Electrochimica Acta 53 (2007) 447–452

Performance degradation study of a direct methanol fuel cell by

electrochemical impedance spectroscopy
Min Ku Jeon, Jung Yeon Won, Kwang Seok Oh, Ki Rak Lee, Seong Ihl Woo ∗
Department of Chemical and Biomolecular Engineering (BK21 Graduate Program) and Center for Ultramicrochemical Process Systems,
Korea Advanced Institute of Science and Technology, 373-1 Yuseong, Daejeon 305-701, Republic of Korea
Received 3 May 2007; received in revised form 10 June 2007; accepted 18 June 2007
Available online 27 June 2007

Abstract
A stability test of a direct methanol fuel cell (DMFC) was carried out by keeping at a constant current density of 150 mA cm−2 for 435 h.
After the stability test, maximum power density decreased from 68 mW cm−2 of the fresh membrane-electrode-assembly (MEA) to 34 mW cm−2
(50%). Quantitative analysis on the performance decay was carried out by electrochemical impedance spectroscopy (EIS). EIS measurement of
the anode electrode showed that the increase in the anode reaction resistance was 0.003  cm2 . From the EIS measurement results of the single
cell, it was found that the increase in the total reaction resistance and IR resistance were 0.02 and 0.05  cm2 , respectively. Summarizing the EIS
measurement results, contribution of each component on the performance degradation was determined as follows: IR resistance (71%) > cathode
reaction resistance (24%) > anode reaction resistance (5%). Transmission electron microscopy (TEM) results showed that the average particle size
of the Pt catalysts increased by 30% after the stability test, while that of the PtRu catalysts increased by 10%.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Direct methanol fuel cell; Performance degradation; Electrochemical impedance spectroscopy; Agglomeration

1. Introduction lysts, chemical degradation of membrane and water flooding in

Recently, direct methanol fuel cells (DMFCs) were focused
because of increasing demand on portable power sources of high
energy density. The best merit of DMFC is easy handling of
liquid fuel, which is an essential condition for application in
portable power sources of notebook computers, cellular phones,
and personal digital assistant. Performance of DMFC was dras-
tically improved during the last two decades [1]. Nowadays,
DMFC is close to commercialization. However, lifetime of
DMFC, which is one of the most important criteria for com-
mercialization of DMFC, was not fully investigated.
We reported operation current density dependence of DMFC
where maximum power density decreased to 55% of the ini-
tial value after operation at 200 mA cm−2 for 145 h [2]. Liu
et al. [3] reported 30% decrease of maximum power den-
sity after operation at 100 mA cm−2 for 75 h. Dissolution and
crossover of Ru from anode to cathode, agglomeration of cata-
∗ Corresponding author. Tel.: +82 42 869 3918; fax: +82 42 869 8890.
E-mail address: siwoo@kaist.ac.kr (S.I. Woo).
cathode were pointed out as key components of the performance
degradation [4–7]. These reports analyzed the performance
degradation by ex-situ methods such as X-ray diffraction (XRD),
scanning electron microscopy (SEM), transmission electron
microscopy (TEM), Raman spectroscopy, and back titration.
To use these methods, membrane-electrode-assembly (MEA)
should be detached from the fuel cell. Furthermore, these meth-
ods could not tell us which component of the fuel cell contributed
on the performance degradation, quantitatively. Though quanti-
tative study on performance degradation will provide important
clues to increase the lifetime of DMFC, separation of anode and
cathode performance was not carried out sufficiently because of
complex electrochemical reactions of DMFC.
Recently, electrochemical impedance spectroscopy (EIS) is
getting focused as an in-situ and quantitative analysis method
for DMFC [8–11]. Further studies showed that EIS results could
provide information of individual fuel cell component [12–16].
Müller and Urban [8] suggested a method to separate anode and
cathode impedance by measuring anode and full cell impedance
data, respectively. By the same method, Piela et al. [6] reported
a relationship between performance and EIS . In spite of these

