Journal of Electroanalytical Chemistry 527 (2002) 65
/70

www.elsevier.com/locate/jelechem

Cathodic oxygen reduction at the interface between Nafion and

electrochemically oxidized glassy carbon surfaces
Jun Maruyama *, Ikuo Abe
Organic Chemistry Department, Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan
Received 26 October 2001; received in revised form 21 February 2002; accepted 4 March 2002

Abstract
The influence of interface structure between Nafion and an electrode surface on cathodic oxygen reduction has not been fully
clarified yet in spite of the need for improving the performance of polymer electrolyte fuel cells (PEFCs) by clarifying the influence.
In the present study, oxygen reduction was investigated at the interface between Nafion and a glassy carbon (GC) surface where
the ratio of the fluorinated region in Nafion contiguous with the GC surface was controlled by electrochemical oxidation of the
GC surface. Measurements of the oxygen reduction current were carried out using rotating GC disk electrodes and those covered
with Nafion , and the kinetic currents were determined for these electrodes. The surface oxidation resulted in an increase in the
oxygen reduction current both at bare GC and Nafion -coated GC; thus, the ratio of the kinetic current at the latter to that at the
former was used for evaluating the effect of change in the interface structure between Nafion and the GC surface. The net current
ratio that was calculated by dividing the kinetic current ratio by the ratio of the GC surface contiguous with the ionic cluster region,
where electrode reactions occur at the Nafion -coated electrodes, increased with a decrease in the blocking of the GC surface by the
fluorocarbon region; while excessive reduction of the region reduced the ratio. This result indicates the possibility of optimization of
the Nafion j electrode interface for O2 reduction by controlling the ratio of the electrode surface contiguous with the fluorocarbon
region. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: PEFC; Oxygen reduction; Nafion ; Glassy carbon; Surface oxidation; Rotating disk electrode

1. Introduction
Cathodic oxygen reduction has long been studied
particularly due to its involvement in energy conversion
processes. Recently, it has attracted considerable attention as the cathode reaction of polymer electrolyte fuel
cells (PEFCs), which are one of the most attractive
power sources of clean energy and are expected to be
used in electric vehicles, portable power generators, onsite cogeneration systems, and so on [1
/4]. The slow
reaction rate of O2 reduction at the PEFC-operation
temperature causes a large cell voltage loss of 0.4
/0.5 V
at a current density of 1 A cm 2 [5]. This problem has to
be overcome to realize the practical use and prevalence
of PEFCs.

* Corresponding author. Tel.: 81-6-6963-8041; fax: 81-6-69638049.

E-mail address: maruyama@omtri.city.osaka.jp (J. Maruyama).

The electrode reactions of the PEFC occur in the gasdiffusion electrode at the interface between the surface
of dispersed Pt particles and the polymer electrolyte
because it covers the Pt-supporting carbon catalyst
particles and forms pathways of proton conduction in
the gas-diffusion electrode, which leads to enlargement
of the three-phase zone [6
/9]. A number of reports have
appeared on the O2 reduction at the Pt j polymer
electrolyte interface to clarify the interfacial reaction
kinetics using smooth Pt electrodes [10
/13] or microelectrodes [14
/18] coated with perfluorosulfonate cation-exchange membranes such as Nafion . Gottesfeld
et al. [10], Lawson et al. [11], and Floriano et al. [12]
reported that the kinetic currents for O2 reduction at
Nafion -coated Pt electrodes are larger than those at
bare Pt in aqueous solutions. Such an enhancement
effect of the Nafion coating has been explained by the
fact that the solubility of oxygen in Nafion is higher
than in aqueous solutions, which is mainly due to the
presence of the hydrophobic fluorocarbon phase; it is

0022-0728/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 2 ) 0 0 8 2 7 - 6

