LETTER

pubs.acs.org/NanoLett

Solution-Processed Graphene/MnO2 Nanostructured Textiles for

High-Performance Electrochemical Capacitors
Guihua Yu,†,z Liangbing Hu,‡,z Michael Vosgueritchian,† Huiliang Wang,‡ Xing Xie,§
James R. McDonough,‡ Xu Cui,† Yi Cui,*,‡ and Zhenan Bao*,†
†
Department of Chemical Engineering, ‡Department of Materials Science and Engineering, and §Department of Civil and
Environmental Engineering, Stanford University, Stanford, California 94305, United States

bS Supporting Information
ABSTRACT: Large scale energy storage system with low cost, high
power, and long cycle life is crucial for addressing the energy
problem when connected with renewable energy production. To
realize grid-scale applications of the energy storage devices, there
remain several key issues including the development of low-cost,
high-performance materials that are environmentally friendly and
compatible with low-temperature and large-scale processing. In this
report, we demonstrate that solution-exfoliated graphene na-
nosheets (∼5 nm thickness) can be conformably coated from
solution on three-dimensional, porous textiles support structures
for high loading of active electrode materials and to facilitate the
access of electrolytes to those materials. With further controlled
electrodeposition of pseudocapacitive MnO2 nanomaterials, the
hybrid graphene/MnO2-based textile yields high-capacitance per-
formance with specific capacitance up to 315 F/g achieved. More-
over, we have successfully fabricated asymmetric electrochemical
capacitors with graphene/MnO2-textile as the positive electrode
and single-walled carbon nanotubes (SWNTs)-textile as the negative electrode in an aqueous Na2SO4 electrolyte solution. These
devices exhibit promising characteristics with a maximum power density of 110 kW/kg, an energy density of 12.5 Wh/kg, and
excellent cycling performance of ∼95% capacitance retention over 5000 cycles. Such low-cost, high-performance energy textiles
based on solution-processed graphene/MnO2 hierarchical nanostructures offer great promise in large-scale energy storage device
applications.
KEYWORDS: electrochemical capacitors, textile, solution process, graphene nanosheets, MnO2

D eveloping a sustainable and renewable energy future has been

one of the most important tasks for scientists and engineers
worldwide to address the rapidly increasing global energy con-
emerge as a very attractive alternative to batteries and offer a number
of potentially high-impact characteristics including high power
density (1
2 orders of magnitude higher than that of batteries)
sumption coupled with the critical issue of climate change. With fast charging and discharging within seconds (i.e., fast response
increased renewable energy production from solar and wind, time), superior cycle lifetime (2
3 orders of magnitude better
efficient energy storage systems are needed to make the best than that of batteries), and high reliability. ECs have been used in
of the electricity generated from these intermittent, renewable a variety of applications ranging from portable consumer electro-
sources. Among the various energy storage systems, chemical nics, computer memory backup systems, to hybrid electric
storage devices (batteries) and electrochemical capacitors (ECs) vehicles and next-generation all-electric vehicles, and to large
are two key technological systems that lead the state-of-the-art industrial scale power and energy management.4,5
electrical energy storage systems.1
3 Batteries have been the Depending on the charge storage mechanism as well as the
technology of choice for many applications; virtually all portable active materials used, ECs can be often distinguished into three
types: electric double-layer capacitors (EDLCs), pseudocapaci-
electronics rely on energy stored chemically in them, because they
tors, and hybrid electrochemical capacitors. EDLCs, which store
can store large amounts of energy in a lightweight and compact charges electrostatically via reversible ion absorption at the
structure and meanwhile provide suitable power levels for certain electrode/electrolyte interface, commonly use carbon-based
applications. However, existing battery technologies have per- active electrode materials with high surface area.6,7 In contrast,
formance and cost limitations such as short shelf and cycle life,
and relatively slow charging/discharging rates at high power Received: April 25, 2011
densities. ECs, also known as supercapacitors or ultracapacitors, Published: June 13, 2011

r 2011 American Chemical Society 2905 dx.doi.org/10.1021/nl2013828 | Nano Lett. 2011, 11, 2905–2911
Nano Letters LETTER

