DOI: 10.1002/fuce.
200700053
Review: Durability and Degradation
Issues of PEM Fuel Cell Components
F. A. de Bruijn1,2*, V. A. T. Dam1, and G. J. M. Janssen2
1
Schuit Institute of Catalysis, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands
2
Energy Research Centre of the Netherlands (ECN), PO Box 1, 1755 ZG Petten, The Netherlands
Received September 26, 2007; accepted December 28, 2007
Abstract
Besides cost reduction, durability is the most important
issue to be solved before commercialisation of PEM Fuel
Cells can be successful. For a fuel cell operating under con-
stant load conditions, at a relative humidity close to 100%
and at a temperature of maximum 75 °C, using optimal
stack and flow design, the voltage degradation can be as low
as 1–2 lV·h. However, the degradation rates can increase by
orders of magnitude when conditions include some of the
following, i.e. load cycling, start–stop cycles, low humidifi-
1 Introduction
Now that power density specifications of PEM fuel cells
for automotive and stationary applications are close to being
met, the focus of PEMFC R&D is shifting to the other require-
ments for successful introduction of the PEMFC, i.e. cost and
durability. Long-term operation of the PEMFC has been pro-
ven, but mostly for fuel cells containing high loadings of
noble metals, and under relatively ideal conditions. However,
especially for automotive application, PEMFCs need to oper-
ate in a wide range of conditions, which may negatively affect
durability and lifetime. The issues of cost and durability are
closely related since reduction of cost is associated with the
use of less or cheaper materials, e.g. reduction of Pt content
or use of thinner perfluorinated, partially fluorinated or non-
fluorinated membranes.
Insight into the mechanisms that lead to irreversible per-
formance loss and the relation between these mechanisms
and the operating conditions, the changes in materials’ prop-
erties that can be observed and the impact on fuel cell perfor-
mance is needed, before either fuel cell materials can be opti-
mised further with respect to their durability, or systems’
controls and operating procedures can be optimised to pre-
vent the most detrimental conditions. This has motivated sev-
eral recent studies on PEMFC degradation using long-term
testing as well as rapid ageing testing.
FUEL CELLS 08, 2008, No. 1, 3–22
REVIEW
cation or humidification cycling, temperatures of 90 °C or
higher and fuel starvation. This review paper aims at asses-
sing the degradation mechanisms of membranes, electrodes,
bipolar plates and seals. By collecting long-term experiments
as well, the relative importance of these degradation
mechanisms and the operating conditions become apparent.
Keywords: Components, Degradation, Durability, Electrodes
Bipolar Plates, Lifetime, Membranes, PEFC, PEMFC, Seals
This review starts with the identification and categorisa-
tion of long-term experiments, focusing on observed degrada-
tion rates and materials’ changes, followed by a detailed
description of degradation mechanisms and their measurable
effects, both on fuel cell performance and on in situ or post-
test diagnostics. The aim is to assess which mechanisms affect
the lifetime of membranes, electrodes, bipolar plates and
seals, how degradation is enhanced or mitigated by opera-
tional conditions and which tools are available to identify
and quantify the degradation.
The emphasis in this study is on PEMFCs operating in the
temperature range up to 120 °C and containing perfluori-
nated, hydrated polymer membranes and electrodes based
upon Pt/C catalysts. Reference to other materials is made in
passing. This review does not cover the influence of contami-
nants present in hydrogen and air. A recent review paper by
Cheng et al. covers this extensively [1].
2 Long-Term Experiments–Observed
Degradation Rates
Long-term experiments can give a good indication of the
severity of degradation mechanisms and their relative contri-
–
[*] Corresponding author, debruijn@ecn.nl
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 3
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components

bution to performance loss under various conditions. Table 1 experiments, but now organised in increasing order of the
REVIEW

compiles key experiments longer than 1,000 h, or otherwise voltage decay rates. The compilations are meant to give a
relevant for this study, with all reported observations of qualitative understanding on the possible relation between
changes in component characteristics. Table 2 gives the same operating conditions and voltage decay rates, because the

Table 1 Long-term PEMFC experiments reported in literature, with materials changes observations.
Company/product Test period Anode/fuel Cathode/feed Membrane j / A cm–2 Voltage decay Observed Reference
(h )/Temp. at V/V ratea) / lVh–1 changes
Ballard 8 cell stack 6,000 X H2 100% RH Air 100% RH 1.076 at 0.62 –1 – [4]
Mark 513 2000 75 °C Reformate + air Air 0% RH 1,000 at 0.43 –24 a)

2,000 Y bleed 100% RH

Ballard 8 cell stack 11,000 X PtRh; 4 mg cm–2 Pt on Pt (4); mg cm–2 Pt Dow 0.538 at 0.82 –1.4 a),b)
[5]
Mark 513 2002 Toray on Toray pure O2 0.861 at 0.78 –1.3
pure H2
LANL 2005 3,400 Y Pt/C; 0.2 mg cm–2 on Pt/C; 0.2 mg cm–2 N 112 Constant V –33 a),c)
[6]
80 °C ETEK ELAT on ETEK ELAT 0.55 at 0.62
Pure H2, RH = 255% air, RH = 100%
d),e),f),-
Nuvera CGS 2-cell >9,000 X PtRu/C Pt/C 36 lm ? at 0.7 –6 [7]
stack 500 cm2 75 °C 75% H2/25% N2 air
g),h),i),j),k)

Daido Institute of 2,700 X Pt/C 0.5 mg cm–2 on Pt/C 0.5 mg cm–2 N112 0.3 at 0.66 –2.5 (0–1,900) d),l)
[8]
Technology 2005 75 °C Toray, H2 80% RH on Toray, air 80% –50 (1,900–2,700)
RH
Commercial MEA 1,000 X, Y Pt/C 0.5 mg cm–2 on Pt/C 0.5 mg cm–2 N112 Cyclic, MEA failure m),d),n), )
° [9]
Fuelcellstore.com 80 °C ETEK ELAT, H2 100% on ETEK ELAT, 0–1.06 A cm–2
RH air 100% RH 1.06 at 0.66 –180 a),d),n), )
°
Gore 5510 2,000 X, Y Pt/C 0.4 mg cm–2, H2 Pt/C 0.4 mg cm–2, Gore 25 lm 0.2 at 0.77 –25 d),e)
[10]
80 °C 100% RH air 100% RH OCV –20 d),e)

Gore 5621 26,000 X PtRu/C 0.45 mg cm–2 Pt/C 0.6 mg cm–2 Gore 35 lm 0.8 at 0.60 –6.4 a),b),d),i),l)
[3]
70 °C on Carbel on Carbel, air
Reformate + air 100% 100% RH
RH
H2 100% RH Air 100% RH 0.8 at 0.62
a),q)
Osaka Gas 36,000 X PtRu/C Pt/C Cyclic, –2.5 Under H2 [11]
70 °C Reformate, 10 ppm air 100% RH 0.15–0.30 A cm–2 –35 under
CO 100% RH reformate
10 ppm CO
d),j)
Asahi Glass 4,000 Y H2 50% RH Air, 50% RH Asahi Glass 0.2 at 0.75 –75 [12]
120 °C NPC
d),g),r)
Toray/Daido Insti- 900 H2 26% RH Air, 26% RH Nafion 0.3 at 0.7 –29 [13]
tute of Technology cyclic –218
0–0.3 A cm–2
Gore 5510 1,000 X H2 20% RH Air, 20% RH Gore 25 lm 0.5 at 0.59 –95 [14]
55 °C stoich = 4! cyclic, –45
0–0.7 A cm–2
Mitsubishi Electric 6,000 X Reformate, 10 ppm CO Air, 74% RH 0.25 at 0.7 –1.5 [2]
75 °C 57% RH

X, endurance test under normal conditions; Y, endurance test under accelerated conditions.
a)
May be recalculated from current density decay using polarisation curve.
b)
Loss of water removal efficiency.
c)
Deterioration of seals.
d)
Increase in cell resistance (unspecified).
e)
Loss of Pt surface area at cathode.
f)
Pt detected in membrane.
g)
Ru detected in anode gas diffusion layer.
h)
Carbon corrosion at anode.
i)
Carbon corrosion at cathode.
j)
Thinning of membrane.
k)
Thinning of electrodes.
l)
Loss of fluorine and sulphur or other components from membrane.
m)
Increase in hydrogen cross-over through membrane.
n)
Macroscopic holes in membrane.
)
° Loss of Pt surface area at anode.
p)
Fluoride ions in outlet water.
q)
Pt detected in cathode ionomer.
r)
Decrease in CO tolerance.
s)
Degradation of ionomer in electrodes.

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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components

Table 2 Voltage decay rates in long-term PEMFC experiments, in increasing order of decay rate.

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Voltage decay Cell T RH anode RH cathode V/V J / mA cm–2 OCV in cycle Cyclic/SS Membrane Reference
rate / lVh–1 % % thickness / lm
1 75 100 100 0.62 1,076 No ss 125 [4]
1.4 75 100 100 0.82 538 No ss 125 [5]
1.3 75 100 100 0.78 861 No ss 125 [5]
1.5 75 57 74 0.7 259 No ss ?? [2]
2.5 70 100 100 Cyclic 150–300 No Cyclic ?? [11]
6 75 100 100 0.7 Not given No ss 36 [7]
6.4 70 100 100 0.62 800 No ss 35 [3]
20 80 100 100 OCV 0 Yes ss 25 [10]
25 80 100 100 0.77 200 No ss 25 [10]
28 80 26 26 0.7 300 No ss ?? [15]
29 80 26 26 0.7 300 No ss ?? [13]
33 80 255 100 0.62 550 No ss 50 [6]
2.5–50 75 80 80 0.66 300 No ss 50 [8]
45 55 20 20 0.6–0.35 0–700 Yes Cyclic 35 [14]
75 120 50 50 0.75 200 No ss ?? [16]
75–114 80 26 26 0.7 0.01–300 Yes Cyclic ?? [15]
95 55 20 20 0.59 500 No ss 35 [14]
180 80 100 100 0.66 1,060 Yes ss 50 [9]
210 80 26 26 0.7 0.01–300 No Cyclic ?? [13]
Failure 80 100 100 Cyclic Cyclic Yes Cyclic 50 [9]

tests are difficult to compare because of differences in e.g.
materials, flow fields, start-up procedures. Note that the volt-
age decay rates in Tables 1 and 2 comprise irreversible as
well as reversible losses.
Table 2 shows that for cells operated in a steady state,
without OCV excursions, temperature 70–75 °C and at 100%
relative humidity of the inlet gases the overall voltage decay
rate is generally in an acceptable range, i.e. <6 lVh–1. The
voltage decay rate can increase sharply when one or more of
the following conditions are applied: temperature above
75 °C, gases not fully humidified, cycles of load or potential
(especially including OCV). These conditions seem to qualify
as non-ideal. The only exception seems to be a recent result
by Mitsubishi Electric [2]. Here the design of the flow pattern
and the MEA was modified to prevent the evaporation of
water in dry areas such as the air inlet region.
A relation with the material properties is not so clear from
these tables. Table 2 is headed by tests with a 125 lm thick
membrane, but as they all refer to the same membrane, the
thickness need not be the decisive property.
Both under ideal and non-ideal conditions, many changes
in materials and fuel cells characteristics were observed after
these tests. A large fraction of these observations are only
indicative, and more detailed investigations are needed to
further elucidate the degradation phenomena, especially by
applying suitable characterisation techniques. However, it is
apparent from this overview of long-term experiments that
loss of water removal efficiency and loss of platinum surface
area at the cathode are the most frequently observed degrada-
tions.
In durability studies it must always be remembered that
part of the decay may be reversible. This is especially true in
the case of under or oversaturation of the gases. Both drying
out and flooding can have a detrimental effect. During the
26,000 h test at Gore [3], a voltage loss of 110 mV was ob-
served at a current density of 800 mA cm–2. It should be
noted that superposed on this voltage loss, a saw-tooth was
observed with a voltage decay rate of more than 40 lVh–1,
which is explained by water management issues, poison for-
mation and platinum oxide formation.
In this review, the focus is on irreversible degradation of
membrane, electrodes, bipolar plates and seals. The contribu-
tion of each mechanism to overall degradation as reported in
Tables 1 and 2 is discussed.
3 Membrane Durability
3.1 Membrane Function and Requirements
The electrolytic membrane serves as the conductor for pro-
tons from anode to cathode, as a gas separator and as an elec-
tronic insulator. During the lifetime of the fuel cell, these func-
tions must remain unimpeded, meaning that the proton
conductivity should be in the range of 0.1 S cm–1, its gas per-
meability should be minimal i.e. <10–12 mol H2 cm–1 s–1 kPa–1
and <10–11 mol O2 cm–1 s–1 kPa–1 [17]. For the electronic resis-
tance, no clear specification exists, as short circuiting is gener-
ally not an issue, except for manufacturing failures.
3.2 Mechanisms for Membrane Degradation
3.2.1 Chemical Attack by Radicals
Chemical degradation is a major cause of failure of PFSA
membrane [18–20]. It is thought that hydroxyl (OH) or per-

