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Highly Compression-Tolerant Supercapacitor Based on


Polypyrrole-mediated Graphene Foam Electrodes
Yang Zhao, Jia Liu, Yue Hu, Huhu Cheng, Chuangang Hu, Changcheng Jiang, Lan Jiang,
Anyuan Cao, and Liangti Qu*
Deformation-tolerant electronic devices have attracted tremendous attention due to their flexibility of integration into unconventional forms of high-tech electronics while maintaining the
desired levels of performance and reliability.[1] As an indispensable component of advanced electronics, stretchable powersource devices have been able to accommodate large strains
without obvious loss of functions.[2,3] Of various power-source
devices, supercapacitors have attracted significant interest as
energy storage devices due to their high power density, long
cycling life, and short charging time. These advantages make
them highly promising for use in electric vehicles and other
high power energy sources.[4,5] Towards the development
of lightweight, flexible, and wearable-electronic devices,[6,7]
achievements have been made to the fabrication of stretchable
supercapacitors,[8,9] which possess high electrochemical capacitance performances even during mechanical stretch. Beyond the
continuous efforts for enhancing the energy/power density of
supercapacitors, however, few attempts have been dedicated to
the development of compressible supercapacitors,[10] although
the compression, a reverse mechanical stress in contrary to the
stretching process, is one of the most influential factors on the
electrochemical performance of the flexible supercapacitors.
Foam-like structures with high porosity, flexibility, and robustness under mechanical strain/stress have many important
applications in actuators, catalytic supports, adsorption and
separation,[1115] which also have the potential as highly compression-tolerant electrode materials for fabrication of compressible
supercapacitors. However, it is of great challenge to synthesize
porous foam-like structures with a high flexibility, robustness
and conductivity. Recently, carbon-based materials have shown
potential as sponge-like structures with high porosity, structural
flexibility and large deformation.[11,1518] As a two-dimensional
monolayer of carbon sheet, graphene has fascinating properties such as large surface areas, giant electron mobility,[19] high
Y. Zhao, J. Liu, Y. Hu, H. Cheng, C. Hu, C. Jiang,
Prof. L. Qu
Key Laboratory of Cluster Science
Ministry of Education, School of Chemistry
Beijing Institute of Technology, Beijing 100081, China
E-mail: lqu@bit.edu.cn
Prof. L. Jiang
Laser Micro-/Nano-Fabrication Laboratory
School of Mechanical Engineering, Beijing Institute of Technology
Beijing 100081, China
Prof. A. Cao
Department of Materials Science and Engineering
College of Engineering, Peking University
Beijing 100871, China

DOI: 10.1002/adma.201203578

Adv. Mater. 2013, 25, 591595

thermal conductivity,[20] extraordinary elasticity and stiffness,[21]


