Electrochimica Acta 56 (2010) 600–606

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Effect of cathode catalyst layer thickness on methanol cross-over in a DMFC

Saif Matar, Hongtan Liu ∗
Clean Energy Research Institute, College of Engineering, University of Miami, Coral Gables, FL 33146, USA

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

Article history: The effects of cathode catalyst layer (CCL) thickness on the detrimental effect of methanol cross-over in a
Received 21 April 2010 direct methanol fuel cell (DMFC) under various operating conditions are studied. Three membrane elec-
Received in revised form 29 June 2010 trode assemblies (MEAs) with different CCL thicknesses but identical catalyst loading and identical anode
Accepted 2 September 2010
catalyst layer are used. The results show that, when a thicker CCL, approximately twice the thickness of
Available online 21 September 2010
the base case, is used, the fuel cell performance increases significantly. The increase in performance with
a thicker CCL is attributed to the oxidation of the methanol crossed-over in part of the catalyst layer and
Keywords:
leaving the rest of the catalyst layer free from methanol contamination, leading to mitigations of the
DMFC
Methanol cross-over
effects of mixed potentials. The results of electrochemical impedance spectroscopy (EIS) show that the
Cathode charge transfer resistance for the fuel cell with twice the thickness of CCL is 30% lower compared to that
Catalyst layer thickness for the base case, indicating that the active catalyst area available for oxygen reduction reaction (ORR) is
Impedance spectroscopy indeed greater. The results of the electrochemical active surface areas (ECA) show that without methanol
ECA contamination, the ECA of the thicker CCL is actually lower, indicating that the better performance and
the lower charge transfer resistance are not caused by a higher original ECA, but a higher active area for
ORR. A much thicker CCL, about 5 times of that for the base case, is also used and the cell performance
is also higher than that for the base case. The experimental results show that there exists an optimum
cathode catalyst layer thickness and the thickness of cathode catalyst layer has a significant effect on
DMFC performance.
© 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Direct methanol fuel cells (DMFCs) are an attractive potential
power source for mobile devices, thanks to their simple and com-
pact designs, quick refueling and low operating temperature. When
compared to a H2 PEM fuel cell, a DMFC does not require humid-
ification because the liquid methanol in the anode and the water
produced in the cathode are sufficient to keep the Nafion® mem-
brane well hydrated. Despite all these advantages, there are several
hurdles that prevent DMFCs from being competitive to existing
power sources, such as lithium-ion batteries. One of these hurdles is
the methanol cross-over from the anode to the cathode, which has
a serious detrimental effect on cell performances due to the adverse
effect caused by the formation of mixed potentials at the cath-
ode. Methanol cross-over also reduces the fuel efficiency of the cell
as the oxidation of the crossed-over methanol does not generate
any electrical power. Many efforts have been focused on methanol
cross-over and its effects. Narayanan et al. [1] reported that over
40% of methanol could be wasted due to cross-over through thin-
∗ Corresponding author at: Department of Mechanical and Aerospace Engineer-
ing, P.O. Box 248294, Coral Gables, FL 33124, USA. Tel.: +1 305 284 2019;
fax: +1 305 284 2580.
E-mail address: hliu@miami.edu (H. Liu).
ner Nafion® membranes. They also reported that the methanol
cross-over rate decreases with increasing current density due to an
increase in methanol consumption to sustain higher current densi-
ties. Besides, the methanol cross-over rate was found to increase
with the cell temperature. Dohle et al. [2] also found a similar
behavior and noticed that the electro-osmotic drag (EOS) coef-
ficient for the methanol/water mixture also increases with tem-
perature. Ren et al. [3] showed the importance of electro-osmotic
drag in methanol transport through the Nafion® membrane and
reported that EOS effects are significant even at low methanol con-
centrations. Ramya et al. [4] measured the methanol flux across the
Nafion® membrane using cyclic voltammetry and chronoamper-
ometry techniques and concluded that the methanol permeability
is dependent on methanol concentration and reported that the opti-
mum methanol concentration is between 1 and 2 M. Han and Liu [5]
conducted real time measurements of methanol cross-over using
a CO2 sensor placed at the exit of the cathode side. They observed
peaks in methanol cross-over rates when the cell voltage suddenly
changes and found that the greater the change in cell voltage is,
the greater is the peak in methanol cross-over. This phenomenon
was attributed to methanol permeation hysteresis. Liu and Wang
[6] developed a three-dimensional 2-phase model to investigate
methanol concentration, current and cross-over current distribu-
tions. They concluded that optimizing the flow field geometry can
lead to uniform current density distribution and better methanol