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J. Maruyama, I. Abe / Journal of Electroanalytical Chemistry 527 (2002) 65
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generally recognized that Nafion has a microscopically

phase-separated structure that consists of hydrophilic
ionic clusters, a hydrophobic perfluorocarbon backbone, and an intermediate region [19
/22].
However, little is known about the detailed mechanism of the enhancement, and it is necessary to clarify the
mechanism in order to improve the PEFC performance.
Maruyama et al. [23] previously used a fluorinated
alcohol,
2,2,3,3,3-pentafluoro-1-propanol
(CF3CF2CH2OH), as a model of the fluorocarbon phase
of Nafion and studied the kinetics of O2 reduction at
Au in sulfuric acid containing the fluorinated additive.
They found that the kinetic current for O2 reduction
increases with an increase in the concentration of
CF3CF2CH2OH up to 1 /102 M and then decreases
with further addition. The increase in kinetic current
was attributed to a higher concentration of O2 in the
adsorption layer of CF3CF2CH2OH, whereas the decrease at concentrations above 1 /102 M was explained by a decrease in the number of reaction sites on
the Au surface due to adsorption. They also found that
this enhancement effect was strongly affected by the
structure of the fluorinated alcohol; it was dependent on
the chain length of the fluorinated alcohol when it was a
linear molecule but was not observed in the case of a
branched fluorinated alcohol [24]. These results indicate
that not only the presence of the fluorocarbon phase but
also the interaction between Nafion or other perfluorosulfonate membranes and the electrode surface is
important to enhance the kinetics of oxygen reduction.
We have recently revealed that the ratio of the
electrode surface contiguous with the fluorocarbon
phase could be controlled by adjusting the hydrophilicity of the electrode surface using a Nafion -coated
glassy carbon (GC) electrode [25]. Electrochemical
oxidation was applied to impart hydrophilicity to the
GC surface and an increase in the surface-oxidation
time reduced the ratio due to weakening of the interaction between the hydrophobic fluorocarbon phase and
the GC surface. Using this technique, in the present
study, we investigated O2 reduction at the interface
between Nafion and the GC surface by controlling the
ratio of the fluorocarbon phase. We found that the net
ratio of kinetic current for O2 reduction at Nafion coated GC to that at bare GC increased with a decrease
in the blocking of the GC surface by the fluorocarbon
region; while excessive reduction of the region reduced
the current ratio, similarly to the previous results
obtained using a fluorinated alcohol as a model of the
fluorocarbon phase [23,24]. Although, O2 reduction in
the PEFC practically occurs on nano-dispersed Pt
particles deposited on the surface of carbon black
powders, the results obtained in the present study
provide fundamental information on the influence of
the interface structure on O2 reduction, which is

necessary for optimization of the polymer electrolyte j electrode interface.

2. Experimental
Detailed description of the electrochemical measurement system including reagents, a cell, and apparatus
was given in Ref. [25]. The GC electrode (BAS) was a
rotating disk electrode (RDE) which consisted of a GC
rod (Sigradur G, made from phenolic resin through
solid phase pyrolysis at 1100 8C followed by hightemperature treatment up to 2200 8C) sealed in a Kel-F
holder. The geometric surface area of the electrode was
0.071 cm 2 (3 mm in diameter). Its surface was polished
with a 0.05-mm alumina suspension on a polishing cloth
(Maruto Instrument) and then cleaned ultrasonically in
high-purity water. Electrochemical surface oxidation of
GC and subsequent Nafion -coating were carried out
in the same way as in Ref. [25]. The surface oxidation
was carried out by holding the GC electrode potential at
2.0 V versus a reversible hydrogen electrode (RHE) for
various lengths of time in 0.5 M H2SO4 at 25 8C. The
thickness of the Nafion film was 0.98 mm when wetted,
which was calculated from the mass of recast Nafion
solution, the surface area, and the hydrated Nafion
density (1.58 g cm 3) [26,27]. Here, the assumption was
made that the recast film swells essentially in the
direction perpendicular to the surface [10].
Cyclic voltammograms were recorded in 0.5 M H2SO4
at 25 8C for surface-oxidized GC electrodes and those
coated with Nafion to obtain the ratio of the ionic
cluster region to the total GC surface. The potential was
scanned between 0.05 and 1.4 V at a scan rate of 50 mV
s 1. Before recording, the potential was scanned
repeatedly in the same range to remove residual
impurities. The ratio of the GC surface contiguous
with the ionic cluster region to the total GC surface, uic,
was estimated using the following equation
uic 

