Vacuum 107 (2014) 269e276

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Vacuum
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Preparation of the graphene oxide (GO)/Nafion composite membrane

for the vanadium redox flow battery (VRB) system
Kwan Ju Lee a, Young Hwan Chu b, *
a
Department of Environmental Engineering, College of Science & Engineering, Sangji University, 124, Sangjidae-gil, Wonju-si,
Gangwon-Do 220-702, Republic of Korea
b
Department of New Energy$Resource Engineering, College of Science & Engineering, Sangji University, 124, Sangjidae-gil, Wonju-si,
Gangwon-Do 220-702, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Graphene oxide (GO) nano-plate was applied to the vanadium redox flow battery (VRB) system as the
Received 2 October 2013 ion-exchange membrane to reduce the vanadium permeation and enhance the VRB system performance.
Received in revised form The GO/Nafion membranes were prepared with the GO composition from 0.001 wt% to 1 wt%. The
22 February 2014
prepared composite membranes were analyzed by SEM to investigate the microstructure of the mem-
Accepted 27 February 2014
branes. Water uptake, proton conductivity, thickness and vanadium ion permeability of the membrane
were observed to evaluate the membrane properties. X-ray diffraction (XRD) analysis was conducted to
Keywords:
observe the inter-planar microstructure of the membranes. The prepared membranes had a lower value
Vanadium redox flow battery
Permeation
of the inter-planar space dimension than that of the Nafion 117 membrane and because of this fact the
Graphene oxide prepared composite membrane had a lower value of the water uptake, vanadium permeability and
Composite membrane proton conductivity than that of the Nafion 117. The value of the proton conductivity and the vanadium
Nafion permeability were decreased when increasing the GO composition in the composite membrane. The
optimum composition of the GO in the composite membranes for the application of the ion-exchange
membrane of the VRB system ranged from 0.01 wt% to 0.1 wt%. The highest EE value of the VRB sin-
gle cell was obtained by using the 0.01 wt% GO composite membrane and the value was 82.5%. We could
suggest that the GO/Nafion composite membrane can be one of the promising candidates for the VRB
membrane electrolyte.
Ó 2014 Published by Elsevier Ltd.

1. Introduction
A redox flow battery (RFB) is a type of rechargeable battery
system where rechargeability is provided by two chemical com-
ponents separated by a membrane electrolyte and dissolved in
liquids contained within the system. Two different redox reactions
take place in the individual chemical components in the RFB system
and the one pair of the redox couple can generate the cell potential.
Recently, the RFB has received much attention as a promising large
scale energy storage device for the purpose of the load-leveling and
other off-grid applications, such as integration with renewable
energy sources [1]. RFB has many advantages compare to the other
energy storage devices in that it has as long cycle life, flexible/
simple design, quick response time, deep-discharge capability, low
* Corresponding author. Tel.: þ82 33 730 0456; fax: þ82 33 730 0403.
E-mail address: yhchu@sangji.ac.kr (Y.H. Chu).
pollution emission and low cost in energy storage [2e4]. So far,
many diverse redox couples have been employed to the RFB system
such as iron/chromium, bromine/polysulfide, vanadium/vanadium,
vanadium/bromine, zinc/bromine, soluble lead acid and iron/iron
[5]. A vanadium redox flow battery (VRB) which consists of the
vanadium/vanadium redox couple was proposed by Skyllas-
Kazacos and co-workers in 1985. The VRB stores energy in the
form of two vanadium solutions which are respectively contained
in two separated electrolyte reservoirs. Hence, the vanadium so-
lution contamination problem induced by the crossover of the
species from the opposite reservoir is less serious compared with
the other types of RBF. During operation of the VRB, two vanadium
solutions are pumped through pipes from the tank into the cells
and separated by an ion-exchange membrane. The individual half-
cell reactions of each positive/negative electrode and the schematic
design of the VRB are shown in Fig. 1 [6].
The ion-exchange membrane of the VRB is one of the most
important components in the VRB system and it should have high