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 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
oxy (OOH) radicals attack polymer end groups that still con-
REVIEW
tain residual terminal H-groups. Characterisation by XPS [21]
revealed that during fuel cell operation the interactions
between carbon, fluorine and oxygen are changing. An exam-
ple given by Curtin et al. [22] is the attack of hydroxyradicals
on carboxylic end groups:
Rf–CF2COOH + OH → Rf–CF2 + CO2 + H2O (1)
Rf–CF2 + OH → Rf–CF2OH → Rf–COF + HF (2)
Rf–COF + H2O → Rf–COOH + HF (3)
In the last few years chemically modified membranes have
been developed by DuPont, which show much lower fluoride
release rates and longer accelerated lifetimes [22]. In these
modified polymers, the number of reactive end groups has
been reduced by an alternative synthesis route.
For a considerable time the hypothesis has been that the
radicals are formed either at the cathode during the oxygen
reduction reaction, e.g. from H2O2 that is formed in small
quantities during the ORR [23], or from a decomposition of
H2O2 formed at the anode as a result of O2 crossing over from
cathode to anode [18]. For the radicals to form from H2O2, the
presence of oxidizable metal ions such as Fe2+ is required. It
was thought that contaminating ions would induce radical
formation. This has led to the use of Fenton’s test where Fe2+,
H2O2 and polymer are mixed and the product is analysed.
Recently, however, evidence has been presented that the
incentive for the chemical attack can also be provided by a
species (likely a radical as mentioned above) that is formed in
a reaction of molecular hydrogen and oxygen in the presence
of Pt, without necessary formation of intermediate H2O2
[24–30]. In fact, in an operating fuel cell the so-called direct
radical pathway is more important than the H2O2 pathway,
as the activity of Pt/C as a reagent in Fenton’s reaction is lim-
ited [9, 28]. According to direct radical pathway, favourable
conditions for degradation are not only at the cathode (cross-
over from H2), anode (cross-over of O2), but also in the mem-
brane when Pt particles deposit there as a result of electrode
degradation [29, 31–33]. It must be noted that LaConti et al.
already reported the degradation of polystyrene sulphonic
acids in a mixture of H2, O2 and Pt [18]. On the basis of these
results replacements of Fenton’s test have been suggested
[24, 25].
The exact mechanism of the direct radical pathway has not
been established yet. Studies on chemical degradation have
shown that the conditions leading to increased radical attack
in PFSAs include higher temperature (especially above
90 °C), low humidification, high gas pressure, use of pure
hydrogen and pure oxygen and high cell voltages [20]. Some
of these conditions are consistent with a higher concentration
of H2 and O2. The role of relative humidity, potential and also
of membrane thickness is still a subject of study [19, 24, 26,
27, 29]. Recent results suggest that the state of the catalyst sur-
face may play an important role [27].
6 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Attack by OOH and OH also has an effect on partially or
non-fluorinated membranes, as was shown in Fenton’s test. It
was noticed that non-sulphonated aromatic membranes like
PEEK are unaffected but severe degradation was observed
for the sulphonated compound. Also in this case has the use
of Fenton’s test been questioned, i.e. stable performance for
4,000 h has been obtained of membranes that did not survive
Fenton’s test [34]. It must be noted that gas cross-over rates
are usually lower in hydrocarbon membranes than in PFSA
membranes [35].
Hydrogenation of CF2 groups in the presence of H2 has
also been proposed as the source of degradation, but in the
light of the above observations this mechanism is less likely
to contribute substantially [19, 21].
Non-fluorinated compounds like PEEK are susceptible to
the loss of the sulphonic acid group by hydrolysis at wet con-
ditions [34]. Also for PFSA have sulphonic acid groups been
reported as degradation products [18]. However, it was
reported by LaConti that the equivalent weight was not
affected, i.e. polymer units with their sulphonic groups were
dissolved, without desulphonation. Recent results at DuPont
confirm the stability of the sulphonic acid containing side
group of Nafion. At temperatures higher than 200 °C thermal
degradation can set in, starting with desulphonation [22].
3.2.2 Mechanical Failure
Although the mechanical properties of most often used
Nafion membranes such as tensile strength, tear strength and
puncture resistance are quite satisfactory, the use of very thin
membranes (25 lm) requires a well-controlled MEA manu-
facturing. Pinholes and foreign materials introduced during
MEA manufacturing can initiate propagating cracks leading
to strongly reduced lifetimes [18].
Non-uniform contact pressure [18], high differential initial
gas pressure over the membrane, punctures as well as fatigue
from stresses occurring during temperature and humidity
cycling [36, 37] can lead to mechanical failure of the mem-
brane. Tang et al. found that relative humidity cycling of
NR111 membranes from water-soaked to 25% RH, as well as
temperature cycling at 100% RH do lead to stresses higher
than the limit of 1.5 MPa that was found to lead to thinning
of the membrane and increased hydrogen cross-over and irre-
versible elongation [38].
It has been reported that reinforcement of the membrane
with e.g. a porous polyethylene or PTFE [37, 39] material
enhances the dimensional stability and reduces the shrinkage
stress in the membrane during drying. Reinforced mem-
branes were shown to be more stable, i.e. showed a lower
decrease in the OCV [36] and longer lifetime at elevated tem-
perature and low humidity [39].
Mechanical failure can be enhanced by chemical degrada-
tion as shown by Cleghorn and Kolde [40]. The Primea 57 ser-
ies failed after 12,000 wet–dry cycles (300 h) in inert N2 atmo-
sphere, and after 2,000 cycles (50 h) in fuel cell mode, due to
sharp increase in hydrogen cross-over. New reinforced struc-
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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
tures lasted more than 64,000 cycles (1,600 h) in inert atmo-
sphere, the test not being ended by failure, and showed a ten-
fold increase in lifetime in MEA.
3.2.3 Contamination by Ionic Species
Metal bipolar plates, humidifiers, tubing materials, air, can
be sources for contaminant ions. The sulphonate sites have a
stronger affinity to metal ions, except Li+, than for protons,
leading to exchange of the protons by the metal ion when
present. There is agreement on the effect of such contamina-
tion, being direct and indirect [18, 41]. The direct effect is a
reduction of the proton conductivity that is proportional to
the decrease in proton concentration. Note that metal ions
will contribute to the ionic conductivity, but not to the proton
conductivity that determines the membrane ohmic loss in a
fuel cell. The indirect effect stems from the lower hydrophili-
city of metal ions in comparison to protons, which can result
in partial drying out of membrane, thus, also reducing the
proton conductivity. It has also been suggested that metal
ions poison the ORR catalyst [41] hence increasing the rate of
hydrogen peroxide and radical formation, resulting in chemi-
cal degradation [18].
3.2.4 Change of Nafion Morphology
Loss of water from the membrane is well known to lead to
an almost immediate loss of fuel cell performance, due to the
strong relation between membrane conductivity and the
water content. This relation is generally believed to be revers-
ible in nature, albeit that rehydration of Nafion membranes to
their original state can be difficult, due to the shrinkage of
hydrophilic domains during drying.
Characterisation by XRD [21] revealed that during fuel cell
operation, the Nafion crystallinity changes, especially at rela-
tively dry conditions. It is believed that a high crystallinity
corresponds to open ion-channels, and dehydrated, collapsed
channels correspond to a decrease in crystallinity [21].
Whether this is a reversible effect or not is not clear, as no
rewetting experiment of the fuel cell membrane has been
reported. Recently, it was suggested on the basis of thermo-
mechanical analysis that Pt2+ ions dissolved in the membrane
may induce physical cross-linking, resulting in stiffer mem-
branes [42].
The effect of freezing of water on membrane properties
has been investigated in several institutes [43–47]. The results
indicate that about 90% of the water can freeze, but that some
water is non-freezable. The temperature at which freezing is
observed varied with the water content. However, it was
found that freeze–thaw cycles did not lead to irreversible
changes. McDonalds et al. studied N112 membranes that
underwent up to 385 freeze–thaw cycles between –40 and
+80 °C [46]. These materials were in a relatively dry state
(only humidified by ambient conditions). These studies did
not indicate any serious physical or chemical damage. The
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REVIEW
toughness of membranes seemed to decrease somewhat as
well as the permeability of the membrane for oxygen. It was
suggested that a rearrangement of the sulphonic acid groups
in the ionomer might have occurred.
3.3 Characterisation of Membrane Degradation
3.3.1 Fluoride Release Rates
The rate of release of fluoride ions in the product water is
correlated to the rate of the chemical degradation of fluori-
nated membranes [see reactions (1)–(3)]. The fluoride analysis
is generally done off-line by ion-chromatography or an ion
selective electrode [20, 39, 48, 49] but recently also a method
based upon a fluoride ion selective electrode has been used
for continuous monitoring [50].
It was already established at the end of the 1980s at Hamil-
ton Standard (part of UTC) that PEM fuel cell lifetime is
directly related to the fluoride release rate [51], as was also
confirmed by recent results from DuPont [36]. In a recent
study the impact of the fluoride release rate was related to
the initial fluorine content of a membrane with 25 lm thick-
nesses, which was estimated to be 3.8 mg F cm–2 (2 g cm–3,
75% F) [20]. This implies that with an average release rate of
0.01 lg F cm–2 h–1, which was measured for membranes at
near-ideal conditions [16, 20], 2% of the F is lost after 6,000 h.
A degradation rate of 3 lg F cm–2 h–1, as was obtained under
harsh conditions, would lead to complete failure within
1,200 h. In this study, it was also remarked that the pH of the
effluent correlated very well with the pF, i.e. decrease in pH
may also indicate increased membrane degradation. How-
ever, Healy et al. also report that data of the fluoride release
rate can show considerable scatter [20].
3.3.2 Hydrogen Cross-Over Rates
Both chemical and mechanical degradation can lead to an
increase in gas cross-over. The hydrogen cross-over can be
measured electrochemically in situ [52]. The fuel cell cathode
is purged with nitrogen, and set at a voltage of about 0.4 V
higher than the anode. Hydrogen that diffuses to the fuel cell
cathode is oxidised and the protons produced are transported
to the fuel cell anode, where they can be reduced to hydro-
gen. The current is directly proportional to the cross-over rate
of hydrogen through the membrane.
The hydrogen cross-over is proportional to the hydrogen
partial pressure at the anode, as is reflected by the pressure
dependency of the measured currents [52]. For a Nafion112
membrane of 50 lm thickness, a cross-over current of
1 mA cm–2 at atmospheric conditions is reported for beginning
of life. This corresponds to 2.6 × 10–13 mol H2 cm–1 kPa–1 s–1.
End-of-life conditions are considered to correspond with val-
ues in the order of 13 mA cm–2 bar–1 [3]. Oxygen cross-over is
usually not measured in situ. The permeability of membranes
for oxygen is usually half of the hydrogen permeability [18, 33].
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 7
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components

3.3.3 Open Circuit Voltage

REVIEW

The open circuit voltage is an easy

method to obtain an indication for increased
reactant cross-over. It is however less selec-
tive than the hydrogen cross-over current
measurement, and far less quantitative. The
OCV is a suitable measure for the state of the
membrane, which follows a negative trend
that coincides with the fluoride release rate
[12]. Under the test conditions, a failing
membrane showed an OCV decline from
1 V at start of the experiment to 0.7 V. At
the same time, a fluoride release rate of
60 lg day–1 cm–2 was measured. A stabi-
lised MEA shows a nearly stable OCV, and a
negligible fluoride release rate.