Qf
Q

(1)

where Qf and Q are the charge calculated from the area

enclosed in the cyclic voltammograms for the surfaceoxidized GC with and without the Nafion film,
respectively [25]. The ratio of the GC surface contiguous
with the hydrophobic fluorocarbon region to the total
GC surface, ufc, was given by
ufc 1uic

(2)

Current
/potential relations were measured in O2 saturated 0.5 M H2SO4 at 25 8C for surface-oxidized
GC RDE and that coated with Nafion at several
rotation speeds. The scan rate of the disk potential was
fixed at 10 mV s 1. Prior to the each measurement, the

J. Maruyama, I. Abe / Journal of Electroanalytical Chemistry 527 (2002) 65
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electrode was polarized repeatedly at /0.5 and 1.4 V by

turns to remove impurities possibly adsorbed on the GC
surface through the preceding measurement [28]. The
potential was finally stepped to 0.5 V and then swept in
the negative direction from 0.5 to /0.5 V to obtain a
current
/potential relationship. All potentials were referred to RHE.

3. Results and discussion

3.1. Hydrodynamic voltammetry for O2 reduction at
surface-oxidized GC coated with Nafion
The structure of the interface between Nafion and
GC, at which O2 reduction occurred, was controlled by
electrochemical oxidation of the GC surface in the
present study. The influence of GC surface oxidation
on O2 reduction was initially investigated at a bare GC
and a Nafion -coated GC. Fig. 1 shows the current
/
potential (I
/E ) relations for O2 reduction at bare GC
surface-oxidized for several lengths of time. The sign of
the cathodic current was taken as negative. The O2
reduction current was increased with an increase in the
surface oxidation time, t. This result is in agreement
with previous studies carried out using alkaline solutions
[29,30]. Such an increase in the electrochemical activity
of carbon electrodes is usually attributed to the catalyst
effect of surface functional groups on the carbon
electrodes generated by surface oxidation [29]. This
elucidation, however, remains controversial, and the
reason for the increased activity has not been fully
clarified yet. Nevertheless, the influence of the surface
state of the carbon surface on O2 reduction has been
recognized to be important. Yang and McCreery [31]
recently studied O2 reduction on a GC surface blocked
by a covalently bonded methylphenyl monolayer or
cleaned with isopropanol and activated carbon and

Fig. 1. Hydrodynamic voltammograms of negative scans for O2

reduction at bare GC RDE in O2-saturated 0.5 M H2SO4. GC surface
oxidation time: 0 min (dotted line); 1 min (thin line); 5 min (thick line);
20 min (very thick line). Scan rate: 10 mV s 1. Rotation speed: 2000
rpm.