pseudocapacitors use fast and reversible redox reactions at the

surface of the electroactive materials for charge storage. The
large specific pseudocapacitance of faradaic electrodes (typically
300
1000 F/g) exceeds that of carbon-based materials using
double layer charge storage, resulting in great interest in these
systems. Typical active pseudocapacitive materials include tran-
sition metal oxides such as RuO2, Fe3O4, NiO, and MnO2,8
11
and conducting redox polymers such as polyanilines, polypyr-
roles, and polythiophenes.12
15 A third group of ECs are hybrid
capacitors, which usually combine one battery-type faradaic
electrode (as energy source) with the other capacitive electrode
(as power source) in the same cell.4 Although this type of ECs Figure 1. Schematic illustration of two key steps for preparing hybrid
generally shows much enhanced capacitance and greatly im- graphene/MnO2-nanostructured textiles as high-performance EC elec-
trodes. (i) Conformal coating of solution-exfoliated graphene nano-
proved energy density compared with EDLCs,16
19 there is still a sheets (gray color) onto textile fibers. (ii) Controlled electrodeposition
significant drawback of these hybrid capacitor devices, namely, of MnO2 nanoparticles (yellow dots) on graphene-wrapped textile
the limited cyclability of the faradaic electrodes (considering fibers.
balanced capacities for positive and negative electrodes).20 The
key to achieving high power and energy density hybrid ECs with
long cycle life is to explore novel electrode material systems with ∼315 F/g achieved, which is ∼5 times as high as that of energy
rational design of material combination, morphology, and size, and textiles coated only with graphene nanosheets. Furthermore,
proper choice of electrolytes that operate at high voltages and high-performance hybrid ECs with graphene/MnO2-textile as the
have excellent ionic conductivity and electrochemical stability. positive electrode and SWNTs-textile as the negative electrode
To enable EC technology for large scale grid applications were fabricated and tested in aqueous 0.5 M Na2SO4 electrolyte.
crucial for the future “smart” grid, which is expected to integrate a We believe that nanoscale electrode structures based on con-
significant amount of renewable energy from solar and wind, ductive, porous, 3D frameworks could provide critical break-
requires the development of low-cost energy storage systems throughs for designing future multifunctional EC architectures.
with appropriate performance characteristics.3 There are two key Such rationally designed ECs also exhibited significantly im-
aspects to meet these requirements: inexpensive yet high-per- proved cycling performance relative to current pseudocapacitors.
formance materials with rationally designed architectures and Our approach for making hybrid graphene/MnO2 nanostruc-
scalable processing for low-cost fabrication. From the point of tures based energy textile as the EC electrode involves two key
view of materials, a promising strategy would be incorporating steps, as shown in Figure 1. The first is to coat highly porous
earth-abundant capacitive carbon materials with low-cost pseudo- textile fibers with graphene nanosheets that are prepared via a
capacitive metal oxides such as MnO2, which offers both cost facile solution-based exfoliation process. The coating is done by a
advantage and potentially high performance benefiting from both simple “dip and dry” process, similar to that widely used in the
mechanisms of electric double layer capacitance and pseudoca- textile industry for dyeing fabrics and fibers. The second is the
pacitance. Given that MnO2 is one of the most promising pseudo- controlled deposition of MnO2 nanomaterials on the as-prepared
capacitive materials due to its low cost, environmental benignity, conductive textile fibers. In our study, electrochemical deposition, a
and most importantly, high theoretical specific capacitance, there are proven efficient method for synthesis of a range of nanomaterials
indeed several research studies that have explored MnO2/ including metal, metal oxide, and conducting polymers,30 has
carbon-based composite materials for EC applications.18,21
26 been used to deposit pseudocapacitive MnO2 nanostructures in a
In addition, from the perspective of the fabrication process, controlled manner on graphene-wrapped conductive textiles.
highly scalable approaches to make functional electrodes and Graphene materials have emerged as a unique class of carbon-
construct ECs, such as facile solution-based process and printing based nanoscale building blocks with substantial potential for
technique, will be of great importance to provide a long-term solution energy conversion and storage devices thanks to an array of their
for making large-scale and low-cost devices. For instance, solu- exceptional characteristics including superior electronic and
tion-based coating and printing techniques have been recently mechanical properties, good electrochemical stability, and large
exploited by our group and others to make conductive carbon specific surface area.31 Recently, they have been explored as promis-
nanotubes (CNTs)-based papers and textiles as electrodes and/ ing electrode materials in a variety of energy applications such as
or current collectors for batteries and supercapacitors.26
29 photovoltaics, batteries, and supercapacitors.32
35 To explore
Although these CNTs-incorporated papers and textiles show tremendous potential of graphene for large scale energy storage
exciting properties, to realize large-scale energy storage applica- devices, we adopted in this work a high-throughput solution-
tions significant cost reduction of CNTs is still needed. based exfoliation technique reported by Coleman et al.,36 to
In the present work, we demonstrate a novel structure based prepare graphene “ink” solution (see Supporting Information).
on graphene/MnO2 nanostructured textiles where solution- The liquid phase surfactant-assisted exfoliation in water allows
exfoliated graphene nanosheets were conformably coated on the facile preparation of large-scale, homogeneous graphene
porous textile fibers, serving as conductive three-dimensional dispersions of varying concentrations, showing great advantages
(3D) frameworks for subsequent controlled electrodeposition of over most other exfoliation routes that often involve the oxida-
MnO2 nanomaterials. Such 3D porous networks not only permit tion and exfoliation of powdered graphite to yield graphene
large loading of active electrode materials but facilitate easy oxide, and subsequent reduction steps either by high-tempera-
access of electrolytes to the electrodes. These graphene/MnO2 ture thermal annealing or chemical methods.37 Moreover, solu-
composite nanostructures based energy textiles yielded greatly tion-exfoliation of graphene nanosheets from graphite provides a
improved capacitive performance with specific capacitance of promising low-cost approach for large-scale energy storage
2906 dx.doi.org/10.1021/nl2013828 |Nano Lett. 2011, 11, 2905–2911
Nano Letters LETTER

