Electrochimica Acta 49 (2004) 2123–2129

Impedance of vapor feed direct methanol fuel cells—polarization

dependence of elementary processes at the anode
Hiroshi Fukunaga∗ , Tomohiro Ishida, Nozomu Teranishi, Chikao Arai, Koichi Yamada
Department of Fine Materials Engineering, Faculty of Textile Science and Technology, Shinshu University, 3-15-1 Tokida, Ueda, Nagano 386-8567, Japan

Received 18 November 2003; received in revised form 15 December 2003; accepted 17 December 2003

Abstract

Membrane electrode assemblies of direct methanol fuel cells (DMFCs) with different catalyst and ionomer loading were prepared. Anode
performance and impedance spectra were measured to clarify the characteristics of vapor feed DMFCs (VF-DMFCs). The impedance spectra
were deconvolved into three semi-circles with different time constants, each showing a different dependence on the anodic polarization. The
middle-frequency range arc decreased as the anodic polarization increased, indicating that this process represents the oxidation reaction of
methanol. The high-frequency range arc showed little dependence on the anodic polarization, but increased with the thickness of the electrode,
indicating that this process might be related to proton conduction through the electrode. The low-frequency range arc was observed only when
the methanol concentration was low, in contrast to liquid feed DMFCs (LF-DMFCs), for which the removal of the product gas presents a
large resistance. A simpler design can therefore be used for a VF-DMFC, giving it an advantage over an LF-DMFC. A decreasing ionomer
to catalyst ratio (I/C) caused the interfacial conductivity (σ E ) to increase, but it intensively decreased when I/C was below 0.25. Thus, the
connection of the catalysts is important for the anode’s performance.
© 2004 Elsevier Ltd. All rights reserved.

Keywords: Direct methanol fuel cell; Vapor feed; ac impedance spectroscopy; Rate-determining step; Interfacial conductivity

1. Introduction needs to be further analyzed to clarify the details. It has also

Direct methanol fuel cells (DMFCs) have recently be-
come the focus of much interest. A DMFC has a simple
structure, and is capable of feeding methanol directly to
the reactor without using a reformer. Therefore, the system
is compact and is suitable for portable and mobile power
generation. DMFCs have been studied by many researchers,
and generation performance has improved every year [1,2].
However, the relationship between operating conditions and
the performance of a DMFC has not been clarified. One
of the conditions that is still generating much debate is the
method to feed methanol, i.e. whether it should be fed as
a vapor or liquid. Each method has its merits and demerits.
It is reported that a vapor feed DMFC (VF-DMFC) has
higher activity than a liquid feed DMFC (LF-DMFC), and
that higher concentrations of methanol solutions can be
used as fuel when fed by vapor [3,4]. However, this point
∗ Corresponding author. Tel.: +81-268-21-5464;
fax: +81-268-25-9548.
E-mail address: fuku@giptc.shinshu-u.ac.jp (H. Fukunaga).
been reported that CO2 production and diffusion hinders
the performance of an LF-DMFC [5]; thus it is likely that
a VF-DMFC has advantages in its mass transfer process.
To clarify the advantages of VF-DMFCs, which ele-
mentary process dominates the electrode reaction needs
to be evaluated. In this paper, we sought to elucidate the
reaction mechanism of VF-DMFCs by utilizing impedance
spectroscopy.
Several studies have reported electrode reactions of LF-
and VF-DMFCs [6]. Oxidation of methanol on the electrode
has been studied [7], but the electrode reaction consists of
many elementary processes, such as gas diffusion, adsorp-
tion and desorption, electron transfer and ion diffusion.
Impedance measurements of a DMFC have been reported
[8–13], since it can separate various elementary steps with
different time constants. In this paper, we prepared a DMFC
with different catalyst loadings, and performed impedance
measurements of a VF-DMFCs under various operating
conditions. The impedance spectra were deconvolved into
several arcs, and the elementary processes for each arc were
elucidated.

