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Current understanding of chemical degradation

mechanisms of perfluorosulfonic acid membranes
Cite this: Sustainable Energy Fuels,
2017, 1, 409 and their mitigation strategies: a review
M. Zatoń, J. Rozière and D. J. Jones*

This article provides a comprehensive and up-to-date perspective of the understanding of

Published on 05 April 2017. Downloaded on 2/26/2021 7:59:49 AM.

Received 20th January 2017
Accepted 13th March 2017
DOI: 10.1039/c7se00038c
rsc.li/sustainable-energy
perfluorosulfonic acid (PFSA) fuel cell membrane degradation phenomena, reviews key concepts for
the mitigation of membrane degradation, appraises the effectiveness of these strategies by discussing
their benefits and drawbacks, and identifies remaining challenges and research priorities for fuel cell
membranes with increased longevity. Identification of stressors and improved understanding of how
scavenging reactions proceed are essential for accelerated development of new fuel cell membrane
materials with antioxidant properties and enhanced durability. Fuel cells convert the chemical energy of
a fuel such as hydrogen into electricity and heat and have the potential to deliver environmental and
economic benefits across various sectors, including transportation, power generation, industrial
equipment, military power, and consumer electronics. The development of Proton Exchange
Membrane Fuel Cell (PEMFC) membranes with increased durability is of crucial importance since it
directly impacts fuel cell system lifetime and, therefore, large scale implementation of fuel cell
technology. The PFSA proton conducting polymer (ionomer) at the heart of the membrane electrode
assembly of a PEMFC is subject to chemical degradation as a result of the attack on the polymer chains
by reactive oxygen species generated electrochemically in the fuel cell. For the first time, this article
reviews the literature both on mechanisms by which this chemical degradation of the ionomer
membrane occurs and the sites on the polymer susceptible to free radical attack, as well as how this
learning and increased understanding have been used to build and develop successful mitigation
strategies designed to annihilate the harmful effect of oxidative species on membrane integrity.

electrolyte, an acid or an alkaline fuel cell can be distin-

1. Introduction
Fossil fuels are currently the main source of energy. The
growing concern for the shrinking availability of the world's
oil and gas supplies and the detrimental impact on the envi-
ronment associated with the use of such sources of energy
have motivated the search for alternative, clean energy tech-
nologies. Fuel Cells (FC) are devices that convert the chemical
energy stored in fuels into electricity via electrochemical
reactions. Since fuel cells can generate electricity continuously
with high efficiency and low or zero pollution emission at the
point of use as long as the fuel and oxidant are supplied, they
represent a promising substitute to heat and electricity
generation from fossil fuels, and can be used for a wide range
of applications from micro power sources to multi – MW
power plants. There are many types of fuel cells that can be
classied according to the ion transport medium and/or to the
operation temperature. Regarding the nature of the
ICGM – Aggregates, Interfaces and Materials for Energy, UMR 5253, Université de
Montpellier 2, Place Eugène Bataillon, 34095 Montpellier, France. E-mail: Deborah.
Jones@umontpellier.fr
guished. According to the operation temperature, fuel cells
may be grouped as low (up to 100
C), intermediate (up to 600


C) and high temperature (up to 1000
C). This review is solely
focused on Low Temperature Proton Exchange Membrane
Fuel Cells (LTPEMFC). PEMFC are known to have interesting
properties such as high power density, easy scale-up and fast
start-up capability. These features make the device an excel-
lent candidate for automotive and small stationary applica-
tions and portable electronics. However the direction of
PEMFC development currently poised to make a real impact
on emissions reduction is in transportation applications.
Prototype Fuel Cell Electric Vehicles (FCEVs) have already been
presented by most automakers and were commercialized in
2015 Toyota, and in 2016 by Hyundai and Honda. Furthermore
PEM fuel cells are already used in certain stationary, portable
and transport applications in most developed countries.1–4 A
lot of research is being done in this area due to the economic
and environmental benets that such systems can offer.
However there are still challenges that are hindering the global
applications of fuel cells. The main issue is the practical long-
term operation of the cell components.5–7 There are several

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losses that limit the long-term stability and the performance of
these devices.8 Those losses are due to the degradation of the
bipolar plates, the gas diffusion layer, the catalysts and the
membranes.9
The loss of the active surface area of the catalyst layer,
which results in the decrease of the performance of the fuel
cell, is caused by platinum oxidation, dissolution and corro-
sion of the carbon material, which can lead to aggregation of
Pt particles and their detachment from the support.10 The high
potential delivered by the system as well as the oxidative
environment favour the growth of Pt particles. Platinum
dissolution is not only accelerated by potential or load cycling
but as well as the elevated temperatures used in these
devices.11–13 Migration of the dissolved ionic Pt and further
precipitation in the membrane can be in certain conditions
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considered as one of the factors contributing to membrane
degradation.14,15 Oxidation of the carbon support is initiated
by high-electrochemical potentials caused either by fuel/air
boundary passing over the active area during the start-up/
shut-down processes or local hydrogen starvation.16 Carbon
corrosion results in the thinning of the electrode16 and growth
of the platinum particles due to detachment and agglomera-
tion.17–19 GDL degradation is related to loss of hydrophobicity
of the macro and microporous layers due to the oxidation of
the carbon and the decomposition of the PTFE component.
These microstructural changes affect the gas transport and
therefore lower the cell performance.20
Degradation of the membrane is one of the major reasons
that can lower the durability of a fuel cell. Membrane
decomposition can be induced by many factors for instance
mechanical degradation which is an effect of non-uniform
contact pressure or fatigue from stress during shrinkage
and swelling of the membrane during humidity cycling.
Reduction of the membrane mechanical strength results in
the formation of pinholes and cracks, which can further
contribute to the failure of the MEA.21 Another factor affecting
the stability of the membrane is the contaminant ions origi-
nated from corrosion of the different cell components.22
Released cations such as Fe and Ni catalyse the decomposi-
tion of hydrogen peroxide, which is the main source of free
radicals. Moreover the counter ions formed tend to associate
with the sulfonic acid sites of the polymer, which causes
partial drying of the membrane and results in loss of
conductivity.23,24 Chemical degradation crucially affects
membrane durability. Chemical decomposition is initiated by
free radicals, highly reactive oxygen species, which are formed
during the chemical and electrochemical reaction of cross-
over gases. Those species attack the polymer structure
causing an “unzipping” reaction on the main chain and the
scissions of the side chain, which nally result in thinning of
the membrane.
All these damaging effects oen occur simultaneously,
thereby creating a very complex mechanism of the overall fuel
cell degradation.25 Since amelioration of durability is crucial for
technology development, understanding the fundamental
degradation mechanisms of the fuel cell components is
primordial.
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Excellent articles by Borup et al.20 and by de Bruijn et al.26
reviewed the literature on degradation and durability of fuel cell
components up to 2008 while that of Wu et al.9 additionally
discussed possible mitigation approaches. In 2014 the article
Dubau et al. provided an updated overview of degradation of
fuel cell components.27 None of these reviews was focussed on
membrane degradation phenomena. Other authors summa-
rized and classify accelerated stress test (AST) protocols,28,29
aiming to provide practical tools for the study of fuel cell
durability. The article from Rodgers et al. reviewed different
accelerated stress test and lifetime tests and correlated them to
membrane decay and fuel cell lifetime.30 Ishimoto et al. pub-
lished a survey of literature on the mechanism of chemical
degradation of PFSA membranes from an atomistic point of
view.31 Despite the signicant number of publications on the
topics of PFSA membrane degradation and mitigation strategies
to reduce this degradation that have been published over the
past decade, there is no article providing a comprehensive and
detailed review of the eld.
The goal here is to review the substantial literature on how
increased understanding of factors that lead to the degradation
of PFSA membranes has led to the development of mitigation
strategies and improvement of membrane and MEA lifetime, in
particular since the ground-breaking work introducing effective
radical scavengers by Endoh et al. at Asahi Glass Company and
by Coms et al. at General Motors.
2. PFSA polymer types
The fuel cell electrolyte must have high proton conductivity in
order to maximize the efficiency. It should also be mechanically
and chemically robust during fuel cell operation to ensure
a long lifetime and nally needs to be impermeable to the direct
transfer of reactant gases and electronically insulating.
Although many types of FC membranes have been developed
over the past two decades32–35 the commonly used proton
exchange membranes are peruorosulfonic acid (PFSA)
membranes. The rst widely used PFSA membrane is Naon®
developed by DuPont.36 The synthesis of Naon® is based on
the copolymerisation of tetrauoroethylene (TFE) with a per-
uorinated vinyl ether co-monomer and sulfonyl acid uoride.
The product obtained from the copolymerisation is hydrolysed
with NaOH and then converted to the acid form. The Naon®
polymer structure comprises two well dened components: the
hydrophobic backbone (polytetrauoroethylene – PTFE) and
the hydrophilic side chain terminated with sulfonic acid
groups. The PTFE part provides mechanical strength and rela-
tively high stability in very harsh chemical environments, while
the conduction properties are due to the presence of hydrated
sulfonic acid groups.37 Commercially available polymers with
equivalent structure are Flemion® (trade mark of Asahi Glass
Company), Aciplex® (produced by Asahi Kasei) and Fumion® F
(developed by FuMA-Tech). This type of composition is now
known as the long-side-chain (LSC) structure; correspondingly
ionomers with a shorter pendant side chain are referred as to as
short-side-chain (SSC) ionomers. The chemical structures of
PFSAs with different side chain lengths are presented in Fig. 1.
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Review
Fig. 1The chemical structure of LSC – Nafion® structure (a) and SSC
perfluorosulfonic ionomer membranes (b) and (c). Reprinted from
Polymer Electrolyte Membrane and Direct Methanol Fuel Cell Tech-
nology, vol. 1, D. J. Jones, Polymer Electrolyte Membrane and Direct
Methanol Fuel Cell Technology, 27–56.38 Copyright (2012), with
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permission from Elsevier.
In the SSC polymer structures there is no –O–CF2CF(CF3)–
group. Furthermore, the length of the peruoro vinylether side
chain varies between 2 and 4 carbons for the two commercially
available SSC ionomers i.e. Aquivion® and 3M™ respectively.
Pioneering studies on the synthesis of a SSC polymer date back
to 1981 at Dow.39 Early investigations of Dow SSC membranes
demonstrated excellent balance between their stability and
transport properties.40–42 However a complex and expensive
synthesis route impeded their wide commercialisation. More
recently, a low cost synthesis route developed by Solvay Solexis
resulted in new benchmark Hyon® Ion membrane,43
renamed in 2010 as the Aquivion® membrane. The parameter
that reects the transport properties of the PFSA membrane
and its mechanical integrity, within a given class of PFSA
types, is the equivalent weight (EW). EW is dened as dry mass
of the polymer in the acid form in grams per mole of
exchangeable groups. Another important feature of PFSA
membranes in relation to the EW is the ion exchange capacity
(IEC). The relationship between these parameters is expressed
by: 1000/EW. The IEC of the membrane can be measured
experimentally by acid/base titration. Differences in side chain
length leads to differences in the molecular weight of the
polymer repeat unit and translates into specic properties
such as higher degree of crystallinity of SSC membranes44
compared to LSC Naon® for a given polymer equivalent
weight, and higher glass transition temperature (Tg).45 Higher
ion exchange capacity46 SSC polymers can be used to higher
temperature due to these properties.47–49 In general PFSA
membranes possesses good mechanical properties, high
proton conductivity and electronic resistance and low gas
permeability. All these properties are necessary in order to
have an efficient barrier for gas separation and to withstand
strong oxidative and reductive environments and severe
mechanical stresses imparted by hydration–dehydration
cycles compounded by the specic electrochemical environ-
ment of the fuel cell. Such harsh conditions nevertheless
initiate decomposition or degradation of the ionomer or
membrane, of which three main types of membrane
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degradation may be distinguished: chemical, mechanical and
thermal.24
3. Mechanical and thermal
degradation of PFSA membranes
Mechanical degradation is an effect of the mechanical forces
affecting the integrity of the membrane. Long term fuel cell
testing shows a time dependent deformation – creep and micro-
crack fracture of Naon®. These phenomena are related to the
repeated stress applied to the membrane between bipolar plates
and strain from local changes of the relative humidity. The most
important factors inducing micro and macro defects of the
membrane are: relative humidity cycling,36,50,51 transients at
open circuit voltage (OCV),52 temperature cycling51 and poten-
tial cycling. Some of those stressors have a bigger impact on the
polymer mechanical durability than others, for example cycling
of the temperature was reported to have less inuence on
membrane breakdown than RH cycling50,53 probably due to the
higher strain oscillation amplitude.54 Repeated swelling and
shrinking of the membrane causes the gradual reduction of the
membrane strength that nally results in membrane dimen-
sional changes, poor interface contact between membrane and
electrode,55–57 and defects such as pinhole formation.57,58
Pinhole formation, due to the local stress applied to the
membrane is one of the main reasons for the failure of PFSA
membranes in PEM fuel cells.59 Accelerated gas crossover of
hydrogen and oxygen to the opposite side of the electrolyte
through pinholes causes combustion reaction on the catalyst
surface and generates local hot spots. The use of high temper-
ature and relative humidity increase gas crossover.60–62
Membrane hydration is a very important factor affecting
mechanical and thermal properties of PFSA membranes.31,63,64
Kundu et al. reported that the transition temperatures of
Naon® decrease with increasing membrane hydration.65
Majsztrik et al. described that high hydration of Naon® at low
temperature plasticises its structure,66 whereas at elevated
temperature opposite behaviour is observed.67 This implies that
at elevated temperature for a highly hydrated membrane,
mechanical creep occurs much faster than for a dry polymer.
Recently Luo et al. reported signicantly higher permeability of
degraded Naon NR211 following 48 h exposure to Fenton
reagent compared to the pristine membrane.68 Increased water
content and proton mobility, despite lower IEC and proton
conductivity of degraded membranes, were explained by the
authors as resulting from enhanced water sorption of
a damaged polymer membrane structure. Water remaining in
non-ionic cavities formed through degradation does not
contribute to ion conduction but can cause hygrothermal stress
and fracture development.69 Also Shi et al. interrogate hetero-
geneity in permeability of ex situ aged Naon membranes.70
Venkatesan reported high water uptake of degraded catalyst
coated membrane (CCM) subjected to combined mechanical/
chemical accelerated stress test.71 Authors demonstrated that
voids regions in severely degraded material, depleted of F and C
are susceptible to micro crack formation. PEM fuel cells require
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to be operated over a wide working temperature range. There-
fore it is important to study the stability of PFSA membranes at
sub-freezing temperature. The existence of three72,73 or even four
different “states” of water in Naon® termed non-freezing
water, bound freezing water and free water has been re-
ported.74 The chemically bound water does not freeze down to
120
C, whereas it is probable that the water which is non-
bonded to the polymer chain freezes below 0
C.73 Phase
transformation as well as difference in densities of water and ice
can cause the degradation of PFSA membranes.75 However
McDonald et al. reported that aer 385 cycles in the tempera-
ture range from 40
C to 80
C no catastrophic failure was
observed.76 On the other hand, Plazanet et al. observed ice
formation outside of the membrane with simultaneous increase
of concentration of hydronium ions in membrane.77 This
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phenomenon was related to desorption of water upon cooling
and contraction of the membrane. In such a scenario, the
formation of ice or frost at the membrane electrode interface is
detrimental for the catalyst layer structure. The impact of
mechanical degradation can be signicantly decreased by
optimizing the design of the fuel cell components i.e. by
choosing appropriate materials and operating conditions.78 On
the other hand, chemical degradation appears more complex
and difficult to mitigate as the process has a larger impact on
the integrity of the whole polymer.79
4. Chemical degradation of PFSA
Chemical degradation of the PFSA membrane is the major issue
considered in this paper and it will therefore be discussed
starting from the structure of the membrane at the microscopic
level. The mechanism of membrane degradation at the meso
and macroscopic levels is also fully described followed by the
classication of free radicals generated under fuel cell operating
conditions. Finally a summary of mitigation strategies that have
been proposed is discussed at the end of this review.
4.1 Radical attack on polymer structure
Chemical degradation of PFSA membranes involves radical-
induced decomposition of the polymer structure. The process
of chemical degradation is not yet fully understood, however the
damage caused to the membrane and its properties are evident,
for instance a decrease in the ion exchange capacity followed by
conductivity losses, as well as uoride emission and subsequent
membrane thinning (subsection 3.2). The current generally
accepted mechanism for chemical degradation of per-
uorosulfonic acid polymers is by radical attack on the polymer
main chain and side chain.80–85 Reactive oxygen species (ROS)
can be generated directly via chemical or electrochemical
reaction of crossover gases over the electrocatalyst surface,86–88
however their short lifetime limits to a large extent their diffu-
sion length.80 Another pathway for radical formation occurs
through homolysis of hydrogen peroxide (H2O2).23,89 H2O2 itself
is not a strong enough oxidant to damage the polymer structure
substantially.90–92 However, iron or other multivalent metal ions
like Cu2+ or Ti3+, originated from corrosion of the cell or stack
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materials or humidiers, catalyse the decomposition of H2O2 to
produce hydroxyl radicals as shown in eqn (1).93,94 Pozio et al.
performed experiments where stainless steel plates were
replaced with iron-free aluminium alloy plates.89 The
membrane degradation aer 1200 h under such conditions was
signicantly reduced, which clearly shows correlation between
uoride emission rate and trace amounts of transition metal
ions. Moreover the amount of iron can be as low as 1 part per 5–
25 parts of H2O2 for the reaction to occur for a concentration of
hydrogen peroxide of <10–25 mg L1.95
H2O2 + Mz+ / M(z+1)+ + HOc + OH (1)
The hydroxyl radical produced via eqn (1) can further
undergo reaction (eqn (2)) with hydrogen peroxide to form
hydroperoxyl radical (more detail in Section 7).
HOc + H2O2 / H2O + HOOc (2)
M(z+1)+ + H2O2 / Mz+ + HOOc + H+ (3)
Furthermore, the hydroperoxyl radical can also be produced
by the reaction of transition metal ions with hydrogen peroxide,
eqn (3). In situ hold at open circuit voltage (OCV hold
testing)96–98 is the accepted means to accelerate membrane
chemical degradation, while outside of the fuel cell environ-
ment, the Fenton reagent comprising hydrogen peroxide and
ferrous ions is frequently used.70,99–102 In both cases accelerated
membrane decomposition is due to high concentration of
hydroxyl radicals that attack the most vulnerable sites in poly-
mer structure: carboxylic acid end groups; C–S bonds; tertiary
carbon atoms and ether groups. These four main mechanisms
of radical attack on the polymer structure are discussed. The
rst, generally referred to as the “unzipping reaction” is
a radical reaction occurring in non-so-called “stabilised” PFSA
polymers, and starting on weak terminal –COOH groups of the
polymer main chain (Fig. 2). Such terminal carboxylic acid
groups can also be generated through transformation of non-
peruorinated groups via hydroxyl radical attack.103 As
described in eqn (4)–(6) end carboxylic groups react with
hydroxyl radicals to produce CO2 and HF, and reform a terminal
–COOH group.104 Several propagation steps of this reaction
brings about decomposition of the uorocarbon main chain by
consistent loss of CF2 units.105 When the polymer unzipping
reaches a junction with a side chain, cleavage of the overall side
chain groups generates peruoro(3-oxa-5-methyl)pentane-1-
sulfonic-5-carboxylic diacid, HCOO–CF(CF3)–O–CF2CF2–
SO3H.105 This species can diffuse out of the membrane or can
undergo decomposition by the unzipping reaction, as a carbox-
ylic acid end group is also present in its molecular structure.
This mechanism was the rst to be identied, following seminal
work at General Motors and DuPont, and this greater under-
standing of what was understood at that time to represent
a primary cause of polymer degradation led directly at DuPont
(and other producers of PFSAs) to post-uorination of terminal
carboxylic acid groups with the aim of stabilising them against
the unzipping reaction.
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rst experimental conrmation of the unzipping mechanism.108