Figure 2. Coating graphene nanosheets onto porous textiles. (a) Photograph of a stable, solution-exfoliated graphene ink suspension prepared by
ultrasonication of the graphite powder in a water
sodium cholate solution, and a 6 cm  8 cm graphene-coated conductive textile sheet (polyester
fabrics). (b) AFM image of solution-exfoliated graphene nanosheets deposited on a SiO2/Si substrate and the corresponding line scan profiles for three
typical graphene flakes (marked in different colors). As-produced graphene nanosheets have an average thickness of ∼5 nm (multilayered graphene) and
an average lateral dimension of ∼0.6 μm. Scale bar: 1 μm. (c) Typical TEM image of solution-exfoliated graphene nanosheets. Scale bar: 1 μm. (d) Sheet
resistances Rs versus the number of dipping cycle for graphene-coated fabric sheets (G-textile) with and without nitric acid treatment. The final
graphene-wrapped textile with nitric acid treatment has a sheet resistance of ∼700 Ω/sq. (e) SEM image of a sheet of graphene-coated textile showing a
large-scale view of polyester fibers. Scale bar: 20 μm. (f) High-magnification SEM image (on the region highlighted in red rectangle in e) showing the
uniform coating of graphene nanosheets on the surface of fabric fibers. Scale bar: 2 μm.

devices, a significant step beyond our earlier work of carbon solutions we used for textile coating (see Materials and Methods
nanotubes-based conductive textiles.26 in Supporting Information) yielded exfoliated graphene “na-
We have employed the simple approach of sonicating the nosheets” with an average flake thickness of ∼5 nm (∼70% in
graphite powder in an aqueous solution containing sodium range of 4
8 nm with ∼25% of flakes <4 nm) and an average
cholate, an amphiphilic molecule surfactant known to stabilize flake dimension of ∼0.6 μm (∼85% of flakes have size in range of
graphene sheets,38 to yield stable dispersions of exfoliated 0.3
1 μm) (Supporting Information Figure S1). We note that
graphene as the ink for coating on textiles (Figure 2a).36 One there is still room for further optimization of graphene ink pre-
of the most important features associated with this solution-phase paration by adjusting the ratio of graphite and surfactant, the
approach is that both the degree of graphite exfoliation (graphene sonication time and centrifugation speed/time, which could
flake size, thickness) and the concentration of graphene dispersions produce graphene dispersions with higher quality of exfoliation
can be readily controlled by adjusting several system parameters (e.g., smaller flake thickness for potentially higher active surface
such as the initial concentrations of graphite and surfactant, area); greater surface area would lead to higher electrode per-
sonication time, and centrifugation speed and time. For example, formance of graphene-coated textiles and final graphene/MnO2
we used atomic force microscopy (AFM) and transmission electron nanostructured textiles.
microscopy (TEM) (Figure 2b,c) to investigate the exfoliation Textiles have been used as unique support materials playing a
state of the graphene in these dispersions including graphene significant role in the development of wearable electronics,40
flake size and flake thickness (corresponding to number of layers owing to their mechanical strength and flexibility, lightweight, and
per flake). We observed that the increase in initial graphite modifiable surface. They usually display a hierarchical structure
concentration leads to a higher final concentration of exfoliated- with complex surface morphology, functional surface groups
graphene but with less uniform flake size, and meanwhile the such as hydroxyl, and high microscopic porosity. In this work,
longer sonication time results in the increase in the final graphene we explore textiles as porous substrate materials for energy
concentration yet with the correlated decrease in flake dimensions, storage devices. Polyester textiles used in our studies are com-
which is consistent with what have been found by others.36,38,39 posed of intertwined fabric fibers with an average microfiber
In order to deposit graphene layers on textiles efficiently and diameter of ∼20 μm. When the textiles are dipped into the
uniformly, an ink solution with reasonable density and uniform graphene ink, they are quickly coated with graphene nanosheets
size of exfoliated graphene is needed. Typical graphene ink because of van der Waals forces between exfoliated graphene and
2907 dx.doi.org/10.1021/nl2013828 |Nano Lett. 2011, 11, 2905–2911
Nano Letters LETTER