and has therefore been regarded as the ideal building blocks
for the fabrication of 3D porous low-density macroassemblies
with high electrical conductivities and large internal surface
areas.[2227] Unfortunately, the pristine 3D graphene structure
tends to collapse or distortion under compression due to the relatively poor compressibility and springiness. As a result, although
graphene has been integrated into the fabrication of capacitor
electrodes,[2830] there is still no report on the compressible supercapacitors based on the graphene electrodes. Herein, by using
a representative conducting polymer of polypyrrole (PPy) as a
mediator, we have developed a unique strategy for in-situ formation of PPy-graphene (PPy-G) foam and demonstrated a highly
compression-tolerant graphene-based supercapacitor.
PPy is one of the most important active materials for supercapacitors due to its good conductivity, facile synthesis, low
cost, stability and the high redox pseudocapacitive charge
storage.[3134] For formation of in-situ polymerized PPy-G foam,
we first prepare the 3D graphene by hydrothermal treatment of
2 mg/mL of homogeneous graphene oxide (GO) aqueous dispersion with 5 vol% pyrrole (Py) in a 10mL Teflon-lined autoclave at 180 C for several hours. The 3D graphene formed in
this pyrrole-containing GO suspension is denoted as 3D G(Py).
The hydrothermally produced 3D G(Py) subsequently acted as
the working electrode in a three-electrode cell with a Pt wire
as counter electrode and Ag/AgCl (3 M KCl) as reference electrode. After a constant potential of 0.8V was applied in 0.2 M
NaClO4 aqueous solution for polymerization of Py monomer,
the 3D PPy-G foam was obtained (Figure 1a).
The key step to 3D PPy-G foam is to introduce the Py monomer into the GO aqueous suspension and form a homogeneous
solution prior to the hydrothermal process. This strategy will
allow the formation of 3D PPy-G framework with maximized
surface areas and excellent mechanical property under compression. As shown in Figure 1a, the 3D graphene derived from Pycontaining GO suspension has a 5 times volume of that formed
from normal pyrrole-free GO suspension under the same condition. The corresponding SEM investigation revealed that the 3D
G(Py) had a looser structure with much thinner connection walls
than the pure 3D graphene derived from normal GO suspension (Figure 1b,c). Consequently, the freeze-dried 3D G(Py) has
a much lower density of 58mg/cm3 compared with that 1520
mg/cm3 for freeze-dried normal 3D graphene (Figure 1a, left).
Brunauer-Emmett-Teller (BET) analyses based on low-temperature nitrogen adsorption measurements show that the freezedried 3D G (Py) has a specific surface area (SSA) of 463 m2/g,
considerably larger than 186 m2/g of freeze-dried normal 3D
graphene (Figure 1a, left) and the BET SSA of 166 m2/g for
freeze-dried graphene hydrogel.[35] 3D graphene framework

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certain amount of added Py in the low-concentration GO suspension (e.g., 0.5mg/ml) will lead to the production of 3D graphene,
which otherwise is not available at all (Figure S1).
To form a 3D porous PPy-G foam, the as-prepared 3D G(Py)
sample was directly used as working electrode under a potential of 0.8V in 0.2 M NaClO4 aqueous solution without additional Py monomer. The uniform polymerization of Py along
graphene sheets was observed in Figures 1e, g and h. The 3D
porous structure is maintained well with a slightly increased
wall thickness and density (ca. 40 mg/cm3) due to the PPy
coating (Figure 1e). The SSA of the freeze-dried 3D PPy-G is
measured to be 144 m2/g, which is lower than that of 3D G(Py)
but still close to that of normal 3D graphene. In contrast, the
polymerization of additional Py along normal 3D graphene
structure will cause the serious aggregations of PPy and the surface porosity loss of 3D graphene (Figure 1d,f). Figures 1h and
i show the TEM images of PPy-G sheets. As can be seen, PPy
layers are uniformly coated along graphene sheets (Figure 1i),
and the electron diffraction spots of graphenes (Figure S2) have
disappeared (Figure 1h, inset). The high resolution TEM image
exhibits direct evidence that a few layers of graphenes are intercalated within the electrodeposited PPy layers (Figure 1i). The
freeze-dried PPy-G foam has an electrical conductivity of about
3 103 S/m by a four-probe method, which is 2 orders of magnitude higher than 3D graphene-based composites.[24]
Figure 2 shows the Raman spectra of 3D PPy-G in comparison
with normal 3D graphene, 3D G(Py) and electropolymerized PPy

Figure 1. (a) Photographs of as-prepared normal 3D graphene, 3D G (Py)


and 3D PPy-G (from left to right). The normal 3D graphene and 3D G (Py)
were prepared by hydrothermal treatment of 2.0mg/ml GO aqueous suspension without and with a 5 vol% Py monomer, respectively. (b,c) SEM
images of normal 3D graphene and 3D G(Py), respectively. (d) SEM image
of normal 3D grapnene (b) after electrodeposition of PPy in the NaClO4
electrolyte containing 5 vol% Py. (e) SEM image of 3D PPy-G. (f,g) The
corresponding magnified view of (d) and (e), respectively. (h) TEM image
of PPy-G sheet from 3D PPy-G and (i) the corresponding high-resolution
TEM image of the edge of PPy-G sheet. Inset in (h) is the selected area
electron diffraction (SAED) pattern. Scale bars: bg, 1 m.