0013-4686/$ – see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2003.12.037
2124 H. Fukunaga et al. / Electrochimica Acta 49 (2004) 2123–2129

2. Experimental

A membrane electrode assembly (MEA) was prepared

using a colloid method [14] as follows. Carbon-supported
catalyst, 54% Pt-Ru/C (TEC61E54, Tanaka Kikinzoku Ko-
gyo K.K.), was used for the anode and Pt/C was used for the
cathode. The catalyst and the butyl acetate were weighed
into a glass beaker in a ratio of 1:30. The solution was kept
in an ultrasonic treatment bath while Nafion solution was
added. The mixture immediately became colloidal. The
mixture was painted on the carbon paper with a brush and it Fig. 2. Schematic diagram of the fuel cell system.
was dried at room temperature until a constant weight was
attained. The weight of the catalyst painted on the carbon Table 1
paper was calculated from the measured weight. Additional Conditions of the experiment, and flow rate and partial pressure of each
Nafion solution was painted on the carbon paper so that the fluid
electrolyte membrane and the electrode would attach easily. Condition Flow rate (cm3 /min) Partial pressure (atm)
The painted carbon paper was then cut to 2 mm × 10 mm CH3 OH H2 O Ar CH3 OH H2 O Ar
and positioned on the electrolyte membrane as shown in (liquid) (liquid) (gas)
Fig. 1. Electrodes with the same dimension as the working ×1 1.0 × 10−3 2.7 × 10−2 40 0.008 0.47 0.52
electrode were positioned on both sides of the electrolyte as ×5 5.0 × 10−3 2.7 × 10−2 38 0.039 0.47 0.49
tentative reference electrodes. The four electrodes were hot ×10 1.0 × 10−2 2.7 × 10−2 34 0.079 0.48 0.44
pressed to the membrane at a temperature of 130 ◦ C under a ×20 2.0 × 10−2 2.7 × 10−2 28 0.16 0.48 0.36
pressure of 30 MPa. Two types of MEA with different anode
catalyst loadings were prepared. The anode catalyst load-
ings were 3.0 mg/cm2 (MEA3) and 7.4 mg/cm2 (MEA7), ing temperature of 80 ◦ C, which was 0.47 atm. As shown in
while the cathode catalyst loading of both MEAs was Table 1, condition ×1 being the standard condition, the par-
5.7 mg/cm2 . tial pressures of methanol were 5, 10, and 20 times higher
The cell was set in an apparatus as described in Fig. 1, in the conditions of ×5, ×10, and ×20, respectively. For
and was located in a thermostatic oven for power genera- the cathode side, water was pumped into the vaporizer us-
tion. Methanol and water were mixed in a flask for fuel, ing oxygen as the carrier gas. The flow rate of the liquid
which was supplied to the reactor in vapor phase by pump- water was 2.6 × 10−2 cm3 /min and that of gaseous O2 was
ing the mixture into a vaporizer which was purged by Ar 40 cm3 /min, which made the partial pressures of vapor and
gas as shown in Fig. 2. The gas flow rate was adjusted by a O2 0.47 and 0.53 atm, respectively. The tubing from the va-
mass flow controller. The temperature of the vaporizer was porizer to the oven was heated by a ribbon heater to prevent
held constant at 150 ◦ C. The conditions of the experiment condensation.
are shown in Table 1 as ×1, ×5, ×10, and ×20. The flow Pt mesh was used as the current collector. Two Au wires
rates of the Ar gas were adjusted so that the total flow rate of were attached to both the cathode and anode for current and
the gas for all experiments would be nearly constant when voltage measurements, and one wire was attached to each
the liquid was vaporized. The flow rate of the water was reference electrode. Current density versus terminal voltage
determined so that the partial pressure of water would be was measured using a potentiostat (HZ-3000; Hokuto Denko
nearly equal to the saturated partial pressure at an operat- or 2000, Toho Giken). Anodic and cathodic polarization

Fig. 1. Schematic view of the reactor and the size of MEA.