Figure 3. Energy textiles based on hybrid graphene/MnO2 nanostructures as EC electrodes. (a) MnO2 electrodeposition curve showing a nearly linear
relationship for deposition mass versus time at an applied deposition current of 0.1 mA/cm2. (b) SEM image of a sheet of graphene-coated textile after
60 min MnO2 electrodeposition showing large-scale, uniform deposition of MnO2 nanomaterials achieved on almost entire fabric fiber surfaces. Scale
bar: 200 μm. (c) SEM image of a typical microfiber with conformal coating of MnO2 nanostructures in the same textile shown in panel a. (Inset) High-
magnification SEM image showing the nanoflower structure of electrodeposited MnO2 particles and a clear interface between MnO2 nanoflower and
underneath graphene nanosheets. Scale bars are 5 and 1 μm for main figure and inset. (d) Impedance of graphene/MnO2-textiles with different MnO2
deposition time. Z0 is real impedance and Z00 is imaginary impedance. (e) Cyclic voltammograms for graphene/MnO2-textile electrode at different scan
rates in 0.5 M aqueous Na2SO4 electrolyte (CV curve for graphene-only textile at a scan rate of 5 mV/s included for comparison). (f) Comparison of
specific capacitance values between graphene/MnO2-textile and graphene nanosheets-only textile at different scan rates.

polyester fibers. Subsequently, the “wet” textiles with graphene surface. The conformal coating is largely due to mechanical
ink are subject to the drying process for water removal by putting flexibility and size uniformity of graphene nanosheets together
them in an oven at 120 °C for 10 min. Through this simple dip with strong adhesion between the graphene and polyester fibers.
and dry process, potentially large-area conductive graphene Moreover, such porous conductive textiles conformally coated
nanosheets-coated textiles can be readily fabricated. Figure 2d with graphene materials exhibit excellent mechanical properties
shows that the sheet resistance, Rs, decreases (conductance increases) and chemical resistance performance. Standard tape test and
as the dipping number in graphene ink increases. After 35 cycles, water washing on samples show little sign of graphene loss and
the graphene-textiles exhibit a Rs of ∼700 Ω/sq. By tuning the no sheet resistance change. These tests indicate good mechanical
graphene ink concentration and the dipping number, conductive adhesion of graphene nanosheets on textiles. Chemical resistance
textiles with a range of sheet resistance could be achieved. It tests in acid (2 M sulfuric acid) and base (2 M sodium hydroxide)
should be noted that an additional step of nitric acid treatment also show a small change in the sheet resistance (∼30% increase
on textiles (see Supporting Information) can help improve the in Rs observed for 1 h immersion for base), as found for carbon
conductivity by a factor of typically 2
3 compared to those nanotubes coated textiles in previous work.26
without the treatment. This increase is possibly due to the effects Controlled deposition of nanostructured MnO2 materials on
of more thorough surfactant removal and the induced hole doping conductive graphene-coated textiles has been achieved through
by nitric acid treatment.41 an electrochemical deposition process. Graphene nanosheets
The representative scanning electron microscopy (SEM) conformably coated on fiber surfaces serve as a conductive support
image shown in Figure 2e reveals the 3D porous structures of with large surface area for the subsequent deposition of nanoscale
graphene-wrapped polyester textile and demonstrates that gra- MnO2 particles. Briefly, nitric acid-treated graphene-textiles were
phene nanosheets are uniformly coated onto the microfibers over immersed into a plating solution containing Mn(NO3)2 and
the entire sheet of fabric. A higher-magnification SEM image NaNO3 and were subjected to electrodeposition using a three-
(Figure 2f), which almost resolves individual graphene flakes on electrode setup (see Supporting Information). The mass loading
fiber surface, confirms conformal coating of graphene nanosheets of MnO2 can be well controlled by adjusting the deposition
on the textile. We note that flake sizes for most graphene current and deposition time. Figure 3a shows a nearly linear
nanosheets (>95%) coated are in the range of 0.3
1 μm, which relationship between deposition mass and deposition time at an
is in agreement with our AFM results, and those large size flakes applied current of 0.1 mA/cm2, and an average deposition rate is
(>2 μm, ∼10% in the ink) are barely observed on the fiber estimated to be ∼5 μg/min. Note that provided highly porous