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.06.063
448 M.K. Jeon et al. / Electrochimica Acta 53 (2007) 447–452
merits of EIS, application of EIS to quantitative analysis on per-
formance degradation was not reported. In the present study,
performance degradation of DMFC was analyzed quantitatively
by measuring EIS of the anode and single cell to clarify con-
tribution of each component on the degradation. XRD, energy
dispersive spectroscopy (EDS), and TEM were also used to
verify the degradation arising from the electrode materials.
2. Experimental
2.1. MEA preparation
PtRu black (HiSpec6000, Johnson Matthey, U.K.) and Pt
black (HiSpec1000, Johnson Matthey, U.K.) were used as anode
and cathode catalysts, respectively. Catalyst inks were prepared
by mixing catalysts, DI water, NafionTM ionomer solution and
isopropyl alcohol. The inks were put through sonication to get
homogeneous phase. Then, the inks were sprayed on PTFE
sheets until a metal loading of 2 mg cm−2 was obtained. The
PTFE sheets were hot pressed with NafionTM 115 (DuPont) at
1000 psi and 120 ◦ C for 3 min, and then, the PTFE sheets were
removed leaving the catalyst layers on both sides of NafionTM
membrane. Active area of the MEA was 4 cm2 .
2.2. Operation and stability test of a single cell
Graphite blocks with a serpentine flow channel were used
as end plates of a single cell. Methanol (1 M, 1 ml min−1 ) and
oxygen (100 cc min−1 ) were fed into the anode and cathode
electrodes, respectively. The cell was operated at 55 ◦ C during
the experiments. For stability test, a constant current density of
150 mA cm−2 was maintained for 435 h.
2.3. Electrochemical measurements
EIS was measured at two conditions:
(1) anode analysis by flowing hydrogen in cathode at a flow rate
of 30 cc min−1 and;
(2) single cell set-up by flowing oxygen in cathode at a flow
rate of 100 cc min−1 .
Methanol (1 M) was fed at a flow rate of 1 ml min−1 for
both cases. During the measurement, frequency was varied from
105 to 0.01 Hz by using a Solartron 1255B frequency response
analyzer.
2.4. XRD and TEM measurements
As the amount of the catalysts used for MEA was too small
to be measured by a conventional XRD machine, XRD pat-
terns of the catalysts were obtained in their MEA form by using
a microbeam XRD (Bruker D8Discover GADDS CS, Cu K␣
radiation).
For TEM measurement, the catalysts were detached from
the MEA. The detached catalysts were dispersed in ethanol and
then collected by copper grids (300 meshes). The copper grids
were dried in air. For the measurement, Tecnai G2 F30 S-TWIN
system was used.
3. Results and discussion
Fig. 1 shows I–V measurement results before and after
the stability test. Maximum power density decreased from
68 mW cm−2 of the fresh MEA to 49 (72%), 39 (57%), and
34 mW cm−2 (50%) after operation for 145, 290, and 435 h,
respectively. Rate of performance decay decreased with an
increase in operation time as shown in the previous report where
significant degradation was observed during the first 200 h oper-
ation [4].
EIS analysis was carried out by two steps of the anode and
single cell measurements. At first, EIS of the anode was mea-
sured by flowing hydrogen in the cathode electrode to act as both
the counter and reference electrodes. Fig. 2(a) shows the EIS
measurement (dot) and fitting (line) results before and after the
stability test. The EIS measurement was done at 100 mA cm−2 .
Equivalent circuit used for the fitting is shown in Fig. 2(b), where
R1 is an IR resistance, R2 is a methanol electro-oxidation reac-
tion resistance and CPE2 is a capacitive component including
diffusion effect. IR resistance includes membrane, electrode and
interfacial resistances, where membrane resistance is dominant
among these resistances. The constant phase element (CPE) is
defined by two values, CPE-T and CPE-P. The CPE is used in a
model in place of a capacitor to compensate for nonhomogeneity
in the system. The CPE can be expressed as
1
Z= √ (1)
T ωP
where ω is angular frequency of the AC signal, T (CPE-T) is
capacitance and P (CPE-P) is nonhomogeneity constant. R3 is
an electro-oxidation reaction resistance of adsorbed CO (COads )
and L3 is an inductive element which induces phase delay by
Fig. 1. I–V measurement results of the fresh MEA and after operation for 145,
290, and 435 h.
 M.K. Jeon et al. / Electrochimica Acta 53 (2007) 447–452 449

Fig. 3. (a) EIS measurement (dot) and fitting (line) results of the single cell at
100 mA cm−2 (b) Equivalent circuit used for simulation.