0013-4686/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.09.001
 S. Matar, H. Liu / Electrochimica Acta 56 (2010) 600–606
utilization at the anode and therefore reducing methanol cross-
over. Wang and Wang [7] employed a 2-phase, multi-component
model to investigate electrochemical kinetics and transport phe-
nomena including methanol cross-over in DMFCs. The results
showed that the main driving force for methanol cross-over is dif-
fusion at low and high current densities. However, at higher current
densities there is a significant contribution from electro-osmosis.
Ge and Liu [8] compared the cell performance with and without
methanol cross-over using their three-dimensional MDFC model.
The modeling results showed that the effect of methanol cross-
over is significant even at low methanol concentrations. Moreover,
they concluded that methanol cross-over is greatly affected by the
porosities of both the anode catalyst and diffusion layers. Electro-
chemical impedance spectroscopy (EIS) has proved to be valuable in
diagnosing the effects of methanol cross-over. Mueller and Urban
[9] proposed a method to separately extract anode and cathode
impedance spectra. Piela et al. [10] conducted a comprehensive
study of EIS diagnostics under various cell parameters and provided
interpretations for the impedance data. Since methanol cross-over
is recognized as a very serious problem in DMFC, many contri-
butions have been made to solve or mitigate the problem. One
focus area was developing alternative membranes that have lower
methanol permeabilities. Li et al. [11] prepared Sulfonated Poly
Ether Ether Ketone (SPEEK) membranes that have methanol per-
meability of one order of magnitude lower than that of Nafion®
115 and similar proton conductivity to Nafion® 115 at temperatures
above 80 ◦ C. Carretta et al. [12] casted Sulfonated Poly-Styrene (SPS)
membranes from sulfonic acid groups in the base polymer. When
compared to the Nafion® membranes, these membranes exhib-
ited comparable proton conductivity and 70% lower permeability
at the highest degree of sulfonation. Carter et al. [13] proposed
Polyphosphazene-based membranes for DMFC. These membranes
showed very low methanol cross-over rate: about 3 times lower
than that of Nafion® 117. Another path researchers took was to
improve the electro-oxidation process in the catalyst layer as well
as improve the structure of the catalyst layer and gas diffusion layer
(GDL). Abdel Rahim and Hassan [14] studied the electro-oxidation
of methanol on titanium and platinum modified titanium elec-
trodes (Pt/Ti). These electrodes manifested less poising effects and
faster methanol electro-oxidation rate when compared to pure Pt.
Carmo et al. [15] developed an alternative method for preparing
Pt/C and PtRu/C catalysts. This method involves impregnation of
the support material with the precursors in ethanol and reduc-
tion under a hydrogen atmosphere to create active materials for
methanol oxidation reaction. Liu et al. [16] compared the difference
in performance between coating the membrane or the GDL with
catalyst. They found that coating the GDL with catalyst instead of
the membrane increases the cell performance and can significantly
reduce methanol cross-over owning to the increase in thickness.
It is important to note that research efforts have been predom-
inantly focused on anode catalyst layer and the membrane, but
little effort has been directed at the cathode side. From experi-
mental results, Ge and Liu [17] found that when there is enough
oxygen supply to the cathode side, the adverse effect of methanol
cross-over is reduced. It is believed that when the methanol per-
meated to the cathode can be oxidized faster, more reaction sites
will be free for oxygen reduction reaction (ORR). Based on these
results, it is hypothesized here that the performance of a DMFC
may be improved if the thickness of the cathode catalyst layer is
increased to a certain value so that the crossed-over methanol can
be oxidized in part of the catalyst layer close to the membrane and