is assembled by the strong interactions of reduced GO sheets


during hydrothermal treatment.[36] The Py monomer has a typical conjugated structure with electron-rich N atom, which may
easily attach on the surfaces and galleries of GO sheets through
H-bonding or interaction.[37] Therefore, the existence of Py
will effectively prevent the self-stacked behavior of GO during
hydrothermal process, and accordingly increase the available GO
sheets for forming large volume of 3D graphene with thin connection walls. Indeed, further control experiments confirm that a
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Figure 2. Raman spectra of the freeze-dried normal 3D graphene, 3D


G(Py), 3D PPy-G and electropolymerized PPy film.

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film. As can be seen, the 3D G(Py) represents two typical bands indexed at 1334 and
1597 cm1 (Figure 2b), which are attributed
to the well-documented D and G bands of
hydrothermally reduced GO (Figure 2a).[28]
After undergoing electropolymerization,
the formed 3D PPy-G (Figure 2c) exhibits a
series of peaks at ca. 930, 1070, 1238, 1370,
1410 and 1597 cm1, characteristic of electropolymerized PPy (Figure 2d),[38] indicating
the successful polymerization of Py along
graphene sheets. It is notable that no any
perceptible peaks associated with PPy were
observed for 3D G(Py) sample in Raman
spectrum (Figure 2b), suggesting that the
content of PPy produced by polymerization
of Py monomer during the hydrothermal
process, if any, is negligibly low, and Py
mainly physically distributes within the 3D-G
structure. Indeed, FT-IR spectra verified that
the hydrothermally synthesized 3D G(Py)
sample mainly contained the Py monomer
rather than polymerized Py (Figure S3).
The as-prepared 3D PPy-G foam sucks up
the aqueous liquid and exists in the fashion
of hydrogel. The conventional freeze-drying
treatment will impair its mechanic elasticity
(Figure S4), while naturally drying process
will cause the drastic shrinkage of 3D PPy-G
(Figure S5). Although PPy-G is not elastic
under dry condition, both the morphology
and mechanic flexiblity of 3D PPy-G remains
well under the aqueous circumstance (Movie
S1) and even organic solvents such as ethanol
and acetonitrile (Figure S6). As a hydrogel,
PPy-G has the capability of expansion/con- Figure 3. (ac) The compression-recovery processes of PPy-G foam. (df) The surface views
of PPy-G foam corresponding to the unloading-loading-unloading status in (ac), respectively.
traction upon absorption/desorption of sol(gi) SEM images of the inner microstructures of PPy-G foam corresponding to the unloadingvent. As shown in Figure 3ac, PPy-G foam loading-unloading status in (ac), respectively. (j) Stress-strain curves of PPy-G foam immersed
can sustain large-strain deformations (e.g., in aqueous liquid at different set strains () of 40%, 60%, and 80%, respectively. (k) Cyclic
= 50%) under manual compression and stress-strains curves of PPy-G foam at = 50%. Inset is the recorded deformation developed
recover most of the material volume without by compression for 200 cycles at = 50%.
structural fatigue within 10 s. During the
Compression tests of several samples at differently set strains
compression process, we found that the zigzag buckles without
(40% to 80%) show reproducible results in which all curves
cracks were formed along the PPy-G body (Figure 3e), while the
contain an approximate linear region at initial < 40% and an
zigzag deformation was entirely disappeared upon release of
increasing slope until very high strains up to 80% (Figure 3j).
the load (Figures 3d&f). This reversible compression-recovery
The unloading curves almost return to the origin, indicating
process is also reflected by the inner microstructure of PPy-G
complete volume recovery without plastic deformations. The
foam. As can be seen, the SEM images of the freeze-dried
large compression on the PPy-G foam is due to the squeeze of
samples reveal that the initial 3D structure (Figure 3g) is coninherent pore-rich 3D structures, rather than the formation of
formably densified while maintaining the porous configuration
heavy stacking of graphene sheets (Figure 3h). The PPy-G foam
under compression (Figure 3h). Once released, PPy-G foam
can be further compressed to more than 90% volume reducinstantaneously recovers to this initial state without any coltion due to its high porosity and structural flexibility. During
lapse of 3D network within 10 seconds (Figure 3i). BET measrepeated compressions at the set strain = 50%, the foam can
urements reveal that the freeze-dried compressive PPy-G foam
recover most of thickness and maintain a similar compreshas a SSA of 151 m2/g similar to that of unloaded countersive stress (ca. 0.088MPa) without degradation of mechanical
parts (144 m2/g), which indicates no significantly irreversible
strength (Figure 3k). The plastic deformation is measured
stacking occurs between graphene sheets network. This comto be smaller than 10% (of volume reduction) after comprespression to self-recovery process is fully reversible as long as
sions at a set strain of = 50% for 200 cycles (Figure 3k, inset).
the PPy-G foam is immersed in aqueous liquid (Movie S2).