Fig. 2 Unzipping mechanism – hydroxyl radical attack on carboxylic
acid groups.
4.2 Mechanism I – “unzipping mechanism”
Rf–CF2COOH + HOc / Rf–CF2c + CO2 + H2O (4)
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Interestingly, for Aquivion® and 3M™ ionomer dispersions, the
magnetic parameters of the DMPO/CCR adduct were identical
and also indicated an unzipping process whereas for Naon®
dispersion those parameters were totally different which could
mean rather side chain cleavage. It was reported that the low
concentration of hydrogen containing terminal groups in PFSA
membranes is disproportionate to the observed level of released
HF,109,110 moreover Naon® membranes that have been chem-
ically stabilised by post-uorination of the carboxylic groups
show reduced, but not eliminated, mass loss (see Fig. 3).104,111
Other studies demonstrated that Naon® converted to the
Na+, Cs+ or Li+ forms shows two orders of magnitude lower
uoride emission rate compared to the acid form membrane.
Such a signicant change in the FER values suggest that radi-

cals also attacked the sulfonic acid groups (Fig. 4).91

Rf–CF2c + HOc / Rf–CF2OH / Rf–COF + HF (5)

Rf–COF + H2O / Rf–COOH + HF (6) 4.3 Mechanism II – attack on C–S bond

A second possible mechanism of membrane degradation is the
attack by free radicals on C–S bonds following the reactions
From a practical point of view some conclusions can be drawn shown below:113
regarding the decomposition model described above. Experi-
mentally, the signicant mass loss of the membrane (the main Rf–CF2SO3H + HOc / Rf–CF2c + SO3 + H2O (7)
degradation product of the unzipping mechanism is HF) can be
correlated to the experimentally determined uoride emission Rf–CF2c + HOc / Rf–CF2OH / Rf–COF + HF (8)
rate (FER). Fluoride emission can be measured using an ion
selective electrode (ISE) or by high performance liquid chro- Rf–COF + H2O / Rf–COOH + HF (9)
matography (HPLC) of exhaust water. The FER depends on the
The radical attack begins at the end of the side chain on the
in situ experimental conditions known to cause macroscopic
C–S bond (eqn (7)). Aer this step the polymer decomposition
membrane degradation such as relative humidity, temperature,
gas type, ow and pressure and cell voltage. Moreover FER is
a good method for investigation of the kinetics of the radical
reaction and it is a useful tool to estimate the life time of the
fuel cell. For a “pure” “unzipping” mechanism i.e. in the
absence of any other degradation mechanisms, the FER should
be constant during the stress test without any signicant
acceleration, and the ratio of –COOH groups to CF2 should
remain unchanged. This observation has been made for ex situ
accelerated ageing i.e. using the aqueous Fenton test.106
Schwiebert et al. questioned the possibility of radical attack
other than on the terminal carboxylic acid groups. Their studies
of sulfonic acid and carboxylic acid functionalised model
compounds such as CF3CF(COOH)OCF2CF(CF3)OCF2CF2SO3H
Fig. 3 Fluorine emission rates as a function of the content of
and CF3CF(COOH)(CF2CF2)nSO3H support the unzipping carboxylic groups in Nafion® structure. Reproduced by permission of
degradation mechanism. Moreover these authors suggested The Electrochemical Society from ref. 112.
that ionomers with a linear side chain (Aquivion®, 3M™ ion-
omer) have similar stability to that with a branched per-
uoroether side chain (Naon, Fumion, Flemion).107 However
using a spin trapping ESR technique and 5,5-dimethylpyrroline-
N-oxide (DMPO) as a spin trap for unstable species, Danilczuk
et al. provided different evidence regarding the stability of LSC
and SSC membranes against radical attack, and concluded that
3M and Aquivion® polymers were signicantly more stable than
the Naon® polymer. Furthermore a DMPO/CCR (carbon cen-
tred radical) adduct formed through hydroxyl radical attack on
the carboxylic acid groups was identied, which constituted the Fig. 4 Hydroxyl radical attack on C–S bond.

