energies

Review
Membrane Electrode Assembly Degradation Modeling of
Proton Exchange Membrane Fuel Cells: A Review
Ahmed Mohmed Dafalla 1,2,3,† , Lin Wei 1,2,3,† , Bereket Tsegai Habte 1,2,3 , Jian Guo 1,2,3
and Fangming Jiang 1,2,3, *

1 Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences (CAS), Guangzhou 510640, China
2 CAS Key Laboratory of Renewable Energy, Guangzhou 510640, China
3 Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development,
Guangzhou 510640, China
* Correspondence: [email protected]; Tel.: +86-20-87057656
† These authors contributed equally to this work.

Abstract: Proton exchange membrane fuel cells (PEMFCs) have been recognized as a promising power
generation source for a wide range of automotive, stationary, and portable electronic applications.
However, the durability of PEMFCs remains as one of the key barriers to their wide commercialization.
The membrane electrode assembly (MEA) as a central part of a PEMFC, which consists of a proton
exchange membrane with a catalyst layer (CL) and gas diffusion layer (GDL) on each side, is subject
to failure and degradation in long-running and cycling load conditions. The real-time monitoring
of the degradation evolution process through experimental techniques is challenging. Therefore,
different numerical modeling approaches were proposed in the literature to assist the understanding
of the degradation mechanisms in PEMFCs. To provide modeling progress in the addressed field, this
paper briefly discusses the different degradation mechanisms occurring in the MEA. In particular, we
present a detailed review of MEA degradation modeling research work, with special attention paid
Citation: Dafalla, A.M.; Wei, L.; to the physical-based models (mechanistic models). Following the most recent relevant literature,
Habte, B.T.; Guo, J.; Jiang, F. the results showed that the combination of microstructure component models with macro-scale
Membrane Electrode Assembly comprehensive PEMFC models provides a better understanding of degradation mechanisms when
Degradation Modeling of Proton compared to single-scale degradation models. In this sense, it is concluded that in order to develop an
Exchange Membrane Fuel Cells: A accurate and efficient predictive degradation model, the different relevant scales ranging from nano-
Review. Energies 2022, 15, 9247. to macro-sized scales should be considered, and coupling techniques for multiscale modeling have to
https://doi.org/10.3390/en15239247
be advanced. Finally, the paper summarizes the degradation models for different MEA components.
Academic Editors: Mario Aparicio It is highlighted that the GDL chemical degradation models that describe damage accumulation are
and Antonio Barbucci relatively limited. The paper provides a useful reference for the recent developments in the MEA
degradation modeling of PEMFCs.
Received: 28 October 2022
Accepted: 1 December 2022
Keywords: PEMFC; membrane electrode assembly; proton exchange membrane; gas diffusion layer;
Published: 6 December 2022
catalyst layer; durability; degradation modeling; real-time monitoring; physical-based/mechanistic
Publisher’s Note: MDPI stays neutral models
with regard to jurisdictional claims in
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iations.

1. Introduction
Currently, fuel cells are considered as one of the most promising technologies for
Copyright: © 2022 by the authors.
transport, electronics, combined heat and power, and industrial applications [1,2]. They
Licensee MDPI, Basel, Switzerland. are locally free of greenhouse gas emissions, and more generally free of polluting waste
This article is an open access article emissions. Unlike other renewable energy sources such as wind energy and solar energy,
distributed under the terms and fuel cells can be employed continuously and stably for power generation, so that they can
conditions of the Creative Commons be a solution to the problem of air pollution in big cities [3].
Attribution (CC BY) license (https:// In comparison with battery electric vehicles, fuel cell vehicles present higher energy
creativecommons.org/licenses/by/ densities, which enable a greater autonomy, and are not subjected to the charging problems
4.0/). encountered with battery technologies [4]. Among different types of fuel cells, the proton

Energies 2022, 15, 9247. https://doi.org/10.3390/en15239247 https://www.mdpi.com/journal/energies

 In comparison with battery electric vehicles, fuel cell vehicles present higher energy
densities, which enable a greater autonomy, and are not subjected to the charging prob-
Energies 2022, 15, 9247 lems encountered with battery technologies [4]. Among different types of fuel cells, the 2 of 26
proton exchange membrane fuel cell (PEMFC) has received considerable attention owing
to its high current density and low operating temperature compared to other types of fuel
cells. The advanced features of the PEMFC set forth the potential of PEMFC technology
exchange membrane fuel cell (PEMFC) has received considerable attention owing to its high
to supplant the current internal combustion power sources. The research interest in de-
current density and low operating temperature compared to other types of fuel cells. The
veloping high-performance long-lasting PEMFC stacks has been dramatically increased.
advanced features of the PEMFC set forth the potential of PEMFC technology to supplant
As a result of this progressive research, the world’s leading automobile companies have
the current internal combustion power sources. The research interest in developing high-
introduced their PEMFC products to the market, such as the Mirai of Toyota, Clarity of
performance long-lasting PEMFC stacks has been dramatically increased. As a result of
Honda, B-Class of Mercedes, Tucson of Hyundai, Granite of Grove Hydrogen Automo-
this progressive research, the world’s leading automobile companies have introduced their
tive, and Roewe 950 of SAIC Motor [5–7]. In addition, various fuel cell stack modules for
PEMFC products to the market, such as the Mirai of Toyota, Clarity of Honda, B-Class of
heavy duty, marine,
Mercedes, Tucsonand stationary
of Hyundai, applications
Granite of Grovewere introduced
Hydrogen by Ballard
Automotive, andPower
Roewe Sys-
950 of
tems, while
SAIC other
Motor portable
[5–7]. electricvarious
In addition, power companies have
fuel cell stack introduced
modules hydrogen
for heavy fuel celland
duty, marine,
chargers for phones
stationary and laptops.
applications Figure 1 by
were introduced shows thePower
Ballard wide Systems,
range of while
PEMFC applica-
other portable
tions/products.
electric power companies have introduced hydrogen fuel cell chargers for phones and
laptops. Figure 1 shows the wide range of PEMFC applications/products.