 H. Fukunaga et al. / Electrochimica Acta 49 (2004) 2123–2129
(voltage between the working and the reference electrodes
on each side) was also measured. ac impedance was mea-
sured with a potentiostat and an impedance analyzer (5080;
NF Electronic Instruments), and was carried out with bias
dc voltage (0–280 mV) applied between the working and
the reference electrodes on the anode side. The cathode was
used as the counter-electrode.
3. Results and discussions
3.1. Voltage versus current density
Fig. 3 shows the voltage versus current density for MEA7
at 80 ◦ C operating under the conditions of ×20 as shown
in Table 1. The voltage between the working and reference
electrodes on both cathode and anode side, and the volt-
age between the reference electrode on the cathode side and
the reference electrode on the anode side, are also shown in
the figure. These voltages are the polarization voltages and
include ohmic losses. The open-circuit voltage (OCV) un-
der the conditions of ×20 was 540 mV, which was not as
high as expected, and was lower than the OCV under the
conditions of ×1, which was 580 mV. In general, when the
methanol concentration is high, methanol crossover occurs,
i.e. the methanol crosses over from the anode side of the
cell to the cathode side, which reduces the OCV. Theoreti-
cally, the chemical potential of methanol in the vapor phase
is lower than in liquid if the partial pressure of methanol is
lower than the saturated vapor pressure. Thus, for the same
methanol concentration, the difference in chemical potential
between the methanol on each side of the electrolyte should
be smaller in a VF-DMFC than in an LF-DMFC, and the
methanol crossover should decrease. However, in this exper-
iment the electrode area was relatively small (two electrodes
of 2 mm × 10 mm) compared to the area of the electrolyte
exposed to the fuel (6 mm×10 mm). For this reason, the per-
600
500
400
V / mV
300
200
100
0
0 100 200 300 400 500 600
j / mAcm -2
Fig. 3. Terminal voltage vs. current density of MEA7 under condition
of ×20. Cathode working vs. anode working (䉱), cathode reference vs.
anode reference (䊉), anode working vs. anode reference (䊏), cathode
reference vs. cathode working (䉬).
2125
400
300
V / mV
200
100
0
0 100 200 300 400 500
j / mAcm -2
Fig. 4. Polarization profile of MEA7 ((䉬) ×1, (䊏) ×5, (䉱) ×10, (䊉)
×20) and MEA3 ((䊐) ×5, () ×10, (䊊) ×20).
meation of methanol through the polymer electrolyte, apart
from the reaction zone, was high, resulting in a relatively
low OCV. However, the slope of the I–V curve was similar,
or even smaller compared to those in other papers, which in-
dicated that the electrode performance was sufficiently high.
The voltage between the two reference electrodes was
approximately equal to the value of the sum of the termi-
nal voltage and the polarization voltages of the anode and
cathode. As can be seen in Fig. 3, the voltage between
the reference electrodes was nearly constant throughout
the experiment, and the dispersion was acceptably small
(±10 mV) compared to the polarization. Thus, each elec-
trode can be used as a tentative reference electrode.
3.2. Influence of the amount of catalyst on
electrode performance
Polarization profiles of the anodes of MEA7 and MEA3
are shown in Fig. 4. It can be seen that the performance of the
electrode depends on the amount of catalyst, the electrode
with the larger amount of catalyst showing higher perfor-
mance. For both MEAs, when the methanol concentration
is lower than the conditions of ×10, the performance of the
electrode increases as the methanol concentration increases.
However, for conditions of ×20, the performance of MEA7
increases whereas the performance of MEA3 decreases. The
limiting current of MEA7 is approximately proportional to
the methanol concentration. These results revealed that when
there is enough catalyst, the rate-determining step (RDS) of
the electrode reaction is the diffusion of methanol to the sur-
face of the electrode. However, when the amount of catalyst
is insufficient, another reaction step (it is not clear in this
study) becomes the RDS.
3.3. Impedance spectra
The impedance spectrum of the anode of each MEA was
measured at various anodic polarizations by using a poten-
tiostat to control the voltage between the working and the
2126 H. Fukunaga et al. / Electrochimica Acta 49 (2004) 2123–2129
0.7
0.5
0.3
-Im Z / Ω cm 2