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proceeds with progressive shortening of the side chain and HF
emission (eqn (8) and (9)). Eqn (8) and (9) seem to be a repeti-
tion of the steps in the unzipping mechanism described in eqn
(5) and (6). This conclusion is partially right, the incorporation
of a new weak –COOH group accelerates the degradation and
therefore the unzipping reaction occurs on both the side and
main chains. However as the Rf have different chemical struc-
tures, the decomposition products of the side chain have
different nature. The detection of –O–CF2–CF2–SO3c and –O–
CF2–CF2c radicals aer a UV – induced Fenton test supports the
above degradation mechanism.114 This type of membrane
decomposition results in the simultaneous loss of weight and
conduction properties of the polymer. Recently Kurniawan et al.
studied the PFSA degradation mechanism using quantum
chemical calculations (QCC) based on density functional theory
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(DFT).115 Triuoromethanesulfonate (TFMS) was used as
a model of the side chain structure. For these authors, the
calculated bond dissociation energies (BDEs) and bond lengths
indicate that radical attack on the C–S bond is favourable due to
its lower dissociation energy in comparison to the other struc-
tural bonds. They further pointed out the behaviour of uorine
atoms as another important factor that can affect the radical
attack on the polymer structure, i.e. the electronegative uorine
atoms efficiently shield the carbon backbone from radical
reaction. Tokumasu et al. also investigated the BDE of a per-
uorosulfonic acid (PFSA) molecule by DFT.116 Similarly to the
work of Kurnawian et al. the C–S bond appeared as the weakest
bond in the side chain structure of the neutral molecule, thus
most susceptible to hydroxyl radical attack. However further
analysis showed that the ionisation of the sulfonic group makes
this C–S bond stronger while the C–O bond becomes weaker.
From thermochemical and kinetic analysis, Coms deduced
further possible route of side chain scissions.117 The mecha-
nism is initiated by sulfonyl radicals, which are formed under
dry conditions, where the sulfonic acid groups are not fully
ionised. Sulfonyl radicals can be formed directly through
hydrogen abstraction from –SO3H by hydroxyl radical or indi-
rectly through reaction with hydrogen peroxide where bissul-
fonyl peroxide is an intermediate product, which further
undergoes homolysis to give sulfonyl radicals (Fig. 5).
Fig. 5 Mechanism of sulfonyl radical formation.
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This author pointed out the weakening effect of sulfonyl
radicals on the C–S bond. In other words, SO3c facilitates the
C–S cleavage and formation of the peruororadical as shown in
mechanism II.
4.4 Mechanism III – attack on ether groups
The above discussion brings us to a third mechanism which
concerns hydroxyl radical attack on the O–C bond.
It was postulated that ether groups next to a C–S bond
represent the preferred site for the radical attack in the side
chain structure.120,121 This nding might support the above
results of Danilczuk et al. where Naon® ionomer exhibited 20
times lower stability than respective SSC ionomers.108 This is
probably due to the absence of OCF2CF(CF3) in the SSC polymer
structure. On the other hand, according to studies of Ghas-
semzadeh et al. the rst point of HOc attack is located near the
sulfonic acid group (a-OCF2) rather than near the main chain (b-
OCF2).118,119 Aer cleaving the a-OCF2 the polymer decomposi-
tion continues as shown in Fig. 6(a) and involves the b-OCF2
and CF units. These results are in agreement with theoretical
studies of Ishimoto et al.122
4.5 Mechanism IV – attack on the tertiary carbon
A further potential site for radical attack leading to PFSA poly-
mer degradation can occur at the tertiary carbon according to
the reaction given in Fig. 7.117 Two tertiary carbons are present
in the Naon® structure; both are adjacent to ether bonds.
Radical attack on the CF of the side chain initiates side chain
decomposition, whereas attack on the main chain CF results in
chain scission. This mode of degradation is characterised by
relatively low uoride emission but with an important increase
Fig. 6 Mechanism of side chain scission by HOc radical attack on C–O
bond (a) direct attack Reprinted with permission from (J. Am. Chem.
Soc., 2013, 135, 15923–15932).118 Copyright (2013) American Chemical
Society. (b) Attack as a consequence of bond weakening after C–S
bond cleavage. Reprinted with permission from (J. Am. Chem. Soc.,
2013, 135, 8181–8184).119 Copyright (2013) American Chemical
Society.
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Fig. 7 Mechanism of chain scission by radical attack at the tertiary
carbon. Reprinted with permission from (J. Am. Chem. Soc., 2013, 135,
15923–15932)118. Copyright (2013) American Chemical Society.
in COOH groups that can then be degraded by the unzipping
mechanism. The vapour phase Fenton test, OCV hold test and
low power demand fuel cell test were reported to accelerate
Naon® degradation according to this mechanism.109 Tertiary
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carbons atoms are assumed to be most fragile to radical attack
among the uorocarbons, due to different thermodynamic
stabilities.117 Strong dependence of the C–F bond dissociation
energies on abstraction of the uorine atoms, gives the
respective order: tertiary > secondary > primary, with tertiary
carbon as the least stable position.116,117
Schiraldi remarked that thermodynamic assumptions
should be re-evaluated in relation to the complex morphology of
Naon®, which is likely to increase the kinetic factor in the
degradation process.111 According to studies using model
compounds, in ex situ accelerated degradation tests a carboxylic
acid terminated compound demonstrates 300 times faster
generation of uoride than the corresponding sulfonic acid
terminated compound.111 However in their studies on Naon®
degradation by applying in depth proling by micro FTIR,
Danilczuk et al. recently proposed mechanism III as a degrada-
tion pathway of membrane decomposition.123 The micro FTIR
spectra of Naon® 115 membrane cross section were recorded
aer OCV hold testing for 180 h at 90
C and 30% RH. Two
bands C]O and C–H characteristic of the degraded membrane
appeared at the same prole depths which indicated their
generation through a single mechanism, which is uorine atom
abstraction from tertiary carbon atom by Hc. C]O and C–H
Fig. 8 Summary of the mechanisms of radical attack on the Nafion® polymer structure.
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bands were observed at depths of 22 mm and 82 mm from the
cathode. The presence of the bands at 22 mm from the cathode
was associated with the location of Pt particles precipitated in
the membrane, however larger damage was observed near the
anode interface at 82 mm where these bands showed highest
intensity.
4.6 Summary of radical attack on PFSA type polymers
A graphical summary of degradation mechanisms proposed in
the literature is provided in Fig. 8.
The “unzipping” mechanism, in this work labelled as
mechanism I, proposed by Curtin et al.104 and Healy et al.124 is
the most frequently cited origin of membrane degradation.
However it should be emphasised that the main role of the
unzipping mechanism in chemical decomposition of PFSA
ionomers changed with the evolution in the ionomer post-
uorination process. A new generation of chemically post-
treated PFSA membranes with reduced number of COOH
groups show considerably improved durability.108,109 Moreover
this improvement signicantly increases with elimination of
the –OCF2CF(CF3) fragment from the polymer structure.108 This
behaviour clearly shows the contribution of radical attack on
the side chain to overall membrane decomposition. It can be
concluded that all the mechanisms discussed above most
probably play a role in the chemical degradation of the
membrane during fuel cell operation, where the working
Fig. 9 Degradation of the Nafion® structure by radical attack and
unzipping of the side and main chains.
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conditions determine the contribution of each of them. Very
likely, a membrane weakened by one type of radical attack is
more susceptible to undergo a second type of radical reaction.119
According to recent reports, hydroxyl radical attack on the
susceptible bond in the side chain initiates “unzipping” along
the side chain110,117,125 and then main chain structure126,127 as
displayed in Fig. 9. Therefore the term “unzipping” cannot be
removed in the discourse of degradation; however, it must be
approached with greater attention.
Finally two possible sites of the radical attack in the side
chain; C–S bond110,113,117,128 and a-OCF2 unit118,119 are suggested
in the literature. There is no agreement concerning the domi-
nance of the radical attack on one of these sites however in both
scenarios the whole moiety OCF2CF2SO3 is lost. According to
Ishimoto et al. the impact of the relative humidity on attack of
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hydroxyl radical on either ether or sulfonic sides has a great
importance.129 Based on DFT calculations these authors
concluded that HOc attack the ether group under high humidity
conditions whereas sulfonic acid groups are more susceptible to
radical attack at low relative humidity.
5. Hydrogen peroxide formation in
membrane-electrode assemblies
(MEA)
The understanding of the different possibilities for radical
attack at weakest points in the polymer chain is essential in
order to decrease membrane decomposition by chemically
stabilising the vulnerable groups in the polymer structure.
However it is also important to identify the fragile points of the
complete membrane electrode assembly (MEA) with regard to
chemical degradation on a macroscopic level. For that reason
many researchers have attempted to localise the formation of
highly oxidative species in an operating fuel cell. As stated
above, it is believed that the main source of hydroxyl radicals is
hydrogen peroxide, which is generated in the fuel cell and
which has been observed in the membrane,87 exhaust water
from the anode and cathode sides and in cathode outlet
gas.60,130 The concentration of the H2O2 depends largely on the
operating conditions as well as on the membrane thickness.
During in situ experiments 8–10 mg cm3 of hydrogen peroxide
was determined in the membrane aer 2 h of operation of the
fuel cell at 65
C with H2/O2 as reactants.131 H2O2 can be formed
within an operating fuel cell at the cathode side by direct
generation during the oxygen reduction reaction (ORR) when
the potential is below 0.696 V.
O2 + 2H+ + 2e / H2O2 (10)
O2 + 4H+ + 4e / 2H2O (11)
Formation of H2O2 at the anode side was rst described by
LaConti et al.132 who proposed that crossover oxygen can react
with hydrogen which was chemisorbed on the Pt catalyst as
displayed in eqn (12)–(14).133,134 Another mechanism is the
chemical combination of crossover gas,135 where reaction on
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platinum at the anode, cathode or present in the membrane
following degradation of the electrode catalyst layer are all
possible.60,86,136
H2 / 2Hc (12)
Hc + O2 / HOOc (13)
HOOc + H+ + e / H2O2 (14)
Regardless of the exact location of hydrogen peroxide
formation, the platinum catalyst is a constant factor in that
process. Pt or Pt alloy is considered as being the best catalyst for
the hydrogen oxidation reaction and the cathodic oxygen
reduction reaction for PEMFC application.137 However, besides
the four-electron pathway for ORR leading to production of
water as displayed in eqn (11), a partial two-electron reduction
reaction to H2O2 also occurs (eqn (10)). Many experiments were
developed to simulate hydrogen peroxide generation on Pt
particles.138–140 Ex situ evaluation of this mechanism using
a rotating ring disc electrode (RRDE) demonstrates an increase
in H2O2 formation with decreasing electrochemical surface area
(ECSA) of the catalyst.138,141 ECSA corresponds to the catalyst
active fraction for the electrode reactions and its decrease is due
to platinum nanoparticles agglomeration, dissolution or inac-
cessibility. Therefore the elevated formation of H2O2 was
explained by the lower probability of further reduction reaction
of hydrogen peroxide re-adsorbed on the sparsely distributed
active sites of the Pt particles. Moreover faster decrease in ECSA
and further increase of the H2O2 fraction was reported for
catalysts with low Pt loading.138,141,142 Adsorption of anions such
as Cl, Br or of CO on the catalyst surface was reported to
accelerate H2O2 formation.139,143 This is in agreement with DFT
calculations where the generation of H2O2 and free radicals is
expected to occur when the ORR is blocked by an adsorbed
species. Four-electron ORR is kinetically promoted for oxygen
molecules adsorbed at two Pt sites, in which case any hydrogen
peroxide or hydroxyl radical generation is energetically unfav-
ourable. However if O2 bonds with only one Pt site, and acces-
sibility to other active sites is hindered by other adsorbed
species, both H2O2 and reactive oxygen species can be easily
generated.144,145
H2O2 generation during PEMFC operation can be affected by
additional factors impossible to mimic ex situ. One such factor
that needs to be considered regarding H2O2/radical formation
and degradation mechanism is the relation of the gas crossover
to membrane thickness and gas partial pressure.146,147 High
oxygen partial pressure leads to high oxygen crossover through
the membrane, which elevates the hydrogen peroxide genera-
tion at the anode catalyst according to LaConti. This nding was
conrmed experimentally by many research groups,60,113,148,149
which have reported negligible membrane degradation in the
absence of O2 crossover. The inuence of membrane thickness
on gas crossover was investigated by Chen et al., who studied
different membranes with various thicknesses ranging from
150 to 280 mm and revealed that with the increase in the
membrane thickness the concentration of H2O2 in the
This journal is © The Royal Society of Chemistry 2017