Figure 1. Scope of fuel cell applications.

Figure 1. Scope of fuel cell applications.
However, despite these very promising recent advances in PEMFC technologies, the
However, despite these very promising recent advances in PEMFC technologies, the
durability of PEMFC technologies remains a major barrier to their commercialization for
durability of PEMFC technologies remains a major barrier to their commercialization for
transportation and stationary applications [8]. That durability challenge mainly resides
transportation
in the induced anddegradation
stationary applications
by dynamic [8]. Thatstartup/shutdown,
load, durability challenge mainly
and resides in(e.g.,
freeze/thaw
the cold
inducedstartdegradation by dynamic
from subfreezing load, startup/shutdown,
temperatures) and freeze/thaw
cycles that are involved (e.g., cold
in transportation appli-
startcations,
from subfreezing temperatures) cycles that are involved in transportation
or the long and continuous operating time required in stationary applications applica- [9].
tions, or the long
Basically, and continuous
the PEMFC operating
system consists timeparts,
of four required in stationary
namely: stack, gasapplications
supply subsystem,[9].
Basically, the PEMFC system consists of four parts, namely: stack, gas
humidification subsystem, and heat management system. The stack is the core part, and it supply subsystem,
humidification
is responsible subsystem, and heat
for converting management
the chemical energy system. The stackThe
into electricity. is the
keycore
factorpart, and
impacting
it isthe
responsible
durabilityfor converting
of the PEMFC is therelated
chemical to theenergy into electricity.
degradation within the The
fuelkey
cellfactor im-
components,
pacting
especially the degradation process that occurs on the membrane electrode assembly cell
the durability of the PEMFC is related to the degradation within the fuel (MEA),
components,
which results especially the degradation
in an irreversible decrease process that occurs on
in performance andthe membrane
limits electrode
the lifetime of PEM-
assembly
FCs [10].(MEA),
Besideswhich results in an irreversible
the performance decay due todecrease in performance
the degradation of the MEAand limits the
components,
lifetime of PEMFCs [10]. Besides the performance decay due to the
the environmentally friendly disposal or the secondary usage of the degraded parts may degradation of the
MEA components,
become a seriousthe environmentally
issue. It was reportedfriendly
that thedisposal or the secondary
overall degradation of fuel usage of the can
cell vehicles
degraded partsimpact
negatively may become a serious
the average fuel issue.
economy It was reported
of the vehiclethat
bythe overall
about 23%degradation
[11]. Therefore,
of fuel cell studies
several vehicleshave
canrecommended
negatively impact the average
consideration fuel
of the economy
fuel of the vehicle
cell degradation factor by
when
about 23% [11]. Therefore, several studies have
evaluating the life cycle of fuel cell vehicles [12,13]. recommended consideration of the fuel
cell degradation
In recentfactor
years,when evaluating
the PEMFC the life
lifetime andcycle of fuel cell
degradation vehicles [12,13].
mechanisms have been investi-
gated using different analytical and numerical modeling and experimental characterization
approaches. Generally, the degradation modeling methods can be classified into three
categories: physical-based models, data-driven models, and hybrid models [14]. The
physical-based models mainly consider physical laws in describing the degradation process
to understand the primary failure mechanism and to forecast the location that is prone
to failure at particular operating conditions; they are also called mechanistic models. In
contrast, the data-driven models utilize previously measured data to learn more about the
 Energies 2022, 15, 9247 3 of 26

degradation behavior to build a model that describes or estimates the degradation process
of the considered system. Besides, as its name indicates, the hybrid model is a combination
of the physical-based and data-driven models. Comparatively speaking, the physical-based
models are relatively useful due to their ability to capture physical phenomena and they
are able to elucidate the underlying mechanisms and theories of degradation evolution pro-
cesses. Nevertheless, the data-driven approach is also needed due to the current difficulties
in developing such physical-based models for the complex systems of PEMFCs, especially
when operated under various ranges of loading conditions [15].
Until now, comprehensive reviews have been conducted to cover the recent progress
in PEMFC performance modeling [16–19], water management [20], failure modes [21,22],
degradation mechanisms [2,9,23,24], degradation indices [25], acerbating aging tests [26,27],
and lifetime prediction [28], while some reviews have discussed the individual components
of PEMFCs, such as GDLs [29], proton exchange membranes [30,31], catalyst layers [32].
However, only relatively few reviews have addressed the degradation modeling aspects in
PEMFC components [14,33]. Therefore, a comprehensive understanding of state-of-the-art
degradation modeling progress is crucial for the future development of PEMFC technology.
As mentioned above, physical model-based analysis is one of the frequently used
methodologies to understand the degradation mechanisms and material aging phenomena
in PEMFC research [34,35]. Therefore, the key purpose of this paper is to review the
existing literature and summarize the advances in the MEA degradation modeling research
of PEMFCs with a special focus on the physical-based model approach, including the key
core components of MEA, namely the proton exchange membrane, catalyst layer (CL), and
gas diffusion layer (GDL). This paper could potentially encourage researchers to develop
more effective and accurate physical-based degradation models for PEMFCs.

2. MEA Degradation Modeling

As illustrated in Figure 2, a PEMFC is composed of the proton exchange membrane,
flow channels, GDLs, CLs, and current collectors on both electrode sides. Oxygen (O2 )
and hydrogen (H2 ) are supplied through gas channels in the cathode and anode sides,
respectively. Then, the supplied gases diffuse through the GDLs to the CLs where the
Energies 2022, 15, x FOR PEER REVIEWreactions take place. The generated protons at the anode CL are transported to the cathode
4 of 29
side, while the electrons are transferred to the external electrical circuit via the anode and
cathode current collectors [36].

