Journal of The Electrochemical Society, 151 1 A64-A68 2004

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0013-4651/2003/1511/A64/5/$7.00 The Electrochemical Society, Inc.

Influence of Nafion Content in Electrodes on Performance

of Carbon Supercapacitors
F. Lufrano,z P. Staiti, and M. Minutoli
Consiglio Nazionale delle Ricerche-Istituto di Tecnologie Avanzate per lEnergia Nicola Giordano,
98126 S. Lucia-Messina, Italy
The effects of Nafion loading in electrodes on the performance of supercapacitors have been investigated in this work. Electrodes
based on carbon material were prepared with Nafion loading varying from 10 to 50 wt %, and the optimal loading was investigated
by electrochemical impedance spectroscopy. The capacitors with lower Nafion content had higher conductivities and better
capacitance performances. A maximum specific capacitance of 110 F/g carbon of the electrode was achieved for the capacitor
with 10% Nafion loading in the electrode. Impedance spectroscopy was also used to evaluate separately the resistance of the
Nafion electrolyte and of the carbon/Nafion layer of the electrodes. The results showed that the electrode with 50% Nafion gives
a resistance about 50% higher with respect to that with 10% Nafion, even if the specific capacitance of the supercapacitor using
the former electrode is only 20% lower. The similar performance exhibited by these all-solid supercapacitors compared to those of
conventional devices, based on liquid electrolytes, is likely due to the high conductivity of Nafion and the contribution of the
bound water surrounding the Nafion electrolyte in the electrode. A life cycling test carried out on a supercapacitor for 20,000
cycles, in cyclic voltammetry mode, showed variations of 3% of capacitance.
2003 The Electrochemical Society. DOI: 10.1149/1.1626670 All rights reserved.
Manuscript submitted April 26, 2003; revised manuscript received June 16, 2003. Available electronically December 9, 2003.

Electrochemical double-layer capacitors are energy storage devices that can be used for applications that require higher power
capabilities than rechargeable batteries and higher specific energies
than conventional capacitors.1,2 The storage mechanism in supercapacitors consists mainly of two types of processes, a purely capacitive and a pseudocapacitive process. The former is based on the
electric charge separation at the electrode/electrolyte interface
double layer, the latter on electrochemical reactions occurring on
the electrodes faradaic process. In double-layer capacitors, the capacitance performance exhibited by the devices is strongly dependent on the nature of the electrode/electrolyte interface. Generally,
the larger the specific surface area of carbon in the electrodes, the
higher the capability of accumulation of electric charges at the interface, and thus the higher the capacitance. However, high surface
area is not a sufficient condition to achieve high capacitance; the
carbon must also contain a large fraction of mesopores. The charge
discharge mechanism in an electrochemical capacitor must involve
an easy access of electrolyte into the carbon pores, possible only in
the presence of macro- and mesopores, which permit a high rate of
charge and discharge, to obtain a large amount of electric charge. A
typical supercapacitor has two electrodes, made of high surface area
carbon, and an aqueous or nonaqueous electrolyte with a porous
separator between them. In most commercial supercapacitors, tetraethylammonium tetraflouroborate in acetonitrile or propylene carbonate is used as the organic electrolyte,1-5 while in others sulfuric
acid or potassium hydroxide is used as the aqueous electrolyte.1,2,6
Many research efforts and studies in this field have been addressed
to the development of new combinations of nonaqueous organic
electrolytes and solvents, and less attention has been paid to the
development of solid polymer electrolytes as alternative materials to
nonaqueous electrolytes. The introduction of polymer electrolytes in
supercapacitors could provide several advantages in the realization
of devices, such as a more flexible structure, a more compact geometry, and easier packaging.7-9 Polymer electrolytes, which could provide these characteristics, are perfluorosulfonate ionomers like
Nafion. Nafion has high ion conductivity (5 102 Scm1 ) at
room temperature, low volatility, and remarkable stability. These
properties make it a promising electrolyte for the realization of an
all-solid double-layer capacitor with appreciable performances. To
date, most known industrial applications of perfluorosulfonate electrolyte membranes are those in chloroalkali and electrodialysis
processes.10 More recently, these electrolytes have been strongly
investigated for fuel cell applications.11-14 Nafion is a well-known