leave the rest part of the catalyst layer close to the GDL relatively
free of methanol. In another word, for a thicker cathode catalyst
layer, it can be divided into two sub-layers, one in contact with the
membrane and the other in contact with the GDL. In the first sub-
layer, significant methanol oxidation reaction (MOR) occurs and the
601
effects of mixed potential are significant; while in the second sub-
layer, its methanol concentration can be very low, if not zero, and
the effect of mixed potential is significantly reduced, thus ORR is
dominant. The overall effect could be a significantly higher cathode
potential, leading to a much better performance of the fuel cell.
2. Experimental system and methodology
2.1. Fuel cell testing system
The fuel cell testing system used in this study is a fuel cell test
station manufactured by Fuel Cell Technologies, Inc. The test station
controls the flow rate, temperature, pressure and humidity of the
air flowing in the cathode as well as the cell operating temperature.
The test station comes equipped with an HP6050 DC electronic load
that controls the load on the fuel cell and measures the potential
and current of the cell. Methanol is pumped to the anode side of the
fuel cell using a Gilson Minipuls 3 pump. A LabView based software
was used in the data acquisition system to control and measure
various parameters of the fuel cell. Moreover, the fuel cell test-
ing system is coupled with a potentiostat (VersaStat 3, Princeton
Applied Research, Inc) capable of data averaging during acquisition
to conduct AC impedance and cyclic voltammetry measurements.
Fig. 1 shows the schematic of the experimental system.
2.2. Fuel cell fixture and membrane electrode assembly (MEA)
The fuel cell fixture used was a 5 cm2 cell consists of two stain-
less steel end plates and two Poco graphite plates machined with
serpentine flow fields. Two gold plated copper plates were used as
current collectors. Two Teflon® gaskets were employed to ensure
uniform MEA/GDL compression and to prevent damage to the MEA.
Three custom-made MEAs were purchased from BCS Fuel Cells,
Inc. The specifications of the MEAs are shown in Table 1. The thick-
ness of 8.4 ␮m was the standard/base thickness for anode and
cathode catalyst layers. The anode catalyst loading and thickness
and the membrane used were identical for all three MEAs; only the
cathode catalyst layer thickness was varied under the same catalyst
loading by varying the wt.% of Pt/C. The platinum catalysts used for
all three catalyst layers are identical and thus have identical particle
sizes and distributions. In addition to the base thickness of 8.4 ␮m,
the thicknesses of the two additional cathode catalyst layers used
are 19 ␮m and 44 ␮m, i.e. about double and 5 times the thickness
of the base one.
The break-in procedure for all three MEAs was identical. First,
to activate the MEA, humidified nitrogen gas at 80 ◦ C and 750 sccm
was fed to both sides of the fuel cell for 6 h. Second, to activate the
catalyst layer, humidified hydrogen at 70 ◦ C and 300 sccm was fed
to the anode and oxygen at 70 ◦ C and 700 sccm was fed to the cath-
ode. Then the fuel cell was run under constant voltage of 0.6 V and
the current response was monitored. After a steady state current
was reached, the break-in process was considered to be completed.
In this paper, each polarization curve was obtained by averaging
three polarization curves obtained at identical operating condi-
tions. When obtaining the individual polarization curves, there was
a 240 s delay between each operating point.
2.3. Electrochemical measurements
The EIS investigation was carried out according to the method
described by Muller and Urban [9]. First, the full DMFC impedance
spectrum was measured with methanol in the anode and air in
the cathode. Second, the anode impedance spectrum was mea-
sured with hydrogen flowing in the cathode side and hence acting
as a dynamic hydrogen electrode. Hydrogen humidification tem-
perature was set to 90 ◦ C and the backpressure to 152 kPa to
602 S. Matar, H. Liu / Electrochimica Acta 56 (2010) 600–606