Figure 2. Schematic diagram and operating principles of PEMFCs.

Figure 2. Schematic diagram and operating principles of PEMFCs.

Considering the MEA of PEMFCs, the structure of the membrane, CLs, and GDLs
are composed of different materials as depicted in Figure 3. During the operation of
PEMFCs under various conditions, the stability and electrochemical performance of these
Energies 2022, 15, 9247 4 of 26

Considering the MEA of PEMFCs, the structure of the membrane, CLs, and GDLs
are composed of different materials as depicted in Figure 3. During the operation of
PEMFCs under various conditions, the stability and electrochemical performance of these
materials may deteriorate, which significantly affects the performance and durability of
the MEA components. It is significant to take into consideration the mechanical, thermal,
and chemical aspects when modeling the degradation phenomenon in the MEA portion
of the PEMFC. Figure 4 represents the most common degradation phenomena in MEA
components along with their resultant structural damage. Modeling these destructive
degradation mechanisms or their resultant failure modes will lead to the development of a
better design and speed up the development of fuel cell technology. In this respect, this
section will address the main degradation mechanisms occurring in MEA components and
will report the degradation modeling efforts that have been reported in the literature.
Figure 2. Schematic diagram and operating principles of PEMFCs.
2.1. Proton Exchange Membrane
Proton exchange
Considering membranes
the MEA are the central
of PEMFCs, and most
the structure ofcrucial part of PEMFCs;
the membrane, CLs, hence,
and GDLs
the entire fuel cell assembly is named after them. Fuel cell membranes
are composed of different materials as depicted in Figure 3. During the operation of commonly consist
of a hydrophobic and rigid backbone to ensure good mechanical strength and chemical
PEMFCs under various conditions, the stability and electrochemical performance of these
stability, and functional groups to enable effective ion transportation [37,38]. DuPont
materials®may deteriorate, which significantly affects the performance and durability of
Nafion is the most commonly used membrane, owing to its higher chemical and thermal
thestability
MEA components.
[39]. The mainItfunction
is significant to take into
of a membrane consideration
in PEMFCs the mechanical,
is to provide thermal,
the easy transfer
andofchemical
protons, toaspects when
effectively modeling
prevent the of
the mixing degradation phenomenon
fuel and oxygen, in the
and to provide an MEA portion
electrical
of insulation
the PEMFC. [40]. The aforementioned properties of the membrane deteriorate both chemically MEA
Figure 4 represents the most common degradation phenomena in
components
and physically along withmembrane
as the their resultant
ages. Thestructural damage.
aim of this sectionModeling
is to providethese destructive
a detailed
review of the
degradation membrane or
mechanisms degradation mechanisms
their resultant failure that hinder
modes willthe desired
lead to thedurability of
development of
the PEMFCs. Generally, fuel cell membranes deteriorate under chemical,
a better design and speed up the development of fuel cell technology. In this respect, thismechanical, and
thermal
section willloads. In most
address thecases,
main thedegradation
degradation modes occur in occurring
mechanisms a coupled manner
in MEA where one
components
mode impacts the other. However, in this section, we will review the individual attributes
and will report the degradation modeling efforts that have been reported in the literature.
of the degradation modes on the membrane.

Figure 3. Representation of the multistate structure of PEMFC.

Figure 3. Representation of the multistate structure of PEMFC.
Energies 2022, 15, x FOR PEER REVIEW 5 of 29
Energies 2022, 15, 9247 5 of 26