http://dx.doi.org/10.1016/j.vacuum.2014.02.023
0042-207X/Ó 2014 Published by Elsevier Ltd.
270 K.J. Lee, Y.H. Chu / Vacuum 107 (2014) 269e276
Fig. 1. Schematics of the vanadium redox flow battery (VRB).
proton conductivity and high durability to endure the harsh oper-
ation conditions. A perfluorosulfonic acid (PSFA) membrane, such
as Nafion (DuPont) for example, is the most commonly used
membrane due to its high chemicalemechanical stability and high
proton conductivity. However, there are serious drawbacks in the
PFSA membrane when it is applied to the electrochemical systems,
especially to the direct methanol fuel cell (DMFC) and to the VRB.
The cost of PFSA membrane is very high and the cross-over of
methanol and vanadium ions induce significant performance drop
[7]. In order to reduce the vanadium ion migration through the ion-
exchange membrane, many approaches have been attempted such
as doping inorganic materials (SiO2, TiO2, WO3, Zirconium phos-
phate etc.) [1,3,8e10], applying other polymers [11e16], applying
layering structures [17,18] and modifying surfaces [4,19].
Carbon-based material has been widely applied to the VRB
electrode system such as graphite felt, carbon cloth, carbon fiber,
and graphite block [20e23]. However, carbon materials are less
frequently applied to the ion-exchange membrane in the VRB.
Graphene oxide (GO) has a two-dimensional layered structure
produced from natural graphite in the conventional oxidizing
method [24], and it has various oxygen functional groups on the
surface of the basal planes and sheet edges such as hydroxyl,
carboxyl acid, epoxy and keton [25]. The specific two-dimensional
structure (low thickness and high lateral dimension) of GO led us
to believe that the Nafion/GO composite membrane could reduce
the vanadium ion permeation in the VRB system. In this study, we
have prepared the Nafion/GO composite membrane to reduce the
vanadium ion permeation, and investigated the membrane prop-
erties such as ion exchange capacity (IEC), water uptake, and va-
nadium ion permeability in comparison with the Nafion 117
membrane. The VRB single cell test was performed to study in
detail other relevant electrochemical properties of the prepared
membranes.
2. Experimental
2.1. GO and GO/Nafion composite membrane preparation
All chemicals were analytic reagents and were used as received.
GO was synthesized from commercially available graphite powder
(Fluka) by modified Hummers and Offeman’s method as originally
proposed by Kovtyukhova and co-workers [24,26]. The graphite
powder (5 g) was put into a 0  C solution of concentrated 98% H2SO4,
(230 ml) and NaNO3 (5 g) in an ice-bath with string, then KMnO4
(30 g) was added slowly into the mixture and stirred the mixture for
2 h at room temperature. Then 400 ml of de-ionized water was
added slowly and the temperature was increased up to 98  C during
this process. The mixture was maintained this temperature for
30 min. The resulting yellowish solution was diluted and further
treated with 30% H2O2 (30 ml) solution to stop the reaction. The final
solution was filtered and washed several times to remove the metal
ion residue. The prepared GO was dispersed (10 mg ml1) in de-
ionized water by thorough ultrasonication for 4 h. The GO suspen-
sion solution was mixed with 5 wt% Nafion perfluorinated ionomer