2908 dx.doi.org/10.1021/nl2013828 |Nano Lett. 2011, 11, 2905–2911

Nano Letters LETTER

structures of polyester textiles, even larger mass loading (>3 mg/cm2) compared to that of graphene nanosheets-only textiles. The
could be achieved by increasing the deposition time to ∼600 highest specific capacitance achieved is ∼315 F/g at scan rate
min. Considering that only a thin surface layer (often <1 μm) of 2 mV/s, exceeding those previously reported based on MnO2/
of MnO2 can actively participate in pseudocapacitive reactions graphene materials system.24,44
due to low proton diffusion constant (∼ 10
13 cm2/(V s)) and Several unique characteristics of our graphene/MnO2 nanos-
low electrical conductivity (∼10
5 S/cm) of MnO2 materials,42 tructured textiles make them a promising candidate for high-
we have focused on the MnO2 material thickness <1 μm in our performance EC electrode materials. These features include the
studies. Figure 3b,c shows the general morphology and detailed following: (i) 3D porous microstructures of the polyester textiles
microstructure of a typical sample prepared by 60 min deposi- allowing conformal coating of graphene nanosheets and subse-
tion. We observe that uniform deposition of MnO2 nanomater- quent loading of MnO2 and facilitating easy access of electrolyte
ials is achieved on the surfaces of individual microfibers over ions (Naþ in our case) to electrode surfaces; (ii) graphene
almost the entire network of porous textiles. Moreover, electro- nanosheets coatings serving as high surface area, conductive paths
deposited MnO2 particles show a nanoflower-shaped hierarch- for the deposition of MnO2 and providing excellent interfacial
ical architecture with a typical dimension of 300
800 nm and contact between MnO2 and graphene for fast electron transport;
hundreds of random branches forming many small mesopores of and (iii) nanoflower architectures of electrodeposited MnO2 offering
size 5
30 nm (inset, Figure 3c). The nanoflower structures large electrochemically active surface areas for charge transfer and
observed for electrodeposited MnO2 are consistent with other reduced ion diffusion length during the charge/discharge process.
previous studies26,43 and could provide large accessible surface Asymmetric EC systems consisting of different types of electrodes
areas that enable effective electrolyte ion transport during super- have been extensively explored recently as they promise a wider
capacitor operations. As the electrodeposition time increases, the operating voltage thus providing higher energy density.9,10,18,19
particle size of the nanoflower MnO2 increases until a continuous We choose our graphene/MnO2-textile as the positive electrodes
thick film is formed on the textile fibers (Supporting Information and SWNT-textile as the negative electrodes to assemble hybrid
Figure S2). Both the 3D porous structures of textiles and the ECs in 0.5 M Na2SO4 aqueous electrolytes, as shown in Figure 4a.
good electronic conductivity of graphene layers make it possible The choice of SWNT-coated textiles as the negative electrodes
to achieve uniform deposition and high mass loading of nano- is based on two facts: (i) that they have been demonstrated
structured MnO2 materials with large electroactive surface areas as high performance electrodes with exceptional cyclability
for high performance supercapacitor electrodes. (∼2% capacitance loss over 100,000 cycles),26 which can elim-
To explore the advantages of these hybrid graphene/MnO2 inate their contribution in capacitance loss during cycling test of our
nanostructured textiles as active EC electrodes, we have inves- hybrid ECs, and (ii) that the operation voltages of asymmetric ECs
tigated their electrochemical properties by performing cyclic based on MnO2 and carbon materials can be achieved up to ∼2 V in
voltammetry (CV) and electrochemical impedance spectroscopy aqueous medium.45,46 Figure 4b shows the impedance of the full cell