Figure 4.
Figure Dominant degradation
4. Dominant degradation mechanisms
mechanisms and
and failure
failure modes
modes in
in MEA
MEA part
part of
of PEMFC.
PEMFC.
2.1.1. Chemical Degradation
2.1. Proton Exchange Membrane
One of the most common membrane chemical degradations is caused by the gen-
Proton
eration exchange
of free radicalsmembranes
such as hydroxyl are the(•central
OH), peroxyland most crucial
(•OOH), and part of PEMFCs;
hydrogen (•H).
hence, the entire fuel cell assembly is named after them.
These radicals are byproducts of the uncontrolled reaction of hydrogen peroxide Fuel cell membranes commonly
(H2 O2 )
consist of a hydrophobic
with transition metal ions and (Fe2+rigid
, Co2+backbone
, and Cu2+to) thatensure
are good
foundmechanical
in PEMFCsstrength and
[41]. Several
chemical stability,
studies suggest thatand functional
hydrogen groups
peroxide to enable
is mainly effectiveation
produced the transportation
anode side via [37,38].
an elec-
DuPont Nafion
trochemical ® is the most commonly used membrane, owing to its higher chemical and
reaction favored by the lower potential of the anode and membrane working
thermal
conditionsstability
[42,43].[39]. The main
However, thefunction
hydrogen ofperoxide
a membrane itselfindoes
PEMFCs
not haveis toaprovide the easy
direct impact on
transfer of protons, to effectively prevent the mixing of
membrane degradation. The following chemical reactions demonstrate the generationfuel and oxygen, and to provide of
an
theelectrical insulation
aforementioned free[40]. The aforementioned properties of the membrane deteriorate
radicals.
both chemically and physically as the membrane ages. The aim of this section is to pro-
vide a detailed review of the
+
M2membrane
+ H2 O2 → M3+ + •OH
degradation + OH− that hinder the desired
mechanisms (1)
durability of the PEMFCs. Generally, fuel cell membranes deteriorate under chemical,
mechanical, and thermal loads. M2+ + 2 O2 →
InHmost M2+the
cases, OOH + H+ modes occur in a coupled
+ •degradation (2)
manner where one mode impacts H2the
+ •other.
OH → However,
•H + H2in O this section, we will review the (3)
individual attributes of the degradation modes on the membrane.
where M is a transition metal that presents in the membrane, for example as manufacturing
flaws,Chemical
2.1.1. and the resultant
Degradation radicals react with the hydrophilic sulphonic acid side chains of
the PTFE hydrophobic backbone, causing the molecular alteration of the main backbone
One of the most common membrane chemical degradations is caused by the gener-
and side chain terminals [44]. The first attack of the free radicals occurs at the outermost
ation of free
side chain radicals
ether groupssuch as hydroxyl
cleaving the side (•OH),
chain asperoxyl
shown in (•OOH),
Figure 5a. and hydrogen
The reactants(•H).
then
These
propagate along the side chain decomposing the CF units, causing the membrane to (H
radicals are byproducts of the uncontrolled reaction of hydrogen peroxide 2O2)
lose its
with transition metal ions (Fe 2+ , Co 2+ , and Cu 2+ ) that are found
hydrophilic channels, which are critical for membrane ion conductivity. Several experimen- in PEMFCs [41]. Several
studies suggest
tal studies thatthe
correlate hydrogen
emission peroxide
of fluorideisand mainly produced
the mass loss ofatthethe anode
PTFE side viawith
membrane an
 chains of the PTFE hydrophobic backbone, causing the molecular alteration of the main
backbone and side chain terminals [44]. The first attack of the free radicals occurs at the
outermost side chain ether groups cleaving the side chain as shown in Figure 5a. The
reactants then propagate along the side chain decomposing the CF units, causing the
membrane to lose its hydrophilic channels, which are critical for membrane ion conduc-
Energies 2022, 15, 9247 6 of 26
tivity. Several experimental studies correlate the emission of fluoride and the mass loss of
the PTFE membrane with the decomposition of the side chains [45–47]. Figure 5b,c de-
picts the continuous cleaving of the side chains causing membrane mass loss via mem-
the decomposition
brane thinning and of the side chains
pinhole/crack [45–47]. which
formation, Figure results
5b,c depicts the continuous
in accelerated cleaving
gas crossover
of the side chains causing membrane mass loss via membrane thinning
[10,48–53]. The crossover of oxygen and hydrogen to the other side of the membrane and pinhole/crack
formation,
causes which results
an exothermic in accelerated
reaction gas crossover
in the catalyst layer and[10,48–53].
generates The
localcrossover
hotspots of oxygen
that give
rise to coupled thermochemical membrane degradation [54]. Towards the end of cata-
and hydrogen to the other side of the membrane causes an exothermic reaction in the the
lyst layerradical
hydroxyl and generates local
attack, the hotspots
main PTFEthat give rise
backbone to coupled
breaks thermochemical
at the side membrane
chain junction, giving
degradation
rise to a number[54]. of
Towards the end
fragmented of the hydroxyl
carbocyclic radical attack,
acid groups, which the main PTFE backbone
is characterized by the
breaks mass
further at theloss
sideofchain junction, giving
the membrane [54,55].rise
At to a number oflevel,
a macro-scale fragmented carbocyclic
the membrane losesacid
its
groups, which is characterized by the further mass loss of the membrane [54,55]. At a
ductility as the degradation worsens and becomes brittle due to the loss of its hydrophilic
macro-scale level, the membrane loses its ductility as the degradation worsens and becomes
transport channels. Figure 5d shows the successive chain reaction of pure Nafion® with
brittle due to the loss of its hydrophilic transport channels. Figure 5d shows the successive
hydrogen radicals.
chain reaction of pure Nafion® with hydrogen radicals.

Figure 5. Molecular degradation mechanism of PTFE: (a) hydroxyl radical attack on the sulphonic
Figure 5. Molecular
termination degradation
of the side mechanism of PTFE:
chain, (b) decomposition (a) group
of the CF hydroxyl radical
along attack
the side on(c)
chain, theintermediate
sulphonic
termination of the side chain, (b) decomposition of the CF group along the side chain, (c) interme-
ionomer cleaving, (d) final unzipping of the main backbone.
diate ionomer cleaving, (d) final unzipping of the main backbone.
Several numerical approaches have been used to investigate the amount of fluoride
release under the variable working conditions of the membrane. Xei and Hayden [56]
developed a quantitative kinetic model to identify the main distinct polymer degradation
initiation mechanisms. Their model is able to distinguish the mechanisms of the side chain
cleavage and the main chain carboxylic acid-unzipping reactions. Wong and Kjeang [57]
developed a transient in situ chemical degradation model for ceria-supported membranes
at voltage levels below OCV. They found that the Ce3+ ionic additives migrate into the
cathode CL creating an insufficient amount of Ce3+ in the membrane and leading to a
higher population of the hydroxyl radicals. Zheng et al. [58] established a 1D macroscopic
numerical approach to investigate the pinhole formation in the membrane associated
to chemical degradation. They employed the membrane-thinning rate obtained from
experimental studies to simulate the chemical degradation of the membrane and the special
distribution of H2 O2 under different operational conditions. Their results showed that the
membrane thinning resulted in pinhole formation and accelerated gas crossover and the
degradation is severe at elevated temperatures and RH values between 40 and 60%.
It was stated in many previous studies that the majority of membrane chemical
degradation stems from hydroxyl radical attacks; the effective way to alleviate the chemical-
induced membrane degradation is to minimize the production of free radicals. According
to reactions one to three, the free radicals are generated through the reaction of hydrogen
peroxide with the transition metals. Limiting the supply of one of the reaction components
Energies 2022, 15, 9247 7 of 26

could drastically reduce the hydroxyl molecules. The transition metals in PEMFC are
the result of impurities during production and component corrosion during storage and
operation. Therefore, reducing the impurities to a minimum level and using materials with
high corrosion resistance have the potential to improve the durability of the membrane.