solution (Aldrich) according to the GO composition in the prepared
dry membrane (0.001, 0.01, 0.1 and 1 wt%) and ultrasonic waves
were applied again to disperse the GO in the mixture solution. The
prepared solution samples, which contain different composition of
the GO, were cast on the leveled glass scales and dried at 105  C for
24 h, and the samples were identified as GO 0 wt%, GO 0.001 wt%, GO
0.01 wt%, GO 0.1 wt% and GO 1 wt%, respectively according to the
GO wt%.
2.2. Sample characterization
The prepared GO microstructure was characterized by using
high-resolution transmission electron microscopy (HR-TEM, JEOL-
2010, Japan). The X-ray diffraction (XRD) was conducted on a
Rigaku X-ray diffractometer using Cu-ka radiation (l ¼ 0.15406 nm)
for observation of the graphite, GO and the membrane micro-
structure. The 2q angles ranged from 5 to 80 exploring at a scan
rate of 2 min1 for the analysis of the graphite and GO structure.
The membrane inter-planar microstructure was observed by the
XRD with the 2q angles ranged from 1.2 to 5 exploring at a scan
rate of 1 min1. The membrane surface and cross sectional
morphology was observed by scanning electron microscopy (SEM,
JEOL-2000, Japan). Raman spectra were obtained with a Labram-HR
Raman microscopy system (Horiba Jobin-Yvon, France) with a laser
wavelength of 514.5-nm (2.41-eV) line of an Ar ion laser.
The definition of membrane water uptake is mass ratio of the
absorbed water to that of the dry membrane and can be calculated
using the following equation:
water uptake ¼ ðWw  Wd Þ=Wd  100%
where Ww is the mass of the wet membrane, and Wd is the mass of
the dry membrane. The ion exchange capacity (IEC) was measured
through a previously used method [27].
The permeability of VO2þ ion through the membrane was
measured using the membrane-separated diffusion cell system
placed with 1.5 M VOSO45$5H2O (Aldrich) in 3 M H2SO4 solution in
one side of the electrolyte tank and 1.5 M MgSO4 in 3 M H2SO4
solution in the other side of the electrolyte tank. The effective area
was 3  3 and the volume of each solution was 50 ml. Samples were
taken from the 1.5 M MgSO4 in 3 M H2SO4 solution reservoir
periodically and the vanadium ion concentration was analyzed by
UVeVisible spectrophotometer (Varian; model Cary 50 conc.).
2.3. VRB single cell performance
The VRB single cell was fabricated by sandwiching a membrane
between two pieces of 4 cm thick carbon felt (Nippon carbon co.,
Ltd., Japan) electrodes of the size 2  2 cm, and two pieces of
graphite plate which were used as the current collector. The indi-
vidual half-cell reactions of each positive/negative electrode and
the schematic design of the VRB are shown in Fig. 1. In the begin-
ning of chargeedischarge cycles, 15 ml of 1.5 M Vanadium (III) in
3 M H2SO4 solution and 15 ml of 1.5 M Vanadium (IV) in 3 M H2SO4
were pumped into the negative and positive electrode, respectively.
The single cell was charged and discharged by using automatic
charge/discharge equipment (WBCS3000, WonATech Co.) by
changing the charge/discharge current density from 20 mA cm2 to
80 mA cm2. To avoid the corrosion of the carbon felt and graphite
plate, charge capacity was controlled to a corresponding redox
couples utilization of 75%. The low voltage limit for the discharge
was controlled to 0.8 V.
 K.J. Lee, Y.H. Chu / Vacuum 107 (2014) 269e276 271