Fig. 1. Schematic of the experimental system.

Table 1
Characteristics of the MEAs used in this study.

Anode loading Cathode loading Membrane Anode catalyst layer Cathode catalyst layer Pt/C wt.%
(mgPtRu cm−2 ) (mgPt cm−2 ) thickness (␮m) thickness (␮m)

MEA 1 4.0 1.0 Nafion 117 8.4 8.4 66

MEA 2 4.0 1.0 Nafion 117 8.4 19 50
MEA 3 4.0 1.0 Nafion 117 8.4 44 40

ensure the reversibility of the cathode electrode. Finally, the cath- 3.1. Comparison of cell performances
ode impedance spectrum was obtained by subtracting the anode
impedance spectrum from that for the full DMFC. The impedance Polarization and power density curves of the three MEAs at
spectra were acquired at frequencies between 10 kHz and 0.1 Hz methanol concentration of 1 M are shown in Fig. 2. These results
with 10 points decade−1 under galvanostatic mode. The amplitude show that the cell performance increased significantly when the
of the input AC current was selected to be 5% of the fuel cell oper- cathode catalyst layer thickness was increased from the base thick-
ating DC current. ness of 8.4 to 19 ␮m and the maximum power density increased
Electrochemical active surface areas (ECA) of the cathode elec- from 44.9 mW cm−2 to 78.4 mW cm−2 . Such a drastic increase in
trode of the three MEAs were measured using cyclic voltammetry performance for 19 ␮m over 8.4 ␮m seems to indicate that the
at sweep rate of 5 mV s−1 with H2 flowing in the anode side as the hypothesis, that a thick cathode catalyst layer can leave part of
reference/counter electrode and N2 flowing in the cathode side as
the working electrode. Both gasses were fully humidified and the
cell temperature was set at 35 ◦ C. ECA (cm2 Pt mg−1 Pt ) values were 0.80 80
calculated using the following equation: 8.4 μm
0.70 19 μm 70
44 μm
Power Density / mW cm-2

QH 0.60 60
ECA = × 0.21 (1)
[Pt]
0.50 50
Voltage / V

where QH is the adsorption charge in mC cm−2 ,

[Pt] is the cata- 0.40 40
lyst loading in mgPt cm−2 and the constant 0.21 (mC cm−2 Pt ) is the
charge required to oxidize a monolayer of H2 on a smooth Pt surface. 0.30 30

0.20 20

3. Results and discussion 0.10 10

0.00 0
In all of the experiments, unless stated otherwise, methanol was 0 100 200 300 400 500
fed to the anode compartment at a rate of 6 ml min−1 at 1 M, 2 M and Current Density / mA cm-2
4 M concentrations, respectively. Air flow rate was set at 600 sccm
Fig. 2. Polarization and power density curves at different cathode catalyst layer
with no humidification and the fuel cell temperature was set at
thicknesses for 1 M methanol concentration. Conditions: 70 ◦ C; air flow rate
70 ◦ C. The operating pressure was atmospheric pressure. 600 sccm; methanol flow rate 6 ml min−1 .
 S. Matar, H. Liu / Electrochimica Acta 56 (2010) 600–606 603

-0.06
20 mA cm-2²
100 mA cm -2²
150 mA cm -2²
-0.04 Model
ZIM / Ω

-0.02

Fig. 4. Equivalent circuit model for DMFC cathode [18].

0
Table 2
Fitting values for 19 ␮m CCL thickness at different current densities and 1 M
methanol concentration.
0.02 Current density C1 (F) R1 () CPE Rct () Ro () Lo (H)
0 0.02 0.04 0.06 0.08 0.1
ZRE / Ω C (F) ˛

20 mA cm−2 0.057 0.0023 0.294 0.78 0.108 0.230 0.028

Fig. 3. Cathode impedance spectra for 19 ␮m CCL thickness at different current
100 mA cm−2 0.057 0.0022 0.294 0.79 0.081 0.204 0.016
densities. Conditions: 70 ◦ C; air flow rate 600 sccm; methanol concentration 1 M;
150 mA cm−2 0.057 0.0021 0.294 0.79 0.058 0.172 0.008
methanol flow rate 6 ml min−1 .

it relatively free from methanol contamination was reasonable.