3.3.4 High Frequency (h.f.) Resistance

A substantial part of the high frequency
(h.f.) resistance of a PEMFC is due to the
membrane resistance. Additional contribu-
tions come from the GDLs and current col-
lector plates. Monitoring this resistance is
feasible by in situ impedance spectroscopy
[3, 49, 53]. Although the h.f. resistance would
certainly signal changes in the membrane
resistance that occurs upon degradation, it
was found not to be a very sensitive charac-
teristic for degradation [3, 49]. Chemical deg-
radation can lead to membrane thinning,
which would not only result in a lower resis-
tance but also in reduced proton conductiv-
ity that compensates this effect. Moreover,
corrosion products from metal plate oxida-
tion or carbon corrosion may have larger Fig. 1 Degradation conditions, mechanisms and effects for perfluorinated membranes.
effect on the total resistance increase. So, al-
though the h.f. resistance is a valuable pa-
rameter to monitor, its usefulness for diag- and the effects that can be measured by the various character-
nostics of membrane failure seems limited. isation tools. Membrane degradation as observed in fuel cell
testing, both under near-ideal and non-ideal conditions, is
3.3.5 Ex Situ Characterisation summarised.
Ex situ characterisation, microscopic analysis can indicate
3.4.1 Near-Ideal Conditions
cracks and especially membrane thinning that has occurred
during operation [37]. Moreover, EDX or chemical analysis In the 26,000 h test by Gore, under fully saturated condi-
can establish the presence of contaminants. 19F NMR has been tions and at 70 °C, severe (though unspecified) thinning of
used by various authors to establish the changes in the chemi- the 35 lm GORE_SELECT® membrane was observed, with
cal composition of the PFSA membranes and degradation ionomer loss most apparent at the cathode side [3]. This was
products [13, 20, 42]. X-ray diffraction is used to study mor- accompanied by an increase in the H2 cross-over rate from 1
phological changes that occurred during ageing [42]. to almost 10 mA cm–2 (at near-ambient pressure) in the first
22,000 h. At 26 300 h the cell reached end-of-life due to
membrane failure, which led researchers to postulate that
3.4 Observed Membrane Degradation in PEMFC Operation
10 mA cm–2 cross-over current density corresponds to end-
Figure 1 schematically represents the relations between of-life conditions. The h.f. resistance did not show significant
operational conditions, the main degradation mechanisms changes.