67

suggested that an increase in the adsorption sites for

+
O 2  species caused the enhancement of O2 reduction.
The increase in the activity for O2 reduction on the
surface-oxidized GC might also be explained by the
increase in the specific surface area of GC. The surface
oxidation of GC might generate a porous carbon film on
the GC surface [32
/34], leading to the increase in the
specific surface area. Sullivan et al. [32] carried out
surface oxidation of GC at the electrode potential of
1.95 V versus SCE in 3 M H2SO4 and showed that the
thickness of the porous carbon film increased linearly
with oxidation time. However, as we discussed in the
preceding paper [25], the film was hardly porous,
because the surface oxidation was carried out under
relatively mild conditions (the electrode potential, 2.0 V
versus RHE; t, 20 min at most) in the present study and
the GC underwent heat-treatment at 2200 8C in its
production process, which makes GC less susceptible to
formation of a thick porous film than GC pyrolyzed
only at 1100 8C [32]. The increase in the activity of the
surface-oxidized GC, therefore, is mainly attributed to
the change in the surface state.
Current
/potential relations for O2 reduction at surface-oxidized GC coated with Nafion are shown in
Fig. 2. The O2 reduction current was increased with an
increase in the surface oxidation time similarly to that at
GC without Nafion , indicating that enhancement of
O2 reduction also occurred after the Nafion -coating.
The current at Nafion -coated GC was, however,
smaller than that at bare GC when the surface oxidation
times were the same at the two electrodes.
3.2. Determination of kinetic current and number of
electrons involved in O2 reduction
Because the decrease mentioned above included the
influence of O2 diffusion in the Nafion film on the GC
surface, the kinetic current, IK, was determined accord-

Fig. 2. Hydrodynamic voltammograms of negative scans for O2

reduction at Nafion -coated GC RDE in O2-saturated 0.5 M
H2SO4. GC surface oxidation time: 0 min (dotted line); 1 min (thin
line); 5 min (thick line); 20 min (very thick line). Scan rate: 10 mV s 1.
Rotation speed: 2000 rpm.

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J. Maruyama, I. Abe / Journal of Electroanalytical Chemistry 527 (2002) 65
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ing to Eq. (3) to examine the influence of the

Nafion j GC interface structure on O2 reduction without the effect of mass transport [11].
1
1
1
df
  

1=6
1=2
I
IK 0:620 nFADcn
v
nFADf cf

(3)

where n is the number of electrons involved in the

reaction, F is the Faraday constant (96485 C mol 1), A
is the geometric surface area of the electrode (0.071
cm 2), n is the kinematic viscosity of the solution, v is
the angular frequency of rotation, df is the thickness of
the Nafion film, D and Df are the diffusion coefficient
of O2 in solution and in the Nafion film, respectively, c
and cf are the equilibrium concentration of O2 in
solution and in the Nafion , respectively. Fig. 3 shows
1/I versus v 1/2 plots (Koutecky
/Levich plots) for O2
reduction at GC surface-oxidized for 5 min and coated
with Nafion . IK was calculated in two steps. The first
step was calculating n from the slope of the 1/I versus
v 1/2 plot at each electrode potential using the values:
D , 1.7 /105 cm2 s 1 [12]; c, 1.1 /10 6 mol cm 3
[12]; n, 9.87 /103 cm2 s 1 [35]. The second step was
obtaining 1/IK from the intercept of the 1/I versus v 1/2
plot by subtracting df/nFADfcf calculated using the
values: Df, 0.3 /10 5 cm2 s1 [12]; cf, 3.2 /10 6 mol
cm 3 [12]; df, 0.98 mm.
Tafel plots of the kinetic current per unit geometric
surface area, /IKA 1, obtained for GC surfaceoxidized for 0, 1, 5, and 20 min and at those covered
with Nafion are shown in Figs. 4 and 5, respectively.
The kinetic current above 0.0 V was not precisely
obtainable at Nafion -coated GC because the O2
reduction current was so small in this potential range
that it was susceptible to the influence of error. The
kinetic current increased with an increase in t both at
bare GC and at Nafion -coated GC. At each t, log(/
IKA 1) linearly increased with a decrease in E above /
0.2 V, while its increase was suppressed below that
potential. This suppression was also observed for O2

Fig. 3. Koutecky
/Levich plots at various disk potentials for O2

reduction at Nafion -coated GC electrode (GC surface oxidation
time: 5 min) under an O2 atmosphere in 0.5 M H2SO4.

