 3 min). At 20 C it retained 74% of the capacity
obtained at 1 C. This battery can be regarded as a hybrid
1385 between a Li-ion battery and a supercapacitor. It should be
1192
1550 1053 pointed out that the system described herein is inferior to the
conventional Li-ion batteries in terms of potential plateau and
charge/discharge capacity. However, this battery system pos­
sesses advantages such as high rate capability, good cycling
stability, mechanical flexibility, and easy processibility. It holds
promise in the application of flexible energy storage devices,
1392
where Li-ion batteries are difficult to be applied.
1198 Electrochemical impedance spectroscopy (EIS) is widely
1554 used to gain a deeper insight into electrochemical systems. The
1049
Nyquist plots for PPy/r-GO and PPy/pTS film with Li foil as
1500 1000 counter and reference electrode are shown in Figure 4D. The
semicircle observed in the high frequency generally corre­
sponds to the charge transfer kinetics at the polymer electrode
interface.[21] The inclined line was close to 45°, typical of the
Warburg impedance, which generally reflects the diffusion
process of lithium ion within the bulk electrode.[22] Much lower
electrical impedance was shown for PPy/r-GO compared with
PPy/pTS, indicative of the improved conductivity of PPy with
the r-GO sheets as dopant. This result is consistent with the
improved charge/discharge performance shown for PPy/r-GO
film in lithium ion batteries.
The dopant, GO, in the PPy matrix had been converted into
r-GO upon the electrochemical reduction, as evidenced from in-
situ UV–vis spectroelectrochemistry, Raman spectra and FT-IR
spectra. It has been shown that the reduced graphene oxide
(r-GO) nanosheets exhibit a large reversible capacity when used
as an electrode material in lithium-ion batteries.[6a,23] The PPy/r-
GO material produced here was tested over the potential range
of 0.005–3.0 V versus Li foil (Figure 5). The PPy/r-GO film
delivered a discharge capacity of 1013 mAh g−1 in the first cycle
and a reversible capacity of 493 mAh g−1 in the second cycle,
using a discharge current density of 100 mA g−1 (Figure 5A).
The corresponding irreversible capacity could be attributed to
the formation of solid electrolyte interface (SEI) film in the first
cycle. In comparison, the PPy/pTS film delivered a specific dis­
charge capacity of 36 mAh g−1 in the first cycle at the current
density of 100 mA g−1 (Figure 5B); only about 7% of the revers­
ible capacity delivered by PPy/r-GO. This large difference high­
lights the advantages delivered by the use of r-GO components
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A) B)
4.0 4.0

Voltage (V vs. Li/Li )

+

Voltage (V vs. Li/Li )

+
3.5
3.5

3.0
3.0

2.5
2.5

2.0
20C 10 5 2 1
2.0
10C 5C 2C 1C
1.5
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70
-1
Capacity (mAh g ) Capacity (mAh g )
-1

120 PPy/pTS
C) D)
1500 PPy/r-GO
100
Capacity (mAh g )
-1

80
1000

-Z'' (ohm)
60

40
500

20

0 0
0 50 100 150 200 0 500 1000 1500
Cycle number Z' (ohm)

Figure 4.  Electrochemical data for PPy/r-GO and PPy/pTS films in lithium-ion batteries in the potential window of 2.0–4.0 V (versus Li/Li+). A)
Voltage profiles for PPy/r-GO film at different current rate. The inset is the cyclic voltammograms obtained for the PPy/r-GO film using a scan rate of
0.1 mV s−1. B) Voltage profiles for PPy/pTS film at different current rate; C) Capacity versus cycle number at 10 C for PPy/r-GO films; D) Nyquist plots
of PPy/pTS and PPy/r-GO films.