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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
Membrane thinning was also observed under near-ideal
operating conditions by Nuvera [7], where the original thick-
ness of 36 lm was reduced to 22–26 lm in 9,000 h. Osaka gas
reports a 36,000 h test on an MEA containing an unspecified
perfluorosulphonic acid membrane without any increase in
ohmic loss and only a slight OCV decrease (20 mV) [11]. This
may imply that a thicker or a more chemically stable mem-
brane was used than in the studies by Nuvera and Gore. A
sudden three-fold increase in F-concentration in the effluent
water after 800 h has been observed by Xie et al. in a 1,000 h
test at oversaturated conditions [49]. As mentioned pre-
viously, at near-ideal conditions fluoride release rates of
0.01–0.02 lg F cm–2 h–1 were measured [16, 20].
3.4.2 Reduced Humidity
Continuous operation at a relative humidity lower than
100% can lead to an increase in membrane degradation. Bal-
lard [54] reports operation time before gas cross-over passes a
certain threshold. For a non-optimised cell configuration,
3,300 h were reported in the case of a fully humidified anode
and a 70% humidified cathode, reduced to 1,100 h for a fully
humidified anode and a dry cathode, and a mere 300 h at
complete dry operation. Yu et al. observed a rather high deg-
radation rate under only slightly under-saturated conditions,
amounting to ca. 60 lVh–1, in parallel with a strong increase
in hydrogen cross-over (from 1.35 to 27 mA cm–2) [8]. As was
observed by Hori et al. [55], fuel cell degradation occurs pri-
marily in the part of the cell that is under-saturated. When
operating at relative dry conditions (at 50 °C, air RH 60%,
hydrogen RH 100%), the fuel outlet/air inlet showed the larg-
est drop in OCV and the highest hydrogen cross-over rate.
Overall cell performance drop was significantly higher at air
humidification at 60% RH of air compared to 100%.
3.4.3 High Cell Voltage
Exposing the fuel cell to low or zero current conditions has
been shown to lead to higher degradation rates and increase
in hydrogen cross-over in comparison to operation at a con-
stant current. Liu and Case [9] and Nakayama et al. [15]
found an increase in hydrogen cross-over at OCV while
operation at a constant current density did not show such an
increase. The higher the OCV/load ratio, the sooner the
increase in hydrogen cross-over started in the experiments of
Nakayama et al. [15].
The detrimental effect of OCV conditions has led to the
use of open circuit tests as accelerated membrane lifetime
evaluation [16, 36, 38]. Also the formation of a band of Pt
deposited in the membrane and its effect on membrane deg-
radation was studied in this way [32, 33]. Lee et al. showed
that replacing H2 by air during OCV reduced the degradation
substantially, another indication of the role of molecular
hydrogen and oxygen in the degradation [56].
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3.4.4 High Temperature
The temperature of the operation appears to be another
decisive factor. Low temperature mitigates the degradation,
as no increase in hydrogen cross-over was measured by Plug-
Power in a study of the influence of start/stop conditions on
fuel cell durability at 50 °C [57]. Although, the fuel cell per-
formance degradation was considerable at conditions in
which the MEA was allowed to lose much water, no lowering
of the open circuit potential was observed, suggesting that no
increase in hydrogen cross-over occurred.
On the other hand, a combination of high temperature and
reduced humidity increases the degradation rate [20]. At GM
an accelerated test was performed at 95 °C, anode 75% RH,
cathode 50% RH and 3 bar gas pressure, with a current den-
sity of 0.2 A cm–2. Depending on the membrane material, the
F release rate was between 0.3 and 2 lg cm–2 h–1[20]. The
chemical degradation led in that study to a substantial thin-
ning of the membrane, to less than half of the initial thickness
after 1,000 h at accelerated conditions.
In an early study by Gore, fluoride release rates of their
reinforced membranes during the accelerated fuel cell condi-
tion (90 °C, 0.8 A cm–2, 75% RH) were in the order of
0.2–0.6 lg F cm–2 h–1 [39]. In these tests, no correlation could
be established between the fluoride release rate on one hand
and the hydrogen permeability and lifetime on the other.
According to Gore, this is because the membrane failure is
mechanical and quite localised. The hydrogen cross-over rate
in reinforced Gore membranes (generation 2001) at the be-
ginning of life amounted to 2 mA cm–2, and increased over
time to values of 5–13 mA cm–2. The value of 13 mA cm–2,
marking end-of-life, was reached after 600–1,600 h. Loss of
ionomer varied between 2 and 28%, and again was not corre-
lated with lifetime [39].
Studies of membrane stability at even more elevated tem-
perature (e.g. 120 °C) are often carried out at reduced humid-
ity (<50%). It is expected that the chemical degradation will
be faster at these conditions than at ideal conditions. Hence, it
is encouraging that Asahi glass reports operation of a new
membrane during 400 h without membrane failure or even
significant fluoride release [12].
3.4.5 Freeze–Thaw Cycles
The effect of freeze–thaw cycles was investigated for
MEAs without [58, 59] and with [60–63] purging with dry
gas. At wet conditions, Cho et al. found a large effect on the
ohmic resistance which was however not corroborated by a
change in polarisation curve [59]. In the other cases no sub-
stantial effect on the membrane was observed. It should be
noted that purging to the extent of drying out the membrane
may not be needed to protect the membrane from freezing
damage but rather to create a reservoir where water can be
stored during start up at freezing conditions [64–66].
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 9
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
3.5 Outlook on Membranes
REVIEW
The recent results on membrane degradation have shown
that conditions associated with automotive applications such
as cycling of voltage, humidity and temperature accelerate
membrane degradation. However, good progress has been
made for PFSA membranes in the past few years by identify-
ing sources of chemical and mechanical failure and by find-
ing solutions, both by chemical modifications and by using
reinforced membranes. Recent results by DuPont [36] show
considerable improvement in durability for new materials
compared to those that were on the market when most of the
tests in Tables 1 and 2 were done. However, a full evaluation
of these improved materials still has to be carried out. This
will be facilitated by the fact that accelerated test protocols
have been developed that are more closely related to realistic
conditions than e.g. Fenton’s test and can, therefore, be
expected to give more reliable predictions of lifetimes. Addi-
tionally, this will enable a better comparison with non-fluori-
nated compounds.
4 Electrodes
4.1 Electrode Function and Requirements
The conventional PEMFC electrode consists of several dis-
tinct phases: the catalyst, composed of a high surface area car-
bon support, loaded with nano-scale catalytic particles of Pt
mixed with an ionomer recast dispersion to form the catalytic
layer. This thin catalytic layer, with Pt loading in the order of
0.4 mg cm–2, is applied between the membrane and a so-
called backing or GDL, which consists of a macro porous car-
bon cloth or carbon paper, and a thin micro porous gas diffu-
sion layer (MPL) (Figure 2). For a fast catalytic reaction, free
Fig. 2 Cross-section of an electrode with gas, proton and electron pathways.
10 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
access of gas, electrons, protons and water is needed. The life-
time issues of the electrodes, which include stability of mate-
rials as well as of structure, are discussed for the different
phases of which the electrodes are composed.
4.2 Mechanisms of Electrode Degradation
4.2.1 Platinum Dissolution and Particle Growth in PEMFC
As was mentioned in Section 2, the loss of electrochemi-
cally active surface area (ECSA) is a major source of degrada-
tion. Several studies have observed the growth of Pt particles
as well as dissolution of Pt in the membrane phase [10, 67,
68]. Both phenomena were already described for the PAFC
[69, 70], and are closely related as will be explained below.
Thermodynamics predict substantial Pt dissolution in acid
media strongly increasing with potential in the region of
0.85–0.95 V versus RHE [71], according to the reaction
Pt $ Pt2‡ ‡ 2e E0 ˆ 1:188 V versus RHE (4)
Such behaviour has been observed for Pt foil in phosphoric
acid at an elevated temperature of 196 °C [69]. The equilib-
rium electrochemical potential of the Pt dissolution decreases
with particle size [72]. Accordingly, higher equilibrium Pt2+
concentrations were measured for Pt/C at 80 °C than pre-
dicted for bulk Pt [10].
However, experiments on Pt thin film, Pt wire as well as on
nanosized Pt on C have shown that at 80 °C in the region
above 0.85 V versus RHE Pt dissolution does not show the
strong Nernstian potential dependence, and even has a maxi-
mum around 1.15 V, as shown in Figure 3 [10, 73, 74]. This
was ascribed to the formation of an oxide layer, as also pre-
dicted by a kinetic model taking into account electrochemical
formation of platinum oxide and its subse-
quent chemical dissolution [72]:
Pt ‡ H2 O $ PtO ‡ 2H‡ ‡ 2e
…5†
E0 ˆ 0:980 V versus RHE
Pt2‡ ‡ H2 O $ PtO ‡ 2H‡ (6)
The surface composition in the various
potential ranges is illustrated in Figure 4.
Surface X-ray scattering by Nagy [75] has
confirmed the formation of an oxygen skin
at potentials higher than 1.2 V, with Pt
atoms replacing oxygen atoms at even high-
er potentials. Note that this leads to disinte-
gration of the Pt surface. The formation of
oxides is also related to the observation that
potential cycling enhances the Pt dissolution.
Kawahara et al. have studied the dissolution
of Pt during cycling ex situ [76, 77]. It is
known from the literature of the early 1990s
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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
Fig. 3 Pt dissolution rate versus dissolution potential and temperature. The
real surface area of the electrode is 24 cm2. From ref. [73].
Fig. 4 Surface layer composition of platinum as function of the potential.
that fast cycling leads to oxides that are difficult to reduce,
often called b-oxides [78, 79], and that the reduction of these
b-oxides are accompanied by the dissolution of platinum [80].
Pt ions can not only dissolve according to reaction 4 or 6 in
the Pt2+ form but also in the Pt4+ form [68]. In the ionomer
they will replace H+, but it has also been suggested that they
form negatively charged anions with degradation products
like F– and SO24 (products of chemical membrane degrada-
tion or of impurities in the support) or Cl– (possible residue
from catalyst preparation). Such a complex formation would
also promote the dissolution of Pt and PtO [68].
Either through diffusion (cations) or due to the electric
field (anions) Pt will migrate towards the anode side of the
membrane [81]. However, Pt dissolved into the ionomer
phase can also redeposit on other (larger) particles in the
cathode, due to the higher equilibrium potential of dis-
solution on these particles [82]. These particles need to be on
the carbon support in order to allow for the exchange of elec-
trons. The difference in dissolution potential is considered to
be related to the surface tension. The above mechanism of
dissolution and redeposit ion is an example of Ostwald ripen-
ing, i.e. minimisation of the surface energy is the driving
force.
In PAFC studies and in some PEMFC studies there has
been some debate on whether particle growth occurs by
another mechanism, i.e. coalescence [10, 70, 83–85]. In this
mechanism Brownian motion is the driving force, causing
surface diffusion of particles with random collisions leading
to coalescence [85]. Usually the fact that sintering does not
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REVIEW
occur significantly in catalysts in the gas phase at tempera-
tures below 500 °C is considered to be an indication that coa-
lescence is not the prevailing mechanism [10, 83, 84]. In recent
PEMFC studies it was found that both potential and
increased humidity enhance the particle growth [86, 87],
which favours the dissolution/redeposition mechanism. Still,
although both mechanisms lead to an increase in the average
particle size with an asymptotic particle size distribution
(PSD) the coalescence mechanism has a log-normal distribu-
tion (tail at large sizes) and the Ostwald ripening has a tail at
the smaller particle sizes but with a maximal particle size cut-
off [88]. In many studies a log-normal distribution of Pt parti-
cle sizes was found in virgin and used electrodes [10, 67, 83,
86, 88]. However, it must be noted that this requires a good
sampling also of small particles and results can be affected by
the fact that several mechanisms are active at the same time
[10, 83]. Moreover, carbon corrosion (see the next section) can
have an effect on Pt particle growth.
4.2.2 Carbon Oxidation
Electrochemical corrosion of the carbon support in PAFCs
has been known since the 1970s and 80s. Thermodynamically,
carbon (graphite) can be electrochemically oxidised to CO2 at
quite low potentials:
C ‡ 2H2 O $ CO2 ‡ 4H‡ ‡ 4e E0 ˆ 0:207 V versus RHE (7)
Due to the slow kinetics of these reactions, carbon can still
be used in fuel cells [89]. A study by Jarvi et al. [90] showed
that on Vulcan XC72 carbon surface oxidation occurs at 65 °C
and potential >0.8 versus RHE. At these conditions a wide
variety of carbon surface oxides was formed resulting in a
reduced hydrophobicity. One specific species is the quinone
group that is electrochemically active with a redox peak at
0.55 V versus RHE that can be identified in cyclic voltamme-
try. Experiments at 1.2 V versus RHE potential hold suggested
a fast increase in surface oxides during the first 16 h and a
slower increase thereafter. The decrease in corrosion rate in
time has also been observed elsewhere [87, 91, 92].
The presence of Pt catalyses the subsequent oxidation to
CO2 as verified by DEMS for carbon activated with 20% Pt
[93]. The mechanism consists of the following steps:
C + H2O → COsurf + 2H+ + 2e– E>0.3 V versus RHE (8)
Pt
COsurf + H2O ! CO2 + 2H+ + 2e– E = 0.8 V versus RHE (9)
At a potential higher than 0.3 V versus RHE, COsurf starts
to form irreversibly on the carbon particle surface. COsurf is
oxidised on neighbouring Pt sites to CO2 at a potential of
0.8 V versus RHE. The amount of CO2 formed is proportional