(EIS) measurements using a three-electrode system. Figure 3d with an ESR of ∼8 Ω at high frequency of 100 kHz. Galvanostatic
shows impedance curves of graphene/MnO2-textile electrodes charging/discharging test was also performed with different current
measured in a 0.5 M Na2SO4 electrolyte solution. The impedances densities in a stable voltage window of 0
1.5 V, as shown in
at high frequency (100 kHz) reflect the equivalent series Figure 4c. The linear voltage
time profiles and the symmetric
resistance (ESR) in the electrode/electrolyte system, which is charge/discharge characteristics indicate good capacitive behavior
contributed from both the electrolyte resistance and electronic with a rapid I
V response for our asymmetric EC devices.
resistance of textile electrodes. As the MnO2 deposition time To evaluate further the device performance of our hybrid ECs
increases, the electronic resistance of the textiles increases due to based on graphene/MnO2-textile and CNT-textile, the energy
the low conductivity of MnO2 leading to an increase in ESR as density (E) and power density (P) were calculated from galvano-
seen in the figure. Figure 3e shows the rate-dependent CVs for static charge/discharge curves (for calculations see Supporting
graphene/MnO2-textile electrodes with 60 min deposition time Information). The total resistance based on the internal resistance
over a range of scan rates of 2
100 mV/s. The potential window (IR) drop from the charge
discharge curves is used to calculate
tested is confined to a range of 0
0.85 V versus Ag/AgCl P and E for the assembled device, and we found these resistance
reference electrode. It can be seen that graphene/MnO2 textile values (∼11
15 Ω) are relatively close to the value (∼8 Ω,
electrodes show relatively rectangular CV curves for scan rates up Figure 4b) obtained from the EIS measurement. Figure 4d shows
to 20 mV/s indicating a nearly ideal supercapacitor behavior, and the Ragone plot of our specific E versus P values considering the
at the same scan rate the resulting current from graphene/MnO2- total mass of active materials from positive and negative electro-
textile is much higher than that of graphene-only textile owing to des. The maximum energy density of 12.5 Wh/kg and the highest
the loading of the pseudocapacitive MnO2. As the scan rate power density of 110 kW/kg are achieved using our hybrid
increases (50 and 100 mV/s), the peak current increases and ECs at an operation voltage of 1.5 V. Compared to similar
the shape of CV curves shows some distortions from an ideal systems reported previously using symmetric MnO2/MnO29 or
capacitor, possibly due to increasing overpotentials from ion other hybrid MnO2/carbon-based materials (CNTs, activated
transport between the electrolyte and MnO2. Meanwhile we carbon),18,19,46 our hybrid ECs exhibit comparable energy den-
found that only ∼40% capacitance loss when scan rate increases sity but substantially higher power density. We believe that
by a factor of 10 (5 mV/s to 50 mV/s), showing a good rate further improvement in energy density can be achieved with
capability of graphene/MnO2-textile electrodes. More impor- higher mass loading of MnO2 nanomaterials and optimized mass
tantly, the specific capacitance values versus scan rates based on balance of both electrodes for hybrid ECs to allow stable, higher
the total mass of active electrode materials, as summarized in voltage operation in ionic liquid electrolytes.
Figure 3f, demonstrate that our hybrid graphene/MnO2 nano- In addition, our high-performance hybrid ECs exhibited excellent
structures based textiles yield greatly improved capacitance cycling stability, which is one of the most critical factors in super-
performance with 4
5 times increase in specific capacitance capacitor operations. MnO2-based supercapacitors often suffer from
2909 dx.doi.org/10.1021/nl2013828 |Nano Lett. 2011, 11, 2905–2911
Nano Letters LETTER