as dopant in polypyrrole. The discharge capacity delivered by
the PPy/r-GO composite was mainly attributed to the progres­
sive intercalation of Li+ ions into r-GO. The pure r-GO film
on Cu foil delivered a discharge capacity of 1184 mAh g−1 in
the first cycle and a reversible capacity of 800 mAh g−1 in the
second cycle at 100 mA g−1 (Figure 5D). This reversible capacity
is much higher than the reported 540 mA h g−1 delivered at
50 mA g−1[6a] using chemically prepared r-GO. Non-usage of a
binder in our electrodes has led to this improvement.
The cyclic voltammograms obtained using PPy/r-GO film
as the working electrode are shown as the inset in Figure 5A.
A cathodic peak only occurred in the first cathodic scan in the
cyclic voltammograms, which is consistent with the irreversile
discharge capacity delivered by PPy/r-GO. This peak at ∼0.66 V
was attributed to the SEI formation, i.e., formation of Li2CO3
and alkyl carbonates on the PPy/r-GO surface.[24] No peak
around 1.5 V in the cathodic scan of cyclic voltammograms nor
a plateau above 2.0 V in the discharge profile were observed.
They are the typical characteristics of oxygen-containing groups
in carbon materials reacting with lithium.[25] This further con­
firms that those oxygen-containing groups in GO were dimin­
ished significantly and GO was effectively converted to r-GO by
this electrochemical reduction route. This film also exhibited a
good rate capability and cycling stability. It delivered a reversible
capacity of 323, 262, and 200 mAh g−1 at the current density of
200, 400, and 800 mA g−1, respectively (Figure 5C). At the cur­
rent density of 800 mA g−1, the energy density and power den­
sity were 173 Wh Kg−1 and 717 W Kg−1, respectively. PPy/r-GO
film maintained a stable specific capacity of 200 mAh g−1 over
200 consecutive cycles at charge/discharge current density of
800 mA g−1 (Figure 5E). This film also exhibited a good rate
capability and cycling stability.
3. Conclusion
In summary, we have demonstrated that a polypyrrole/
graphene film (PPy/r-GO) can be synthesized by direct electro­
chemical reduction of polypyrrole/graphene oxide (PPy/GO)
composite. PPy/r-GO can not be reoxidized to PPy/GO upon
applying an anodic potential, indicating that this electrochem­
ical reduction process is irreversible. FT-IR confirms that the
content of oxygen-containing groups is significantly reduced
after the electrochemical reduction of PPy/GO. High rate capa­
bility and cycling stability have been shown for this composite
as a cathode material in lithium ion batteries due to its porous
structure and the introduction of the highly conductive r-GO
component. It delivers a specific capacity of 55 mAh g−1 at high
20 C rate (74% of that obtained at 1 C rate), and no capacity fade
was observed during 200 consecutive charge/discharge cycles at
10 C rate. This composite film also exhibits a large reversible
capacity in the potential window of 0.005–3 V (versus Li/Li+),
mainly attributed to the r-GO component. These enhanced elec­
trochemical properties could be further improved by optimizing
the electrodeposition parameters of PPy/GO and the subse­
quent electrochemical reduction process. This electrochemical

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A)
Voltage (V vs. Li/Li )
3.0
B) 3.0
+

2.5 0.2
2.5

Voltage (V vs. Li/Li+)

0.1

2.0 0.0 2.0

Cu rren t (A g )
-1
-0.1

1.5 -0.2 1.5

-0.3

1.0 -0.4 1.0

-0.5

0.5 -0.6
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.5
Po tential (V vs L i/L i+)

0.0 0.0
3rd 2nd 1st 3rd 2nd 1st
0 200 400 600
-1
800 1000 0 5 10 15 20 25 30 35 40
Capacity (mAh g ) Capacity (mAh g-1)

C) 3.0

2.5
Voltage (V vs. Li/Li )
+

2.0

1.5

1.0

0.5

0.0 -1
800 400 200 100 mA g
0 50 100 150 200 250 300 350 400 450 500
-1
Capacity (mAh g )

D) E)
3.0 280

2.5
Voltage (V vs. Li/Li )
+

Capacity (mAh g )
-1

240
2.0

1.5 200

1.0
160
0.5

120
0.0
3rd 2nd 1st
0 200 400 600 800 1000 1200 0 50 100 150 200
-1
Capacity (mAh g ) Cycle number
Figure 5.  Electrochemical data for PPy/r-GO and PPy/pTS films in lithium-ion batteries in the potential window of 0.005–3.0 V (versus Li/Li+).
A) Voltage profiles for PPy/r-GO film at the current rate of 100 mA g−1. The inset is the cyclic voltammograms obtained for the PPy/r-GO film using
a scan rate of 0.1 mV s−1. B) Voltage profiles for PPy/pTS film at the current rate of 100 mA g−1. C) Voltage profiles for PPy/r-GO film at different
current rate. D) Voltage profiles of r-GO film on Cu foil at the current rate of 100 mA g−1. E) Capacity versus cycle number at 800 mA g−1 for PPy/r-
GO films.

system could be used both as a power system between 2 and 4. Experimental Section
4 V, and an energy system between 0 and 3 V. Currently, we
are working on the fabrication of a battery system composed Potassium permanganate and hydrogen peroxide (30%) were purchased
of PPy/r-GO electrodes as cathode and anode. In addition, from Chem Supply. Pyrrole and phosphate buffered saline were obtained
from Sigma-Aldrich. Toluene-4-sulphonic (sodium salt) and graphite
this simple electrochemical synthesis process could be applied
were from BDH and Fluka, respectively. Pyrrole was freshly distilled,
broadly to the fabrication of other types of conducting polymer/ while all other chemicals were used as-supplied.
graphene composites, e.g., polythiophene/graphene or poly­ Materials Synthesis: Graphite oxide was synthesized using the
aniline/graphene composites. modified Hummers method described previously.[15a,26] Exfoliation of