E-mail: lufrano@itae.cnr.it

ion-exchange membrane produced by DuPont, characterized by very

stable perfluorinated polymer chains, with outstanding chemical and
electrochemical properties. The Nafion membrane, which contains
sulfonate groups, exhibits a proton conductivity comparable to that
of dilute acid solutions e.g., 0.1 M H2 SO4 ) and lower than that of
more concentrated liquid electrolytes e.g., 3 M H2 SO4 ).15 Therefore, it could also be utilized as an alternative to replace the traditional electrolytes in electric double-layer capacitors EDLCs.
Moreover, as the Nafion is both electrolyte and binder, it can be used
to enhance the capability of electric charge separation and to impart
mechanical stability to the electrodes. These claimed advantages
have been preliminarily considered and evaluated in a previous paper, which reported the results obtained by a new type of all-solid
EDLC that utilized Nafion as the electrolyte.16 In particular, with
this supercapacitor, a capacitance performance of about 70% of that
measured for a capacitor that utilized similar electrodes with a 1 M
solution of sulfuric acid as electrolyte was obtained.
To prepare efficient electrodes with solid polymer electrolytes, a
homogeneous carbon/Nafion layer and large electrode/electrolyte interface must be realized. Therefore, an appropriate preparation procedure requires a well-mixed dispersion of carbon powder and polymer electrolyte precursor Nafion in solution before layer
formation. The layer preparation is realized by spraying the welldispersed ink on the conductive substrate. The all-solid supercapacitors are realized by coupling two electrodes with a Nafion electrolyte membrane. Clearly, the composition of the carbon layer and the
preparation procedure of the carbon/Nafion electrodes must be optimized.
In this paper, the preparation procedure of electrodes based on
the spraying method is presented and discussed, and the effects of
polymer electrolyte loading in electrodes on supercapacitor performances are evaluated by electrochemical characterizations.
Experimental
Preparation of electrodes.All the electrodes used in the EDLC
experiments were prepared by the spraying method. The following
materials were used in the electrode preparation: Norit SA Super
activated carbon Brunauer, Emmett, and Teller method surface area
1150 m2/g, 5% Nafion 1100 DuPont ionomer solution, AvCarb
1071 HCB carbon cloth, and N,N-dimethylacetamide DMA. The
activated carbon was generously furnished by Norit Italia SpA,
Ravenna, Italy, the AvCarb 1071 HCB carbon cloth was purchased
from Ballard Material Products, Lowell, MA, and both the Nafion
solution and DMA solvent were purchased from Aldrich. As a first
step, an ink containing activated carbon, DMA, and Nafion solution