to the total length of the two-dimensional grain boundaries
between the Pt particles and the carbon support [93]. These
results were confirmed by Roen et al. [94] who in the absence
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 11
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
of Pt observed CO2 emission only at potentials above 1.1 V
REVIEW
versus RHE. In the presence of Pt, CO2 emission was already
observed in a potential range of 0.55–0.6 V versus RHE. The
influence of Pt on the carbon corrosion became less pro-
nounced at temperature higher than 50 °C. By using the field
emission-scanning electron microscopy (FE-SEM) to examine
a highly oriented pyrolytic graphite (HOPG) electrode with
the Pt nanoparticles on top, CO2 formation is mostly found
around the Pt particles, but interestingly these Pt particles are
still present without becoming detached, despite carbon cor-
rosion and blister formation [95]. In a recent paper Ball et al.
found no effect of Pt on the corrosion. This conclusion, how-
ever, was based upon corrosion current measurement and
not on the direct measurement of CO2 evolution [92].
The thermal degradation of carbon and platinum support-
ed on carbon in air at an elevated temperature has been stud-
ied by Stevens [96]. Whereas the Black Pearls carbon is stable
in air at temperatures as high as 195 °C, a high platinum load-
ing can lead to a loss of more than 80% of all carbon, where
the time needed to reach the maximum amount of combusted
carbon is determined by the temperature and the platinum
loading. At platinum loadings used in commercial PEMFC
catalysts, 40 wt% and higher, the loss of carbon at the lowest
experimental temperature, 125 °C, amounted to 15% after
1,000 h. From the relation between carbon loss and tempera-
ture, it was concluded that below 100 °C thermal oxidation of
platinum loaded carbon in air did not take place [96].
However, the humidification of air substantially enhanced
the thermal corrosion rate of carbon, by providing an addi-
tional pathway for chemical carbon oxidation through a
direct reaction with water [97, 98]. In these studies, the corro-
sion rate was also found to be higher for high surface area
carbon blacks, which was ascribed to a finer dispersion of Pt
particles on this material, i.e. more particles per unit weight.
4.2.3 Oxygen Evolution
Electrochemical oxidation of water takes place at electrode
potentials >1.5 V versus RHE, i.e. in the same region where
carbon corrosion can occur:
H2O ↔ 1/2O2 + 2H+ + 2e– E0 = 1.229 V versus RHE (10)
At the cathode this will not be very harmful although it
can lead to the formation of cracks. When O2 evolution occurs
at the anode, reaction with residual hydrogen (not abundant
at high potentials) may result in a more serious damage.
4.2.4 Ionomer Degradation
The ionomer in the electrode is susceptible to many of the
same degradation mechanisms that were described for the
fuel cell membrane. In comparison to the membrane, the
ionomer is in a state that is more soluble than the Nafion
membrane, which only starts to dissolve when in water at
210 °C and high pressure of 68 atm for more than 2 h. The
stability of recast Nafion ionomer in catalyst layer is reported
12 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
to be much lower [67]. The trace of the soluble ionomer is
found in the cathode effluent water [67]. The dissolution
becomes more severe over time.
As a result of the chemically ionomer degradation, the
interface between catalyst and ionomer is lost, consequently
reducing the electrochemically active surface of the electrode.
As the ionomer acts as a binder in the electrode, it has a
strong impact on the ionic and electronic conductivity of the
electrode. The structural instability due to ionomer swelling
and dissolution during long-time exposure in high humidi-
fied conditions can change the electrical properties, leading to
degradation of the fuel cell.
4.2.5 Degradation of the GDL and MPL
The GDL and MPL are responsible for gas phase transport,
electronic contact, heat transport and water removal. The
GDL is a macroporous layer consisting of carbon fibres,
usually cloth or paper, that have to some extent been made
hydrophobic by a Teflon (PTFE) coating. The MPL, posi-
tioned between the GDL and the catalyst layer consists of car-
bon black particles and Teflon as a binder. Unlike the carbon
black in the catalyst layer, the carbon black in the MPL is not
susceptible to electrochemical corrosion and contains no Pt to
catalyse oxidation reactions, but chemical surface oxidation
by water or even loss of carbon due to oxidation to CO or
CO2 cannot be excluded [96, 98]. This will lead to increased
hydrophilicity of the MPL. The carbon fibres of the GDL may
be more stable, but otherwise are susceptible to the same
reactions. Also decomposition of PTFE, used as a binder or
hydrophobic coating has been suggested. Schulze et al. pres-
ent evidence for this on the basis of XPS data, but a mecha-
nism has not been proposed [99].
The result of these degradation mechanisms is that both
the GDL and the MPL lose their hydrophobic character [4, 6,
99], and that the pore structure of the materials changes. Both
these phenomena can have a substantial effect on the water
content of the GDL and MPL and therefore, on the mass
transport properties. Increased liquid water content of the
GDL and MPL will impede gas phase mass transport, as
pores initially used for gas phase mass transport will be
increasingly blocked by water. The relation between micro-
structure and surface properties on the one hand and mass
transport properties on the other has been the subject of sev-
eral recent experimental [100, 101] and modelling [102–105]
studies which indicate that indeed mass transport can be ser-
iously affected by the hydrophobicity of the GDL and MPL as
well as by the pore size.
The GDL properties can also be changed by mechanical
degradation as a result of the compression forces in a fuel cell.
From ex situ tests in which the material was aged under a
compression force, Lee and Mérida [106] concluded that the
compressive strain increased with the applied pressure but
even more strongly with temperature. From this it was con-
cluded that the GDL strain was influenced by the PTFE stabil-
ity. Properties like in plane electrical resistivity, surface con-
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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
tact angle, bending stiffness and porosity were not affected.
However, it was found that convective air flow through the
GDL can lead to loss of material.
4.3 Characterisation of Electrode Degradation
4.3.1 Electrochemical Characterisation
Cyclic voltammetry, carried out in situ, is used to establish
the ECSA of the electrodes. The electrode under investigation
(working electrode) is flushed with nitrogen, the other elec-
trode (counter and reference electrode) is flushed with hydro-
gen. The ECSA is measured from the hydrogen adsorption/
desorption region [52]. Cyclic voltammetry also gives infor-
mation on the double layer capacitance of the electrode or on
other electrochemically active species on the surface such as
the carbon quinone. Yoda et al. blocked the Pt catalyst sites
by CO prior to measuring the cyclic voltammogram to elimi-
nate the effect of Pt on the double layer capacitance. This gave
a clearer indication of changes at the carbon surface [107].
Impedance spectroscopy at high frequency (1–100 kHz)
can be used to determine the proton resistance of the elec-
trodes, both with O2 or with N2 on the working electrode
[53]. Impedance spectroscopy involving lower frequency and
otherwise under operational conditions can be used to inves-
tigate the charge transfer as well as the mass transport behav-
iour of the cathode [3, 99, 108].
Voltage–current characteristics measured under fuel cell
conditions yield, after correction for the ohmic losses and
neglecting the anode contribution, the polarisation curve.
Comparison of such curves obtained under oxygen and
air results in the oxygen gain, which gives indications of
limitation of transport of oxygen and/or protons in the elec-
trode.
4.3.2 Chemical Analysis of Effluents
Evolution of CO2 can be monitored by gas chromatogra-
phy or mass spectroscopy [94, 109]. Chemical analysis of
effluent water by ICP–MS or ICP–AES can detect ionomer
degradation species both at the cathode and the anode, but
results often cannot distinguish between electrode or mem-
brane degradation [49].
4.3.3 Ex Situ Characterisation
Microscopy techniques like (FEG)-SEM and TEM are com-
monly used to establish Pt particle growth, Pt deposition in
the ionomer and electrode thinning [10, 67, 68, 83]. Pt particle
size growth can also be determined by X-ray diffraction [86].
Solid-state 19F NMR [13] can be used to analyse the chemical
composition of the ionomer in anode and cathode after opera-
tion. EDX/EDS as well as ICP-AES and XPS have been used
to study the chemical composition of catalyst layers and
GDLs [7, 68, 83, 99]. Whereas EDX and ICP-AES give infor-
mation on the bulk composition of the materials, XPS has a
high surface sensitivity and gives information of surface com-
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REVIEW
position. EDX probes the sample in a broader region closed to
the surface. Raman spectroscopy can be used to characterise
the carbon surface area [13].
Methods to characterise the GDL include water and mer-
cury porosimetry. The hydrophobicity of the material can be
probed by contact-angle measurements including sessile drop
and Wilhelmy balance methods [6].
4.4 Electrode Degradation Observed in Fuel Cell Operation
A scheme of conditions enhancing electrode degradation
processes and the measurable effects is presented in Figure 5.
The results from degradation studies under relevant condi-
tions are discussed in the following sections.
4.4.1 Near-Ideal Conditions
The 26,000 h test by Gore at 0.8 A cm–2, at 70 °C and full
humidification of the gases revealed a 66% decrease in the
ECSA at the cathode, 25% decrease in the proton resistance of
the cathode and an increase in the polarisation resistance. The
decrease in the ECSA corresponded to 34 mV voltage loss, by
the relation blog(a1/a2), with b being the kinetic Tafel slope
and a1 and a2 the ECSA before and after the test, respectively.
The total electrode loss increased by 116 mV, which indicates
substantial mass transport losses. Post-test analysis revealed
no significant changes in the backings or catalyst layer, i.e. no
corrosion of the carbon support or measurable change in
hydrophobicity of the backing. In addition, SEM did not
detect Pt in the membrane or further substantial changes in
the Pt distribution in the electrode [3]. Pt particle growth
seems to have been the main factor for ECSA loss. A loss of
ECSA at the Pt/C cathode was also reported by Ferreira in a
2,000 h test at 0.3 Acm–2. In this case a reduction of 43% was
measured [10]. Nuvera reported 60% loss of ECSA cathode
after 9,000 h at 0.7 V [7].
Pt particle growth at the anode under near-ideal condi-
tions was observed by Xie et al. [67], with particles increasing
from 1–6 to 3–15 nm after 500 h in a MEA operated at
1.07 Acm–2. Also Pt migration to the membrane interface and
into the membrane seemed to have occurred. Liu and Case
report a larger decrease in ECSA at the anode than at the
cathode under constant current conditions [9]. Pt particle
growth may occur by coalescence, as the mechanism of dis-
solution and redeposition is not favoured by the potential at
the anode. On the other hand, it has been suggested that Pt
particle growth can arise from Pt crossing over from cathode
to anode. This was observed for PAFC [70], and predicted by
the model of Darling and Meyers [81]. Recently Guilminot et
al. reported an apparent net migration of Pt from cathode to
anode [83]. On the other hand Zhang et al. measured a con-
stant Pt content at the anode [33]. Due to the fast hydrogen
oxidation kinetics, the ECSA loss at the anode is not expected
to lead to a decrease in cell voltage.
Carbon corrosion was suggested by Nuvera for a cell that
had operated for 5,000 h both from a reduction of the C/F
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 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
REVIEW
Fig. 5 Degradation conditions, mechanisms and effects for electrodes.
atomic rate (established by EDX) and a thinning of the elec-
trodes [7].
Increase in mass transport losses was observed by several
groups [3, 4, 6, 9, 99], and in most cases ascribed to increased
hydrophilicity of the electrode. Note that these mass trans-
port losses were in some cases quite substantial and indeed
dominated the observed voltage loss, e.g. in the stationary
state test by Liu and Case [9] and in the long-term study by
Gore (70% of the 116 mV) [3], although in this case mass
transport may have been enhanced by the increased compres-
sion force (see Section 6). However, at Ballard only a slight
increase was observed in the 11,000 h test [5]. Other studies
at Ballard have shown that the increase in mass transport can
be enhanced by exposure of the electrode to liquid water [4],
which would be in agreement with the mechanism of carbon
(surface) oxidation discussed previously. On the other hand,
it was reported in the same paper that insufficient humidifi-
cation can also increase mass transport effects, which led the
14 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
authors to conclude that optimal water man-
agement would be a key parameter to miti-
gate voltage loss from increased mass trans-
port limitations. The fact that excess liquid
water cannot be the sole cause for loss of
hydrophobicity was illustrated in a recent
paper by Schulze where it was observed that
PTFE decomposition was more pronounced
on the anode than on the cathode side [99].
Xie et al. [49] also observed washing out
and degradation of the ionomer phase in the
electrode by measuring F and S release in
the effluent water. Note that gas transport
rather than electronic or protonic transport
is the most probable cause of increased
polarisation losses not directly related to
ECSA loss. The effect of carbon corrosion
and ionomer degradation on the electronic
and protonic transport has not been estab-
lished unambiguously. Some results indicate
improved transport due to better contacts
arising from swelling of the ionomer [3, 107],
or due to thinning of the electrode. On the
other hand, loss of structural integrity of the
catalyst layer may add to the ohmic resis-
tance [49].
4.4.2 Potential Cycling and OCV Conditions
Several authors report results from poten-
tial cycling of MEAs. This can involve differ-