3. Results and discussion

3.1. Graphene oxide (GO) characterization

Transmission electron microscopy (TEM) characterization was

performed to analyze the GO morphology. Fig. 2 shows that the
wrinkled transparent single or few-layers of the GO sheet was
successfully obtained by the GO preparation method [24]. The sheet
revealed flexible shape and it had many wrinkles which were more
than few hundreds of nanometers in size laterally. This morphology
was well matched with previous reports about the GO [28]. No
graphite particles were observed in this image.
XRD patterns of the pristine graphite and the GO were
observed and are shown in Fig. 3. The diffraction peaks at 2q angles
of 26.4e54.6 in XRD patterns of the pristine graphite could be
assigned to hexagonal crystalline graphite (JCPDS No. 41-1487), and
the sharp intensive peak at 26.4 was indexed to be the (002) peak
of graphite, which indicates a highly organized crystal structure
Fig. 3. XRD patterns of pristine graphite and GO.
with an interlayer spacing of 0.336 nm. In case of the GO, the typical
native peak at 26.5 had disappeared, and new peak appeared at the
peak position of 10.8 , corresponding to the 001 inter-planar A 2D band is normally observed in the crystalline graphitic
spacing of 0.818 nm. This inter-planar space expansion could be materials and it is sensitive to the p band in the graphitic electronic
explained by the generation of the abundant oxygen functional structure, while the combination mode of D þ G is induced by
group attached on the both sides of the GO and the atomic-scale disorder [32]. The intensity ratios of I2D/IDþG of the pristine graphite
roughness formation by the structural defects (sp3 bonding) gen- and GO were 24.32 and 0.79, respectively. This indicates that the
eration on the pristine flat graphene surface after oxidation [29,30]. crystalline graphitic properties of the graphite had mostly dis-
Raman spectra of the pristine graphite and GO are shown in appeared when the graphite was changed into GO.
Fig. 4. There were four distinguished peaks for the pristine graphite
and GO samples, assigned to G band (1580 cm1), D band (1310e 3.2. Membrane properties
1430 cm1), 2D band (2700e28001) and D þ G band (2900e
30001). Among these four peaks, two dominant G band and D General properties of the Nafion 117 membrane and prepared
band peaks are considered: the E2g vibrational mode in-plane and composite membranes such as membrane thickness, water uptake
the A1g breathing mode, respectively [31]. The G band is Raman and ion exchange capacity were obtained and listed in Table 1. It has
active for sp2 hybridized carbon-based material, while the D band been shown that the general membrane properties of the prepared
is activated only if defects participate the double resonance Raman composite membranes are similar to one another but much different
scattering near the K point of the Brillouin zone [32]. In the case of from that of the Nafion 117 membrane. Prepared composite mem-
GO, the G band peak was less sharp compared with that of the branes showed higher ion exchange capacity (IEC) and lower water
pristine graphite and the peak location was shifted to the right. This uptake compared with a Nafion 117 membrane. The amount of the
could be attributed to the presence of isolated double bonds that containing water inside the membrane in the hydrated state will be
resonate at higher frequencies than that of the G-band of the directly affected by the microstructure of the membrane. X-ray
graphite. On the other hand, the D band peak was well developed in diffraction (XRD) analysis was performed at the low 2q angle from
the case of GO and the intensity ratios of ID/IG of the pristine 1.5 to 10 with the scan rate of 1 min1 to observe the inter-planar
graphite and GO were 11.5 and 1.1 respectively. This indicates that microstructure change of the membranes and the data is shown in
the defects were generated abundantly on the surface of the GO by Fig. 5. All patterns were similar and exhibited a single diffraction
the GO preparation process from the pristine graphite.

Fig. 2. TEM (Transmission Electron Microscopy) image of prepared GO. Fig. 4. Raman spectra of pristine graphite and GO.
272 K.J. Lee, Y.H. Chu / Vacuum 107 (2014) 269e276

Table 1 containing capacity of the membrane and increase the number

Comparison of the general properties between Nafion 117 and the prepared density of the sulfonyl groups inside the hydrated membrane, and
composite membranes.
these microstructure changes could result in the decrease of the
Nafion membrane types Properties water uptake and increase of the IEC.
Thickness Water I.E.C Fig. 6 shows the cross-sectional images of the membranes ob-
(mm) uptake (%) (mmol(Na)/g) tained by SEM analysis. The thicknesses of the composite mem-
Nafion 117 membrane 181.45 35.01 0.89 branes were approximately 30e40 mm. Fig. 6 shows that the
GO 0 wt% composite 28.03 21.15 0.83 composite membranes had cleaner cross-sectional morphology
GO 0.001 wt% composite 31.14 21.61 0.92 than the Nafion 117 membrane. This could be attributed to the fact
GO 0.01 wt% composite 27.75 22.41 0.96
that the prepared composite membranes had a denser micro-
GO 0.1 wt% composite 32.28 22.84 0.97
GO 1 wt% composite 28.57 32.38 0.94 structure than the Nafion 117 membrane. Fig. 7 showed the photo
images of the prepared GO/Nafion ionomer mixture and the com-
peak. The main peak of the Nafion 117 membrane appeared at 1.7 posite membranes according to the GO composition and it shows
that the composite membranes have been successfully prepared.
and the inter-planar space dimension, which can be directly related
with the ion cluster pore size in the membrane, was calculated by The color of the solution changed from transparent to dark brown
and the membrane color also changed from transparent to dark
Bragg’s law as 5.1 nm [33]. On the other hand, the main peak of the
composite membranes was shifted to the right and appeared at brown as the GO composition increased.
Fig. 8 shows the proton conductivity of the membranes. The
approximately 2.9e3.0 . The inter-planar space was calculated to be
about 2.9e3.0 nm. According to the conclusion of the previous report proton conductivity of the Nafion 117 membrane was obtained as
90.0 mS cm1 (dashed line). On the other hand, the proton con-
[34,35] and our XRD results, we could suggest that the contraction of
the membrane inter-planar space dimension could reduce the water ductivities of the prepared composite membranes decreased
compared with the Nafion 117 membrane [36]. This behavior is
associated with the contraction of the inter-planar space, which
determines the proton transfer channel dimension of the mem-
branes [34]. The proton conductivity tended to be decreased as the
GO composition increased. This may due to the existence of the GO
which has a role as the blocking barrier of the proton transfer inside
the membrane.