Journal of The Electrochemical Society, 151 1 A64-A68 2004

was prepared with a carbon/DMA ratio of 1:10 and (carbon
Nafion)/solvent ratio of 0.08 0.01. The ink was blended in an
ultrasonic bath for 30 min, then sprayed with an air spray gun 0.5
mm orifice nozzle on the carbon cloth substrate, and dried. The
desired amount of carbon/Nafion loading is obtained by repeated
spraying and drying steps. The carbon cloth in these electrodes acts
as a mechanical support and an electronic current collector. The
so-prepared carbon/Nafion electrodes were dried and pressed at
70C and then thermally treated for 1 h at 120C and for 20 min at
160C to impart mechanical strength. After the thermal treatment,
the electrodes were rinsed several times in water and then chemically treated in 1 M H2 SO4 solution to ensure that all the metallic
cations, which were attracted to the sulfonate groups during the
preparation process, were completely exchanged with protons. The
electrodes were finally washed in warm distilled water to eliminate
the free sulfuric acid adsorbed in the porous structure. To study the
effect of Nafion loading on supercapacitor performance, electrodes
with 10, 20, 30, and 50 wt % Nafion in the dry carbon layer were
prepared. The carbon loading in the active layer was 8.2
0.9 mg/cm2 for all prepared electrodes. By visual evaluation, the
electrodes prepared by this spraying technique were characterized
by a uniform distribution of the carbon/Nafion agglomerates in the
layer, and they showed a good mechanical strength on handling.
Polymer electrolyte membrane.Samples of Nafion 115 membrane produced by DuPont were utilized in all the experiments as an
electrolyte separator between the electrodes. The water-swelled
membrane was approximately 160 m thick. It was purified in 3 wt
% hydrogen peroxide for about 1 h at 70C to remove organic impurities. It was then treated in 1 M sulfuric acid solution at 70-80C
to remove metallic impurities. The membrane was finally rinsed in
distilled water.
Membrane and electrode assembly.The membrane electrode
assembly MEA was obtained by contacting a membrane and two
electrodes face-to-face. The contact was realized by a hot-pressing
procedure carried out at 100 kg/cm2 and 130C for 10 min. The dry
assembly obtained after hot-pressing was rehydrated by immersion
in 1 M H2 SO4 solution and subsequently washed in warm distilled
water. The different humidified assemblies were inserted in the test
cell for the electrochemical characterization. In the text they are
named NSN10, NSN20, NSN30, and NSN50, being formed respectively of pairs of electrodes with 10, 20, 30, and 50% Nafion in the
carbon composite layer. The same names are also used to identify
the respective capacitors. The assemblies exhibit good mechanical
characteristics, and they do not require particular precautions in handling during insertion in the test cell.
Test cell and electrochemical characterizations.All the electrochemical tests were performed at room temperature using a test cell
composed of two graphite end plates connected with some specific
analytical instruments. Insulating adhesive rubber gaskets were fixed
on both the internal faces of the two graphite end plates to prevent
lateral short circuits, to delimit the central region where the assembly was positioned, and to seal the assembly in the cell to avoid
drying of the electrolyte during the test. Conductivity data were
obtained by measuring the internal resistance of the assemblies and
sometimes of the electrodes with an impedance analyzer and a universal bridge LCR meter at 1 kHz.
The electrochemical characteristics were evaluated by cyclic voltammetry CV using AMEL equipment composed of a high power
potentiostat, model 2055, an integrator, model 731, and a function
generator, model 568. The CV measurements were carried out in
potentiodynamic mode at different scan rates in a range from 10 to
40 mVs1 and in the voltage window 0-1 V. At least 100 cycles
were made at a constant scan rate for each capacitor before registering the experimental results shown and discussed in the next section.
A life cycling test in CV mode at a scan rate of 40 mVs1 was
carried out on capacitor NSN30 for more than 20,000 cycles to
evaluate the cycling stability.

A65

Figure 1. CV curves of capacitors with 10, 20, 30, and 50 wt % Nafion

loading in electrode. The current is normalized for the weight of active
carbon material in the electrode. Voltage sweep rate: 10 mVs1.

Electrochemical impedance spectroscopy EIS measurements

were performed at ambient temperature using a test cell in supercapacitor configuration. The electrochemical cell was connected to a
potentiostat PGSTAT30, Autolab/Eco Chimie NL with a frequency
response analyzer FRA2 module interfaced to a PC. Electrochemical impedance software by Autolab was used to carry out the impedance measurements between 10 MHz and 1 mHz. The amplitude
of the sinusoidal voltage used in the tests was 10 mV. All the electrochemical characterizations and EIS measurements were carried
out on 4 cm2 MEAs.
Results and Discussion
The CV curves carried out at 10 mVs1 on the different capacitors are shown in Fig. 1. The current plots are normalized for the
weight of carbon in the electrode. From the shape of the curves, it is
evident that redox effects in the potential range from 0 to 1 V are not
present; i.e., a purely capacitive storage mechanism occurs. As reported in the literature, sometimes redox processes, determined by
surface functional groups or low level impurities, can be present in
high surface carbons.17,18 A comparison of the curves shows very
little variation in charge/discharge current from the supercapacitors
with Nafion loading in electrodes varying from 10 to 30%, while a
lower current is obtained by the capacitor with 50% Nafion. The
analysis of the curves shows a quasi-rectangular ideal shape. From
the rectangle drawn around the curve of the sample at 10% Nafion,
it is possible to identify the regions where larger deviations from
ideal behavior are present. The main causes of these deviations are
likely due to the distributed resistance in the porous electrodes,
which appears after voltage inversion when the electric current
should instantaneously change sign. The influences of electrolyte
and distributed resistance in the different carbon electrodes have
been analyzed and discussed by interpreting the impedance behavior
of complete supercapacitors.
Nyquist impedance plots, related to the tests carried out on the
different samples in capacitor configuration, are reported in Fig. 2.
The inset in the figure reports the plots at high frequencies of the
capacitors having electrodes with Nafion loading ranging from 10 to
50%. The curves show a slope of 45 in the region of higher frequency, which is a consequence of the distributed resistance and
capacitance of typical porous electrodes. At lower frequencies, the
plots assume a shape close to that of an ideal capacitor, with an
almost vertical line. The resistances of the different capacitors,
evaluated from the Nyquist plots, indicate that the capacitors with
lower Nafion content are less resistive. However, at low frequencies,
a clear difference is not evident because the data points in the plots
at the same frequencies are very close.