Since the total catalyst loadings are identical on both the cath-
ode and anode and everything else are also identical except for
the cathode catalyst layer thickness, the drastic improvement can
only be attributed to the increased cathode catalyst layer thick-
ness as no other mechanisms can explain such a large increase in
performance. It is believed that for the base case, most, if not the
entire cathode catalyst layer was contaminated with the crossed-
over methanol and consequently the effects of mixed potentials
were severe; while with a thicker cathode catalyst layer, methanol
could be oxidized within the part of the catalyst layer adjacent to
the membrane and leave the rest of the catalyst layer free from
methanol contamination. Therefore, the mixed potential effect is
significantly reduced.
Experiments were also conducted with a much thicker cath-
ode catalyst layer, i.e. the CCL was further increased from 19 ␮m to
44 ␮m. Even with such an extremely thicker cathode catalyst layer,
the fuel cell performance is still better than that for the base case,
as shown in Fig. 2. The maximum power density is 63.5 mW cm−2 ,
compared with 44.9 mW cm−2 in the base case. As can be seen from
Fig. 2, with a 44 ␮m CCL, the cell performance lies between the
base case and the one with 19 ␮m CCL. Obviously, with a 44 ␮m
CCL, even though the crossed-over methanol can be oxidized in
part of the CCL and leave the rest relatively free from methanol
contamination, it is so thick that the mass transfer loss for oxygen
transfer and/or the ohmic loss due to the additional ionic and elec-
tronic paths in the thicker CCL are significant enough to cause a
decrease in cell performance. Comparing with the other two cases,
19 ␮m CCL is thick enough to significantly mitigate the effects of
mixed potentials, but it was not too thick to significantly increase
other losses due to a thicker CCL. Therefore, there exists an opti-
mum cathode catalyst layer thickness, with which the maximum
fuel cell performance can be attained.
fer resistance in the cathode backing. The inductive loop at the
lowest frequency is a result of slow response of CO coverage to
the changes in electrode potential.
The impedance spectra were fitted with the equivalent circuit
model proposed by Du et al. [18] shown in Fig. 4. A parallel com-
bination of a capacitor (C1 ) and a resistor (R1 ) was employed to
fit the high frequency straight line, the faradic branch is fitted by
a series combination of a resistor (Ro ) and an inductor (Lo ) con-
nected in parallel to a parallel combination of a resistor (Rct ) and a
constant phase element (CPE). The constant phase element is used
to account for the non-homogeneity in the surface of the electrode
and its impedance is defined by:
1
ZCPE = ˛ (2)
C(jω)
where C is the magnitude of the capacitance, ω is the angular fre-
quency and ˛ is a unit-less parameter that has a value between
−1 and 1. The cathode impedance spectrum does not show the
membrane resistance because it is canceled out in the subtraction
process of anode impedance from the full impedance.
The fitting values for the impedance spectra for the MEA with a
CCL thickness of 19 ␮m at different current densities are shown in
Table 2. It can be seen that the values of R1 , C1 , C and ˛ are indepen-
dent of current density and do not contribute to the electrochemical
process, as indicated in [18] and reported in [19].
-0.06
8.4 μm
19 μm
44 μm
Model
-0.04
ZIM / Ω