Figure 4. Asymmetric (hybrid) ECs based on graphen/MnO2-textile as positive electrode and CNT-textile as negative electrode. (a) Schematic of the
assembled structure of hybrid EC cells in a 0.5 M Na2SO4 aqueous electrolyte. (b) Nyquist plot for the assembled hybrid EC over the frequency range of
100 kHz ∼ 0.1 Hz. Equivalent series resistance extracted is about 8 Ω. (c) Galvanostatic charging/discharging curves measured with different current
densities for the assembled hybrid EC. (d) Ragone plot of energy density versus power density for our hybrid ECs (black points) and others using similar
systems reported in literatures (refs 9, 18, 19, and 46). (e) Cycling performance of our hybrid ECs showing capacitance retention of ∼95% after 5000
cycles of charging and discharging at a current density of 2.2 A/g, and subtle change in EC's equivalent series resistance taken from impedance
measurement every 1000 cycles. (f) Nyquist plots showing the corresponding impedance curves measured after each 1000 cycles during cycling test for
assembled ECs.

limited cyclability due to some of the following issues: mechan- architecture of these designed textiles allows efficient use of
ical expansion of MnO2 during ion insertion/desertion process, pseudocapacitive MnO2 nanomaterials for charge storage with
MnO2 film detachment from electrode surfaces, Mn dissolution facilitated transport of both electrolyte ions and electrons, thus
into electrolyte, and imbalanced capacity on two electrodes rendering the composite materials with high specific capacitance,
causing the instability of the electrode potential.20 In contrast, good rate capability and remarkable cycling performance. We believe
the cycling test of our hybrid EC cells shows ∼95% capacitance that such low-cost, lightweight, and high-performance energy textiles
retention over 5000 cycles at a high current density of 2.2 A/g, realized by earth-abundant and environment-friendly materials
which is significantly better than those reported in previous and scalable solution processing, can offer great promise in grid-
work (typically 70
85% retention over 1000 cycles).18,24,45 EIS scale energy storage device applications.
measurements after each 1000 cycles demonstrate a subtle
change in ESR over the entire 5000 cycles and Nyquist plots of ’ ASSOCIATED CONTENT
experimental impedance data show the consistent impedance
spectra, further demonstrating exceptional electrochemical stability bS Supporting Information. Materials and Methods and
of the hybrid ECs. The excellent cycling performance achieved in additional supporting figures. This material is available free of
our EC system can be attributed to a number of factors. Besides charge via the Internet at http://pubs.acs.org.
the key advantages aforementioned for this unique electrode
architecture, excellent interfacial contact between MnO2 nanos- ’ AUTHOR INFORMATION
tructures and graphene layers that likely resulted from hydrogen
Corresponding Author
bonding between MnO2 and carboxylated edge surface of
*E-mail: (Y.C.) [email protected]; (Z.B.) [email protected].
graphene may be another important enabling factor. In fact, we
characterized the morphology and structure of our graphene/ Author Contributions
MnO2-textile electrodes after 5000 cycles, and found that the z
These authors contributed equally.
nanoflower MnO2 structures were well maintained and the
MnO2 was still uniformly coated on textile fibers (Supporting
Information Figure S3). ’ ACKNOWLEDGMENT
In summary, we have developed a scalable solution-based We thank Dr. Yan Yao and Dr. Hanying Li for their helpful
approach to fabricate hybrid graphene/MnO2 nanostructured discussion and assistance in some sample characterizations. Y.C.
textiles as high-performance supercapacitor electrodes. The unique and Z.B. acknowledge the funding support from the Precourt
2910 dx.doi.org/10.1021/nl2013828 |Nano Lett. 2011, 11, 2905–2911
Nano Letters LETTER

Institute for Energy at Stanford University. Y.C. also acknowl- (34) Stoller, M. D.; Park, S.; Zhu, Y.; An, J.; Ruoff, R. S. Nano Lett.
edges the funding support from the King Abdullah University 2008, 8, 3498.
of Science and Technology (KAUST) Investigator Award (No. (35) Zhang, L. L.; Zhou, R.; Zhao, X. S. J. Mater. Chem. 2010,
KUS-l1-001-12). X.C. acknowledges the support from Stanford 20, 5983.
Undergraduate Research Experience Program. (36) Lotya, M.; King, P. J.; Khan, U.; De, S.; Coleman, J. N. ACS
Nano 2010, 4, 3155.
(37) Zhu, Y.; Murali, S.; Cai, W.; Li, X.; Suk, J. W.; Potts, J. R.; Ruoff,
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