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Journal of The Electrochemical Society, 151 1 A64-A68 2004

Figure 4. Capacitance in F/g weight of carbon in electrode and in F/cm2 as

a function of Nafion content in electrode.

In Fig. 3, the specific capacitance as a function of the frequency

from about 6 kHz to 2.33 mHz is shown for the different capacitors.
The values of specific capacitance are obtained using the imaginary
component of the impedance (Z ) in the following expression: C
1/(2 f Z ). The values of capacitance F/g are normalized for
the weight of the active carbon material in the electrodes. The trends
of the capacitances indicate clearly that the capacitor with lower
Nafion content displays better performance, even if the differences
of capacitance showed by other capacitors are not large less than
20%. Electrodes with Nafion loading lower than 10% were not
prepared because they are mechanically less stable and difficult to
handle. Thus, any small improvements in capacitance performance
that could be obtained are not justified by the realization of electrodes with worse mechanical characteristics. At higher frequencies
100 Hz, because of the prevailing influence of the electrolyte
resistance, the behavior of the supercapacitors is like that of an ideal
resistor, and the capacitance is very low. In frequencies from 100 Hz
to 100 mHz, the supercapacitors show a transition behavior from

resistor to capacitor typical of an EDLC based on porous carbon

material. At frequencies 10 mHz, the capacitances approach a plateau, and at this time scale, the electric signal reaches the maximum
possible penetration in the pores of the carbon.
To further show the characteristics of the different capacitors, the
capacitance data were reported in F/g active carbon material for
electrode and F/cm2 as a function of the Nafion content in the
electrodes Fig. 4. The capacitance data in terms of F/g decrease
with Nafion loading, whereas expressed in F/cm2 they do not reveal
a definite trend; they depend only on the carbon loading of the
electrodes.
To better show the effect of Nafion content of electrodes on
capacitor performance, the variations of thickness (l), resistance
(R), and time constant (t) vs. Nafion content are reported in Fig.
5. The percentage variations were calculated taking the electrode
with the 10% Nafion as a reference. Therefore, at constant carbon
loading, the increase in the Nafion loading increases the thickness of
the electrodes. The electrode resistance and the time constant of the
capacitors are calculated taking into account electrode thickness and
capacitance see Fig. 5. The values of the electrode thicknesses are
obtained as average values between that obtained from direct measurement and that calculated as a proportional increase in total
weight of electrodes, i.e., as a sum of the weight of carbon and
Nafion. The Nafion loading of the carbon/Nafion layer influences the
resistance of the different capacitors as evidenced by the Nyquist

Figure 3. Specific capacitance F/g for the weight of active carbon material
in the electrodes as a function of the frequency.

Figure 5. Percentage of variation of thickness (l), resistance (R), and

time constant (t) vs. Nafion content in carbon electrodes with respect to the
electrode with 10% of polymer electrolyte.

Figure 2. Nyquist plots of capacitors with 10, 20, 30, and 50 wt % Nafion
loading in electrodes. The inset shows the high frequency region of impedance.