Fig. 4. Tafel plots of kinetic current per unit geometric surface area at
bare GCs. GC surface-oxidation time: 0 (k), 1 (m), 5 (I), and 20 min
(m).

Fig. 5. Tafel plots of kinetic current per unit geometric surface area at
Nafion -coated GCs. GC surface-oxidation time: 0 (k), 1 (m), 5 (I),
and 20 min (m).

reduction at an Au electrode [36] and is probably

attributed to surface blocking by intermediates generated during O2 reduction, which were indicated in Ref.
[31]. Tafel slopes for bare GC showed a nearly constant
value of /0.15 V per decade, which was in agreement
with the value observed for O2 reduction at pyrographite electrodes in acidic solutions [37]. It has been
reported using Pt and Au electrodes that the O2
reduction mechanism at Nafion -coated electrodes is
the same as that at bare electrodes [10
/12,36]. Accordingly, it was assumed that the mechanism at Nafion coated GC was also the same as that at bare GC and
that the linear region in the Tafel plots appeared above
/0.2 V for Nafion -coated GC, as appeared in Fig. 4.
Fig. 5 shows the linear region and similar Tafel slopes to
that at bare GC, suggesting the validity of the assumption. In the present study, however, the shortness of the
linear region of the plots prevented precise determination of the value of the Tafel slopes.
The kinetic current at Nafion -coated GC was
smaller than that at bare GC at the same t. This result
was entirely different from those observed for O2
reduction at Nafion -coated Pt and at Nafion -coated
Au; it is enhanced at the former [10
/12] and nearly

J. Maruyama, I. Abe / Journal of Electroanalytical Chemistry 527 (2002) 65
/70

unchanged at the latter [36], as compared to the bare

electrodes. One possible reason for the diminution
observed at Nafion -coated GC is the effect of pH.
The activity for O2 reduction at the carbon electrode
decreases as the pH decreases according to the results
reported by Tarasevich et al. [38]. Nafion is a superacid and the H  concentration in Nafion is higher
than that in 0.5 M H2SO4 [11]; hence, the activity of
Nafion -coated GC may be lower than that of bare GC.
Another possible reason is the blocking of the GC
surface by the side chains of the Nafion polymer in the
ionic cluster region. As mentioned above, Maruyama et
al. reported that the blocking of the Au electrode surface
by fluorinated alcohols led to a decrease in the O2
reduction current [23,24]. The fluorocarbon part of the
side chains probably interacts with the carbon surface
due to its hydrophobic character, leading to a decrease
in the O2 reduction current similarly to the fluorinated
alcohols adsorbed on Au electrodes, although the
adsorption state of the side chains is not clear.
3.3. Influence of the ratio of the fluorocarbon region to
the total GC surface on O2 reduction
The surface oxidation of GC had two effects simultaneously: increasing uic as well as the O2 reduction
current; hence, the influence of Nafion on O2 reduction at GC was evaluated using a normalized value
calculated by dividing IK at Nafion -coated GC by IK
at GC surface-oxidized for the same length of time, and
plotting it, IK(Nafion)/IK(bare), as a function of uic, as
shown in Fig. 6. IK(Nafion)/IK(bare) increased with an
increase in uic. A steep rise around uic /0.75 was
probably due to an abrupt change in the interface
structure between Nafion and the GC surface without
the influence on uic; the side chains of Nafion polymer
in the ionic cluster region might desorbed from the GC
surface. The interaction between their fluorocarbon part
and the GC surface might be weakened by the increasing
hydrophilic character of the GC surface and uic hardly

Fig. 6. Relationship between the ratio of kinetic current for O2

reduction (E 0.10 V vs. RHE) at Nafion -coated GC electrodes
to that at bare GC electrodes and the ratio of the GC surface
contiguous with the ionic cluster region.