2.1.2. Mechanical Degradation

The mechanical degradation of the membrane is characterized by membrane cracking,
pinhole formation, membrane delimitation, and thickness reduction. These failure modes
are mainly caused by the fuel cell assembly procedure and different cell operation and
cycling conditions. The membrane is a delicate part of PEMFCs; hence, slight pressure
non-uniformity on the membrane during the assembly procedure may lead to membrane
deflection and creep under constant clamping stress. Unlike chemical-induced gradual
membrane degradation, mechanical-based degradation can cause acute failure to the fuel
cell. To achieve an optimal current collection and provide adequate gas sealing, PEMFCs
require a certain degree of clamping force. Furthermore, adjusting a proper clamping
force was proved to improve the mechanical properties of the membrane. However, the
clamping force exerts a non-uniform pressure distribution in the membrane due to the
geometrical nature of the flow-field [59,60]. The non-uniform pressure distribution creates
heterogeneous transport properties between different compressed layers. Ding et al. [61]
employed a finite element model to study the effect of clamping pressure on the mechanical
behavior of the membrane. They applied fixed support boundary conditions at the bipolar
plates and utilized three displacement cases of the membrane, namely 0.0 mm, 0.05 mm,
and 0.1 mm relative to the fixed surface, to imitate the different levels of clamping pressure.
The results showed that the number of humidity cycles (wet phase: 100% RH for 10 s, dry
phase: 30% RH for 50 s) obtained by 0.0 mm and 0.05 mm clamping conditions to achieve
the same crack length of 5.6 µm was 185 and 259, respectively. On the other hand, for a
prescribed displacement of 0.1 mm the membrane cracked 1.2 µm after 335 cycles.
Another commonly accruing mechanical mode of failure is the gradual fatigue of
the membrane under humidity cycling [62–64]. This type of degradation takes place
during the fuel cell operation when the membrane swells and shrinks (membrane breath)
in response to humidity variations. Its cycling nature leads to an eventual membrane
failure due to fatigue. Thermal induced compression and the expansion of the membrane
also have a similar effect on the membrane lifetime for fuel cells working under extreme
environmental temperatures. The above failure theories have been confirmed by numerous
experimental and numerical studies. Kusoglu et al. [65] developed a numerical model
of membrane mechanical response to humidity cycling between 30% RH and 90% RH.
They employed temperature- and humidity-dependent plastic material properties with
isotropic hardening behavior and various levels of anisotropy for membrane swelling.
They observed an inverse relationship between the degree of swelling anisotropy and the
stress amplitude generated on the membrane due to humidity cycling. The results implied
that the durability of the membrane could be enhanced by modifying the membrane-
swelling anisotropy. Kusoglu and Weber [66] presented a theoretical model to study the
membrane mechanical degradation associated with humidity cycling. They integrated the
plastic material nonlinearity of the membrane into their model to simulate the void growth
mechanics in the membrane. The size of the void (pinhole) was then correlated with the
membrane gas crossover to predict the rate of membrane degradation.
Besides clamping pressure and humidity cycling, fuel cell membranes are exposed to
vibrations and shocks that may gradually vary and lead to mechanical failures [67]. For
example, the fuel cell engines that are used for transportation applications are subjected to
rough road conditions and random vibrations of certain amplitude and frequency ranges.
Membrane cracking and delamination from catalyst layers are the most susceptible failures
of the fuel cell membrane under random vibration excitations [68]. Ahmed et al. [69]
applied finite element modeling to determine the relationship between fuel cell compo-
nent parameters and the corresponding natural resonant frequencies and mode shapes
Energies 2022, 15, 9247 8 of 26

of PEMFCs. They concluded that the minimum natural frequency could be calibrated by
altering the thickness, density, and Young’s modulus of the fuel cell components. Banan
et al. [70,71] developed a numerical model based on the cohesive element approach to
study the delamination propagation of the membrane from the catalyst layer under various
frequencies (5 Hz, 10 Hz, 20 Hz, and 40 Hz) and amplitudes (1 g, 2 g, 3 g, and 4 g) of the
excited vibration. They found the maximum damage propagation when the frequency and
amplitude of the excitation were 40 Hz and 4 g, respectively, three times larger than the
damage propagation under the 5 Hz and 1 g condition.
Generally, all the mechanical degradation discussed above can be a sequential or
co-existent process. The membrane defect caused by manufacturing and/or assembly error
is always taken over by the operational degradation such as humidity cycling and vibration
loads. An effective way to mitigate membrane mechanical degradation is to improve the
manufacturing tolerances of the fuel cell components, developing a novel design of the
flow-field [72,73], or enhancing the physical properties of the membrane itself.