Journal of The Electrochemical Society, 151 1 A64-A68 2004

A67

Figure 7. Real impedance vs. frequency for the supercapacitors with different amounts of Nafion loading in the electrodes.
Figure 6. Resistance cm2 of the different capacitors. Abscissa reports
the sum of the two carbon/Nafion layer thicknesses for each capacitor without carbon cloth substrate. Measurements were carried out using universal
bridge B LCR and impedance Imp on the complete capacitors , and
on the electrodes . The horizontal line at 0.17 cm2 represents the
Nafion 115 resistance at room temperature.

plots Fig. 2 as well as the time constant of the capacitors (RC),

which that increases from 0.35 to 0.53 s with the Nafion content in
the electrodes.
As a further step, the different contributions to the total resistance values are represented in Fig. 6. In this figure, we have considered the Nafion 115 membrane to have an absolute value of resistance of 0.17 cm2 0.095 Scm1 at room temperature,
according to the literature.19-22 This value corresponds to that of a
highly swelled membrane, free from contact resistances or other
possible problems of the resistance measurement. In Fig. 6, the resistances of the different capacitors are displayed, as contributions
of both membrane Nafion 115 and electrode resistances, as a function of the thickness of the carbon layer of the electrodes. On two
samples of electrode 20 and 50 wt % Nafion, an additional measurement of resistance was carried out by a bridge LCR meter. Good
agreement of the resistance values measured with the different methods has been obtained. Figure 6 also reports the range of fluctuation
of resistance values as a function of the thickness of the various
electrodes with different Nafion loading. Almost all values obtained
show some oscillation; we believe that the data also may be influenced by material composition or loading. The resistance increases
with the electrode thickness. The calculated resistivity of the electrodes varies between 2 to 4 cm as the Nafion loading increases
from 10 to 50%. These values of resistivity, as well as the thicknesses of the electrodes, are less accurate than the measurement of
simple resistance because many errors can occur in the evaluation of
the thickness. For example, the carbon cloth substrate changes thickness with pressure. It is useful to specify that measured values include the contact and carbon cloth resistance.
The real impedance resistance as a function of the frequency
for the capacitors with different amounts of Nafion loading is reported in Fig. 7. The resistance behavior of these supercapacitors is
greatly influenced by the porous nature of carbon electrodes; e.g., an
additional distributed resistance is generated along the thickness of
the electrodes which may be due to the low accessibility of ions of
the electrolyte in the smaller pores and could include the resistances
of the interface, i.e., due to carbon/Nafion and/or carbon/carbon contact. The increase in resistance with decreasing frequency, from a
physical point of view, can be seen as the difficulty of penetration of
the electric signal into the deeper pores filled with electrolyte
and/or in the smaller particles. We can imagine that at very low
frequencies mHz range, some regions of electrode with a low

amount of electrolyte or with poor particle contact do not take part

in the charge separation in the electric double layer. A different
explanation may be that the deeper carbon pores, not containing
polymer electrolyte but filled with water, give, in the proximity of
the electrolyte, a minor contribution to the ion conductivity. In Fig.
7, the resistance of the capacitor with 50% Nafion is lower than
those of all other samples at lower frequencies 10 mHz, while an
opposite trend is observed at higher frequencies see inset in Fig. 2.
These observations could explain the small differences in capacitance in the range from 90 to 110 F/g shown by capacitors with
different Nafion content, whereas in the literature larger changes in
specific capacitance occurred by using increasingly nonconductive
polymer binders in the electrodes. Accordingly, Osaka23 showed that
in the range 10-50 wt % polyvinylidene fluoride gel electrolyte, the
capacitance of electrodes may vary up to 80%. Similarly, Richner24
found that by increasing the carboxymethyl cellulose binder in electrodes from 5 to 15 wt %, a decrease in capacitance of about 30%
was observed. In this study, with Nafion loading varying from 10 to
50%, a more restricted variation of specific capacitance is obtained;
accordingly, the polymer electrolyte appears to have a beneficial
effect on the performance of the supercapacitor.
The highest attained performance is about 110 F/g active carbon
material for electrode for 1150 m2/g surface area carbon. This value
is not far from that obtainable with capacitors based on a liquid
electrolyte.
Many studies1,25,26 have shown that the carbon microporosity
hinders the achievement of high specific capacitance due to the difficulty of penetration of the electrolyte into the smaller pores. For an
organic electrolyte, for which the size of ions is much larger than
those in aqueous electrolytes, only access to meso- and macropores
may occur. For Nafion, the formation of self-aggregates of micelles
with large size27 and the hydrophobic nature of their surfaces28,29
further hinder the accessibility. Nafion is very likely covering only
the macropores and the external surface of the carbon. Nevertheless,
because the capacitance of Nafion-based supercapacitors is comparable to that obtainable with aqueous electrolytes, one can envisage
that the polymer electrolyte extends its ionic conductive effect into
the small pores of carbon through the surrounding water. In practice,
the water could behave as a proton carrier between the bulk electrolyte and the internal surface of carbon pores. Further studies are
necessary to better understand the high rate of proton diffusion and
the ion conduction mechanism occurring in the pores of carbon,
which are not in direct contact with the solid electrolyte.
Finally, to verify the reliability and the electrochemical stability
of these supercapacitors, a life cycling test was carried out in CV
mode at a scan rate of 40 mVs1 on the capacitor NS30N. It gave
a very stable performance for more than 20,000 cycles. Three representative curves, recorded during the 100th, 10,000th, and