69

influenced by the adsorption of the side chains, from the

analogy to the CV results for adsorption of fluorinated
alcohols on Au [23,24].
It should be noted here that O2 reduction occurs only
at the GC surface contiguous with the ionic cluster
region. [I K (Nafion)=I K (bare)]u1
ic ; therefore, permits
correct evaluation of the influence of uic or ufc on O2
reduction, in contrast to IK(Nafion)/IK(bare), which
reflects the O2 reduction current per unit surface area
of the total GC surface including both the ionic cluster
region and the fluorocarbon region, resulting in underestimation of the current at Nafion -coated GC. Fig. 7
shows the [I K (Nafion)=I K (bare)]u1
ic versus ufc plot. ufc
was used here instead of uic for correlating Fig. 7 with
the relationship between IK and the concentration of
fluorinated
alcohol
in
Ref.
[23].
[I K (Nafion)=I K (bare)]u1
increased slightly with an
ic
increase in ufc up to 0.24 and then decreased. This
behavior resembles the dependence of IK on concentration
of
CF3CF2CH2OH.
The
decrease
in
[I K (Nafion)=I K (bare)]u1
occurred
at
relatively
small
ic
ufc, corresponding to the beginning of the decrease in IK
at relatively low concentration of CF3CF2CH2OH.
However, the reasons for the increases in the two cases
are somewhat different because only the region where
O2 reduction occurs is taken into account in Fig. 7.
Gottesfeld et al. [10] suggested, on the basis of their
study on O2 reduction at Nafion -coated Pt, that
enhanced O2 reduction currents are possible only at a
limited number of Pt sites that are immediately adjacent
to a surface region covered with the O2-rich hydrophobic fluorocarbon phase. The result shown in Fig. 7
accordingly indicates that the number of the sites
producing higher current than other sites on the GC
surface contiguous with the ionic cluster region depends
on ufc and the maximum value is obtained at around
ufc /0.24.

Fig. 7. Relationship between the uic-divided ratio of kinetic current for

O2 reduction (E  0.10 V vs. RHE) at Nafion -coated GC electrodes to that at bare GC electrodes and the ratio of the GC surface
contiguous with the fluorocarbon region.

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J. Maruyama, I. Abe / Journal of Electroanalytical Chemistry 527 (2002) 65
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4. Conclusions
RDE measurements were carried out for cathodic O2
reduction at surface-oxidized GC electrodes and those
coated with Nafion where the ratio of the GC surface
contiguous with the ionic cluster region was changed.
The kinetic current for O2 reduction increased with an
increase in surface-oxidation time both at bare GC and
at Nafion -coated GC; while the latter needed a longer
surface-oxidation time than the former to show the same
current. There are two possible reasons for the fact that
the current was smaller at Nafion -coated GC than at
bare GC. One is the higher pH environment for O2
reduction at Nafion -coated GC because the activity
for O2 reduction at the carbon electrode decreases as the
pH decreases. The other is the blocking of the GC
surface by the side chains of the Nafion polymer in the
ionic cluster region, caused by the interaction between
the fluorocarbon part of the side chains and the GC
surface having a hydrophobic character.
The ratio of the kinetic current at Nafion -coated
GC to that at bare GC showed the dependence of O2
reduction on the ratio of the GC surface contiguous
with the fluorocarbon region of Nafion to the total
GC surface. When the current ratio was divided by the
ratio of the ionic cluster region to derive the net current
ratio, it increased slightly with an increase in the ratio of
the fluorocarbon region up to 0.24 and decreased with a
further increase in the ratio. This increase is attributed
to the presence and the change in the number of active
sites for O2 reduction that lie immediately adjacent to
the fluorocarbon region and benefit from the high O2
concentration in the region. The decrease could be
explained by the adsorption of the side chains of
Nafion polymer in the ionic cluster region, which
was due to the increasing hydrophobicity of the GC
surface. This result indicates the possibility of optimization of the Nafion j electrode interface for O2 reduction by controlling the ratio of the electrode surface
contiguous with the fluorocarbon region.

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