3.2. Electrochemical analyses -0.02

The EIS is a robust diagnostic tool that provides details to pos-

sible losses in a fuel cell. In this work, all reported impedance data
were collected under kinetic conditions to minimize the effect of 0
mass transfer limitations. The cathode impedance spectra for the
one with CCL thickness of 19 ␮m at different current densities are
shown in Fig. 3. The characteristics of a typical cathode Nyquist 0 0.02 0.04 0.06 0.08 0.1 0.12
impedance plot are as follows [10]: the high frequency straight line ZRE / Ω
is due to electrode porosity. The intermediate frequency distorted
Fig. 5. Cathode impedance spectra at different cathode catalyst layers thicknesses.
arc is due to electrode charging capacitance and charge transfer Conditions: 70 ◦ C; current density: 100 mA cm−2 ; air flow rate 600 sccm; methanol
resistance (Rct ). The low frequency portion is related to mass trans- concentration 1 M; methanol flow rate 6 ml min−1 .
604 S. Matar, H. Liu / Electrochimica Acta 56 (2010) 600–606
Table 3
Fitting values for cathode impedance spectra at different CCL thicknesses at
100 mA cm−2 and 1 M methanol concentration.
Cathode C1 (F) R1 () CPE Rct () Ro () Lo (H)
C (F) ˛
MEA 1 0.015 0.0065 0.294 0.76 0.114 0.352 0.172
MEA 2 0.057 0.0022 0.294 0.79 0.081 0.204 0.016
MEA 3 0.030 0.0030 0.294 0.75 0.104 0.455 0.192
Unlike R1 , C1 , C and ˛, the values of Rct , Ro and Lo decrease as
the current density increases, indicating that methanol is being
consumed in the anode and less permeates thorough the mem-
brane. Therefore, it can be concluded that Rct , Ro and Lo define the
electrochemical process at the cathode.
The cathode impedance spectra for the three MEAs at 1 M
methanol concentration are shown in Fig. 5. The fitting values for
8.4 ␮m, 19 ␮m and 44 ␮m CCL thicknesses impedance spectra are
shown in Table 3. During the fitting process, it was noticed that
the fitting results were very sensitive to changes in charge trans-
fer resistance, Rct , but not so much to the changes in Ro and Lo,
which shows that when the operating parameters are held constant
(flow rates, current density, anode thickness, catalyst loadings, etc.)
and only cathode catalyst layer thickness is being changed, charge
transfer resistance is the main factor that determines the perfor-
mance of the cell.
From Fig. 5 and Table 3, the impedance for the cell with a
CCL thickness of 19 ␮m is much lower than that for the base
case with a CCL thickness of 8.4 ␮m, and the reduction is mainly
due to the reduction in charge transfer resistance, Rct . When the
cathode catalyst layer thickness increases from the base thick-
ness of 8.4 to 19 ␮m, the charge transfer resistance changes from
0.114  to 0.080 ; approximately a 30% decrease in charge trans-
fer resistance was achieved. Since charge transfer resistance is
approximately inversely proportional to the active area, it can be
deduced that the active area for oxygen reduction is significantly
increased with the thicker cathode catalyst layer of 19 ␮m. Such a
significant increase in the active area of the ORR with identical cat-
alyst loading clearly shows that the effects of methanol cross-over
are significantly reduced by increasing cathode catalyst layer thick-
ness from the base thickness of 8.4 to 19 ␮m. These results further
corroborate the original hypothesis that a thicker cathode cata-
lyst layer could have the crossed-over methanol oxidized in part of
the catalyst layer and leave the rest relatively free from methanol
contamination, thus reducing the mixed-potential effects.
From Fig. 5 it can be seen that the impedance for the cell with
the cathode catalyst layer thickness of 44 ␮m lies between the
other two cases and from Table 3 it can be seen that the charge
transfer resistance is 0.104 , which falls between the values for
the base case of 8.4 ␮m and the one for 19 ␮m thicknesses. These
results clearly indicate that when the catalyst layer is too thick the
Fig. 6. Hypothetical methanol concentration profiles for different cathode catalyst layer thicknesses.
30
8.4 μm
20 19 μm
10 44 μm
0
-10
-20
Current / mA
-30
-40
-50
-60
-70
-80
-90
-100
-110
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Voltage/ V
Fig. 7. Cyclic voltammograms for different cathode catalyst layer thicknesses. Con-
ditions: 5 mV s−1 ; 35 ◦ C; H2 and N2 flow rates 200 and 50 sccm, respectively.
adverse effects of other factors become significant enough to cause
an increase in the charge transfer resistance.
Hypothetical methanol concentration profiles for different
thicknesses of cathode catalyst layer are shown in Fig. 6 to assist
in the following discussion. For the base case, when the catalyst
layer is too thin, probably the entire catalyst layer is contaminated
with methanol (Fig. 6a), and hence the area available for oxygen
reduction is small, resulting in a higher value of charge transfer
resistance. As the thickness increases (Fig. 6b), part of the catalyst
layer can be free from methanol contamination. Thus the active cat-
alyst area available for oxygen reduction is greater and the charge
transfer resistance is lower. But when the catalyst layer is too thick
(Fig. 6c), oxygen transfer through the catalyst layer is hindered and
cannot effectively oxidize the methanol in a thin layer of the cat-
alyst layer close to the membrane, resulting in a lower available
area for oxygen reduction, again leading to a higher value of charge
transfer resistance. Besides, even the thickness of the catalyst layer
that is free from methanol contamination in this case is not thinner,
due to the much lower catalyst loading per unit volume, the active
catalyst surface area for oxygen reduction can still be significantly
lower. The optimal performance can only be achieved when the
CCL is thick enough to effectively oxidize the permeated methanol
within part of the CCL, but not too thick to have significant adverse
effect on the oxygen transfer and to significantly increase ohmic
losses.
To eliminate the possibility that the thicker CCL has a higher
original ECA, further experiments were conducted to measure the
ECA of the three different CCLs without methanol contaminations.
The pristine ECA of the three catalyst layers were measured using
standard cyclic voltammetry (CV) and the detailed parameters are
provided in Section 2.3. Fig. 7 shows the CV voltammograms and the
 S. Matar, H. Liu / Electrochimica Acta 56 (2010) 600–606 605