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(a)

Motor

(b)

Au foil
Separator
Foam electrode

Current (A/g)

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Initial
50% Compression
0% Compression

6
3
0
-3
-6
0.0

Controller

initial
50% Compression
0% Compression

1.0
0.8
0.6
0.4
0.2
0.0

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100

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0.6

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1.0

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150

200

250

Time (s)

(d)420
Capa
acitance (F/g)

Potential (V)
P

(c) 1.2

0.2

360
300
240
50% compression
0% compression

180
120
0

200

400

600

800

1000

Compression times

Figure 4. (a) Schematic illustration of PPy-G based supercapacitor devices. (b) CVs of the compressible supercapacitor cells based on PPy-G foam
electrodes under 0% and 50% compression for one cycle. The scan rate is 30 mV/s. (c) The corresponding galvanostatic charge-discharge curves at a
current of 1.5 A g1 under 0% and 50% compression. (d) The specific capacitances at different compression states for 1000 cycles.

Impressively, the PPy-G foam shows no significant strength


degradation after compression at the maximum strain ( =
50%) for 1000 cycles (Figure S7), indicating the highly reversible and durable foam behavior.
In contrast, the compressive properties of 3D pure graphene
prepared by the similar hydrothermal method showed no
obvious elastic properties, and its structure was destroyed
without recovering phenomena after being compressed at =
50% (Figure S8a). Even post-synthesis polymerization of Py was
applied onto 3D graphene structure, which could not exhibit the
foam behavior (Figure S8b) due to the 3D pore loss and uneven
deposition of PPy (Figure 1d,f). On the other hand, the 3D
graphene synthesized in the presence of Py but without electropolymeriazation has also presented an irreversible compressibility (Figure S9). Further observation shows that, unlike that
PPy-G foam having compressible properties (Figure 3b), some
cracks appear on the bodies of 3D pure graphene and 3D G(Py)
(Figure S10). It seems that the highly uniform deposition of
PPy layers along graphene sheets with well-defined 3D porous
graphene structures is the key to achieve the compression-tolerant foam feature. Apart from the contribution to the capacitance performance, the presence of conjugated polymer of PPy
could increase the strength of 3D structure via strong interaction to bear a certain extra force as demonstrated here.
To explore the application of PPy-G foam as deformable
electrode materials for compressible supercapacitor, we assembled a two-electrode capacitor with a controlled compression
state (Figure 4a and Figure S11). The electrochemical performances were evaluated by both cyclic voltammetry (CV) and