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membrane decreases.131 Also relative humidity plays an
important role in the formation of hydrogen peroxide:
Sethuraman et al., described a decrease of the concentration of
H2O2 in high water activity conditions (i.e. high humidity) in
studies of the oxygen reduction reaction on the RRDE.150 Chen
et al. reported an increase of H2O2 emission with decrease of
relative humidity on both anode and cathode side, which he
explained by a low membrane water content and an increase of
gas partial pressure that led to higher gas crossover.131 Moreover
higher concentration of H2O2 was observed on the anode site.
For those reasons low humidity conditions are commonly used
to accelerate the polymer degradation rate.78
Decomposition of hydrogen peroxide is one of the possible
mechanisms for radical formation in an operating fuel cell.
Taking into account only this route to generate reactive oxygen
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species (ROS), already three different possible areas of chem-
ical attack need to be considered: anode side, cathode side and
membrane bulk. Studies carried out in this area show con-
icting conclusions. Some researchers propose propagation of
the chemical attack from the anode side towards the
membrane to the cathode side.151 Others observed that the
predominant degradation is at the anode103,123,152–154 or the
cathode side,89,98,155,156 while others, did not nd any signi-
cant difference between anode or cathode membrane–elec-
trode interfaces in term of chemical degradation.157 It is very
difficult to distinguish the degradation phenomena as those
arising from mechanical and chemical processes respec-
tively.25 To facilitate the analysis of areas of membrane
degradation, a bilayer catalyst coated membrane method was
proposed.98,156 With such a conguration, post-test analysis
could be performed on the detachable membrane and the
MEA centre could be easily identied. This method, resulting
in membrane thickness much higher than usually applied, can
be replaced by using commercially available thin reinforced
PFSA membranes such as Naon XL or GORE-SELECT. The
middle of those membranes is clearly determined by the
ePTFE reinforcement. Still the difficulty in obtaining answers
to the questions on where exactly the chemical attack
occurred, and which mechanism dominates in PEM
membrane failure, is due to the morphology of the Naon®
membrane, the short life time and the low concentration of
the radical species, but also, more importantly, due to the
different conditions applied for accelerating the degradation
process. Accelerated stress tests (AST) are commonly used in
order to avoid thousands of hours of in situ life test to deter-
mine membrane durability; however that usually introduces
some incertitude as to the relevancy of the methods employed.
As an example, open circuit voltage (OCV) hold test is,
currently, the most applied in situ stress test to assess the
chemical stability and provide better understanding of fuel
cell failure mechanisms. It was reported that OCV hold
accelerates to greater or lesser extent, depending on the
conditions used, such parameters as ECSA losses, voltage
decay and gas crossover in comparison to long duration
operation.158 The degradation rates calculated from acceler-
ated stress tests tend to be higher than those obtained from
a lifetime test. Moreover the H2O2 and concentration prole of
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the ferrous (Fe2+) at OCV condition also differ from those in
normal working mode.159 At OCV, hydrogen peroxide produc-
tion at the cathode side can be neglected due to high cathode
potential and lack of faradic current.80
6. Gas crossover and membrane
degradation
Gas crossover is an inevitable process in an operating PEMFC
as typically applied electrolyte membranes have a thickness of
20–50 mm. Greater thickness could decrease the permeation of
the reactants across the membrane,87,131 however it simulta-
neously increases the membrane area specic resistance. It
should be mentioned that besides the fact of the inevitability
of gas crossover, this process is much more pronounced under
open circuit conditions as there is no consumption of H2 and
O2 through the electrochemical reactions.60 The key role of gas
crossover in membrane degradation was demonstrated in
series of ex situ experiments. Independently, using different
experimental set-ups and methods of evaluation of membrane
degradation, several researchers drew the conclusion that the
polymer decomposition occurs only when O2, H2 and Pt
coexist.113,135,148 That initiated further studies on hydrogen
crossover investigated in an operating fuel cell. Inaba et al., in
their work on membrane degradation at OCV, demonstrated
the incontestable increase of hydrogen crossover with simul-
taneous drop of OCV and increase of uoride emission.60 It
was pointed out that measurement of the hydrogen perme-
ation across the electrolyte might be a reliable indicator of
membrane degradation.60,160 Other authors have investigated
the inuence of cell temperature, humidication (refer to
Fig. 10) and gas pressure on hydrogen crossover. Clearly the H2
crossover current density increases with increasing tempera-
ture (from 40 to 80
C), relative humidity (here from 40 to 80%)
and (not included on Fig. 8) gas pressure. This nding was
further conrmed by Baik et al. in similar range of tempera-
ture and relative humidity.161 Moreover a particular design of
the bipolar plate allowed the measurement of the hydrogen
crossover rate over a local area. The local variation of crossover
Fig. 10 Effect of temperature and relative humidity on H2 crossover
current density at atmospheric pressure. Reprinted from (vol. 51, M.
Inaba et al., Gas crossover and membrane degradation in polymer
electrolyte fuel cells, 5746–5753).60 Copyright (2006), with permission
from Elsevier.
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(higher H2 crossover was measured near the inlet of the gas
than near the outlet) was attributed to the partial pressure
gradient of H2.
As stated above, high temperature162 and gas pressure lead to
elevated crossover rates and accelerate membrane degradation.
For this reason, those parameters are typically applied in AST.
However the inuence of relative humidity on the mechanism
of membrane chemical decomposition is much more complex.
According to the previous discussion, H2 permeation increases
with increasing relative humidity. This observation was inter-
preted using a multi-structural model of Naon®, comprising
an ion cluster region, an interfacial region and a uorocarbon
phase.163 Based on the assumption that H2 permeates through
exible, amorphous interfacial uorocarbon regions,164 it was
proposed that water absorbed by the membrane increases the
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size of the ion clusters, plasticizes the interfacial regions60 and
enlarges the free volume165 where gas permeability can occur.
Keeping in mind the relationship between H2 crossover and
membrane degradation, the observation that low relative
humidity166 or humidity cycling167 accelerates the polymer
decomposition to larger extent than high relative humidity is
rather surprising. This discrepancy clearly shows that for the
mechanism of radical formation and membrane degradation,
the degree of humidication itself is one of the critical factors.
Inaba et al. argued that it might be related to a higher
concentration of hydrogen peroxide under low RH,60 no exper-
imental conrmation was provided. Some more light on this
issue is given by research performed recently by Prabhakaran
et al.168 These authors investigated formation of the reactive
oxygen species (ROS) in an operating fuel cell using in situ
uorescence spectroscopy. Again a clear correlation between
generation of ROS and PFSA membrane degradation was
demonstrated under different fuel cell operating conditions.
ROS formation was found to be enhanced at lower relative
humidity (50% > 75% > 95%), elevated cell temperature (100
C
> 80
C > 60
C > 40
C) and nally at higher cathode potential
(0.8 V > 0.6 V > 0.4 V). An excellent graphical summary of these
results is shown in Fig. 11, which plots the uoride emission
Fig. 11 Correlation between in situ reactive oxygen species ROS
formation rate and membrane degradation expressed as fluoride
emission rate. Reproduced from ref. 168 with permission of the PCCP
Owner Societies.
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ux vs. the in situ radical formation rate for all conditions
investigated.
This experiment validates the assumption of a high
concentration of reactive oxygen species at low relative humidity
and conrms the role of the high temperature and cathode
potential as stressors for membrane degradation.
The mechanism of the membrane decomposition depends
largely on the experimental conditions; however it always
results in scission or cross-linking133 of polymer chains. Recent
publications in this eld show that attention is increasingly
paid to chemical analysis of exhaust gas and water, since this
analysis can provide information about the presence of three
general groups of species considered from the perspective of
membrane degradation. The rst group consists of products of
membrane decomposition such as uoride ion,169,170 sulfate ion
or polymer fragments.109,113,124,170 The second group are pollut-
ants171,172 which act as degradation catalyst. Contaminants in
a fuel cell set up originate from gas or water supplied to the
system, from the cell hardware or the alloy catalysts. Gaseous
impurities such as HCOOH, CO, NO2, SO2, H2S, Cl2 can cause
blocking of the catalyst active sites, affect the ORR mechanism
or accelerate Pt dissolution.173,174 Hydrated cations such as Fe2+,
Fe3+, Cu2+ or Al3+ accelerate membrane degradation and cause
performance losses.175,176 Also certain degradation compounds
such as: in case of Naon – peruoro(2-methyl-3-oxa-5-sulfonic
pentanoic) acid and 3M membranes – peruoro(4-sulfonic
butanoic) acid may migrate and adsorb into the catalyst layer
leading to a loss of ECSA and ORR activity.177 The last group of
species consists of free radicals, which are initiators but oen
also products of chemical degradation or of the decomposition
of hydrogen peroxide.
7. Influence of Pt band on membrane
degradation
The above discussion concludes that there are different
contributions of the cathode and anode catalyst to the overall
chemical degradation, however recently more attention has
been focused on the inuence of platinum in the membrane
(PTIM) on the acceleration/diminution of its chemical degra-
dation.136 One of the rst reports concerning Pt band formation
in PFSA membrane appears in 2005, when Ferreira observed the
existence of a Pt band in the membrane aer 2000 h of OCV
hold test,12 and further studies revealed that a Pt band can be
formed already aer the rst 50 h of OCV hold.136 The Pt catalyst
is unstable in the acid environment of the fuel cell at high
voltage and can dissolve at the cathode due to electrochemical
oxidation to Ptz+ ions178,179 as displayed in eqn (15):180
Pt / Pt2+ + 2e (15)
Then Pt ions migrate into the membrane due to the
concentration gradient and undergo reduction in the presence
of the crossover hydrogen according to the eqn (16).
Pt2+ + H2 / Pt0 + 2H+ (16)
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Pt atoms formed on that way (Pt0) can further diffuse and
agglomerate in the membrane in order to minimise their high
surface energy forming Pt particles.180
(Pt)n + Pt0 / (Pt)n+1 (17)
Pt ions can also precipitate electrochemically at low
potentials.
(Pt)n + Pt2+ / (Pt)n+12+ (18)
(Pt)n+12+ + H2 / (Pt)n+1 + 2H+ (19)
Such dynamic oxidation/dissolution and reduction/
deposition processes results in Pt band formation. The Pt
particle shape, size and distribution is strongly inuenced by
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the composition and partial pressure of the crossover oxygen
and hydrogen gases.10,180 Kim et al. studied the location of the Pt
band in a Naon® membrane with 25 mm thickness and
a ePTFE reinforcement incorporated at the centre.181 A Pt band
was observed between 1 and 10 mm from the cathode membrane
interface, where oxygen is typically depleted. These authors re-
ported a greater deposition of Pt nanoparticles in the polymer
structure under OCV hold test conditions than under constant
current operation. Similarly OCV hold was reported to accel-
erate polymer degradation. It was proposed that the presence
and location of the platinum band might correlate with the
formation of highly reactive oxygen species.182 Hatanaka et al.
carried out studies with pristine Naon® and with a membrane
where a Pt-band had been intentionally introduced.183 Aer the
OCV hold testing, the FER of the membrane containing plat-
inum was clearly higher than that of the pristine membrane.
Ohma et al. employed micro-Raman spectroscopy to investigate
the degradation prole of in situ aged membranes and found
enhanced degradation of the polymer around the Pt band.14,15
Also post-mortem SEM study of an aged MEA revealed
membrane thinning at the cathode site in presence of PTIM and
conductive AFM measurements showed electronic connections
Fig. 12 Formation of free radicals on Pt and the Pt dissolution
mechanism. Reprinted from (vol. 195, D. Zhao, B. L. Yi, H. M. Zhang and
M. Liu, The effect of platinum in a Nafion® membrane on the durability
of the membrane under fuel cell conditions, 4606–4612).185 Copyright
(2010), with permission from Elsevier.
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across the membrane.184 These results were interpreted as
formation of electronic short-circuits due to accumulation of Pt
particles. Studies of Liu and co-workers revealed an increased
degradation when a membrane exposed to H2O2 solution was Pt
catalyst coated in comparison to a bare membrane in an H2O2
ow cell experiment.135 Hydrogen peroxide formed at the elec-
trode surface can potentially decompose to hydroxyl radicals on
the active Pt sites,186 and free radicals can also be directly
generated from the crossover gases on the platinum particles
precipitated in the membrane (Fig. 12).137,187 Evidence for such
a mechanism was provided by the work of Kim et al. where
formation of carbon radicals on the Pt particles was conrmed
by using electron spin resonance.187 Ohguri also demonstrated
the formation of HOc in the presence of dispersed Pt particles83
however it is necessary to keep in mind that metallic platinum is
a less active Fenton catalyst than iron and therefore direct
formation of HOc radical is much less effective.188
Pt(II) species present within the membrane can lead to the
generation of free radicals136 and can affect the membrane
physical properties due to the interaction with the per-
uorosulfonic groups resulting in loss of conductivity and
membrane stiffening.189 The lowest uoride emission rate153
and no Pt band formation was observed for MEAs with air
supplied to the cathode;14,190 on the contrary to induce PTIM
formation in the membrane pure oxygen is commonly used as
the reactant gas.156 All those ndings conrm the destructive
effect of the Pt particles deposited in the membrane on its
degradation.
Fig. 13 The effect of membrane thickness and Pt particle size on FER
for different platinum loadings (B) and spacing (A) in the membrane.
Reproduced by permission of The Electrochemical Society from ref.
186.
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Table 1 Overview of reactions involving formation and decay of intermediates in a fuel cell environment. Reproduced by permission of The
Electrochemical Society from ref. 81. Listed rate constants were estimated at room temperature and low pH. Reactions of hydroxyl radical with
polymer structure (reactions 1 & 2); reaction of formation, decomposition and consumption of hydrogen peroxide (reactions 3–8), Fenton
reaction and reaction of hydrogen peroxide and radicals catalysed by iron impurities
Reaction
1 HOc + RfCF2SO3H / unzipping
2 HOc + RfCF2COOH / unzipping
3 H2O2 / 2HOc
4 HOc + H2O2 / HOOc + H2O
5 HOOc + H2O2 / HOc + H2O + O2
6 HOc + H2 / Hc + H2O
7 Hc + O2 / HOOc
8 2HOOc / H2O2 + O2
9 Fe2+ + H2O2 + H+ / Fe3+ + HOc + H2O
10 Fe2+ + HOc + H+ / Fe3+ + H2O
11 Fe2+ + HOOc + H+ / Fe3+ + H2O2
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12 Fe3+ + HOOc / Fe2+ + O2 + H+
13 Fe3+ + H2O2 / Fe2+ + HOOc + H+
On the other hand, some studies show no correlation
between the presence of the PTIM and membrane degrada-
tion152 or even a decrease of PFSA ionomer degradation (lower
uoride emission rate) of Pt-containing membranes in
comparison to pristine polymer, due to the scavenging of
hydrogen peroxide and hydroxyl radicals by Pt particles.148,152,191
Macauley et al. reported enhanced stability of a eld-operated
MEA with a PTIM compared to a freshly prepared MEA. The
pristine membrane showed higher OCV decay and uoride
emission rate aer 10 hours of AST cycle as well as a decrease in
IEC aer exposure to Fenton's reagent.191 This group developed
an Accelerated Membrane Durability Test (AMDT) protocol to
mimic membrane degradation during heavy duty fuel cell
operation.192 Once again PTIM prolonged MEA life-time under
these AMDT conditions. Peron et al. suggested that this
discrepancy arises from coexistence in the membrane of
different Pt species such as Pt(0), Pt(II) or Pt(IV). While metallic
platinum might act as radical quencher, Pt(II) catalyses the
hydrogen peroxide decomposition and radical formation. Later
Gummalla et al. explained these nonlinear trends by two
competitive reactions which can occur on the Pt surface:
production and deactivation of free radicals.186 In that context
such parameters like: the Pt particle size,186 shape,193 loading
and spacing186,194,195 (see Fig. 13) dene its potential radical
scavenging or generating properties.
Furthermore those parameters combined with temperature,
level of hydration or concentration of crossover gases appear as
crucial key factors impacting polymer decomposition. The
proposed model nds conrmation in recently performed
studies, on the degradation of a Pt-containing membrane.195
Rodgers et al. studied the effect of precipitated platinum with
concentrations of 0, 10, 30 and 50 mol% on membrane degra-
dation. The highest FER with similar magnitude to that
observed with Pt/C catalyst coated on the polymer, was found
for a membrane containing 10 mol% Pt. In contrast, samples
containing 0, 30 and 50 mol% Pt gave very low FER. It was
proposed that a dense distribution of Pt particles in the two last
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Rate constant (M1 s1)
—
<106
1.2  107
2.7  107
#1 (reasonable upper limit value)
4.3  107
1.2  1010
8.6  105
63
2.3  108
1.2  106
2  104
4  105
membrane samples, enabled the deactivation of the generated
radicals prior to the polymer decomposition.196 Finally, non-
platinum-group-metal ORR catalysts are being increasingly
investigated as an option for fuel cell application. However,
catalysts with Fe or Co and N species anchored on carbon
substrates (Fe/Co–N–C) have to be considered in the context of
PFSA membrane degradation. Fe/Co–N–C catalysts have low
stability197 and suffer from dissolution/leaching of (Fenton
active) metal, oxidative attack of hydrogen peroxide and
protonation of active sites on neighbouring N species.198 All
three mechanisms not only cause a strong decrease in catalyst
activity, but also threaten the integrity of PFSA membranes.199
Surprisingly little work has been carried out on membrane
degradation in the presence of non-noble metal catalysts, and
well designed in situ accelerated stress testing is required to
develop proper understanding.
8. Radical types, reactivity and
lifetime
Aer examining the degradation mechanisms in the context of
the polymer structure susceptible to radical attack, as well as
H2O2 formation area and conditions, in this section we will
consider the radical types and their generation in a fuel cell in
more detail, up to this point the membrane degradation was
described mainly as hydroxyl radical HOc attack on polymer
structure. However in a working fuel cell Hc and HOOc radicals
are present in concentrations much higher than those of HOc
which, once generated from hydrogen peroxide, is further
consumed to produce HOOc or scavenged by crossover gases. An
excellent summary of reactions likely taking place in a fuel cell
(Table 1) was given by Gubler et al.81
This inventory of relevant mechanisms helped to create
simulation of possible radical attack. Simulation based on the
reaction (2) represents the chemical attack of the hydroxyl
radical on the terminal –COOH groups, i.e. the “unzipping
mechanism” discussed in the previous section. In their studies
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Table 2 Overview of reduction potentials of free radicals (pH ¼ 0).
Reproduced by permission of The Electrochemical Society from ref.
118
Standard electrode
Half-cell reaction potential (V)
1 HOc + H+ + e / H2O 2.59
2 Hc + H+ + e / H2 2.32 (ref. 80)
3 HOOc + H+ + e / H2O2 1.48
4 H2O2 + 2H+ + 2e / 2H2O 1.74
of the kinetics of membrane degradation, Gubler et al. did not
take into consideration the radical attack on the side chain
(cited previously as mechanisms II and III and represented in
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the table by reaction (1)) due to the lack of information on the
kinetics of these reactions in the literature. Two sets of reactions
used by Gubler et al. in their studies can be distinguished with
hydrogen peroxide as the precursor for the radical
intermediates.
Reactions (3)–(8) describe the homolytic dissociation of
H2O2 (reaction (3)) and consumption of free radicals origi-
nating from H2O2 in the absence of iron catalyst. Reaction (3)
occurs with very low rate constant approximately 1.2  107
M1 s1. As displayed in eqn (4), HOc reacts with hydrogen
peroxide, to form HOOc, while reaction (5) follows a similar
pathway but in this case HOOc is the reactant for the genera-
tion of hydroxyl radicals. Furthermore the reaction of Hc and
HOc radicals with crossover gases in a fuel cell follows the eqn
(6) and (7). Finally hydrogen peroxide can be regenerated as
described by eqn (8) due to HOOc disproportionation. However
in real working fuel cell conditions, reactions (9)–(13) are the
most relevant, since H2O2 decomposition is catalysed by Fe ion
impurities. Reaction (9) is widely known as the Fenton reac-
tion and it is the primary source of hydroxyl radicals, where
Fe2+ is the reducing agent regenerated aer the reaction of
Fe3+ with H2O2 and HOOc. The rate constant of reaction (9)
(here 63 M1 s1) is much higher that previously cited in the
homolytic dissociation of hydrogen peroxide, which further
means higher rate of HOc generation.
Indeed the simulation studies of the radical attack per-
formed by Gubler showed higher rate of the ionomer attack
under ex situ, Fenton reagent conditions, in comparison to that
observed in an OCV hold test.81 It is most likely due to a higher
concentration of hydroxyl radicals. Moreover, based on the
kinetic model the theoretically estimated uoride emission rate
aer Fenton aging was in good agreement with FER reported in
the literature.100,150,200 However a similar FER estimation for in
situ accelerated tests were 2–3 orders of magnitude lower than
the literature values.91,188 The differences between the in situ
measurement and the kinetic simulation might be due to the
absence in the provided model of reaction (1), which describes
the side chain decomposition. Moreover two other factors were
not included in Gubler's model i.e. the inuence of the direct
formation of free radicals on Pt nanoparticles in the membrane
and the inuence of the electrode surface on membrane
degradation. A large difference between simulated and
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Scheme 1 Factors impacting PFSA fuel cell membrane degradation.
experimental values of FER on OCV hold indicates the
substantial role of these factors on the chemical decomposition
of the ionomer membrane in the MEA.
Another important issue is the oxidative strength of free
radicals. The most cited radical with regard to chemical
degradation is the hydroxyl radical HOc. This is due to the
ranking of the reactivity of the oxidative species, where the
hydroxyl radical takes a rst position: HOc > Hc > HOOc >
H2O2.80 High oxidising power of HOc is reected in higher
reduction potential of HOc in comparison to the hydroperoxyl
radical and hydrogen peroxide (Table 2).
Similarly, the difference in the rate of hydrogen abstraction
can be estimated based on the experimental bond strength.117
As the O–H bond in water is very strong, the hydroxyl radical has
strong thermodynamic driving force (497.9 kJ mol1) to abstract
the hydrogen and form an H2O molecule. In contrast it is very
unlikely that hydrogen peroxide or HOOc will cause hydrogen
abstraction with direct detrimental effect on the PFSA
membrane. The main role of those species is therefore as
a source of much more reactive HOc.
9. Impact of operating conditions on
PFSA membrane chemical degradation
The evaluation of membrane durability in an operating fuel cell
is challenging since many factors including operation temper-
ature, pressure, humidity, operating voltage and current, start-
up/shut-down conditions, the composition and design of
other cell components and the effect of contaminants have to be
considered. The synergetic effect of all these factors in oper-
ating fuel cell make identication of the local phenomena
leading to membrane chemical decomposition quite complex.
Test protocols have been designed to limit certain phenomena
and exacerbate others, and furthermore harmonized methods
provide the basis for comparing results and facilitate assess-
ment of technology status. In real operation these conditions
are rarely separated and performance losses can arise from
pinhole formation201 following mechanical/chemical
Sustainable Energy Fuels, 2017, 1, 409–438 | 421