0.1
-0.1
-0.3
-0.5
-0.7
0 0.2 0.4 0.6 0.8
Re Z / Ω cm2
Fig. 5. ac impedance spectra (real and imaginary parts of impedance Z)
of MEA7 operating at 290 mV under conditions of (䊐) ×5, () ×10
and (䊊) ×20. HFR arc is the sum of the two arcs in dotted line.
reference electrodes on the anode side by a potentiostat. The
impedance spectra of MEA7 at 290 mV under conditions
of ×5, ×10, and ×20 are shown in Fig. 5. Using an equiv-
alent circuit program, “EQUIVCRT.exe” [15], most of the
spectra were deconvolved into three semi-circles, each rep-
resenting a reaction step with a different time constant. The
equivalent circuit expressed with combinations of parallel
resistance and capacitance circuit elements closely repro-
duced the impedance characteristics. The frequency ranges
of each of the steps were 10−2 –102 Hz for a low-frequency
range (LFR), 101 –104 Hz for a medium-frequency range
(MFR), and 103 –105 Hz for a high-frequency range
(HFR).
As it can be seen in Fig. 5, a semi-circle, which was
not observed under the conditions of ×20, appeared under
conditions of ×5 and ×10 in the low-frequency range. This
semi-circle was not observed when the concentration of
the methanol solution was high or when the anodic polar-
ization was low. We thus considered that this step appears
when the methanol diffusion to the surface of the electrode
becomes the RDS, which supports the results shown in
Fig. 4.
It has been reported that CO2 bubbles, the reaction prod-
uct, increase the LFR semi-circle for an LF-DMFC [8]. On
the other hand, for a VF-DMFC, the LFR semi-circle only
appeared when there was a lack of fuel. For a VF-DMFC,
the CO2 diffusion process does not affect the electrode re-
action; thus, VF-DMFCs have an advantage regarding the
process for the removal of the reaction product.
Fig. 6 shows the impedance spectra of MEA3 and MEA7
when the anodic polarization was 160 mV under the condi-
tions of ×10. An LFR arc was not observed, or was negli-
gible, under these conditions. The largest arc observed was
in the MFR, the sizes of the MFR arcs being approximately
the same for MEA3 and MEA7 when the anodic polariza-
tion was lower than 160 mV.
The MFR arc was strongly influenced by the anodic polar-
ization, and decreased in size as the anodic polarization in-
0.6
0.4
-Im Z / Ω cm -2
0.2
0
-0.2
-0.4
0 0.2 0.4 0.6 0.8 1
1 1.2 1.4
Re Z / Ωcm-2
Fig. 6. Potential dependence of ac impedance spectra under condition
of ×10 at 160 mV for (䊊) MEA3 and (䊉) MEA7. The lines are the
calculated fitting arcs. HFR arcs are the sum of the two arcs in dotted
line.
creased. Also, the size of the MFR arc for MEA7 (which had
a larger amount of catalysts) was smaller than that of MEA3
when the anodic polarization was higher than 220 mV. These
correlations suggest that the MFR arc is related to the pro-
cess of the electrochemical oxidation reaction of methanol,
and not to the process of gas or proton diffusion. This re-
lationship is consistent with the relationship reported for
LF-DMFCs [8].
For the HFR, the size of the arc was not strongly af-
fected by the anodic polarization, i.e. the spectra overlapped
each other in the HFR regardless of the anodic polariza-
tion; indeed, the HFR arc was the sum of two arcs though
it was treated as one arc since its resistance was small com-
pared to other arcs. The HFR arc for MEA7, which had
a higher catalyst loading, was larger than that for MEA3.
Since the thickness of the electrode of MEA7 is larger,
the HFR process might be related to the proton conduction
process.
3.4. Electrode reaction mechanism
The interfacial conductivity (σ E ) was calculated as
1
σE = (1)
ARE
where RE is the interfacial resistance and A the electrode
area. The σ E of the process at HFR (σ H ), MFR (σ M ), and
LFR (σ L ) is plotted as a function of anodic polarization in
Fig. 7.
As mentioned above, σ L was not observed in VF-DMFCs
when the methanol concentration was high or when the
anodic polarization was low, appearing only when the
methanol concentration was below the ×10 condition
and the anodic polarization was over 220 mV. Further, it
decreased with increasing anodic polarization. σ M was
strongly influenced by the anodic polarization, such that
it intensively increased with increasing anodic polariza-
tion. This relationship indicates that this process is neither
 H. Fukunaga et al. / Electrochimica Acta 49 (2004) 2123–2129 2127