2.1.3. Thermal Degradation

The thermal degradation of the fuel cell membranes usually occurs during extreme
working conditions and temperature cycling. Usually, fuel cells operate under a wide range
of temperature fluctuations that negatively impact the life of the membrane. It is suggested
that the favorable working temperature for a well-hydrated membrane is 60 to 80 ◦ C [9].
Above 80 ◦ C, the membrane experiences breakdown due to the glass transition tempera-
ture. Quick startup from subzero temperatures and normal operation above 100 ◦ C remain
temperature-related challenges for the wide commercialization of PEMFCs. However, ther-
mal degradation in fuel cell membranes can be initiated under normal operating conditions
(<100 ◦ C) due to the post-mechanical degradation conditions of the membrane. Alentiev
et al. [74] observed a significant reduction in the proton conductivity of the membrane at
a temperature of 95 ◦ C. They linked the loss in conductivity to the decomposition of the
hydrophilic proton conductive sulfonic acid groups. For fuel cells without proper humidifi-
cation, high-temperature operation leads to low protonic conductivity of the membrane as
a result of its lower water content. Moreover, dry membranes are prone to crack formation,
which critically affects their mechanical stability and promotes the formation of pinholes
and gas crossover. Membrane pinholes are usually characterized by higher gas crossover
rates that cause hotspots in the membrane owing to the higher rates of chemical reactions.
The temperature spike at the local hotspots in turn triggers further physical, chemical, and
thermal decomposition of the membrane [75]. Thermal degradation can also be initiated by
membrane thickness irregularity. At extremely thin regions of the membrane, where the
anode and cathode come into very close contact with each other, the rate of gas crossover in-
creases significantly causing the inception of hotspots [21]. Kreitmeier et al. [76] employed
thermos-chromic pigments to observe a temperature as high as 140 ◦ C at the local hotspot
regions. The glass transition of Nafion® membrane occurs at around 110 ◦ C; however,
macro level thermal polymer decomposition may occur at relatively higher temperatures.
Several strategies have been proposed to alleviate the temperature build-up in the
membrane to enhance thermal-related membrane degradation. Among the effective meth-
ods suggested is to improve the coating uniformity of the GDL during the manufacturing
process. Evenly coated electrodes can substantially mitigate the hydrogen crossover and
enhance the life of fuel cells [77]. Exhaust product water from fuel cells is also considered as
an efficient heat dissipation mechanism for heat generated by the oxygen catalytic reaction
during fuel cell operation. Moreover, improving the hydrophobicity of the GDL and CL
showed an enhanced water flow rate that led to a higher heat dissipation rate. The addition
of hydrophobic polymers such as PTFE in the GDL not only improves the exhaust water
flow rate [78,79] but also enhances the heat conductivity of the material and thus results
in better heat management of the system [80]. Apart from integrated heat management
systems, external fuel cell cooling systems based on air and water proved to be an effective
way of maintaining a relatively uniform heat distribution in PEMFCs.
Energies 2022, 15, 9247 9 of 26

2.1.4. Brief Summary of Membrane Degradation Models

This section attempts to cover the modeling of major membrane degradation mech-
anisms, namely chemical, mechanical, and thermal degradations. A summary of the
membrane degradation models is provided in Table 1. Although it is inaccurate to assume
the degradation mechanisms exist separately, for the purpose of simplicity they are pre-
sented and discussed independently. The majority of degradation modeling is focused on
specific processes. We believe a unified degradation model consisting of hydrogen peroxide
and hydroxyl radical formation followed by the unzipping of the main membrane backbone
and cleaving of the sulfonic acid side chains that cause conductivity loss would provide
valuable information on understanding membrane degradation mechanisms. Similarly,
a unified model for membrane mechanical degradation that includes clamping stresses,
humidity cycling, and vibration excitations is required to provide a full image of membrane
mechanical degradation mechanisms. Compared to mechanical and chemical degradation
models, the modeling of the thermal degradation of fuel cell membranes has received
less attention; hence a very limited literature is available dedicated to the pure thermal
degradation of membranes.

Table 1. Summary of the membrane degradation models.

Authors Year Model Description

Chemical degradation: Modeling main chain carboxylic acid unzipping
Tao Xie et al. [56] 2007
and side chain cleaving
Mechanical degradation: Modeling the physical response of membrane
Ahmet Kusoglu et al. [65] 2007
under humidity cycling
Chemical degradation: Modeling formation of hydroxyl radicals via
A. A. Shah et al. [81] 2009
Fenton reactions
Chemical degradation: Modeling hydroxyl radical formation via
Romain Coulon et al. [82] 2010
Fenton reaction and a radical mechanism of side chain decomposition.
Mechanical degradation: Modeling natural frequency and mode
H. E. U. Ahmed et al. [69,71] 2011
shapes under exited vibration
Roshanak Banan et al. [70,71] 2013, 2015 Mechanical degradation: Modeling mechanical vibration
Mechanical degradation: Modeling of pinhole growth under
Kusoglu and Weber et al. [66] 2014
environmental cycling loads
Thermo-chemical degradation: Modeling the degradation of long-run
Seongyeon Won et al. [83] 2016
cell voltage
Mechanical degradation: Modeling crack growth and fatigue due to
Guoliang Ding et al. [61,84] 2016, 2017
clamping pressure under humidity cycling
Physio-chemical degradation: Temperature, relative humidity, and cell
L. Karpenko-Jereb et al. [50] 2016
voltage
Chemical degradation: Modeling low-voltage degradation of
Ka Hung Wong et al. [57] 2017
Ceria-supported membrane
R. Singh et al. [52] 2018 Chemical degradation: Modeling the sequential degradation of PFSA
Georg A. Futter et al. [53] 2019 Chemical degradation: Modeling of hydrogen peroxide formation
Physio-chemical degradation: Modeling of pinhole growth under
Victoria M Ehlinger et al. [48,49] 2019, 2020
couples mechanical and chemical effect
Mechanical degradation: Modeling of stress and strain evolution
Wenqing Liu et al. [85] 2020
during assembly and operation
Chemical degradation: Modeling spatial distribution of hydrogen
Weibo Zheng et al. [58] 2021
peroxide
Mechanical degradation: Modeling of crack growth under humidity
Y.X. Wang et al. [51] 2021
cycling

2.2. CL
The catalyst layers are typically attached to the two sides of the membrane to serve as
anodic and cathodic electrodes. There are two key functions of the CL: the first one is the
transport of reagents and products through the porous electrode; the second function is
related to the electrochemical reaction that occurs within the CL as hydrogen oxidation and
oxygen reduction with anode and cathode sides, respectively, where the CL is responsible
Energies 2022, 15, 9247 10 of 26

for controlling the transport of protons and electrons within the MEA [86–89]. Therefore,
the catalyst layers should be porous, ionic, and electronic conductors, and should have a
large active area since the electrochemical reactions only occur at active catalytic sites [22].
The anode and cathode CLs usually contain platinum (Pt) particles or Pt-based cata-
lysts and carbon grains, commonly clusters of Pt/C covered by ionomer thin films [88]; the
carbon support is normally added to the Pt particles to enhance the mechanical strength
Energies 2022, 15, x FOR PEER REVIEW 11 of 29
of the CLs [90]. The microstructure of the catalytic layer is schematically demonstrated in
Figure 6 [91].