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membrane degradation cycling, while RH uctuations,
temperature and loading cycling and start-up, shut-down can all
cause membrane dimensional change, and lead to plastic
deformation, cracks and pinhole formation. Following pinhole
formation, high hydrogen crossover causes accelerated radical
formation and further polymer decomposition. The degrada-
tion pathway continues until the membrane, thinned and
weakened by radical attack membrane, can no longer withstand
mechanical stress when, regardless of the decomposition mode
by chemical attack or shear forces, the consequence is a MEA
failure (Scheme 1).
10. Mitigation of membrane
degradation
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The foregoing discussion shows that degradation of PFSA
membranes is currently considered to involve complex inter-
connected mechanical and chemical mechanisms. Due to the
complexity of these factors contributing to the overall degra-
dation, many different approaches have been developed to
minimise polymer cleavage processes. The main mitigation
strategies proposed in the literature include development of
new reinforced or composite membranes, stabilisation of most
vulnerable PFSA polymer groups, incorporation of a hydrogen
peroxide decomposition catalyst or radical quencher in the
membrane/electrode, development of new electrode/GDL
material.
10.1 Development of new reinforced or composite
membranes
Preparation of a reinforced material was proposed to improve
the durability of the PFSA polymer.107,202–205 In general two
widely investigated routes to achieve this goal can be distin-
guished: chemical modication of the polymer structure and
physical reinforcement.203 Chemical modications include
membrane annealing206–212 uniaxial stretching213,214 and chem-
ical cross linking of the polymer,203,215 these were used to reduce
swelling of the membrane and improve mechanical durability.
Annealing of PFSA polymers leads to more efficient chain
packing and higher polymer crystallinity. Thermal treatment is
extremely important, especially for a solvent cast membrane, as
the annealing procedure improves intrinsic properties of the
polymer and makes them similar to those of an extruded
membrane. Treatment by uniaxial stretching has been
demonstrated to effectively increase Young's modulus, reduce
area swelling and slightly increase proton conductivity. Other
chemical modications such as polymer cross linking can be
carried out by conversion of the sulfonic acid side chain
however such method leads to inevitably high conductivity
losses and therefore was not widely studied. Incorporation in
the polymer structure of new cross-linkable functional groups
appears as the more appropriate method and was performed
with sulfonyl uoride and sulfonamide216,217 or sulfonyl uoride
and 3-aminopropyltriethoxysilane (APrTEOS) as reactants. A
different method based on pendant alkyl bromide group, which
can be cross linked by thermal treatment or electron beam
422 | Sustainable Energy Fuels, 2017, 1, 409–438
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irradiation has also been investigated.218 In general new cross
linked materials show reduced dimensional swelling and
higher mechanical stability in comparison to non-reinforced
PFSA membranes. However a similar effect can be achieved
using physical reinforcements, in which the membrane prepa-
ration is further simplied. To fabricate a reinforced composite
membrane, a highly mechanically stable organic or inorganic
matrix is impregnated or otherwise associated with the PFSA
dispersion. A large spectrum of membrane reinforcements has
been developed, including expanded porous PTFE
sheets204,219–221 or brils as well as nanobre mats prepared by
electrospinning of polymers such as poly(vinylidene uoride)
(PVDF),222,223 poly(vinyl alcohol) (PVA),223,224 polybenzimidazole
(PBI),225 poly(phenyl sulfone), UHMWPE (ultrahigh molecular
weight polyethylene)226 or nanober network silicon carbide
SiC.227 Among these, low cost expanded PTFE (ePTFE) supports
have been particularly successful. ePTFE reinforced membranes
are usually prepared by soak or spray methods.228 The ionomer
lls the pores of the thin ePTFE lm and forms a layer of ion-
omer on either side of PTFE mat. The advantages of using PTFE
as the membrane support include the reduction of membrane
cost228 and improved dimensional stability and durability of
composite membrane229 when subjected to mechanical accel-
erated tests such as freeze/thaw or, humidity cycling230,231 as
PTFE suppresses swelling of PFSA electrolyte within the porous
matrix. However, PTFE/PFSA membranes demonstrate higher
proton transport resistivity than the respective non modied
membranes.228 This negative effect can be minimized by
applying ultrathin PTFE mats with high porosity,232,233 or by
hydrophilic treatment of hydrophobic PTFE structure.230 Such
treatment improves the wettability and adhesion of more
hydrophilic polymer which in turn allows good interfacial
compatibility. However according to Kundu et al. the ePTFE
reinforced PFSA membranes undergo accelerated chemical
degradation at low relative humidities 20–50%.166 Thus
increased mechanical durability of the membrane might extend
lifetime but not suppress chemical failure. Inorganic llers
resulting in nanocomposite membranes like Naon® –
SiO2,234–238 Naon® – TiO2,236,238–242, Naon® – SnO2,243–246
Naon® – ZrO2 (ref. 236, 238, 247 and 248) or Naon® –
ZrP248–251 deserved special attention. Incorporation of inorganic
particles can not only enhance the mechanical properties of the
PFSA membranes, but also increase the water retention, which
allows higher performance at elevated operating temperatures
and low relative humidity.249 Furthermore inorganic particles
can be successfully applied as a hydrogen peroxide decompo-
sition catalyst or radical scavenger, as will be discussed in the
later section of this review. PFSA-inorganic nanoparticles
composite membranes can be prepared either from a disper-
sion of oxide particles in the ionomer solution prior to
membrane casting or by in situ generation of inorganic particles
within the membrane/ionomer through a sol–gel-like process.
The properties of such prepared composite membranes depend
to large extent on the type of the polymer, the particle size, their
dispersion through the membrane and any preferential orien-
tation, in the case of inorganic particles with large aspect
ratio.252
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10.2 Stabilisation of most vulnerable PFSA polymer groups –
development of SSC PFSA membrane
Stabilisation of the most vulnerable groups of the PFSA polymer
is another method to mitigate membrane degradation. It was
discussed previously in connection with different variants of
chemical decomposition and should be considered in relation
to the mechanism of free radical attacks on the polymer struc-
ture. Naon® with chemically stabilised carboxylic acid end
groups – the most susceptible point in polymer – shows reduced
but not eliminated mass loss. Lower uoride emission of
chemically stabilised Naon® is due to limited participation of
the unzipping mechanism in the overall decomposition reac-
tion, however weight decrease is still noticeable and it is related
to the continuously occurring side chain degradation with
tertiary carbon, ether bonded carbon and/or sulfonic acid
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groups as the points of initial attack as these are the most
vulnerable points. Although the development of a per-
uorinated ionomer with a shorter pendant side chain than
Naon®, the so-called short side chain (SSC) ionomer pre-dates
understanding of membrane degradation, the short side
structure is expected to bring several advantages regarding
membrane durability. Elimination from the side chain struc-
ture of the tertiary carbon (–CF) and one of the ether bonded
carbon atoms (–O–CF2) decreases the susceptibility of the SSC
membrane to radical attack, a nding that was conrmed in
several studies.100,108,149 More recently attention has been drawn
to low EW multi-acid side chain proton exchange membranes
developed by 3M.253–256 In these new materials high number of
tetrauoroethylene units in the backbone structure has been
combined with side chains which carry more than one acid site.
3M peruoro-imide acid (PFIA) membranes have high acid
content while preserving excellent mechanical stability when
compared to similar EW PFSA membranes.253 Although funda-
mental studies regarding mechanical, conductive properties of
3M PFIA membranes have been carried out no reports have
been published so far on PFIA durability. Only conclusion
which might be drawn today is that both the SSC (including
PFIA) and long side chain (LSC) membranes have a sulfonic acid
as functional ion transporting groups, therefore they both can
suffer the decomposition which begins under certain condi-
tions at the C–S bonds. To mitigate degradation of the side
chain, incorporation of a free radical scavenger as a chemical
trap for highly reactive oxygen species was proposed.
10.3 Incorporation into membrane/electrode hydrogen
peroxide decomposition catalyst (HPDC) or radical quencher
In this manner we come to the highly effective approach to
minimize the chemical degradation, which involves incorpora-
tion, into the membrane electrode assembly, of species with
peroxide decomposition or radical scavenging properties. This
concept has been investigated already before 2005. Convincing
results in this area have led to the increased interest of many
researchers and several patents.257–262 Examples of hydrogen
peroxide decomposition catalysts (HPDC) applied for mitiga-
tion of membrane degradation are: metal oxides like
TiO2,239,263–265 MnO2 (ref. 266) and ZrO2,200 heteropoly acids,267–270
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carbon–tungsten oxide (C/WO3) or carbon–phosphotungstic
acid (Pt/C-PTA).271,272 Metal particles such as Ce,108,273–277
Mn,274,276,277 Pd, Ag, Au or Pt,278 metal oxides CeO2,279–289
MnO2,290,291 SnO2 (ref. 292 and 293) and terephthalic acid
(TPA)294 also demonstrate ability to mitigate chemical
degradation.
The main role of HPDC is to lower the H2O2 concentration
and indirectly decrease the formation of free radicals. In
contrast introduction of a regenerative radical scavenger into
MEA components causes direct reduction of the concentration
of already created highly oxidative species. For these reasons
two potential areas for HPDC/radical scavenger incorporation
may be distinguished: the polymer membrane and the elec-
trode. In the rst case, preparation of a composite membrane
was accomplished by mixing the HPDC/radical scavenger
nanoparticles or chemical compounds with the ionomer
suspension prior to formation of the membrane. In this
approach, hydrogen peroxide can be neutralised only aer its
diffusion into the polymer membrane. In the work of Xiao et al.,
zirconia particles were prepared by a hydrothermal method and
incorporated in the Naon® membrane. The resulting ZrO2
composite membrane was examined under OCV hold (80
C;
50% RH; H2/O2) and Fenton's test conditions. Accelerated stress
tests show reduced FER (by up to an order of magnitude) and
thinning, relative to native Naon®.200 As zirconium oxide
enhances the membrane durability (due to its radical scav-
enging ability) and water retention at high temperature and low
relative humidity, development of composite ZrO2/PFSA
membranes is an interesting approach to mitigate mechanical
and chemical degradation. A similar concept to reduce both
mechanical and chemical degradation was investigated by Patil
et al. by using a TiO2/Naon® composite membrane.265 A titania
“quasi-network” in the polymer structure was developed by in
situ sol–gel polymerisation of titanium isopropoxide. The EW of
the modied membrane remains unaltered, however the
hydration capacity decreased in relation to the pristine
Naon®. The authors postulated that the incorporation of
small (nano size) and evenly dispersed particles, placed along
the gas diffusion pathways, potentially increase tortuosity and
reduce fuel crossover. Additionally, if the titania particles form
a slightly interconnected network, due to the presence of weak
metal oxide bonds, they can constitute a mechanical membrane
reinforcement.252 Indeed the modication provides signicant
dimensional membrane stability (higher modulus and lower
creep) and minimised voltage loss at OCV hold test.239 It should
be noted that use of ZrO2 and TiO2 as additives for PFSA
membranes was carried out with the aim of improving their
water-retention and mechanical properties, and the radical
scavenging effect of those compounds was discovered later.
Similarly heteropolyacid/PFSA membranes were initially devel-
oped to maintain proton conductivity of membrane at elevated
temperature and low relative humidity conditions.295–298
Haugen et al., investigated the durability of 3M membrane
modied by the addition of various heteropolyacids (HPAs) as
HPDC.267 Of these, l-H3P2W18O62, H6P2W21O71 and H4SiW12O40
signicantly reduced the amount of uorine released under
accelerated stress test conditions. Incorporation of the HPAs
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enhanced performance of the MEA in a narrow concentration
range of HPA. The efficacy of the mitigation properties of metal
nanoparticles such as Au, Ag, Pt and Pd in Naon® was studied
by Trogadas et al.278 The idea of using those elements as radical
scavengers was rst provided by their known activities in
biology as antioxidant species. Composite membranes were
prepared by casting dispersions with 3 wt% metals loading.
Such a metal content lowers the conductivity of Naon® due to
dissolution of the metal particles above a certain potential i.e.
>0.4 V vs. SHE for Ag and >0.8 V vs. SHE for Pd, and the
formation of ionic species that exchange with protons. Plat-
inum particles were an exception, where in situ water produc-
tion on Pt surface compensates metal dissolution and ion
exchange with the sulfonic acid groups. Regarding the radical
scavenging properties of the incorporated metals, the addition
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of Ag, Pt, Pd and Au nanoparticles decreased the uoride
emission rate by 35%, 60%, 80% and 90% respectively. To
minimise the impact of metal dissolution on membrane
conductivity or further performance, metal particles were sup-
ported on silica, SiO2. Indeed, the conductivity of the composite
membrane with SiO2-supported metal particles increased
signicantly and reached values similar to the reference
Naon®. The impact of silica incorporation was especially
visible for SiO2/Pt Naon® membrane. However a lower
concentration and simultaneously larger size of the supported
metal nanoparticles brought considerable FER increase. a-
Tocopherol (a-TOH) is other natural antioxidant (vitamin E
component) which, when embedded into Naon® prevented
membrane degradation and performance losses.299 a-TOH acts
as a trap for hydroxyl and peroxyl radicals once oxidized, a-TOH
can be further reduced by crossover hydrogen during fuel cell
operation. The reversibility of a-TOc/a-TOH system assures its
high efficiency as a radical scavenger. However the long-term
stability of a-TOH incorporated into electrolyte is unknown.
Recently Zhu et al. reported a new method to increase the
chemical stability of PFSA membrane by the incorporation of an
organic radical scavenger – terephthalic acid (TPA).294,300 Fig. 14
Fig. 14 Mechanism of HOc radical trapping process by TPA proposed
by Zhu. Reprinted from (vol. 432, Y. Zhu, S. Pei, J. Tang, H. Li, L. Wang,
W. Z. Yuan and Y. Zhang, Enhanced chemical durability of per-
fluorosulfonic acid membranes through incorporation of terephthalic
acid as radical scavenger, 66–72).294 Copyright (2013), with permission
from Elsevier.
424 | Sustainable Energy Fuels, 2017, 1, 409–438
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displays a possible mechanism of the reaction of TPA with
a hydroxyl radical. The generated intermediate, hydrox-
ycyclohexadienyl radical can either undergo a disproportion-
ation reaction to form hydroxylated terephthalate and
regenerate TPA, or can be catalysed by an Fe3+ ion to form the
hydroxylated terephthalate.
A composite TPA/PFSA membrane aged under ex situ Fenton
test conditions shows higher durability than pristine PFSA
membrane, which indicates HOc scavenging ability. However
these promising results need to be further conrmed in situ in
a fuel cell in order to verify the performance, stability and
impact on other MEA components of this newly developed
approach.
The second strategy involving the addition of peroxide
decomposition catalysts or radical scavengers in the catalyst
layers has the advantage that the H2O2 can be decomposed
already at the catalyst surface. Typically a catalyst ink includes:
carbon support, metal catalyst and ionomer. The ionomer can
comprise an HPDC associated with anion groups in the ion-
omer salt form or suspended as particles in the catalyst ink.
Trogadas et al. validated the second approach by preparing
various hybrid catalysts such as C/WO3, C-PTA271 or Pt/C–
MnO2,266 which were studied for their efficacy of hydrogen
peroxide decomposition and mitigation of membrane degra-
dation. RRDE measurements showed signicant reduction in
the concentration of H2O2 produced during ORR on these
catalysts. Also in situ OCV hold tests of the MEAs with HPDC
additives revealed decrease of the rate of membrane degrada-
tion which was reected in lower uoride emission rate. The
best results in H2O2 decomposition were given by the incorpo-
ration of MnO2 particles with mixed valence state whereby they
can undergo relatively easy reversible redox reaction with H2O2,
moreover the free hydroxyl radicals – HOc can be scavenged at
the same time. On the other hand, the performance of an MEA
containing an MnO2 hybrid catalyst was inadequate, due to low
stability of MnO2 in acidic media at high potentials. Recently
developed MnO2 nanotubes and nanowires in small content did
not affect the available catalyst area.290 The performance of
manganese oxide doped catalyst layer measured at 100% RH
was similar to that with a conventional catalyst material.
Interestingly for lower RH values, incorporation of 1D MnO2
decreased the sensitivity of the fuel cell to variation in hydration
level. Moreover, OCV hold degradation tests have shown much
lower OCV decay with an MnO2 composite catalyst in compar-
ison to commercial material especially if incorporated on the
anode side (see Table 3) Tacconi et al. developed a Pt/C–TiO2
composite catalyst by using photocatalytic synthesis,263 and
found that the incorporation of TiO2 in the catalyst layer brings
signicant increase to the electrode and membrane durability
with comparable performance of a Pt/C–TiO2 composite for
oxygen reduction reaction to that with a commercial catalyst.
Finally, Brooker et al.268 incorporated adsorbed HPAs on high
surface area carbon at the membrane–electrode interface. Aer
OCV hold testing, a cell with a sub-layer enriched with phos-
photungstic acid (PW12O43) showed decreased OCV loss and
uoride release of around 50% over that of the non-HPA sub-
layer cell. However the inclusion of the carbon sub-layers
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Table 3 Overview of hydrogen decomposition catalyst and radical scavenger incorporated in MEA components