ent experiments, i.e. under H2/N2 [10, 31, 86,
110] or H2/air [111, 112] with a potentiostat,
by load on–load off cycles [9, 13] or by a
simulated drive cycle [86]. Also studies at
OCV [10, 32, 86] or near OCV [107] condi-
tions were performed. In all cases a faster
decrease in the cathode ECSA was observed
than under constant load conditions. The results suggest that
the ECSA decreases faster as a result of cycling to high volt-
ages [10, 86, 110, 112] and that the reduction increases with
the maximum applied voltage (range 0.96–1.5 V). This can be
illustrated by data by Ferreira et al. [10]. A 46% loss of ECSA
was measured at 0.2 Acm–2 (0.75 V) after 2,000 h. At OCV
(0. 95 V) conditions 75% loss was observed over the same pe-
riod. However, after 10,000 cycles between 0.87 and 1.2 V in
only 100 h, 69% of the Pt ECSA was lost.
The faster decrease in ECSA is generally ascribed to faster
dissolution of Pt at higher potential and during cycling, pro-
moting the dissolution/redeposition mechanism. Also carbon
corrosion may add to the ECSA loss [98]. In general the
decrease in ECSA is slower on lower surface area carbons,
with graphitised carbon showing the slowest rate of ECSA
loss [87, 97, 98]. This may be not only due to larger initial par-
ticle size, but also be related to a lower rate of carbon corro-
sion.
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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
Since the dissolution is faster, Pt particles are also more
often detected in the membrane after cycling or exposure to
OCV. A quite frequent observance is a Pt band at a certain
distance from the cathode [10, 31–33, 110–112]. In the case of
PAFC, Pt was able to move to the anode and deposit there
[70]. It was found that in PEMFC the position of this band
depends on the H2 and O2 partial gas pressures, with the
band moving towards the anode upon a reduction of the H2
partial pressure or an increase in the O2 partial pressure [31,
33, 111]. Burlatsky et al. [31] presented a model that shows
precipitation occuring at a location where there is a stepwise
change of the electrochemical potential. In turn, such an
increase occurs at Pt particles >20 nm, on which the reaction
of H2 and O2 is diffusion controlled, and at the location in the
membrane where this reaction results in complete local
depletion of H2 and O2. Burlatsky also observed smaller
(5–10 nm) particles throughout the membrane. At these parti-
cles the potential is constant. Results were confirmed by
Zhang et al. and Bi et al. [33, 111]. Zhang et al. remarked that
the presence of a Pt band may affect the H2 concentration pro-
file in the membrane, which may have consequences for the
membrane degradation.
There has been some doubt whether Pt particles observed
in the membrane were result of oxidation and reduction of Pt
or resulted from carbon oxidation which made them come off
the support. TEM studies have revealed that the particles
have a flower-like dendrite structure, more in agreement with
the first explanation [10, 68].
Enhanced carbon corrosion was also reported at higher cell
voltage [86, 107], but appears for voltages up to OCV not to
be a major factor. The corrosion of the carbon surface can lead
to a minor positive as well as to a major negative influence on
the fuel cell performance. Part of the platinum surface can be
covered by carbonaceous species after electrode preparation,
making it inaccessible for oxygen and thus reducing the activ-
ity of the fuel cell [113]. In the initial operation period, the car-
bon corrosion can unblock these Pt particles and therefore
increase the catalyst surface available for reaction. However,
in the long run, the negative effects of carbon corrosion domi-
nate through increased hydrophilicity of the oxidised carbon
surface, reduced location sites and electronic contact for Pt
particles and modified gas permeability of the gas diffusion
layer [95].
Fig. 6 Reactions in a fuel cell under start-up/shutdown when hydrogen and air are both present in the anode compartment. Left-hand side contains
hydrogen, right-hand side contains air. Adapted from ref. [106].
FUEL CELLS 08, 2008, No. 1, 3–22 www.fuelcells.wiley-vch.de
REVIEW
4.4.3 Start–Stop Cycles
At cell potentials of ≥1.2 V, carbon corrosion is accelerated.
This was confirmed by Borup et al. [86] and also by Mathias
et al. who demonstrated that a standard Pt/C catalyst lost
15% of its weight during 20 h at 1.2 V [87]. Although cell volt-
ages higher than OCV are not expected to occur during nor-
mal operational conditions, it was shown by Reiser et al. [114]
that high cathode potentials (versus RHE) can be expected
during start–stop cycles, when due to leakage of air a hydro-
gen/air front develops at the anode. This is illustrated in Fig-
ure 6. The presence of O2 at the right-hand side of the cell
results in a drop of the electrolyte potential in the order of
0.6 V, which results in cathode potentials at the right-hand
side in the order 1.4 V versus RHE. The electron balance is
restored by the normal fuel cell reactions occurring at the left-
hand side. Alternatively, the result can be considered as two
fuel cell reactions occurring in the horizontal direction of the
fuel cell. At the right-hand side, the species to be oxidised are
water, carbon and platinum. The protons however are
exchanged vertically, as the horizontal pathway is too long.
At OCV conditions both oxygen reduction reactions occur at
the same speed. Mathias et al. estimated that a fuel cell car
would spend 100 h during its envisaged lifetime experiencing
such harsh conditions. The present materials would therefore
appear inadequate for automotive application [87].
Experiments by Reiser et al. confirmed severe carbon deg-
radation as a result of the above conditions [114]. However,
water and Pt can also be oxidised at these potentials. Pt oxi-
dation may be limited by oxide formation (see above). The
importance of water oxidation, i.e. oxygen evolution, cannot
be ignored. At the relevant potentials the respective rates are
of the same order of magnitude [115, 116] and will be affected
by e.g. the type of carbon and catalyst dispersed on it [87] or
by the humidity. In experiments by Ballard and Borup et al. it
was observed that carbon corrosion during start–stop cycles
was enhanced at low humidity [57, 86, 116].
A better insight in the role of water at these conditions will
help to develop mitigation strategies as oxygen evolution is
considered to be less harmful than carbon corrosion, i.e. may
even result in increased active area [57]. Development of stra-
tegies or catalysts promoting water oxidation can also be con-
sidered. Yu et al. assumed that at OCV conditions the ORR
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 15
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
reaction at the right-hand side is the rate-limiting factor for
REVIEW
the reaction occurring at OCV. Reduction of the anode cata-
lyst loading to 0.05 mg Pt cm–2 seemed to reduce the carbon
and water oxidation rate, while not affecting anode losses
during normal operation [117].
4.4.4 Fuel Starvation
Experiments at Ballard showed that during severe fuel
starvation, mimicked by replacing H2 by N2 at the anode, the
cell voltage became negative, i.e. cell reversal occurred. The
negative cell voltage corresponded to a potential >1.23 V ver-
sus RHE at the anode allowing for water oxidation to sustain
the imposed current density [54]. Further experiments
showed that in time the potential decreased further, creating
potentials favourable for carbon oxidation, which was con-
firmed by the presence of CO2 in the effluent gas [109].
Taniguchi et al. [118] have shown that fuel starvation led
to cell potentials of –2 V, where the anode potential increased
to 2.2 V, while the cathode potential only dropped slightly.
Three minutes of fuel starvation (utilisation in experi-
ment = 100%) led to a 25% lower current density at 0.7 V,
and starvation for 7 min led to 50% lower current density. At
the anode, enrichment of platinum in the Pt/Ru catalyst was
observed, indicating the loss of ruthenium. Determination of
the average particle size by TEM revealed that the mean par-
ticle size increased from 2.6 to 5 nm at the anode and from
2.8 to 4 nm at the cathode. The increase at the cathode was
somewhat unexpected at the time but may have been related
to effects of local starvation described below.
Reiser et al. already have described that the situation giv-
ing rise to high cathode potentials during start–stop cycles is
similar to that occurring during local fuel starvation, e.g. dur-
ing flooding of the anode compartment [114]. In more de-
tailed studies it was confirmed that when the fuel starvation
area is larger than a critical dimension of ca. 20 mm, then
again high cathode potentials arise [116, 119]. The situation is
similar to that depicted in Figure 6, with the exception that
the oxygen at the anode now results from oxygen cross-over
to a hydrogen-depleted region at the anode. The oxygen
cross-over rate now determines the reaction rate in the fuel
starvation section, and hence the combined rates of carbon
corrosion and oxygen evolution at the cathode. In these
experiments, severe carbon corrosion was observed.
4.4.5 Air Starvation
When oxygen is depleted at the cathode (an event called
air starvation) hydrogen evolution takes over from oxygen
reduction by the reduction of protons. In this case, the cell
voltage is slightly negative, as both hydrogen oxidation and
reduction are facile reactions. Although not directly as detri-
mental as fuel starvation, the mixture of hydrogen and air at
the cathode can lead to undesired heat generation [109]. In
the 26 000 h test by Gore, a 24 h situation of air starvation
seems to have led to a decrease in the available electrochemi-
cally active platinum surface area [3].
16 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
4.4.6 Low Relative Humidity–High Temperature
In potential cycling experiments it was found that reduced
humidification slows down Pt particle growth in agreement
with reduced Pt dissolution rates [86, 87]. The effect of low
relative humidity on carbon corrosion has already been dis-
cussed previously. An increase in temperature on the other
hand promotes Pt particle growth [86, 87]. A similar result
was obtained by Yoda et al., who also reported enhanced car-
bon oxidation at 90 °C compared to 80 °C [107].
Guilminot et al. report on a stack test of 529 h at 60 °C, air
75% RH and dry hydrogen operated at 0.18 Acm–2 (about
0.67 V). In spite of the low temperature, short test duration
and relatively dry conditions, a substantial redistribution of
Pt in the cell was reported as well as carbon corrosion. How-
ever, it is possible that the results were affected by a rest peri-
od of 123 h in cell operation after 63 h. The conditions at rest
were not completely clear, whereas in a first publication it
was stated that the cell was purged with H2, in a subsequent
paper the rest period was used to explain the occurrence of
carbon corrosion [68, 83].
4.4.7 Freeze–Thaw Cycles
Freezing of the water contained in the membrane-electrode
assembly can lead to performance loss [59, 60]. With (partial)
water removal prior to freezing, the cell voltage loss can be
limited to the order of 0.1–0.3 mV per freeze–thaw cycle
[61–63, 120]. Observed physical changes in the electrode
structure observed in these studies included faster loss of
ECSA as well as increased porosity. Effective removal of the
water is possible by either gas purging, or washing away
with antifreeze liquids [54, 120].
4.5 Outlook on Electrode Degradation
Many factors that enhance membrane degradation, such as
potential cycling and elevated temperature, also accelerate
electrode degradation. The role of relative humidity is more
ambiguous, but additional complications come from start–
stop cycles and incidents of fuel starvation. The exact effect of
most of these conditions on lifetime still has to be established,
but from estimates by e.g. GM it appears that state-of-the-art
Pt/C catalysts will not meet the requirements [87]. Alterna-
tives for Pt have been suggested, such as PtCo alloys that
have in some tests shown to be more stable as well as more
active [87, 110, 121, 122], but their stability and activity
require much further research.
The issue of carbon corrosion seems to be of even greater
concern. Graphitic carbon is more stable than the conven-
tionally used carbon black, but has a lower surface area. This
limits the minimum metal particle size, which reduces the
activity. In combination with the requirement for further
reduction of the Pt loading this is not a promising situation.
The carbon corrosion may also be mitigated by promoting
competing reactions. Development of catalysts for oxygen
evolution has been suggested, but this concept still has to be
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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
proven and may introduce new durability issues. The same
holds for alternative supports [121]. A new electrode concept
is based upon non-conductive organic whiskers coated by Pt
[123]. In this concept by 3M the support is not exposed to the
electrolyte, and Pt forms a continuous structure that is much
less susceptible to dissolution and shows a high specific activ-
ity towards the ORR. In spite of the low active surface area
that is obtained and anticipated mass transport problems
[121], this may, from a durability point of view, be a superior
concept.
The issue of gradual performance loss due to degradation
in the GDL is still largely uninvestigated. This may seem
somewhat surprising in view of the fact that the effects can be
more severe than the loss of ECSA that has received much
more attention recently. Development of techniques that
enable investigation of GDL degradation in situ seems highly
desired.
In spite of the recent research that has led to many new
insights, testing protocols and characterisation methods,
improvement of the electrodes to meet the durability targets
still appears to be a formidable task.
5 Bipolar Plate Durability
The bipolar plate serves as a separator between two adja-
cent cells. It conducts the electronic current between these
two cells, separates the gases and contains the flow patterns
both for the reactants and for the coolant, in most cases a liq-
uid coolant. For this review, graphite, polymer–graphite com-
posites as well as metal-based bipolar plates have been con-
sidered.
With respect to the electric conductivity of bipolar plates,
the contact resistance is more important than the bulk re-
sistance, especially with regard to long-term behaviour.
Whereas a beginning of life resistance of 10 mXcm2 is sug-