Energies 2022, 15, x FOR PEER REVIEW 11 of 29

Figure
Figure 6. Illustration
6. Illustration of theofcatalyst
the catalyst layer structure
layer structure [91]. “Reprinted/Reproduced
[91]. “Reprinted/Reproduced from J. Electro-from J. Electrochem.
Soc, 162, Hao, L.; Moriyama, K.; Gu, W.; Wang, C.-Y., Modeling and Experimental
chem. Soc, 162, Hao, L.; Moriyama, K.; Gu, W.; Wang, C.-Y., Modeling and Experimental Valida- Validation of Pt
tion of Pt Loading and Electrode Composition Effects in PEM Fuel Cells, F854–F867., Copyright
Loading and Electrode Composition Effects in PEM Fuel Cells, F854–F867., Copyright (2015), with
(2015), with permission from IOP Publishing”.
permission
Figure from
6. Illustration of theIOP Publishing”.
catalyst layer structure [91]. “Reprinted/Reproduced from J. Electro-
chem. Soc, 162, Hao, L.; Moriyama, K.; Gu, W.; Wang, C.-Y., Modeling and Experimental Valida-
2.2.1. Degradation Mechanism
tion2.2.1. Degradation
of Pt Loading and ElectrodeMechanism
Composition Effects in PEM Fuel Cells, F854–F867., Copyright
Onepermission
(2015), with of the main
from IOPfactors affecting the PEMFC lifetime is related to catalyst
Publishing”. layer
One [8,92].
degradation of theTherefore,
main factors affecting
the durability of Ptthe PEMFC
or Pt/C lifetime
remains is related
as a barrier to catalyst layer
to the de-
degradation
2.2.1. Degradation
velopment [8,92]. The
Mechanism
of PEMFCs. Therefore,
deteriorationtheofdurability
the CL fallsof Ptthree
into or Pt/C remains
categories, whichasare
a barrier to the
One of the main
Ptdevelopment
degradation, factors
of
carbon affectingcorrosion,
PEMFCs.
support the PEMFC
The lifetime
deterioration
and ionomeris of
related
the toCLcatalyst
decomposition layer
falls [93].
intoThe three categories, which
Pt deg-
degradation
radation [8,92]. Therefore,
includes the durability
Pt dissolution, of Pt or Pt/Cand remains as a barrier to degradation
the de-
are Pt degradation, carbonPtsupport
detachment,corrosion, Pt sintering.
and ionomer
velopment of PEMFCs. The deterioration of the CL falls into three categories, which are
The of the [93]. The Pt
decomposition
CL due to the above-mentioned
degradation includes Pt degradationPtmechanisms
dissolution, detachment, has and
been Pt reviewed
sintering.very The
re- degradation
Pt degradation, carbon support corrosion, and ionomer decomposition [93]. The Pt deg-
cently includes
by ArayPtet al. [22], and thus is not repeated hereThe(See Figure 7). In addition, as
of the CL due to the above-mentioned degradation mechanisms has been reviewed very
radation dissolution, Pt detachment, and Pt sintering. degradation of the
CLdisplayed
due to theinabove-mentioned
Figure 8, the interface of CLs
degradation can be dissociated
mechanisms or cracked after long oper-
recently
ation time by Aray
[94,95] et al.cold
or under [22], and thus nothas
is[96]. been reviewed
repeated here very
(Seere-Figure 7). In addition, as
cently by Aray et al. [22], and thus isstart operation
not repeated here (See Figure 7). In addition, as
displayed
displayed in Figure
in Figure 8, theofinterface
8, the interface CLs can beofdissociated
CLs canorbecracked
dissociated
after longoroper-
cracked after long operation
time
ation time[94,95]
[94,95] oror under
under cold cold start operation
start operation [96]. [96].

Figure
Figure 7. Schematic
7. Schematic of chemical ofdegradation
chemical mechanisms
degradation mechanisms
for platinum for
particles onplatinum particles on a carbon support
a carbon sup-
Figure 7. Schematic of chemical degradation mechanisms for platinum particles on a carbon sup-
portininfuel
fuel cells
cells [22].
[22]. “Reprinted/Reproduced
“Reprinted/Reproduced from PEMfrom Fuel Cells:
PEM Fundamentals,
Fuel Cells: Advanced
Fundamentals, Advanced Technolo-
port in fueland
Technologies, cells [22]. Araya,
Practical, “Reprinted/Reproduced from PEM and
S.S.; Li, N.; Liso, V, Degradation Fuelfailure
Cells:modes
Fundamentals,
in proton Advanced
gies,
exchange and
Technologies, Practical,
membrane andfuel Araya,
Practical, Araya,
cells, 199-222, S.S.; Li, N.; Liso,
S.S.; Li,(2022),
Copyright N.; Liso, V,
with V, Degradation
Degradation
permission and failure modes in proton exchange
and failure modes in proton
from Elsevier”.
exchange
membranemembrane fuel cells,
fuel cells, 199-222,
199–222, Copyright(2022),
Copyright (2022), with
withpermission
permissionfrom Elsevier”.
from Elsevier”.
Energies 2022, 15, x FOR PEER REVIEW 12 of 29
Energies 2022, 15, 9247 11 of 26