3.3. Vanadium ion permeability

Fig. 9 indicates the vanadium ion (VO2þ) permeation behavior

through the membranes. Fig. 9(a) shows the concentration change
of the VO2þ ion in the MgSO4 containing reservoir with time. The
VO2þ ion concentration increased as the permeation time increased
in all the membranes. The permeability was calculated with several
hypotheses according to suggestions in a previous report [3]. It is
assumed that the change in vanadium ion concentration in the
vanadium ion reservoir side can always be negligible during the
calculation of permeability due to the fact that the concentration of
the vanadium ion in the magnesium ion reservoir is low. Inside the
membrane, a pseudo-steady-state condition is applied. According
to the above hypotheses, the flux of the vanadium ion is constant,
and its concentration in the right-hand reservoir (magnesium ion
side) as a function of time is given by the equation [3]
h i
VR *ðdCR ðtÞ=dtÞ ¼ A*P=L* CL  CRðtÞ

where CL is the vanadium ion concentration in the left-hand

Fig. 5. XRD patterns and inter-planar space dimension of Nafion 117 and prepared
composite membranes .(a) XRD patterns of the membranes (b) Inter-planar space
dimension of the membranes calculated Brag’s eqn.
reservoir, and CR(t) refers to the vanadium ion concentration in
the right-hand reservoir as a function of time. A and L are the area
and thickness of the membrane, respectively. P is permeability of
the vanadium ions, and VR is the volume of right reservoir,
respectively. An assumption is also made here that P is independent
of concentration [3].
The VO2þ ion concentration change of the VO2þ ion reservoir was
neglected and the pseudo-steady-state condition was applied for
the inside of the membrane. The permeability of the VO2þ ion for
the Nafion 117 membrane was 310  108 cm2 min1. However, the
permeability of the composite membranes dropped dramatically
around 50  108 cm2 min1, and it decreased more as the GO
composition in the composite membranes increased. It is well
known that the membrane conductivity is closely related to the
methanol permeability. The methanol permeability of the Nafion
membrane tends to increase with increasing proton conductivity. In
 K.J. Lee, Y.H. Chu / Vacuum 107 (2014) 269e276 273

Fig. 6. Cross-sectional SEM image of the Nafion 117 and prepared composite membranes. (a) Nafion 117 membrane (b) GO 0 wt% composite membrane (c) GO 0.001 wt% composite
membrane (d) GO 0.01 wt% composite membrane (e) GO 0.1 wt% composite membrane. (f) GO 1 wt% composite membrane.

Fig. 7. Digital camera image of the prepared mixture solutions and prepared composite membranes. (a) GO/Nafion ionomer mixture solutions. (b) Prepared composite membranes.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
274 K.J. Lee, Y.H. Chu / Vacuum 107 (2014) 269e276

100 the same way, we could suggest that the decrease of the vanadium
Nafion 117 membrane permeability could be attributed the decrease of the conductivity
which was induced by the membrane microstructure contraction
80 and the simultaneous decreasing behavior of the vanadium
permeability with increasing GO is in correspondence with the
Conductivity (mS/cm)

result of the conductivity as well. From these results, we could

60 suggest that there exists an optimum range of the GO composition
in the composite membrane for the VRB system application because
there is a positive effect of the vanadium permeability decrease and
40 a negative effect of the conductivity decrease with increasing GO
composition in the composite membrane.