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Journal of The Electrochemical Society, 151 1 A64-A68 2004

as demonstrated by the life cycling test for a 30% Nafion capacitor.
The life cycling test carried out for more than 20,000 cycles CV
mode at 40 mVs1 demonstrated stable capacitance performance.
A 3% maximum variation in specific capacitance values was registered during the whole period of the cycling test.

Acknowledgments
The authors acknowledge Professor P. Antonucci University of
Reggio Calabria for helpful discussions and comments, Dr. A. S.
Arico` of Consiglio Nazionale delle Ricerche CNR-ITAE-Istituto di
Technologia Avanzate per lEnergia, for his help in impedance measurements, and CNR for financial support.
CNR-ITAE, Istituto di Technologie Avanzate per lEnergia Nicola Giordano assisted in meeting the publication costs of this article.

References
Figure 8. Representative CV curves recorded during life cycling test on
supercapacitor with 30% Nafion loading in the electrodes NSN30. Voltage
sweep rate: 40 mVs1.

20,000th cycle, are shown in Fig. 8. During the life cycling test,
periodic integration measurements were carried out on the discharge
process to evaluate the performance stability. A maximum variation
of 3% of the specific capacitance values was evaluated by comparing numerous measurements. These results demonstrate that supercapacitors that use the carbon-Nafion composite in the active layer
of the electrodes exhibit advantages such as high specific capacitance as well as excellent mechanical and electrochemical stability.
Conclusions
Electrodes based on carbon and Nafion have been prepared by
the spraying technique. This procedure allows one to obtain electrodes with a uniform and homogeneous distribution of carbon/
Nafion layer and excellent mechanical characteristics. Electrodes
with 10, 20, 30, and 50 wt % Nafion loading in the carbon layer
have been assembled with Nafion 115 membranes and tested in a
supercapacitor configuration. CV measurements have proved that
the amount of Nafion content, in the range from 10 to 30%, has little
influence on specific capacitance; however, the capacitor with 50%
Nafion in the electrodes exhibits lower capacitance performance due
to its higher internal resistance. EIS analysis has shown the highest
specific capacitance 110 F/g for the capacitor with 10% Nafion
loading; a lower performance is exhibited by the capacitor with 50%
Nafion 90 F/g. This is attributable to the high resistance and low
accessibility of the electrolyte into the carbon pores. However, only
20% of capacitance was lost despite an increase in resistance of
about 50% for this capacitor. These results demonstrate that a low
resistance favors the achievement of high specific capacitance. The
use of Nafion electrolyte also as a binder in carbon electrodes has
a beneficial effect, attaining high conductivity as well as high capacitance performance. As an interpretation of these results, one
supposes that the bound water surrounding the Nafion clusters acts
as a carrier for proton transport from bulk electrolyte to the smaller
carbon pores.
The interesting capacitance performance of supercapacitors is
also supported by excellent reliability and electrochemical stability,

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