that EIS results of cathode includes inductive component caused

Fig. 2. (a) EIS measurement (dot) and fitting (line) results of the anode at by COads oxidation due to methanol crossover. However, we
100 mA cm−2 . Hydrogen was fed hydrogen in the cathode electrode at a flow could find only one inductive element from Fig. 3(a), indicat-
rate of 30 cc min−1 (b) Equivalent circuit used for simulation. ing that the EIS spectra were not sensitive enough to separate
COads oxidation from the anode and cathode electrodes. In
slow relaxation of COads [12]. Detail fitting results are listed in addition, this observation shows why we have to measure EIS
Table 1. Significant change was observed from CPE2-T, which of anode as a complementary method to obtain contribution
decreased from 0.54 to 0.40 F cm2 indicating increase of cov- of each component on the performance degradation from EIS
erage by COads after the operation for 435 h [11]. The increase results. Fig. 3(b) shows the equivalent circuit used for fitting,
of COads coverage means lower catalytic activity for electro- where R1 is an IR resistance, R2 is COads oxidation reaction
oxidation of COads . The anode reaction resistance (ARR) was resistance, L2 is an inductive element and R3 and R4 are
calculated by (R2 × R3)/(R2 + R3). ARR increased by 0.003  methanol electro-oxidation and oxygen electroreduction reac-
(3%), from 0.097 to 0.10 , after the stability test. This small tion resistances, respectively. CPE3 and CPE4 are capacitive
change of ARR is an interesting result because significant components including diffusion effect for anode and cathode,
changes such as agglomeration of catalyst and dissolution of respectively. Detailed simulation results are listed in Table 2.
Ru were observed in previous reports [2,3]. Further investiga- After the stability test, the IR resistance increased by 0.05 ,
tion on the anode catalyst was shown in the last part of this from 0.14 to 0.19 , and total reaction resistance from the anode
section. and cathode, increased by 0.02 , from 0.16 to 0.18 . Here,
In the second step, EIS of the single cell was measured and we could not separate the total reaction resistance to the anode
Fig. 3(a) shows the EIS measurement results at 100 mA cm−2 and cathode reaction resistances because COads oxidation in the
before and after the stability test. Here, we had to construct a anode and cathode electrodes was not distinguishable. In the
suitable equivalent circuit for the measurement results as previ- anode measurement results, ARR increased by 0.003 , hence,
ous reports showed only anode or cathode spectra. In DMFC, increase of the cathode reaction resistance can be deduced to
methanol is oxidized in both the anode and the cathode elec- 0.017 . We could conclude, from the EIS results, that the con-
trodes because of methanol crossover. Piela et al. [11] reported
Table 2
Table 1 Fitting results of EIS results
Fitting results of EIS results
Fresh After 435 h
Fresh After 435 h
R1 () 0.14 0.19
R1 () 0.14 0.17 R2 () 0.36 0.53
R2 () 0.31 0.27 L2 (H) 0.16 0.17
CPE2-T (F) 0.54 0.40 R3 () 0.22 0.22
CPE2-P 0.85 0.88 CPE3-T (F) 0.37 0.24
R3 () 0.14 0.16 CPE3-P 0.96 0.91
L3 (H) 0.078 0.072 R4 () 0.067 0.054
Anode reaction resistance, 0.097 0.10 CPE4-T (F) 0.075 0.071
(R2 × R3)/(R2 + R3), () CPE4-P 0.99 1.00

Methanol (1 M, 1 ml min−1 ) and hydrogen (30 cc min−1 ) were fed into the anode Methanol (1 M, 1 ml min−1 ) and oxygen (100 cc min−1 ) were fed into the anode
and the cathode electrodes, respectively. and the cathode electrodes, respectively.
450 M.K. Jeon et al. / Electrochimica Acta 53 (2007) 447–452

Fig. 4. XRD measurement results of (a) the PtRu and (b) the Pt catalysts before and after the stability test.