20 3.4. VRB single cell performance

Chargeedischarge curves at different current densities were

0 obtained by the VRB single-cell performance test to find out the
GO 0wt% GO 0.001wt% GO 0.01wt% GO 0.1wt% GO 1wt% optimum composition of the GO or the composite membrane for the
GO concentration of the prepared membranes VRB system application. The charge capacity was controlled to
450 mA h corresponding to a redox couples utilization of 75% and
Fig. 8. Proton conductivity of the Nafion 117 and prepared composite membranes. the performance test was carried out with all the membranes. Fig. 10
shows the chargeedischarge performance data of the Nafion 117
membrane and the selected GO 0.01 wt% composite membrane. It

Fig. 9. VO2þ ion permeation comparison of the Nafion 117 and the prepared composite
membranes. (a) VO2þ ion concentration change in the MgSO4 reservoir. (b) Compari- Fig. 10. Chargeedischarge curves for VRB single cell test. (a) Nafion 117 membrane. (b)
son of permeability of the VO2þ ion. GO 0.01 wt% composite membrane.
 K.J. Lee, Y.H. Chu / Vacuum 107 (2014) 269e276
showed that the discharge capacity increased as the charge current
density increased. This is simply explained because the decreased
chargeedischarge time at a higher current density could reduce the
time of the vanadium ion cross-over through the membrane.
Fig. 11 shows the coulombic efficiency (CE), voltage efficiency
(VE), and energy efficiency (EE) of the VRB single cell test with all the
membranes at different chargeedischarge current densities. The CE
of the VRB was increased as the chargeedischarge current density
increased, which could be explained by the reduction of the time of
the vanadium ion permeation. VE behavior showed the opposite
trend to the CE behavior due to the increase of the internal resis-
tance of the VRB system with increasing chargeedischarge current
density. Hence the EE, the product of the CE and VE, showed a
parabolic behavior which has a local maximum value and this local
maximum value appeared at the current density of 40 mAcm2
Fig. 11. Coulombic efficiency (CE), Voltage efficiency (VE), and Energy efficiency (EE) of
the VRB with the Nafion 117 and the prepared composite membranes under different
current densities.
275
generally. In general, the CE of the Nafion 117 membrane showed a
higher CE value than that of the composite membranes due to its
higher thickness compared with that of the composite membranes.
However, some composite membranes such as those with GO
composition of 0.01 wt% and 0.1 wt% showed higher CE than that of
the Nafion 117 membrane in spite of the lower membrane thickness.
This could be attributed the quite low vanadium ion permeability of
the composite membranes compare to that of the Nafion 117
membrane as shown in Fig. 9. The VE is directly related to the in-
ternal resistance of the VRB system induced by the membrane
electrolyte. Therefore the thinner membrane thickness could play
an important role in reducing the internal resistance and increase
the VE of the VRB system. Because the prepared composite mem-
branes had thinner membrane thickness than the Nafion 117
membrane, these membranes had higher VE values than that of the
Nafion 117 membrane. Due to the higher value of the VE and the CE
of the GO 0.01 wt and 0.1 wt% composite membranes, the EE of those
two membranes were much higher than that of the Nafion 117
membrane in all the range of the chargeedischarge current density
and a value up to the 82.5% was reached with the 0.01 wt% GO/
Nafion composite membrane at the current density of 40 mAcm2.
From these results, we could conclude that the prepared GO/
Nafion composite membrane can be one of the promising candi-
dates for the membrane electrolyte of VRB system, and we can
suggest that the optimum GO composition range is from 0.01 wt%
to 0.1 wt%.
4. Conclusions
Graphene oxide nano-plate was applied in the VRB system as the
ion-exchange membrane to reduce the vanadium permeation and
to enhance the performance of the VRB system. The GO/Nafion
composite membranes were successfully prepared with t GO
composition from 0.001 wt% to 1 wt%. The prepared composite
membranes were analyzed by SEM and the thickness was observed
as about 30e40 mm. The value of the water uptake, the proton
conductivity and the vanadium ion permeability were much lower
than that of the Nafion 117 membrane. This behavior could be
attributed to the lower value of the inter-planar space dimension of
the composite membranes than that of the Nafion 117 membrane.
The value of the proton conductivity and the vanadium permeability
decreased as the GO content in the composite membrane increased.
The optimum composition of the GO in the composite membranes
for the application of the membrane electrolyte of the VRB system
ranged from 0.01 wt% to 0.1 wt%. The highest EE value of the VRB
single cell performance test was obtained by using the 0.01 wt% GO
composite membrane and the value was 82.5%. We suggest that the
GO/Nafion composite membrane can be one of the promising can-
didates for the membrane electrolyte of the VRB system.
Acknowledgment
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education, Science and Technology (No.
2012R1A1A1012410).
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