Accelerated durability test

REF Form/location Content Ex situ ageing In situ ageing

271
Hybrid catalyst 15 wt% RRDE OCV: 90
C 50% RH O2/H2
C/WO3 30–40% reduction in the amount FER: (ppm)
of H2O2 produced for 15 wt%
C/WO3 and C/PTA versus Pt/C.
C/PTA Anode:
C – 1.3
C/WO3 – 0.5
C/PTA–0.7
Cathode:
C – 0.55
C/WO3 – 0.38
C/PTA–0.36
OCV: 90
C 50% RH Air/H2
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266
Hybrid catalyst 5 wt% RRDE
FER: (ppm)
CATHODE 50–60% reduction in the amount of Anode:
Pt/C/MnO2 H2O2 produced for 5 wt% Pt/C/MnO2 Pt/C1.1
versus Pt/C. Pt/C/MnO20.22
Cathode:
Pt/C0.84
Pt/C/MnO20.59
290
Hybrid catalyst – OCV: 60
C 75% RH Air/H2 decay: (mV min1)
CATHODE/ ANODE Pt/C51.2
Pt/C/MnO2 Cathode : Pt/C/MnO2  nanowire  39.4
Cathode : Pt/C/MnO2  nanotubes  38.8
Anode : Pt/C/MnO2  nanowire  17
Anode : Pt/C/MnO2  nanotubes  18.6
283
Hybrid catalyst 20 wt% – OCV: 90
C 30% RH O2/H2 decay: (mV)
CATHODE Pt/C  0.72
Pt/C/CeO2 Cathode : Pt/C/MnO2  0.079
326
Hybrid catalyst TiO2 – FER: (mmol cm2 h1)
CATHODE 0 wt% ETEK (Pt 5 wt%)  0.03
Pt/C/TiO2 5 wt% SIDCAT (Pt 5 wt%)  0.3
5 wt% SIDCAT (Pt 10 wt%)  0.05
0 wt% TKK (Pt 50 wt%)  0.75
5 wt% SIDCAT (Pt 50 wt%)  0.06
10 wt% SIDCAT (Pt 50 wt%)  0.02
294
Composite membrane 0.5 wt% Fenton test F (%) –
TPA/PFSA  12% (48h)
TPA/PFSA PFSA  14% (48h)
TPA/PFSA  21% (120h)
PFSA  29% (120h)
278
Nanocomposite membrane 3 wt% – OCV: 90
C 30% RH O2/H2
FER:(mmol cm2 h1)
Ag Naon  0.41
Pt Naon/Ag  0.275
Pd Naon/Pt  0.18
Au Naon/Au  0.05
Naon/Pd  0.08
280
Nanocomposite membrane – – OCV: 90
C 30% RH O2/H2
– FER: (mmol cm2 h1)
CeO2/Naon® CeO2: Anode:
0 wt% Naon®  0.2
0, 5 wt% Naon®/CeO2  0.007
1 wt% Naon®/CeO2  0.006
1 wt% Naon®/CeO2(nc)  0.005 (nc – non commercial)
3 wt% Naon®/CeO2  0.008
– Cathode:
0 wt% Naon®  0.08
0,5 wt% Naon®/CeO2  0.006
1 wt% Naon®/CeO2  0.005

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Table 3 (Contd. )

Accelerated durability test

REF Form/location Content Ex situ ageing In situ ageing

1 wt% Naon®/CeO2(nc)  0.003

(nc – non commercial)
3 wt% Naon®/CeO2  0.007
286
Nanocomposite membrane 1 wt% – OCV: 90
C 30% RH Air/H2 FER: (mmol)
PFSA  3800
CeO2/Naon® Ceria(nc)  340 (nc – non commercial)
Ceria(com.)  33 (com commercial)
287
Nanocomposite membrane CeO2: Fenton test F (mmol g1) –
0 wt% PFSA: 2600(LF) 2600(GF)
CeO2/Naon® 0.5 wt% Ceria(nc): 500(LF) 1100(GF)
1 wt% Ceria(nc): 400(LF) 800(GF)
2 wt% Ceria(nc): 200(LF) 250(GF)
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0.5 wt% Ceria(com.): 400(LF) 1600(GF)