Table 4 (a)
ECA values for cathode catalyst layers with different thicknesses. 0.80
8.4μm
Cathode ECA (cm2 Pt mg−1 Pt ) 0.70 19μm
44μm
MEA 1 282.88
0.60
MEA 2 254.37
MEA 3 243.28
0.50

Voltage / V
0.40
pristine ECA results are provided in Table 4. Each of the ECA values 0.30
listed in Table 4 is an average value of 4 independent CV results. As
can be clearly seen, the pristine ECA for the thicker catalyst layer 0.20
(19 ␮m) is not higher than the base case (it is actually lower). This 0.10
result further supports the original hypothesis.
To further determine if the anode side has any effect on the 0.00
0 100 200 300 400 500
different performances of the cells with different cathode catalyst
Current Density / mA cm-2
layer thickness, anode impedance spectra for the three MEAs at
1 M methanol concentration are measured and shown in Fig. 8. It is (b)
0.80
clear that all three MEAs have the same anode impedance spectra. 8.4 μm
This result suggests that the three MEAs have comparable cell resis- 0.70 19 μm
tances and mass transfer and electro-oxidation parameters in the 44 μm
anode. Therefore, the variation in performance shown in the polar- 0.60
ization curves (Fig. 2) and the variation in the cathode impedance 0.50

Voltage / V
spectra (Fig. 5) are solely due to the difference in cathode cata-
lyst layer thicknesses with no interference from the anode. This 0.40
approach of isolating the effects of cathode side from those from
0.30
the anode can also be used in future studies.
0.20

3.3. Higher methanol concentrations 0.10

Further studies were carried out with higher methanol concen-
trations. As shown in Fig. 9a and b, when 2 M and 4 M methanol
concentrations were used, performance of the cell with the 19 ␮m
CCL thickness is still much better than that of the base case, but
the performance of the cell with the very thick CCL of 44 ␮m is
now much better. It can be seen from these two figures, as the
concentration of methanol increases, the performance of the cell
with thicker CCL increases. As the input methanol concentration
increases, methanol cross-over becomes more severe and even
the 19 ␮m CCL may not be thick enough to provide a meaning-
ful amount of CCL that is free from methanol contamination. Only
a much thicker CCL may provide a significant amount of CCL that is
relatively free from methanol contamination, however due to the
much higher oxygen transfer resistance and higher ohmic losses,
the overall cell performance remains low.
-0.1
MEA 1, 8.4 μm CCL
MEA 2, 19 μm CCL
-0.08
MEA 3, 44 μm CCL
Model
-0.06
-0.04
ZIM / Ω
0.00
0 100 200 300 400 500
Current Density / mA cm-2
Fig. 9. Polarization curves at different cathode catalyst layer thicknesses for (a) 2 M
and (b) 4 M methanol concentrations. Conditions: 70 ◦ C; air flow rate 600 sccm;
methanol flow rate 6 ml min−1 .
4. Conclusion
Earlier experimental results by Ge and Liu [17] found that when
there is enough oxygen supply to the cathode side, the adverse
effect of methanol cross-over can be reduced. It is believed that
when the methanol permeated to the cathode can be oxidized
faster, more reaction sites will be free for ORR and thus mitigat-
ing the effect of methanol cross-over. Based on these results, a
hypothesis was proposed that the performance of a DMFC can be
improved if the thickness of the cathode catalyst layer is increased
to a certain value so that the crossed-over methanol can be oxi-
dized in part of the catalyst layer close to the membrane and leave
rest of the catalyst layer free from methanol contamination, thus
reduce the detrimental effect of methanol cross-over and increase
the active surface area for the ORR. In order to verify this hypothesis,
the performances of DMFCs with three different MEAs each having
a different thickness of cathode catalyst layer have been studied.