1 1.5

0 1

- Im Z / Ωcm 2
log (σ / S cm -2 )

0.5
-1

0
-2

-0.5
0 0.5 1 1.5 2
-3
0 100 200 300 ReZ / Ωcm 2
V / mV
Fig. 8. ac impedance spectra of anode under condition of ×10 at 160 mV
Fig. 7. Interfacial conductivity vs. anodic polarization (×5: () σ H , (䉱) for catalyst loading of (䊊) 0.25, (䊐) 1 and () 2.
σ M , ( ) σ L ; ×10: (䉫)σ H , (䉬) σ M , ( ) σ L ; ×20: (䊊) σ H , (䊉) σ M ).

an RDS, a simple structure would be an advantage for VF

related to the gas diffusion process nor the conduction of compared to LF.
proton, but rather is related to the electrochemical oxida-
tion reaction of methanol. The ratio of σ M in the total σ E
3.5. Effect of the ratio of catalyst and conductive polymer
increased, i.e. it was two orders of magnitude smaller than
on performance
the others at 0 mV, but was only two or three times smaller
at 290 mV. σ H was the largest σ E in the total process, and
The ionomer content in a catalyst layer might vary the
since σ H was much larger than σ M at 0 mV, the quantitative
DMFC anode performance [20]. In this study, the relation-
value is not as accurate as σ M . Qualitatively, it showed little
ship between the ionomer to catalyst ratio (I/C) and σ E was
dependence on anodic polarization, indicating a possibility
studied. Fig. 8 shows the impedance plot of the electrode
that this process is related to the ionic conduction in the
for different I/C values. The impedance spectra were decon-
electrode layer, but further analyses have yet to be com-
volved into two arcs by the equivalent circuit program. The
pleted. However, the change of the RDS in the electrode
HFR arc was calculated as the sum of the two smaller arcs.
reaction, with the change in anodic polarization, is clearly
σ E of HFR and MFR was calculated from the equivalent cir-
shown.
cuit, and was plotted against the I/C in Fig. 9. Both σ E de-
VF-DMFCs have advantages over LF-DMFCs for the fol-
creased steeply at I/C = 0.25. For an I/C higher than 0.5, σ H
lowing reasons. In an LF-DMFC, the production of CO2 af-
increased with decreasing I/C, whereas σ M showed a smaller
fects the performance [16], and hence the removal of CO2
dependence on I/C. This supports the assumption that the
from the flow channel and the diffusion layer needs to be
HFR process is related to ionic conduction in the electrode
considered [17–19]. Especially, when residual methanol is
layer. Fig. 10 shows the SEM images of the cross-sections of
recycled, bubbles are easily formed since the solution is
the MEA for I/C = 1 and 0.25. As it can be seen in the fig-
saturated with CO2 . Furthermore, when the temperature is
ure, connections of the catalyst particles were observed for
high and fuel utilization is also high, bubbles form easily
I/C = 1, whereas no binding was observed for I/C = 0.25.
even when the fuel is not recycled. The solubility of CO2 is
Thus it is likely that the catalyst was not in effective contact
6.1 × 10−4 at 25 ◦ C and 2.3 × 10−4 at 80 ◦ C; so using a 2 M
with the ionomer, and therefore some catalyst was not ac-
methanol solution as the fuel, the solution will be saturated
tive in I/C = 0.25, leading to the lower performance. Thus,
when the utilization ratio is above 98 and 37% at operating
temperatures of 25 and 80 ◦ C, respectively. At these condi-
tions, bubbles will form even when the cell is a continuous 10
stirred tank reactor. When the concentration is 0.5 M, the-
oretically, it is not saturated at a utilization ratio of 10%,
σ / Scm -2

but there still remains a possibility for it to be saturated lo-

cally. At a high current density, the RDS of an LF-DMFC
is the removal process of CO2 from the electrode surface.
Thus, design optimization of the structure is very important
for an LF-DMFC. On the other hand, this is not so much 1
of a problem in a VF-DMFC where as long as the concen-
tration is high enough, the methanol oxidation process will 0 0.5 1.0 1.5 2.0
be the RDS. Thus a simpler structure can be used. The oxi- I/C
dation process of methanol does not differ between LF and Fig. 9. Interfacial conductivity vs. ionomer/catalyst ratio: (䊊) σ H ; (䊉)
VF; however, since the removal of CO2 does not become σM.
2128 H. Fukunaga et al. / Electrochimica Acta 49 (2004) 2123–2129

Fig. 10. SEM image of the cross-section of MEA: (a) I/C = 1 and (b) I/C = 0.25.

the connection of the catalysts is important for the anode’s
performance.
4. Conclusion
DMFC anode with different catalyst and ionomer load-
ing was prepared. Anode performance and impedance
spectra were measured to clarify the characteristics of
VF-DMFCs. VF-DMFC was capable of operating with
high concentration methanol solution when the catalyst
loading was high. Impedance spectra were deconvolved
into three semi-circles with different time constants.
Each of them showed different dependence to the anodic
polarization.
MFR arc decreased as the anodic polarization increased,
indicating that this process represents the oxidation reac-
tion of methanol. HFR arc showed little dependence to the
anodic polarization, but increased with the thickness of the
electrode, indicating that this process might be related to
proton conduction through the electrode. LFR arc was ob-
served only when the methanol concentration was low, in
contrast to LF-DMFCs, for which the removal of the prod-
uct gas presents a large resistance. A simpler design can
therefore be used for a VF-DMFC, giving it an advantage
over an LF-DMFC.
A decreasing ionomer to catalyst ratio caused the σ E to
increase, but it intensively decreased when I/C was below
0.25. Thus, the connection of the catalysts is important for
the anode’s performance.
 H. Fukunaga et al. / Electrochimica Acta 49 (2004) 2123–2129
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific
Research on the priority area of DMFC (grant no. 13134101)
from The Ministry of Education, Science, Sports and Cul-
ture, Japan.
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