1 wt% Ceria(com.): 350(LF) 700(GF)
2 wt% Ceria(com.): 100(LF) 350(GF)
(LF) – Fenton reaction in solution phase
(GF) – Fenton reaction in gas phase
282
Nanocomposite membrane CeO2: Fenton test F (mg h1) OCV: 95
C RH cycling Air/H2 decay: (mV s1)
0 wt% Naon  55.78 Naon  11.7  104
CeO2/Naon® 1 wt% Ceria(self assembled)  43.05 –
3 wt% Ceria(self assembled)  8.67 –
5 wt% Ceria(self assembled)  6.01 Ceria(self assembled)  1.13  104
10 wt% Ceria(self assembled)  4.47 –
5 wt% Ceria(sol–gel)  11.64 Ceria(sol–gel)  5.78  104
281
Nanocomposite membrane – – OCV: 90
C 30% RH O2/H2
Pt: FER: (mmol cm2 h1)
Pt/CeO2/Naon® 0 wt% Naon®  0.6
– Naon®/CeO2  0.01
0.5 wt% Naon®/Pt/CeO2  0.007
1 wt% Naon®/Pt/CeO2  0.007
2 wt% Naon®/Pt/CeO2  0.007
– Naon®/MnO2  0.008
327
Nanocomposite membrane 1 wt% Fenton test F (mmol/gh) OCV: 80
C 50% RH O2/H2
Naon®: 2.25 FER: (mmol cm2 h1)
CsxH3xPW12O40/CeO2 Naon®/CeO2: 0.6 Anode:
H3xPW12O40/CeO2: 0.5 Naon®  0.6
Naon®/CeO2  0.4
H3xPW12O40/CeO2  0.025
Cathode:
Naon®  0.8
Naon®/CeO2  0.5
H3xPW12O40/CeO2  0.1
264
Nanocomposite membrane 20 wt% – OCV: 90
C 30% RH O2/H2 FER: (mg cm2 h1)
Anode:
TiO2/Naon® Naon®  3.681
TiO2/Naon®  0.354
Cathode:
Naon®  4.98
TiO2/Naon®  0.1755
265
Nanocomposite membrane 20 wt% – OCV: 100
C 25% RH O2/H2
FER: (mg cm2 h1)
Anode:
TiO2/Naon® Naon®  1.43
TiO2/Naon®  0.07
Cathode:
Naon®  1.46
TiO2/Naon®  0.12

426 | Sustainable Energy Fuels, 2017, 1, 409–438 This journal is © The Royal Society of Chemistry 2017
 View Article Online

Review Sustainable Energy & Fuels

Table 3 (Contd. )

Accelerated durability test

REF Form/location Content Ex situ ageing In situ ageing

200
Nanocomposite membrane 3 wt% Fenton test OCV: 80
C 50% RH O2/H2
FER (mmol g1 h1) FER: (mmol cm2 h1)
ZrO2/Naon® Anode:
Naon® < 85 Naon®  0.6
ZrO2/Naon® < 75 ZrO2/Naon®  0.06
Cathode:
Naon®  0.8
ZrO2/Naon®  0.02
291
Nanocomposite membrane 3 wt% Fenton test OCV: 90
C 50% RH Air/H2
FER (mmol g1 h1) FER: (mmol cm2 h1)
MnO2/SiO2–SO3H Anode:
Naon®  0.8 Naon®  0.8
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MnO2/Naon®  0.04 MnO2/Naon®  0.04

MnO2/SiO2/Naon®  0.05 MnO2/SiO2/Naon®  0.05
Cathode:
Naon®  1.1
MnO2/Naon®  0.2
MnO2/SiO2/Naon®  0.08
279
CeO2 free particles in 1 mM, Fenton test – EPR STUDIES –
fenton solution 10 mM Higher radical scavenging properties
of CeO2 with lower (10 mM) concentration
267
HPAs doped membranes – – OCV: 90
C Air/H2 FER: (mg per cm2 per day)
HP2W18 10 wt% 0.6
HP2W21 10 wt% 0.8
HSiW 20 wt% 0.84
275
Ce ion exchange membrane Ce: – OCV: 90
C 30% RH Air/H2 FER: (g cm2 h1)
0 wt% Naon®  1  106
5 wt% Naon®/Ce  1  109
10 wt% Naon®/Ce  1.6  1010
– – OCV: cold start conditions FER: (mmol)
0 wt% Naon(50) 0.45
(Naon50 – aer 50 OCV cycles)
10 wt% Naon(50) z 0
276
Ion exchange membrane (mmol) Hydrogen peroxide ow cell experiments OCV: 95
C 50% RH O2/H2 FER: (g cm2 h1)
Mn2+  anode 2.2 Co-doping of Ce into membrane containing 2  107
Mn2+  cathode 2.2 25 ppm of iron eliminates the accelerating 3  107
Ce3+ – anode 2.2 impact of Fe catalyzed hydroxyl 5  108
Ce3+ – anode/cathode 2.8 radical generation. 3  108
Ce3+ – membrane 45 3  108
268
HPA-carbon membrane- mg cm2 – OCV: 90
C 30% RH Air/H2 FER: (mmol cm2)
electrode sublayers
PW12O403 – PTA 0.13 No sublayer  40
PW11O404 – PTA-1V No HPA  48
SiW11O405 – STA-1V PW12O403  27
PW11O404  35
SiW11O405  40

signicantly increased the electrode ohmic and diffusion losses
as well as OCV losses in comparison to the cell with no sub-
layer. To overcome these problems Chen et al. impregnated
catalyst layers of CCM with phosphotungstic acid (PTA).272
Composite PTA-CCM exhibited better performance (especially
at high current density) and stability than a standard non
modied CCM. The power density of PTA-CCM decreased by
14% in comparison to 33% of non-modied CCM aer 100 h
aging, and the authors related these results to scavenging
properties of PTA and low degradation of ionomer in catalyst
layer.
Finally stabilisation301 or development of new ORR electro-
catalysts can also be considered as a mitigation strategy as
elimination of potential catalytically active sites for hydrogen
peroxide and radical generation is of great importance in
increasing membrane durability. Platinum alloys are promising
candidates for PEMFC application due to their lower cost and
high performance.302 Rodgers et al. carried out studies on the
inuence of a PtCo/C catalyst on membrane durability.303 They

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showed that higher stability of the PtCo/C material in compar-
ison to the Pt/C catalyst is translated into lower membrane
degradation which results in reduced FER, lower hydrogen
crossover and voltage decay. Ramaswamy et al. also reported
higher durability of a membrane associated with an electro-
catalyst enriched with cobalt using novel segmented cell design,
where membrane decay is correlated to losses in its ionic
conduction.95 Based on RRDE measurement they concluded
that such behaviour is due to lower adsorption of oxygenated
species on the Pt in the presence of Co, thereby diminishing
H2O2 formation.
Both cerium and manganese in ionic or oxide form have
been commonly applied to increase MEA durability by their
incorporation into the membrane or electrode. Due to the high
effectiveness in mitigation of the membrane degradation and
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exceptional mechanism of the radical decomposition they
deserve special attention. The idea of incorporation in the
polymer matrix of cerium and manganese ions by partial ion
exchange, was developed by Endoh et al.274,304
The concept proposed by Endoh assumed that when the
ionomer is ionically cross-linked with a radical scavenger
cation, it can show improved mechanical properties and higher
chemical stability (Fig. 15). The in situ durability studies of
newly developed material called NPC – New Polymer Composite
membrane performed by Endoh under the following fuel cell
conditions: OCV hold test, 20% RH and temperature 120
C,
demonstrated excellent stability of the NPC of over 1000 h with
FER in range of 2  108 g cm2 h1.
Further research of Coms et al. in this area shed more light
on the scavenging properties of both Mn and Ce cations.276
Coms et al. concluded that there is no impact of the initial
location of the radical quencher on the membrane stability
based on in situ degradation test of pristine and cation-
containing MEAs, where an ion-exchanged ionomer was used
for preparation of the catalyst ink. In other words, doping of the
anode or cathode electrode with radical scavenger gave a similar
effect on the MEA durability. Coms argued that the hot-pressing
procedure promoted cation migration from the catalyst layer to
a low concentration area – here the membrane – and that such
migration occurred irrespective of which electrode was initially
doped. These authors did not nd evidence of cation leakage
out of the system however. Another important conclusion con-
cerned the higher efficiency of cerium cation in comparison
Incorporation of radical quencher – concept of highly durable
Fig. 15
PFSA membrane developed by Endoh.274
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with manganese. Both cations undergo easy redox reaction with
HOc to form water as displayed in eqn (20) and (21). These
reactions have higher rate constants than those of hydrogen
abstraction reactions by hydroxyl radicals, which results in the
scavenging properties of Ce3+ and Mn2+ ions. However, the
studies of Coms et al. demonstrated that for an equal molar
basis, cerium was much more effective at reducing FER. The
authors explained such behaviour by a higher rate constant of
radical reduction reaction by cerium ions k ¼ 3  108 M1 s1. A
similar rate constant of Ce3+ with HOc was reported Danilczuk
et al.273 based on the competitive kinetics approach.
HOc + Ce3+ + H+ / H2O + Ce4+, k ¼ 3  108 M1 s1 (20)
HOc + Mn2+ + H+ / H2O + Mn3+, k ¼ 4  107 M1 s1 (21)
An excellent overview of all reaction involving Ce and Mn
cations was described by Gubler et al. in the framework of their
kinetic modelling studies.81 Gubler conrmed the correlation
presented by Coms between reaction rate constants of HOc with
radical quenchers and their scavenging efficiency. As an
example, the concentration of 1% of Mn cations with respect to
the sulfonic acid groups scavenges 46% of HOc whereas the
same concentration of Ce cations scavenges 89%. Further
studies in this area underline the signicant impact of the ratio
of the oxidation states of Ce and Mn on their mitigation prop-
erties. Only Ce3+ in the Ce3+/Ce4+ redox couple is able to react
with hydroxyl radicals, therefore high dynamic equilibrium of
Ce3+/Ce4+ is necessary to keep high efficiency of the system.
Cerium has advantage to be self-regenerative, especially in an
acidic medium. Fast reduction of Ce4+ via reaction with H2O2
ensures rapid reactivation of Ce3+. It was reported that Ce4+ can
be also reduced by H2, H2O or HOOc on the Pt catalyst layer273,276
but, as argued by Gubler, the reaction of Ce4+ with H2O2 is fast
enough to convert essentially all cerium ions to Ce3+ form.
Similarly to cerium ions, Mn2+ is also effectively restored via
reaction with H2O2 or HOOc.81 However the Mn2+/Mn3+ system
is much more complex than that of cerium. Species with
different oxidation states such as Mn+; Mn2+; Mn3+; and MnO2+
need to be considered.81,305 Indeed Tanuma et al. provided
conrmation for this through their studies where the X-ray
absorption spectroscopy (XAFS) was employed to measure
a shi in absorption energy in the XANES (X-ray adsorption near
edge structure) spectra of Ce and Mn ion exchanged
membranes before and aer OCV hold.305 No difference was
found in the XANES spectra of Ce exchanged membrane before
and aer accelerated degradation, whereas in the case of the
Mn exchanged membrane, a shi in the XANES spectrum to
higher energy aer OCV hold conrmed presence of Mn atoms
with valence state higher than +2.
HOOc + Ce4+ / O2 + Ce3+ + H+ (22)
H2O2 + Ce4+ / HOOc + Ce3+ + H+ (23)
HOOc + Mn3+ / O2 + Mn2+ + H+ (24)
H2O2 + Mn3+ / MnO2+ + 2H+ (25)
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Experimental evidence of the Ce3+/Ce4+ redox couple was
provided by Danilczuk et al.93 by in situ monitoring of radical
formation at the anode and cathode sides of pristine (MEA/H)
and Ce ion exchanged (MEA/Ce) Naon® 117 membrane. The
5,5-dimethylpyrroline-N-oxide (DMPO) was applied as a spin
trap.
Both MEAs types examined showed completely different
behaviour under OCV hold testing. For baseline MEA/H the
dominant adducts were DMPO/OH and DMPO/CCR – carbon
centred radicals derived from Naon®, whereas for MEA/Ce the
main adduct detected aer membrane aging was DMPO/OOH.
The absence of hydroxyl radicals as well as the absence of
carbon centred radicals conrmed the scavenging properties of
Ce3+. Moreover, the presence of DMPO/OOH indicates reaction
of hydrogen peroxide with Ce4+ to restore the Ce3+. Another
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study of the same research group performed with an ionomer
dispersion demonstrated a concentration of OH and CCR
adducts lower by a factor of 12 for a dispersion enriched with
cerium ions than for a pristine polymer dispersion.108 These
studies also indicate scavenging properties of cerium, but also
point out the role of membrane morphology in the radical
attack as different degradation products were found for
membrane and polymer dispersion.
Endoh et al. investigated the inuence of the incorporation
of Ce3+ ions in PFSA membranes on their degradation under the
low humidity subzero conditions of 30
C.275 Aer 50
temperature cycles from 70
C to 30
C, a 10% Ce3+ doped
MEA showed very low 1.6  1010 g cm2 h1 FER in contrast to
1  106 g cm2 h1 with pristine Naon®. This result indicates
Fig. 16 Mitigation of ionomer degradation as a function of total Ce-
ion content (Ce3+ + Ce4+). (a) HOc concentration and rate of PFSA
ionomer attack, expressed as fluoride emission rate (FER) assuming
a membrane thickness of 50 mm, at a carboxylic end-group concen-
tration of [–COOH] = 18 mM. (b) Fraction of HOc reacting with the
ionomer and Ce3+. Reproduced by permission of The Electrochemical
Society from ref. 81.
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Sustainable Energy & Fuels
that Ce3+ ions can mitigate the membrane degradation under
repeated cold-starts.
However besides obvious advantages of the incorporation of
Ce or Mn ions in MEAs, there are some disadvantages mainly
a decrease of membrane conductivity resulting in fuel cell
performance losses. Another important problem is the mobility
of the ions. As was reported by Coms et al., cerium ions incor-
porated in the catalyst layer aer hot pressing migrated into the
PFSA membrane.276 It can be expected that scavengers can
migrate under fuel cell operation conditions from an initially
ion exchanged membrane to the electrodes as well, and further
be washed out with exhaust water. Decrease of the scavenger
concentration can be reected in the simultaneous decrease of
mitigating efficiency, which makes this strategy inappropriate
for long-term use. According to Gubler et al. the relation
between the membrane degradation rate and ions concentra-
tion can be expressed by the Fig. 16.81
Cheng et al. postulated scavenger migration from membrane
to electrode layers. He demonstrated accelerated performance
degradation aer AST for MEAs with Ce and Mn ions added to
the membrane.277 This author assumed that this higher
performance degradation might be due to increased cathode
catalyst layer (CCL) ionic losses. However further studies
showed no impact of scavengers on Pt dissolution, agglomera-
tion, carbon corrosion or oxidation.
Trogadas and co-workers developed an alternative approach
to include cation radical scavengers, namely incorporation of
cerium oxide in the membrane.280 Ceria particles, commonly
known as a crucial component in three-way catalysts, emerged
as an efficient hydrogen peroxide decomposition catalyst.306 A
CeO2 – Naon® composite membrane showed decrease in the
FER of greater than an order of magnitude aer accelerated
degradation testing.280 This observation was attributed to
quenching of the highly oxidative species by the non-
stoichiometric CeO2. This assumption nds a conrmation in
further studies of Prabhakaran et al. with a uorescent molec-
ular probe in conjunction with in situ uorescence spectroscopy
to investigate the membrane chemical degradation and CeO2
mitigation properties in an operating fuel cell.284,285 This is
probably due to the particular electron structure and mixed
Fig. 17 Scavenging mechanism of CeO2 and regeneration of Ce3+
active sites. Reprinted with permission from ref. 284.
Sustainable Energy Fuels, 2017, 1, 409–438 | 429