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galvanostatic charge/discharge tests in 3M NaClO4 aqueous


electrolyte. As shown in Figure 4b, owing to the high porosity,
conductivity, and excellent mechanical strength of PPy-G foam
electrodes, the CV curves of the assembled capacitor retain a
rectangular shape with ideal capacitive behavior. No significant
change was observed in the CVs of the compressed supercapacitors with a 50% applied strain (Figure 4b), which is also the
case for 1000 measured cycles (Figure S12a). The cycling stability of the assembled supercapacitor subjected to compressive
strain is also illustrated by galvanostatic chargedischarge with
a constant current of 1.5 A g1 (Figure 4c and Figure S12b). The
specific capacitance calculated from the discharge slopes is ca.
350 F/g, which is much higher than that of both compact PPy
film (ca. 50 F/g in Figure S13) and pure 3D graphene (e.g., 151
F/g in Figure S14, and even 220F/g in alkaline medium[35]).
These results indicate the synergetic function of PPy and 3D
graphene for largely enhanced capacitance of PPy-G. The density of freeze-dried 3D PPy-G is about 40 mg/cm3. The volumenormalised capacitance is 14 F/cm3 for the uncompressed
sample and 28 F/cm3 for the 50% compressed one, which is
much higher than that ca. 4 F/cm3 for the normal 3D graphene
supercapacitor.[35] Remarkably, the specific capacitances of the
supercapacitor with or without compressive strain of 50% do
not alter significantly even up to 1000 cycles (Figure 4d), which
concludes the excellent electrochemical stability of the compressible supercapacitor based on PPy-G foam electrodes. In
fact, the compressible supercapacitor of PPy-G foam also performs properly in nonaqueous electrolytes as demonstrated
in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4)

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[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]

[12]
[13]

[14]
[15]
[16]
[17]
[18]

Experimental Section

[19]

Preparation of 3D PPy-G foam: GO suspension was obtained as


reported in our previous papers.[40,41] 3D G(Py) was prepared by
hydrothermal reduction of GO aqueous dispersion with 5 vol% pyrrole
monomer, which was directly used as working electrode under a potential
of 0.8V in 0.2 M NaClO4 aqueous solution to form a 3D porous PPy-G
foam (Figure S17 and S18).
Preparation of compressible supercapacitors: Two slices of PPy-G foam
with a thickness of about 2.1 mm were separated by a filter paper soaked
with 3M NaClO4 aqueous electrolyte. Two Au foils in contact with the
PPy-G foams act as the current collectors. The compression process was
controlled by electric-drive-motor with moving speed at 0.2 mm/s. The
experimental setup was illustrated in Figure 4a and Figure S11.
More experimental details and characterizations are included in the
Supporting Information.

[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]

Supporting Information

[29]

Supporting Information is available from the Wiley Online Library or


from the author.

[30]

Acknowledgements

[31]
[32]
[33]

We thank the financial support from the 973 project (2011CB013000) of


China and NSFC (21174019, 51161120361).
Received: August 28, 2012
Published online: October 18, 2012

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Adv. Mater. 2013, 25, 591595

[34]
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medium (Figures S15 and S16). Since the compression-recovery


process involves the electrolyte desorption and absorption, the
compressible supercapacitor of PPy-G foam developed in this
preliminary study requires a relatively large amount of solvent,
which, to some extent, decreases the device performance considering the device as a whole.
It is notable that hydrogels of other materials with viscoelastic
properties were reported decades ago.[39] However, the current
work develops a unique strategy to form a hydrogel that rationally
combined 3D graphene with PPy to achieve a remarkable compression tolerance, and demonstrates the concept of compressible
supercapacitor based on PPy-G foam for the first time. Robust
3D PPy-G foam was formed by pre-mixing Py monomer with
GO for hydrothermal production of Py-containing 3D graphene,
followed by direct electropolymerization. The as-formed PPy-G
foam is durably tolerant to the large compressive strain without
any structural collapse and loss of springiness. We further demonstrate that the PPy-G foam can be used as the deformable
electrodes for assembly of highly compression-tolerant supercapacitors, which perform high specific capacitances without significant variation under long-term compressively loading and
unloading process. This work will benefit the development of
next generation advanced supercapacitors with tolerance to harsh
conditions such as mechanical concussion and compression.

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