All the three MEAs have identical anode catalyst layer and identical
-0.02 cathode catalyst loading. The only difference is in the thickness
of the cathode catalyst layers. The technique of electrochemi-
0 cal impedance spectroscopy (EIS) has also been used to further
study the causes for the differences in fuel cell performances.
0.02 From the experimental results, the following conclusions can be
made:
0.04
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0.22 0.24
ZRE / Ω • The thickness of the cathode catalyst layer has a significant effect
on DMFC performances. Comparing with the base case, when the
Fig. 8. Anode impedance spectra at different cathode catalyst layers thicknesses.
thickness of the cathode catalyst layer is doubled, fuel cell current
Conditions: 70 ◦ C; current density: 100 mA cm−2 ; methanol concentration 1 M;
methanol flow rate 6 ml min−1 .
densities increased drastically.
606 S. Matar, H. Liu / Electrochimica Acta 56 (2010) 600–606
• Such significant increase in cell performance supports the
hypothesis that a thicker cathode catalyst layer allows the oxi-
dization of methanol in part of the catalyst layer and leave the
remaining part free of methanol contamination, thus leading to
a significant reduction in the mixed-potential effect.
• Further study by the EIS technique shows that the charge transfer
resistance for the fuel cell with thicker cathode catalyst layer is
significantly lower, indicating that the active catalyst area avail-
able for oxygen reduction reaction is indeed greater, thus further
supporting the original hypothesis.
• The experimental results also indicate that there exits an
optimum cathode catalyst layer thickness and the optimal
CCL thickness depends on operating conditions, especially the
methanol concentration.
References
[1] S.R. Narayanan, A. Kindler, B. Jeffries-Nakamura, W. Chun, H. Frank, M. Smart,
T.I. Valdez, S. Surampudi, G. Halpert, Battery Conference on Applications and
Advances (1996) 113.
[2] H. Dohle, J. Divisek, J. Mergel, H.F. Oetjen, C. Zingler, D. Stolten, Journal of Power
Sources 105 (2) (2002) 274.
[3] X. Ren, T.E. Springer, T.A. Zawodzinski, S. Gottesfeld, Journal of the Electro-
chemical Society 147 (2) (2000) 466.
[4] K. Ramya, K.S. Dhathathreyan, Journal of Electroanalytical Chemistry 542
(2003) 109.
[5] J. Han, H. Liu, Journal of Power Sources 164 (1) (2007) 166.
[6] W. Liu, C.-Y. Wang, Journal of Electrochemical Society 154 (2007) B352.
[7] Z.H. Wang, C.Y. Wang, Journal of Electrochemical Society 150 (2003) A508.
[8] J. Ge, H. Liu, Journal of Power Sources 160 (1) (2006) 413.
[9] J.T. Mueller, P.M. Urban, Journal of Power Sources 75 (1) (1998) 139.
[10] P. Piela, R. Fields, P. Zelenay, Electrochemical Society 153 (10) (2006) A1902.
[11] L. Li, J. Zhang, Y. Wang, Journal of Membrane Science 226 (2003) 159.
[12] N. Carretta, V. Tricoli, F. Picchioni, Journal of Membrane Science 166 (2000)
189.
[13] R. Carter, R. Wycisk, H. Yoo, P.N. Pintauro, Electrochemical and Solid-State
Letters 5 (9) (2002) A195.
[14] M.A. Abdel Rahim, H.B. Hassan, Thin Solid Films 517 (11) (2009) 3362.
[15] M. Carmo, V.A. Paganin, J.M. Rosolen, E.R. Gonzalez, Journal of Power Sources
142 (2005) 169.
[16] F. Liu, G. Lu, C.-Y. Wang, Journal of the Electrochemical Society 153 (2006) A543.
[17] J. Ge, H. Liu, Journal of Power Sources 142 (2005) 56.
[18] C.Y. Du, T.S. Zhao, W.W. Yang, Electrochimica Acta 52 (2007) 5266.
[19] C.Y. Du, T.S. Zhao, C. Xu, Journal of Power Sources 167 (2) (2007) 265.