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FULL PAPER
graphite oxide to graphene oxide (GO) was achieved by ultrasonication
of graphite oxide dispersion (0.5% w/w) for 40 min at 45% amplitude
using a Branson sonicator. This exfoliated material was subjected
to centrifugation at 3000 rpm for 30 min to remove settled GO
agglomerates. The exfoliated GO was diluted to 0.05 wt% and
ultrasonicated for 40 min at 45% amplitude. The zeta potential of the
0.05 wt% GO dispersion produced ranged between -30 to -40 mV with
a particle size distribution between 350–550 nm (Malvern Instrument).
PPy/pTS or PPy/GO film was galvanostatically electrodeposited on a
stainless steel mesh (Hongye Stainless Steel Wire Cloth Co. Ltd.) from
an aqueous solution containing the dopant and 0.1 m pyrrole monomer.
The concentration of GO and sodium p-toluenesulfonate used in this
work was 0.05 wt% and 0.1 m, respectively. The applied current density
was 0.5 mA cm−2 and the amount of charge consumed was 1.2 C cm−2.
PPy/r-GO film was obtained by electrochemically reducing PPy/GO film
in PBS (pH = 7.4) at a constant potential of -1.1 V (versus Ag/AgCl)
for 40 min. GO film on Cu foil was obtained by drop casting using GO
dispersion (0.25%), followed by being electrochemically reduced in PBS
at -1.1 V (versus Ag/AgCl) for 15 min. PBS is a common electrolyte used
to electrochemically reduce GO.[14a–c] The electrochemical synthesis of
these films was carried out in a standard three-electrode cell. A stainless
steel mesh counter electrode and a Ag/AgCl reference electrode were
used in the experiments.
Characterization: The surface morphologies of the films were
investigated using a FESEM (JEOL JSM7500FA). For the in-situ
spectroelectrochemical measurements, a thin layer of PPy/pTS and
PPy/GO was electrodeposited on Au-coated quartz at a current density
of 0.5 mA cm−2 for 2 min, and it was equipped with a Pt mini-grid
counter electrode and a Ag/AgCl reference electrode with a 10 mm
optical path length. The spectroelectrochemistry of the PPy/GO film on
Au-coated quartz was investigated in PBS over the applied voltages of
+0.50 V to -1.1 V (versus Ag/AgCl). When the current produced and
the absorption at 1100 nm reached a steady value at a given applied
potential, the corresponding UV–vis absorbance was recorded using
a UV spectrophotometer (UV-1800, Shimadzu) in the range from 200
to 1100 nm. FT-IR spectra were recorded on a FT-IR spectrometer
(IRpretige-21, Shimadzu) over the range from 600 to 4000 cm−1. Raman
spectra were obtained using a confocal Raman spectrometer (Jobin Yvon
HR800, Horiba) utilizing 632.8 nm diode lasers. Cyclic voltammetry of
the cell was performed using a Solartron SI 1287 and scanned between
0.005 to 3.0 V at a scan rate of 0.1 mV s−1. EIS measurements were
performed using a Gamry EIS 3000 system, and the frequency range
spanned from 100 kHz to 0.01 Hz with an AC amplitude of 10 mV at
open circuit potential (i.e., 2.28 and 2.49 V for batteries using PPy/pTS
or PPy/r-GO as electrodes, respectively). These cells were subjected to
25 charge/discharge cycles at 1.0 C and then fully discharged to 2.0 V at
0.1 C prior to the EIS measurement.
Battery Assembly and Testing: PPy/pTS and PPy/r-GO films were
dried in a vacuum oven at 60 °C overnight, and the electrodes were
assembled into LR 2032 type coin cells in a glove box. The electrolyte
used was 1.0 m LiPF6 in 1:1 (v/v) ethylene carbonate (EC): dimethyl
carbonate (DMC). Galvanostatic charge/discharge cycling tests for the
cells were performed using a battery test system (Land CT2001A, Wuhan
Jinnuo Electronics Co. Ltd.). The specific capacities of the samples were
calculated based on the mass of the PPy/pTS or the PPy/r-GO material
used.
Acknowledgements
Financial support from the Australian Research Council is gratefully
acknowledged. Yang Yang acknowledges the support of the CSC
Scholarship from the Ministry of Education of PR China.
Received: August 5, 2011
Revised: November 3, 2011
Published online: January 19, 2012
272 wileyonlinelibrary.com © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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