gested as a specification [124], for long-term stability a com-
bined specification for anode and cathode side of lower than
50 mXcm2 has been used as a target specification which has
to be maintained up to 5,000 h of fuel cell operation [125].
The release of contaminants from the bipolar plates is a
feature which can determine to a large extent the lifetime of
the fuel cell. Whereas it does not so much affect the properties
of the bipolar plates itself, it leads to poisoning of the mem-
brane and the catalysts. For Nafion 117 membranes (thickness
175 lm), it was calculated that when using metal bipolar
plates, a total release of cations of 8 × 10–7 mol cm–2 during
the total lifetime (5,000 h) was acceptable, limiting the
exchange of protons in the membrane to 5% [125]. As nowa-
days thinner membranes are used, this maximum release
should amount to 2–3 × 10–7 mol cm–2 during the total life-
time.
5.1 Graphite and Graphite Composite Plates
For graphite and graphite composite plates, corrosion and
release of contaminants under normal operation is not an
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REVIEW
issue. Davies et al. [126] report stable fuel cell performance
using POCO Graphite for 1,750 h. Mueller et al. found no sig-
nificant release of sodium and organics from SGL injection-
molded and compression-molded polymer–graphite plates ex
situ in diluted sulphuric acid at 85 °C and in concentrated
phosphoric acid at 200 °C after more than 2,000 h [127]. Mak-
kus et al. [125] have measured, after 300 h fuel cell testing
with graphite plates, concentrations of 40 mgkg–1 membrane
for iron and 15 mgkg–1 membrane for nickel, without loss of
fuel cell performance.
At normal operating conditions the cathode potential is
not high enough for oxide formation on the surface, and the
contact resistance remains constant during fuel cell operation
[125, 126]. Although not reported, under extreme conditions
corrosion of the graphite is conceivable. Especially under
start–stop or fuel starvation conditions, electrodes can be
exposed to potentials promoting carbon corrosion. In our
own laboratory, we have observed the complete erosion of a
POCO graphite flow pattern during an accidental exposure of
the flow plate under cell reversal for several hours.
5.2 Metal Bipolar Plates
For metal-based bipolar plates, the stability depends on
the nature of the metal, the potential and relative humidity.
Corrosion of the bipolar plates takes place when the plate
material is oxidised at the potential to which it is exposed,
and the surface oxide layer is soluble in the medium it is situ-
ated in. The medium is often not well defined. When in direct
contact with the electrolytic membrane, the plate–membrane
contact can lead to direct exchange of cations with protons of
the electrolyte. On the other hand, the water produced in the
fuel cell also contains ions, emanating from the electrodes
and the membranes. It has been measured to have a pH
around 4 [20] and thus, can be considered as a weak corrosive
medium.
When using stainless steel bipolar plates, corrosion is a
generally observed phenomenon, which varies strongly
between the various stainless steel grades [125, 126, 128, 129].
Corrosion generally takes place at the anode, where most
stainless steels are operated in their active region [130]. This
means that metals directly dissolve in the medium they are
exposed to, without the formation of an oxide layer. When in
direct contact with the membrane, no suitable metals could
be identified which were not subjected to corrosion at the
anode [125]. When direct contact between membrane and
bipolar plate is avoided, some metals could be selected with
an acceptable low corrosion rate [125]. The composition of
alloy B of that study, which could at that time not be dis-
closed, was stainless steel 904L. The suitability of that steel
with respect to corrosion resistance has also been reported by
Iversen [129]. Many other stainless steels suffer from corro-
sion, even when avoiding direct contact.
The use of SS316L stainless steel end plates was shown by
Pozio et al. to contribute to the performance loss of PEMFCs
[48]. Although the end plates were not in direct contact with
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 17
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
the MEA, the MEA is contaminated by iron through contact
REVIEW
with humidified oxygen and hydrogen. At a rather low cur-
rent density, 141 mA cm–2, and using very low current densi-
ties of 9 mA cm–2 overnight and during weekend periods, a
steadily decreasing cell voltage was observed, amounting to
30 lVh–1. When using aluminium end plates, no performance
loss was observed. At the same time, a low pH and fluoride
release was measured at the anode and cathode. A direct link
between performance loss and materials properties was not
provided.
Elemental analysis of the membrane after 5,000 h testing at
Nuvera, using metallic current collector and bipolar plates,
did not lead to detectable amounts of foreign metal ions in
the membrane, except for platinum [7].
At the cathode side, the potential is high enough to form a
partly conducting passive layer on the metal surface. Al-
though, it protects the surface from corrosion, this layer
results in an increase in contact resistance. Many metals show
a build up of such a passive layer under long-term testing in
a fuel cell. This is a process which can take place over thou-
sands of hours, thus finally exceeding a maximum tolerable
resistance [125]. Although, not directly influencing the build
up of the passive layer, the compression force has a signifi-
cant influence on the contact resistance, and can explain dif-
ferences in various studies where one qualifies a stainless
steel as 316L [126], while the other rejects it on the basis of
increasing contact resistance [125]. Switching gases in the
cathode compartment from air to hydrogen is an effective
method to cause a breakdown of the passive layer at the cath-
ode side of the bipolar plate, leading to a decrease in contact
resistance in a couple of hours [125].
6 Seals
Fuel cell stacks contain seals on the MEA side as well as on
the coolant side of the bipolar plate. Not only are they meant
to prevent leakage of the gases and the coolants outside their
containments, seals function as electrical insulation, stack
height control and variability control as well [131]. The degra-
dation phenomena connected to seals do not only refer to the
loss of the functionality of the seals themselves, but also to
the leakage of seal components that could poison the MEA.
Degradation phenomena on seals are in general poorly
understood, and only a very few number of papers have been
published on seal degradation [131–134]. Papers from Frisch
[131] and Du et al. [132] report on the selection of seals that
meet fuel cell requirements. Plugpower used an ex situ
method to test the seals resistance against a specific coolant
as well as against acids that mimic the fuel cell environment
[132]. Weight change and the release of contaminants are
used as indicators for the compatibility of the seals. Without
giving hints to specific materials, the differences between var-
ious materials appeared to be huge.
18 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Dow Corning [131] considered silicone elastomers as seals.
The stability against coolant is not seen as a problem by Dow
Corning for these silicone elastomers, while there is concern
about the stability in the MEA compartment. Exposure of
sealing materials to a mixture of various acids in a 1 M con-
centration at undefined temperature is used as ex situ ageing
test. General-purpose silicone elastomers show cracks after
336 h in such a test, while special fuel cell grade silicone elas-
tomers survive such a test for over a year without showing
cracks.
In a recent study [133] the stability of various sealing mate-
rials has been tested in a simulated environment at 60 and
80 °C. This simulated environment consisted of solutions
containing HF and H2SO4, in two different concentrations. It
was concluded that silicone S and silicone G are heavily
degraded in the concentrated solutions as well as the diluted
concentrations, although most of the data are collected in the
concentrated solutions. Degradation reveals itself by weight
loss, complete disintegration, as well as by leaching of Mg
and Ca. The latter stem from magnesium oxide and calcium
carbonate, which are used as fillers for obtaining the desired
tensile strength, hardness and resistance to compression.
When these components are leached out, mechanical proper-
ties will be lost, and one might expect a negative influence on
fuel cell performance as well, as these components can
replace protons in the membrane as well as affect the proper-
ties of gas diffusion media and electrodes. An increase in
temperature, as well as exposure to stress accelerates the deg-
radation. The degradation mechanism is thought to involve
decross-linking as well as backbone scission. Materials that
much better survive the exposure to the solutions are ethyl-
ene-propylene-diene-monomer (EPDM) and fluoroelasto-
mers.
Only in a couple of long-term experiments was seal degra-
dation observed, and this might have been the consequence
of an inappropriate materials selection. Silicone seals in direct
contact with a perfluorosulphonic acid membrane suffer from
degradation, at the anode as well as at the cathode [134]. The
degradation is probably caused by acidic decomposition of
the sealing material, leading to colouration of the membrane
and detectable amounts of silicon on the electrodes. No fuel
cell performance loss or increase in gas leakage along the seal
has been observed. The same observation has been made by
St.-Pierre and Jia after a 11,000 h test with a Ballard Mark 513
stack [5]. The seals were visibly oxidised, albeit more in the
humidification section than in the active section. In the
26,000 h testing by Gore, complete degradation of the glass
reinforced silicone seal has been observed [3]. It forced them
to increase the compression force to keep the cell gas tight.
This might have had an impact on the effective porosity of
the gas diffusion media. The silicon of the seal could be
detected throughout the MEA, especially on the gas diffusion
media.
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de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
Table 3 Dominant degradation mechanisms at conditions that fuel cells might be exposed to during their operational life and mitigation strategies.
Condition Dominant degradation mechanism
Ideal (T≤75 °C, RH ≥ 95%, GDL loss of hydrophobicity
voltage ≤ 0.8 V)
Low RH (<95%, voltage ≤ 0.8 V) Membrane degradation (EOL)
RH cycling Membrane mechanical properties (EOL)
Open circuit voltage Membrane degradation
Potential cycling Pt particle growth cathode
Pt dissolution cathode
Start–stop cycles Carbon corrosion
Fuel starvation Carbon corrosion
Freezing Mechanical stability GDL
EOL, leading to a sudden end-of-life.
7 Conclusion
For a fuel cell operating under constant load conditions, at
a relative humidity close to 100% and at a temperature of
maximum 75 °C, using optimal stack and flow design, the
voltage degradation can be as low as 1–2 lVh–1. For station-
ary applications this would result in 40–80 mV performance
loss over 40,000 h, i.e. an efficiency and power loss of 10%
over 40,000 h lifetime. At these near-ideal conditions the
dominant cause of degradation issue is the decrease in water
removal capacity of the GDL. Other degradation issues are (i)
chemical degradation of the PFSA membrane, which does not
result in significant voltage degradation but can determine
end-of-life, (ii) Pt particle growth which results in a steady
decrease in cell voltage. Bipolar plates, if made of graphite or
graphite composite, do not present durability issues. Sealing
materials on the other hand require further investigation as
there are incidents of severe deterioration.
However, the degradation rates can increase by orders of
magnitude when conditions include load cycling, start–stop
cycles, low humidification or humidification cycling, tem-
peratures of 90 °C or higher and fuel starvation. Such condi-
tions are expected for automotive applications, which means
that a target for automotive of 10% efficiency loss, albeit over
only 5,000 h, cannot be met with state-of-the-art materials. It
does not seem realistic that such conditions can always be
avoided by system optimisation without making the system
too complex. This implies that the materials need to be more
robust. Most of the degradation issues for the materials are
the same as for ideal conditions, but are much accelerated
under these harsh conditions. Moreover, the fact that they
can reinforce each other has a larger impact under these con-
ditions. Additionally, carbon corrosion, which is not so
apparent at steady-state conditions, can be very detrimental
during start–stop cycles and fuel starvation. Table 3 sum-
marises the dominant degradation mechanism for each oper-
ating condition, the factors that enhance the mechanism, and
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REVIEW
Mitigation strategies Factors leading to even more
severe degradation
Optimisation of flow field design
Chemically stable membranes High T
Reinforced membranes
Optimisation of flow field design
Reinforced membranes
Chemically stable membranes Low RH
Reinforced membranes
More stable Pt alloys High RH, high T
More stable (carbon) supports Low RH
Operating procedures
More stable carbon supports
Catalysts enhancing water oxidation
Sufficient removal of water after shutdown
the mitigation strategy for that mechanism. It does not
exclude that other mechanisms contribute to the irreversible
loss of performance under that condition.
As regards PFSA membranes, it is concluded that consid-
erable progress in durability has been made in recent years,
by chemical modifications and reinforcement with inert mate-
rial. It can be expected that these improvements will not ser-
iously affect cost and performance. For the electrodes, the
severity of durability issues was perhaps recognised at a later
stage (although known from earlier PAFC studies). Conse-
quently, solutions are further away. State-of-the-art Pt and
carbon-black support materials do not meet the requirements.
Alternatives are being investigated, but still have to be evalu-
ated with respect to performance, cost and durability. A final
issue is the research into the loss of water-removing capacity
of the GDLs, which is still in its infancy. As these water man-
agement issues contribute a major part of the overall degrada-
tion, they deserve more attention.
Acknowledgements