tribution of each component on the performance degradation
was as follows: IR resistance (0.05 , 71%) > cathode reaction
resistance (0.017 , 24%) > anode reaction resistance (0.003 ,
5%). Possible reasons of IR resistance increase are:
(1) delamination between catalyst layers and membrane as
shown in [9] and;
(2) decrease of conductivity by chemical degradation.
In our previous report, degradation of membrane by removal
of SO3 H+ from NafionTM membrane was observed [2]. The
increase of equivalent weight by removal of SO3 H+ must be
one of the main reasons of the large increase of IR resistance
observed in this study. The mechanism of chemical degradation
is not clear yet, however, reaction between SO3 H+ and OH radi-
cals, formed by decomposition of H2 O2 , is widely accepted [17].
H2 O2 is generated during oxygen reduction at anode electrode.
Oxygen crossover from cathode to anode leads to the formation
of H2 O2 . Large degradation of membrane shown in this paper
shows that reduction of oxygen crossover from the cathode to
the anode and quick removal of H2 O2 at the anode can provide
longer lifetime of DMFC. For the case of catalysts, previous
reports focused on the changes of anode catalysts, however, from
the EIS analysis results, it was found that the degradation caused

Fig. 5. TEM images and distribution of particle size of the PtRu catalysts (a) before and (b) after the stability test.
 M.K. Jeon et al. / Electrochimica Acta 53 (2007) 447–452
Fig. 6. TEM images and distribution of particle size of the Pt catalysts (a) before and (b) after the stability test.
by the Pt catalysts was more serious than that by the PtRu cata-
lysts. To verify degradation of the PtRu and Pt catalysts, XRD,
EDS, and TEM measurements were carried out.
Fig. 4 shows XRD patterns of (a) the PtRu and (b) Pt catalysts
before and after the stability test. In the case of the PtRu catalysts,
a peak at 40.4◦ of the fresh catalysts moved to 40.2◦ indicating
dissolution of Ru. Dissolution of Ru was confirmed by EDS
measurement. (Pt:Ru) atomic ratio changed from (53:47) of the
fresh catalysts to (56:44) after the stability test. Particle size cal-
culated from the Debye–Scherrer equation increased from 3.3 to
4.2 nm. In the case of the Pt catalysts, peak shift or generation of
new peaks by formation of secondary phases were not observed.
Particle size of the Pt catalysts increased from 9.1 to 11.1 nm,
while no changes were observed in the previous report [2]. This
difference might have come from the longer operation time of
435 h of this study than 145 h of the previous study.
Fig. 5 shows TEM images and distribution of particle size of
the PtRu catalysts (a) before and (b) after the stability test. Aver-
age particle size increased from 5.1 to 5.5 nm after the stability
test. The average particle sizes measured by TEM were much
larger than 3.3 and 4.3 nm of XRD results before and after the
stability test, respectively. Low crystallinity of the PtRu catalysts
by alloy formation might be the reason of the different average
particles sizes between XRD and TEM results. TEM images and
particle size distribution of the Pt catalysts are shown in Fig. 6
(a) before and (b) after the stability test. Average particle size of
451
the Pt catalysts increased from 7.1 to 9.4 nm after the stability
test. Here, average particle size of the PtRu and the Pt catalysts
increased to 110 and 130% of their initial values, respectively.
Assuming that the catalyst particles have spherical shapes, sur-
face area per unit mass of the catalysts is in reverse proportion to
diameter. Therefore, surface area per unit mass of the PtRu and
Pt catalysts became 91 and 77% of initial value, respectively.
The larger decrease of surface area in the Pt catalyst than that
in the PtRu catalyst might have caused the larger contribution
of the Pt catalyst on the performance degradation, which is in
agreement with the EIS results.
4. Conclusion
A stability test of a DMFC was carried out at 55 ◦ C and
a constant current density of 150 mA cm−2 for 435 h. Maxi-
mum power density decreased to 50% of the initial value after
the stability test. EIS results for the anode and the single cell
showed that contribution of each component on the performance
degradation was as follows; IR resistance (71%) > cathode reac-
tion resistance (24%) > anode reaction resistance (5%). TEM
results showed that the average particle size of the Pt catalysts
increased by 30% while that of the PtRu catalysts increased by
10% after the stability test. The more contribution of cathode
degradation in the performance decay was also observed in EIS
study.
452 M.K. Jeon et al. / Electrochimica Acta 53 (2007) 447–452
Acknowledgements
This research was partially funded by the Center for Ultra-
microchemical Process Systems (CUPS) sponsored by KOSEF
(2007). The authors also would like to thank Research Park/LG
Chem, Ltd. and Ministry of Commerce, Industry and Energy for
funding this research in the framework of the Korean govern-
ment/industry joint project for the development of 50W direct
methanol fuel cell systems.
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