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valence state of CeOx.307–309 It was proposed that scavenging
properties of ceria are mediated at oxygen vacancies or defects
in the lattice structure.310 Thus the hydroxyl radical can be
scavenged by Ce3+ ions, which are further oxidised to Ce4+.
Oxidised Ce3+ is regenerated in acidic media through the
mechanism displayed in Fig. 17. This regeneration of the Ce3+
form appears as important factor for CeO2 mitigation ability.
To tune the Ce3+/Ce4+ ratio, Trogadas et al. proposed two
strategies.309 A rst approach was based on particle size control,
as the concentration of oxygen vacancies and Ce3+ formation
might depend on particle size. The second strategy included
doping of ceria particles with Zr4+ cations in order to improve
the stability and oxygen storage capacity of the CeO2 micro-
structure. To investigate the inuence of ceria particle size and
Zr incorporation, Ce0.25Zr0.75O2 nanoparticles and ceria parti-
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cles with varying Ce3+ surface concentrations were synthesised
incorporated in Naon, and operated in a fuel cell MEA. Aer
accelerated in situ degradation testing, the MEAs with
composite membranes containing CeO2 or Ce0.25Zr0.75O2
demonstrated one order of magnitude lower uorine emission
rate compared to that of an MEA with a pristine membrane.
Furthermore, the Ce3+ surface concentration of incorporated
particles was reected in FER values. The general conclusion
can be drawn from this study is that a higher Ce3+ content
lowers the FER from OCV hold-tested MEAs. Following this
concept, Trogadas et al.281 performed another interesting
investigation by platinum incorporation in the polymer
membrane. Naon® doped with CeO2 – supported platinum
demonstrated over an order of magnitude reduction of uoride
emission rate. This system showed increased scavenging ability
of cerium oxide nanoparticles independently of the Pt concen-
tration (0.5–2 wt%). This observation was explained in terms of
enhanced rate of Ce4+ to Ce3+ reduction in the presence of Pt.
Wang et al. also studied the durability and performance of a Pt/
CeO2-Naon composite membrane.311 This author pointed out
the higher performance of the Pt/CeO2-Naon composite
membrane in comparison to NRE-211 membrane at 35% RH
that can be due to a self-hydrating function of Pt particles,
a concept rst introduced by Watanabe.312 Furthermore, the
composite material demonstrated stable OCV over 180 h of AST
performed at 70
C/35% RH and H2/O2 as reactants. Aer the
pioneering studies of Trogadas with CeO2 as radical scavenger,
several authors investigated membrane durability with CeO2
additives in the MEA components. Similarly to the above
described Ce and Mn ion radical scavengers, CeO2 can be
incorporated in both the membrane and electrode structure.
Wang and co-workers reported the reduction of ionomer
degradation through incorporation of CeO2 in the catalyst
layer.283 A newly prepared catalyst was applied either on the
anode or the cathode side. MEAs containing CeO2, regardless of
the initial position of the radical scavenger, showed similar
improvement of the membrane durability aer in situ OCV hold
testing performed at 90
C and 30% RH in comparison to the
baseline MEA. Aer 200 hours of accelerated testing, no
membrane thinning or pinhole development was observed for
the MEA with anode or cathode cerium-rich catalyst. The MEA
with CeO2 incorporated in the anode demonstrated a slightly
430 | Sustainable Energy Fuels, 2017, 1, 409–438
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lower performance than the baseline MEA. On the other hand,
performance of the cell with CeO2 incorporated on the cathode
side was slightly higher than that of baseline MEA. The author
linked this result to the oxygen storage ability of CeO2.
Increased local concentration of oxygen on the catalyst surface
might improve the electrocatalytic reaction. In another study,
the enhanced performance observed with a catalyst based on
self-assembled mesoporous carbon with ceria nanoparticles has
been explained by improved water retention of the modied
catalyst.313 The idea of using CeOx as an active and durable
catalyst support was followed by Lei et al.314 These authors re-
ported lower chemical degradation of Naon binder in catalyst
layers during CV-cycles in the high voltage region when using
CeO2 nanocubes–graphene oxide (CeO2–GO) catalyst support.
They observed a slightly increased performance of a single cell
with CeO2–GO when CeO2 loading was lower than 8 wt%. Other
studies based on ex situ electrochemical characterisation
revealed that incorporation of a low content (between 2 and 4
wt%) of amorphous CeO2 in a Pt catalyst enhances its tolerance
to SO2 and CO.315 It was reported that the presence of nano-scale
ceria facilitates the oxygen transfer thus assists CO oxidation
and inhibits SO2 oxidation on Pt surfaces.
Weissbach et al. investigated stability of PFSA membranes
co-casted with CeO2, ZrO2 and yttria-stabilized zirconia (YSZ)
exposed to Fenton reagent.316 It was found that incorporation of
CeO2 into the membrane signicantly reduced FER, mass loss
and loss of sulfonic groups, while PFSA-ZrO2 and PFSA-YSZ
membranes did not present improved stability. Naon – CeO2
nanocomposite membranes prepared through a “self-assem-
bled” route, where ceria nanoparticles were incorporated into
the polymer structure through in situ sol–gel process, were
studied by Wang et al.282 The composite material demonstrated
slightly lower proton conductivity at 100% RH, whereas at
relative humidity below 75%, it showed higher values than
pristine Naon®. Both in situ and ex situ accelerated degrada-
tion tests revealed superior durability of self-assembled
Naon® – CeO2 membranes in comparison to the non-
modied membrane, as well as to Naon® – CeO2
membranes prepared by recasting from CeOx – Naon colloidal
suspension. D'Urso et al. studied the effect of the presence of
silica supported CeOx in an ePTFE reinforced membrane on its
chemical stability.221 The authors did not provide any FER or
OCV decay measurement to assess the efficiency of their system.
However they reported seven times longer lifetime of MEA
enriched with CeOx in comparison to the non-modied
membrane. Also Pearman et al. performed in situ and ex situ
membrane degradation tests on composite materials consisting
of porous PTFE supported cerium oxide impregnated with
Naon.286,287 Mechanical reinforcement of the membrane,
enhanced with radical scavenging ability of ceria resulted in
high durability over 500 h in an OCV hold test. Moreover the
inuence of the CeO2 incorporation on Pt band formation was
reported. It was found that Pt formed larger particles deposited
further into the polymer membrane. The author connected this
behaviour with the presence of the ceria particles which affected
the potential prole through the membrane thus altered the Pt
band. Contrary to reports by Trogadas et al., on the inuence of
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size of ceria particles on FER, Pearman et al. did not nd
evidence for a lower FER for small CeOx in comparison to larger,
commercial ceria particles. A recent study of Schlick et al. shed
some new light on the subject.317 These authors emphasize that
the effectiveness of Ce nanoparticles may depend not only on
the initial particle size or oxidation state but also on the extent
of particle dispersion and agglomeration.
It might be concluded that ceria is very efficient radical
scavenger. However it should be noted that recent studies on
MEAs containing either cerium ions or cerium oxide clearly
showed migration of cerium ions through the MEA compo-
nents,287,318–320 which indicates dissolution of ceria in acid
medium and creates a new question regarding the stability of
ceria during fuel cell operation. Prabhakaran et al. reported loss
of the efficiency of ceria already aer 7 hours of an accelerated
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stress test, based on in situ uorescence spectroscopy
studies.284,285 However the authors related this observation to
a decreased concentration of Ce3+ reactive centers rather than to
dissolution of ceria particles. In order to improve its regenera-
tive abilities, ceria nanoparticles have been doped with nitrogen
by annealing in nitrogen-rich atmosphere.321 Aer treatment
the N-tuned CeOx demonstrated high efficiency in radical
scavenging over 90 h of testing which was associated with
increased number of Ce3+ active clusters aer exposure to the N-
rich atmosphere. The possibility of ceria dissolution and cerium
ion migration through MEA components was not considered.
A detailed analysis of the effect of positioning of ceria in the
MEA was performed by Zatoń et al.319,322 The authors used
electrospinning to develop a thin protective composite layer of
PFSA nanobers enriched with cerium oxide particles – NFCeOx
that was incorporated into the MEA at the desired anode/
cathode interface. In the previous reports incorporation of
CeOx has been realized through preparation of a ceria enriched
membrane281,287 or catalyst layer.318,323–325 The presence of CeOx
in the membrane bulk can restrict the transport pathways and
increase tortuosity and thus decrease proton conductivity.
Moreover such an approach does not allow studies of the
impact of ceria particles on membrane degradation when
located at respective anode and cathode sides. The incorpora-
tion of CeOx in the catalyst layer gives such possibility, however
affects the MEA performance as the charge transfer of ceria is
rather low. Zaton et al. demonstrated that the lifetime of MEAs
with anode or cathode sides protected by NFCeOx was eight
times longer relative to an unmitigated MEA and FER and OCV
decay were signicantly reduced. The authors also reported that
additional protective interlayer was more effective when incor-
porated on the anode side, possibly due to the reductive envi-
ronment that accelerates regeneration of active Ce3+ scavenging
centers, as well as a result of partial dissolution of CeOx at the
anode interface and migration of cerium ions through
membrane. In contrast, cerium species created aer dissolution
of CeOx on the cathode side might be easily leached from the
MEA.
Table 3 summarises the results obtained aer AST on various
composite materials with scavenging properties. This provides
a clearer view on the state of the art for mitigation of membrane
degradation. Moreover the effectiveness of parameters like
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scavenger loading, nature of the introduced species, or their
location on the membrane durability can be compared using
the uoride emission rate.
11. Summary and outlook
The objective was to review and analyse the reaction mecha-
nisms leading to PFSA membrane degradation and failure, and
to examine methodologies and means to reduce this degrada-
tion in an operating fuel cell. As discussed in Section 3,
membrane degradation is not a single isolated reaction and
cannot be classied by any known model. It is a complex
combination of different factors including intrinsic properties
of the material used for MEA preparation and the operating
conditions applied. This work has reviewed the factors that can
promote membrane degradation and which, once clearly iden-
tied, provide the basis for design of materials with enhanced
robustness. Beyond that, this review has also provided the rst
survey of mitigation strategies designed to annihilate the
harmful effect of oxidative species on membrane integrity and
has comprehensively appraised their effectiveness by discus-
sing the benets and drawbacks of each strategy. By identifying
stressors and through improved understanding of how scav-
enging reactions proceed can certainly accelerate development
of new materials with antioxidant properties and enhanced
durability. To meet fuel cell durability and lifetime targets over
the widest range of temperature, pressure and relative humidity
operating conditions requires membranes that are highly
heterogeneous, comprising not only a reinforcing component,
or designed architecture at nano- to micro-metric length scales,
but also an advanced radical scavenger component and/or
hydrogen peroxide decomposition catalyst. The choice of
radical scavenger will be dictated by its efficiency and stability
in operating conditions. Controlled release of a radical scav-
enger or hydrogen peroxide decomposition catalysts in
response to a chemical signal from a repository within the
membrane would represent a paradigm shi by providing the
requisite groundwork for the elaboration of self-healing fuel cell
membranes. Further development of the other cell compo-
nents: GDL, catalyst and bipolar plates will also have, of course,
signicant inuence on membrane stability. This is especially
salient in the context of emerging non platinum group metals
cathode catalysts of which the most active are iron or cobalt
based. Chemical stabilisation of PFSA membranes in an MEA
with a catalyst based on Fe2+ ions will require the development
of radical scavengers of magnied efficacy, to which early
consideration should be given in support of a future generation
of fuel cell catalysts using earth-abundant metals.
Acknowledgements
The research leading to these results has received funding from
the European Community's Seventh Framework Programme
(FP7/2010-2013) for the Fuel Cells and Hydrogen Joint Under-
taking under grant agreement IMMEDIATE no. 3034.
Sustainable Energy Fuels, 2017, 1, 409–438 | 431

Sustainable Energy & Fuels
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