This work was part of the Dutch EOS-LT PEMLIFE project,
supported by the Ministry of Economic Affairs, contract no.
EOSLT01029.
Reference
[1] X. Cheng, Z. Shi, N. Glass, L. Zhang, J. Zhang, D. Song,
Z.-S. Liu, H. Wang, J. Shen, J. Power Sources 2007, 165,
739.
[2] S. Yoshioka, A. Yoshimura, H. Fukumoto, O. Hiroi,
H. Yoshiyasu, J. Power Sources 2005, 144, 146.
[3] S. J. C. Cleghorn, D. K. Mayfield, D. A. Moore, J. C.
Moore, G. Rusch, T. W. Sherman, N. T. Sisofo,
U. Beuscher, J. Power Sources 2006, 158, 446.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 19
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
[4] J. St-Pierre, D. P. Wilkinson, S. D. Knights, M. Bos, J.
REVIEW
New Mater. Electrochem. Syst. 2000, 3, 99.
[5] J. St-Pierre, N. Jia, J. New Mater. Electrochem. Syst. 2002,
5, 263.
[6] D. Wood, J. Davey, F. Garzon, P. Atanassov, R. Borup,
2005 Fuel Cell Seminar Abstracts, Courtesy Associates,
Palm Springs, 2005.
[7] Y. Shi, A. Horky, O. Polevaya, J. Cross, 2005 Fuel Cell
Seminar Abstracts, Courtesy Associates, Palm Springs,
2005.
[8] J. Yu, T. Matsuura, Y. Yoshikawa, N. Islam, M. Hori,
Electrochem. Solid-State Lett. 2005, 8, A156.
[9] D. Liu, S. Case, J. Power Sources 2006, 162, 521.
[10] P. J. Ferreira, G. J. la O’, Y. Shao-Horn, D. Morgan,
R. Makharia, S. Kocha, H. A. Gasteiger, J. Electrochem.
Soc. 2005, 152, A2256.
[11] O. Yamazaki, Y. Oomori, H. Shintaku, T. Tabata, 2005
Fuel Cell Seminar Abstracts, Courtesy Associates, Palm
Springs, 2005.
[12] E. Endoh, 2005 Fuel Cell Seminar Abstracts, Courtesy As-
sociates, Palm Springs, 2005, pp. 180.
[13] R. Miyoshi, Y. Sakiyama, Y. Miwa, Y. Aoki, T. Yamamo-
to, Y. Ueno, A. Masuda, Y. Nakagawa, G. Katagiri,
H. Nakayama, M. Hori, 2006 Fuel Cell Seminar Abstracts,
Courtesy Associates, Hawaii, 2006.
[14] B. Wahdame, D. Candusso, X. Francois, F. Harel, M.-C.
Pera, D. Hissel, J.-M. Kaufmann, Int. J. Hydrogen Energy
2007, 32, 5493.
[15] H. Nakayama, T. Tsugane, M. Kato, Y. Nakagawa,
M. Hori, 2006 Fuel Cell Seminar Abstracts, Courtesy As-
sociates, Hawaii, 2006.
[16] E. Endoh, S. Terazono, H. Widjaja, Y. Takimoto, Electro-
chem. Solid-State Lett. 2004, 7, A209.
[17] C. Wieser, Fuel Cells 2004, 4, 245.
[18] A. B. LaConti, M. Hamdan, R. C. McDonald in Handbook
of Fuel Cells, Vol. 3 (Eds. W. Vielstich, A. Lamm, H. A.
Gasteiger), Wiley, Chichester, 2003, pp. 647.
[19] D. P. Wilkinson, J. St-Pierre in Handbook of Fuel Cells,
Vol. 3 (Eds. W. Vielstich, A. Lamm, H. A. Gasteiger),
Wiley, Chichester, 2003, pp. 611.
[20] J. Healy, C. Hayden, T. Xie, K. Olson, R. Waldo,
R. Brundage, H. Gasteiger, J. Abbott, Fuel Cells 2005, 5,
302.
[21] C. Huang, K. S. Tan, J. Lin, K. L. Tan, Chem. Phys. Lett.
2003, 371, 80.
[22] D. E. Curtin, R. D. Lousenberg, T. J. Henry, P. C. Tange-
man, M. E. Tisack, J. Power Sources 2004, 131, 41.
[23] A. Panchenko, H. Dilger, J. Kerres, M. Hein, A. Ullrich,
T. Kaz, E. Roduner, Phys. Chem. Chem. Phys. 2004, 6,
2891.
[24] H. Liu, H. A. Gasteiger, A. B. LaConti, J. Zhang, ECS
Trans. 2006, 1, 283.
[25] M. Aoki, H. Uchida, M. Watanabe, Electrochem. Com-
mun. 2005, 7, 1434.
[26] R. He, R. Vohra, 2006 Fuel Cell Seminar Abstracts, Cour-
tesy Associates, Hawaii, USA, 2006.
20 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[27] V. O. Mittal, H. R. Kunz, J. M. Fenton, J. Electrochem.
Soc. 2006, 153, A1755.
[28] V. O. Mittal, H. R. Kunz, J. M. Fenton, Electrochem. Solid-
State Lett. 2006, 9, A299.
[29] V. O. Mittal, H. R. Kunz, J. M. Fenton, J. Electrochem.
Soc. 2007, 154, B652.
[30] M. Inaba, Water, Steam and Aqueous Solutions for Electric
Power: Advances in Science and Technology, Proceedings of
the 14th International Conference on the Properties of Water
and Steam, (Eds: M. Nakahara, N. Mabubayas, M. Ueno,
K. Kasuoka and K. Watanabe), Maruzen Co. Ltd. Tokyo,
Japan, 2005, pp. 395.
[31] S. F. Burlatsky, V. Atrazhev, N. Cipollini, D. Condit,
N. Erikhman, ECS Trans. 2006, 1, 239.
[32] A. Ohma, S. Suga, S. Yamamoto, K. Shinohara, J. Electro-
chem. Soc. 2007, 154, B757.
[33] J. Zhang, B. A. Litteer, W. Gu, H. Liu, H. A. Gasteiger,
J. Electrochem. Soc. 2007, 154, B1006.
[34] J. Rozière, D. J. Jones, Ann. Rev. Mater. Res. 2003, 33, 503.
[35] L. Zhang, C. S. Ma, S. Mukerjee, Electrochim. Acta 2003,
48, 1845.
[36] G. Escobedo, K. Raiford, G. S. Nagarajan, K. E. Schwie-
bert, ECS Trans. 2006, 1, 303.
[37] C. Stone, G. H. M. Calis, 2006 Fuel Cell Seminar Abstracts,
Courtesy Associates, Hawaii, 2006.
[38] H. Tang, S. Peikang, S. P. Jiang, F. Wang, M. Pan,
J. Power Sources 2007, 170, 85.
[39] W. Liu, K. Ruth, G. Rusch, J. New. Mater. Electrochem.
Syst. 2001, 4, 227.
[40] S. Cleghorn, J. Kolde, 2005 Fuel Cell Seminar Abstracts,
Courtesy Associates, Palm Springs, 2005, pp. 138.
[41] T. Okada in Handbook of Fuel Cells, Vol. 3 (Eds. W. Viel-
stich, A. Lamm, H. A. Gasteiger), Wiley, Chichester,
2003, pp. 627.
[42] C. Iojoiu, E. Guilminot, F. Maillard, M. Chatenet, J. Y.
Sanchez, E. Claude, E. Rossinot, J. Electrochem. Soc. 2007,
154, B1115.
[43] M. Cappadonia, J. W. Erning, S. M. Niaki, U. Stimming,
Solid State Ionics 1995, 77, 65.
[44] M. Cappadonia, J. W. Erning, U. Stimming, J. Electroa-
nal. Chem. 1994, 376, 189.
[45] Y. S. Kim, L. M. Dong, M. A. Hickner, T. E. Glass,
V. Webb, J. E. McGrath, Macromolecules 2003, 36, 6281.
[46] R. C. McDonald, C. K. Mittelsteadt, E. L. Thompson,
Fuel Cells 2004, 4, 208.
[47] M. Saito, K. Hayamizu, T. Okada, J. Phys. Chem. B 2005,
109, 3112.
[48] A. Pozio, R. F. Silva, M. De Francesco, L. Giorgi, Electro-
chim. Acta 2003, 48, 1543.
[49] J. Xie, D. L. Wood, III, D. M. Wayne, T. A. Zawodzinski,
P. Atanassov, R. L. Borup, J. Electrochem. Soc. 2005, 152,
A104.
[50] T. A. Aarhaug, S. Kjelstrup, S. Møller-Holst, 2006 Fuel
Cell Seminar Abstracts, Courtesy Associates, Hawaii,
2006.
www.fuelcells.wiley-vch.de FUEL CELLS 08, 2008, No. 1, 3–22
de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
[51] R. Baldwin, M. Pham, A. Leonida, J. McElroy, T. Nal-
ette, J. Power Sources 1990, 29, 399.
[52] S. S. Kocha in Handbook of Fuel Cells-Fundamentals, Tech-
nology and Applications, Vol. 3 (Eds. W. Vielstich, H. A.
Gasteiger, A. Lamm), John Wiley and Sons, Chichester,
UK, 2003, pp. 538.
[53] R. Makharia, M. F. Mathias, D. R. Baker, J. Electrochem.
Soc. 2005, 152, A970.
[54] S. D. Knights, K. M. Colbow, J. St-Pierre, D. P. Wilkin-
son, J. Power Sources 2004, 127, 127.
[55] M. Hori, M. Kato, Y. Yoshikawa, J. Yu, T. Matsuura,
2005 Fuel Cell Seminar Abstracts, Courtesy Associates,
Palm Springs, 2005.
[56] S. Y. Lee, E. Cho, J. H. Lee, H. J. Kim, T. H. Lim, I. H.
Oh, J. Won, J. Electrochem. Soc. 2007, 154, B194.
[57] B. Du, R. Pollard, J. Elter, 2006 Fuel Cell Seminar Ab-
stracts, Courtesy Associates, Hawaii, 2006, pp. 61.
[58] M. S. Wilson, J. A. Valerio, S. Gottesfeld, Electrochim.
Acta 1995, 40, 355.
[59] E. Cho, J. J. Ko, H. Y. Ha, S. A. Hong, K.-Y. Lee, T.-W.
Lim, I.-H. Oh, J. Electrochem. Soc. 2003, 150, A1667.
[60] Q. Guo, Z. Qi, J. Power Sources 2006, 160, 1269.
[61] J. Hou, H. Yu, S. Zhang, S. Sun, H. Wang, B. Yi, P. Ming,
J. Power Sources 2007, 162, 513.
[62] J. Hou, H. Yu, B. Yi, Y. Xiao, H. Wang, S. Sun, P. Ming,
Electrochem. Solid-State Lett. 2006, 10, B11.
[63] J. St Pierre, J. Roberts, K. Colbow, S. Campbell, A. Nel-
son, J. New Mater. Electrochem. Syst. 2005, 8, 163.
[64] L. Mao, C. Y. Wang, J. Electrochem. Soc. 2007, 154, B139.
[65] M. Oszcipok, A. Hakenjos, D. Riemann, C. Hebling, Fuel
Cells 2007, 7, 135.
[66] K. Tajiri, Y. Tabuchi, F. Kagami, S. Takahashi, K. Yoshi-
zawa, C. Y. Wang, J. Power Sources 2007, 165, 279.
[67] J. Xie, D. L. Wood, III, K. L. More, P. Atanassov, R. L.
Borup, J. Electrochem. Soc. 2005, 152, A1011.
[68] E. Guilminot, A. Corcella, F. Charlot, F. Maillard,
M. Chatenet, J. Electrochem. Soc. 2007, 154, B96.
[69] P. Bindra, S. J. Clouser, E. Yeager, J. Electrochem. Soc.
1979, 126, 1631.
[70] J. Aragane, T. Murahashi, T. Odaka, J. Electrochem. Soc.
1988, 135, 844.
[71] M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous
Solutions, National Association of Corrosion Engineers,
New York, 1974, pp. 379.
[72] R. M. Darling, J. P. Meyers, J. Electrochem. Soc. 2003, 150,
A1523.
[73] V. A. T. Dam, F. A. de Bruijn, J. Electrochem. Soc. 2007,
154, B494.
[74] X. Wang, R. Kumar, D. J. Myers, Electrochem. Solid-State
Lett. 2006, 9, A225.
[75] Z. Nagy, H. You, Electrochim. Acta 2002, 47, 3037.
[76] S. Kawahara, S. Mitsushima, K. Ota, N. Kamiya, ECS
Trans. 2006, 3, 625.
[77] S. Kawahara, S. Mitsushima, K. Ota, N. Kamiya, ECS
Trans. 2006, 1, 85.
FUEL CELLS 08, 2008, No. 1, 3–22 www.fuelcells.wiley-vch.de
REVIEW
[78] L. D. Burke, D. T. Buckley, J. Electroanal. Chem. 1994,
366, 239.
[79] L. D. Burke, K. J. O’Dwyer, Electrochim. Acta 1992, 37,
43.
[80] V. I. Birss, M. Chang, J. Segal, J. Electroanal. Chem. 1993,
355, 181.
[81] R. M. Darling, J. P. Meyers, J. Electrochem. Soc. 2005, 152,
A242.
[82] A. N. Virkar, Y. Zhou, J. Electrochem. Soc. 2007, 154,
B540.
[83] E. Guilminot, A. Corcella, M. Chatenet, F. Maillard,
F. Charlot, G. Berthome, C. Iojoiu, J. Y. Sanchez, E. Ros-
sinot, E. Claude, J. Electrochem. Soc. 2007, 154, B1106.
[84] A. Honji, T. Mori, K. Tamura, M. Hishinuma, J. Electro-
chem. Soc. 1988, 135, 355.
[85] K. Kinoshita, Electrochemical Oxygen Technology, John
Wiley & Sons, Inc., New York, 1992, pp. 203.
[86] R. L. Borup, J. R. Davey, F. H. Garzon, D. L. Wood,
M. A. Inbody, J. Power Sources 2006, 163, 76.
[87] M. F. Mathias, R. Makharia, H. A. Gasteiger, J. J. Conley,
T. J. Fuller, C. J. Gittleman, S. S. Kocha, D. P. Miller, C.
K. Mittelsteadt, T. Xie, S. G. Yan, P. T. Yu, Electrochem.
Soc. Interface 2005, 14, 24.
[88] P. Ascarelli, V. Contini, R. Giorgi, J. Appl. Phys. 2002, 91,
4556.
[89] K. Kinoshita, Carbon. Electrochemical and Physicochemical
Properties, John Wiley & Sons, Inc., New York, 1988,
pp. 316.
[90] K. H. Kangasniemi, D. A. Condit, T. D. Jarvi, J. Electro-
chem. Soc. 2004, 151, E125.
[91] N. Giordano, P. L. Antonucci, E. Passalacqua, L. Pino,
A. S. Arico, K. Kinoshita, Electrochim. Acta 1991, 36,
1931.
[92] S. C. Ball, S. L. Hudson, D. Thompsett, B. Theobald,
J. Power Sources 2007, 171, 18.
[93] J. Willsau, J. Heitbaum, J. Electroanal. Chem. Interfacial
Electrochem. 1984, 161, 93.
[94] L. M. Roen, C. H. Paik, T. D. Jarvi, Electrochem. Solid-
State Lett. 2004, 7, A19.
[95] Z. Siroma, K. Ishii, K. Yasuda, Y. Miyazaki, M. Inaba,
A. Tasaka, Electrochem. Commun. 2005, 7, 1153.
[96] D. A. Stevens, J. R. Dahn, Carbon 2005, 43, 179.
[97] D. A. Stevens, M. T. Hicks, G. M. Haugen, J. R. Dahn,
J. Electrochem. Soc. 2005, 152, A2309.
[98] M. Cai, M. S. Ruthkosky, B. Merzougui, S. Swathirajan,
M. P. Balogh, S. E. Oh, J. Power Sources 2006, 160, 977.
[99] M. Schulze, N. Wagner, T. Kaz, K. A. Friedrich, Electro-
chim. Acta 2007, 52, 2328.
[100] L. R. Jordan, A. K. Shukla, T. Behrsing, N. R. Avery,
B. C. Muddle, M. Forsyth, J. Power Sources 2000, 86, 250.
[101] M. V. Williams, E. Begg, L. Bonville, H. R. Kunz, J. M.
Fenton, J. Electrochem. Soc. 2004, 151, A1173.
[102] U. Pasaogullari, C. Y. Wang, Electrochim. Acta 2004, 49,
4359.
[103] U. Pasaogullari, C. Y. Wang, K. S. Chen, J. Electrochem.
Soc. 2005, 152, A1574.
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 21
 de Bruijn et al.: Durability and Degradation Issues of PEM Fuel Cell Components
[104] A. Z. Weber, R. M. Darling, J. Newman, J. Electrochem.
REVIEW
Soc. 2004, 151, A1715.
[105] A. Z. Weber, J. Newman, J. Electrochem. Soc. 2005, 152,
A677.
[106] C. Lee, W. Merida, J. Power Sources 2007, 164, 141.
[107] T. Yoda, H. Uchida, M. Watanabe, Electrochim. Acta
2007, 52, 5997.
[108] S.-Y. Lee, E. Cho, J.-H. Lee, H.-J. Kim, T.-H. Lim, I.-H.
Oh, 2005 Fuel Cell Seminar Abstracts, Courtesy Associ-
ates, Palm Springs, 2005.
[109] T. R. Ralph, M. P. Hogarth, Platinum Metals Rev. 2002,
46, 117.
[110] P. Yu, M. Pemberton, P. Plasse, J. Power Sources 2005,
144, 11.
[111] W. Bi, G. E. Gray, T. F. Fuller, Electrochem. Solid-State
Lett. 2007, 10, B101.
[112] T. Patterson, Fuel Cell Technology: Opportunities and Chal-
lenges, Topical Conference Proceeding, 2002 AIChE Spring
National Meeting (Eds. G. J. Igwa and D. Mah), AIChE,
New York, USA, 2002, pp. 313.
[113] K. Kanamura, H. Morikawa, T. Umegaki, J. Electrochem.
Soc. 2003, 150, A193.
[114] C. A. Reiser, L. Bregoli, T. W. Patterson, J. S. Yi, J. D.
Yang, M. L. Perry, T. D. Jarvi, Electrochem. Solid-State
Lett. 2005, 8, A273.
[115] J. P. Meyers, R. M. Darling, J. Electrochem. Soc. 2006, 153,
A1432.
[116] J. Zhang, J. Owejan, M. Fay, B. A. Litteer, P. T. Yu,
W. Gu, H. A. Gasteiger, Prepr. Symp. – Am. Chem. Soc.,
Div. Fuel Chem. 2007, 52, 388.
[117] P. T. Yu, W. Gu, F. T. Wagner, H. A. Gasteiger, Prepr.
Symp. – Am. Chem. Soc., Div. Fuel Chem. 2007, 52, 386.
[118] A. Taniguchi, T. Akita, K. Yasuda, Y. Miyazaki, J. Power
Sources 2004, 130, 42.
[119] T. W. Patterson, R. M. Darling, Electrochem. Solid-State
Lett. 2006, 9, A183.
[120] E. Cho, J. J. Ko, S.-A. Ha, S. A. Hong, K.-Y. Lee, T.-W.
Lim, I.-H. Oh, J. Electrochem. Soc. 2004, 151, A661.
______________________
22 © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[121] R. Borup, J. Meyers, B. Pivovar, Y. S. Kim, R. Mukun-
dan, N. Garland, D. Myers, M. Wilson, F. Garzon,
D. Wood, P. Zelenay, K. More, K. Stroh, T. Zawodzins-
ki, J. Boncella, J. E. McGrath, M. Inaba, K. Miyatake,
M. Hori, K. Ota, Z. Ogumi, S. Miyata, A. Nishikata,
Z. Siroma, Y. Uchimoto, K. Yasuda, K. I. Kimijima,
N. Iwashita, Chem. Rev. (Washington, DC, U. S.) 2007,
107, 3904.
[122] H. A. Gasteiger, S. S. Kocha, B. Sompalli, F. T. Wagner,
Appl. Catal., B 2005, 56, 9.
[123] M. K. Debe in Handbook of Fuel Cells-Fundamentals, Tech-
nology and Applications, Vol. 3 (Eds. W. Vielstich, H. A.
Gasteiger, A. Lamm), John Wiley and Sons, Chichester,
UK, 2003, pp. 576.
[124] A. Hermann, T. Chaudhuri, P. Spagnol, Int. J. Hydrogen
Energy 2005, 30, 1297.
[125] R. C. Makkus, A. H. H. Janssen, F. A. de Bruijn,
R. K. A. M. Mallant, J. Power Sources 2000, 86, 274.
[126] D. P. Davies, P. L. Adcock, M. Turpin, S. J. Rowen,
J. Appl. Electrochem. 2000, 30, 101.
[127] A. Mueller, P. Kauranen, A. von Ganski, B. Hell, J. Power
Sources 2006, 154, 467.
[128] R. F. Silva, D. Franchi, A. Leone, L. Pilloni, A. Masci,
A. Pozio, Electrochim. Acta 2006, 51, 3592.
[129] A. Iversen, Corros. Sci. 2006, 48, 1036.
[130] F. A. de Bruijn, R. C. Makkus, R. K. A. M. Mallant,
G. J. M. Janssen in Advances in Fuel Cells, 1 (Eds. T. S.
Zhao, K. D. Kreuer, T. Nguyen), Elsevier, Oxford, Uni-
ted Kingdom 2007, pp. 235.
[131] L. Frisch, Sealing Technol. 2001, 2001, 7.
[132] B. Du, Q. Guo, R. Pollard, D. Rodriguez, C. Smith, J. El-
ter, JOM 2006, 58, 45.
[133] J. Tan, Y. J. Chao, J. W. Van Zee, W. K. Lee, Mater. Sci.
Eng. A 2007, 445–446, 669.
[134] M. Schulze, T. Knöri, A. Schneider, E. Gülzow, J. Power
Sources 2004, 127, 222.
www.fuelcells.wiley-vch.de FUEL CELLS 08, 2008, No. 1, 3–22