Figure 8. (a) Cracked CL and (b) CL delamination [97]. “Reprinted/Reproduced from J. Power
Figure 8. (a) Cracked CL and (b) CL delamination [97]. “Reprinted/Reproduced from J. Power
Sources, 179, Kim, S.; Ahn, B.K.; Mench, M.M, Physical degradation of membrane electrode assemblies
Sources, 179, Kim, S.; Ahn, B.K.; Mench, M.M, Physical degradation of membrane electrode as-
undergoing
semblies freeze/thaw
undergoing cycling: Diffusion
freeze/thaw media effects,
cycling: Diffusion media140–146.,
effects,Copyright
140–146., (2008), with(2008),
Copyright permission
with
from Elsevier”.
permission from Elsevier”.
2.2.2. Degradation Modeling
2.2.2. Degradation Modeling
The catalyst degradation phenomenon in PEMFCs has been modeled to understand
The catalyst degradation phenomenon in PEMFCs has been modeled to understand
the fundamental mechanism of Pt degradation [98,99], carbon support corrosion [100], and
the fundamental
ionomer decompositionmechanism
[101–110]of PtAlso,
degradation [98],[99],
the occurrence carbon support
of cracking corrosion [100],
and delimitations in the
and ionomer decomposition [101–110] Also, the occurrence
interface of the two sides of the CL was investigated via modeling [95,111–114]. of cracking and delimitations
in theThe
interface of the two
first numerical sidesthat
model of the CL wasthe
describes investigated via modeling
Pt dissolution and oxidation [95,111–114].
degradation
The first numerical model that describes the Pt dissolution
process was developed by Darling and Meyers [115]. They presented a one-dimensional and oxidation degrada-
tion process was developed by Darling and Meyers
transient model that accounts for the MEA cross section of PEMFCs. A two-particle size [115]. They presented a
one-dimensional transient model that accounts for the MEA
scheme was used to model the cathode electrochemical surface area (ECA) loss due to cross section of PEMFCs. A
two-particle size scheme was
Pt dissolution/deposition andusedPt ion to transport
model theincathode MEA. They electrochemical
stated that surface
their modelarea
(ECA) loss due
reasonably to Ptwith
agreed dissolution/deposition
the experimental data. and Based
Pt ion transport
on Darling inand
MEA. They stated
Meyer’s model, that
Bi
their model reasonably agreed with the experimental data. Based
and Fuller et al. [103] proposed a new Pt catalyst degradation model that includes some on Darling and Meyer’s
model,
differentBifeatures,
and Fuller such etas
al.cathode
[103] proposed
Pt mass loss a new intoPtthe
catalyst
membrane.degradation modelwas
Their model thatalso
in-
cludes some different features, such as cathode Pt mass loss into
able to predict the cathode platinum mass, catalyst particle size, and platinum surface area. the membrane. Their
model was etalso
Moore able proposed
al. [116] to predict the cathode
a multi-scale platinumthat
framework mass,
fullycatalyst
coupled particle size, and
a one-dimensional
platinum
micro-scale surface area.
ionomer-filled agglomerate model with a two-dimensional macro-scale MEA
model. Moore
Their et al. [116] proposed
computational model wasaused multi-scale
to study the framework
impact of the thatcatalyst
fully aggregation
coupled a
one-dimensional
of the cathode CL micro-scale ionomer-filled
on the different agglomerate
charge, mass, modeltransport
and kinetic with a two-dimensional
mechanisms of
macro-scale
PEMFCs. Their MEA model.show
findings Their that
computational
changes in model was usedagglomerate
the micro-scale to study the impactpropertiesof the
of
catalyst
the cathode aggregation of the cathode
CL can considerably influenceCL agglomerate
on the different charge, and
effectiveness mass, and density
current kinetic
transport
distributions.mechanisms of PEMFCs. Their findings show that changes in the micro-scale
agglomerate properties
Li et al. [101] of the investigated
numerically cathode CL can considerablyphenomena
the degradation influence agglomerate
in the cathode effec-
CL.
First, a one-dimensional
tiveness and current density model was established to study the Pt degradation and ECA loss
distributions.
in theLicathode CL. The
et al. [101] model considers
numerically investigatedthe Ptthedegradation
degradation duephenomena
to the Ostwald ripening
in the cathode on
carbon support and Pt dissolution-re-precipitation through the
CL. First, a one-dimensional model was established to study the Pt degradation and ECA ionomer phase. Besides, the
model
loss in accounts
the cathode for CL.
the effect
The modelof thermal variations
considers the Pton the ECA evolution,
degradation due to the and in addition
Ostwald rip-
relative
ening onhumidity effects and
carbon support on Pt Ptdegradation were studied. They
dissolution-re-precipitation through statedthethat ECA phase.
ionomer loss is
non-uniform
Besides, acrossaccounts
the model the cathode for CL
the with
effecta of
zone of aggravated
thermal variationsPton degradation and thus
the ECA evolution,
much
and inlower
additionECA is found
relative near theeffects
humidity membrane. They also quantified
on Pt degradation were studied. the effect
They of thin
stated
cathode CLs on Pt degradation. Then, in another study, Li
that ECA loss is non-uniform across the cathode CL with a zone of aggravated Pt deg- and Wang [117] combined the
one-dimensional degradation model with a comprehensive
radation and thus much lower ECA is found near the membrane. They also quantified transient M2 PEMFC model to
analyze non-uniform Pt degradation and its impacts on long-term
the effect of thin cathode CLs on Pt degradation. Then, in another study, Li and Wang PEMFC performance.
Their combined
[117] simulationthe predictions revealed degradation
one-dimensional the cause andmodel consequence of non-uniform transient
with a comprehensive Pt degra-
dation,
M2 PEMFC the performance
model to analyze loss of low Pt-loading
non-uniform PEMFCs with
Pt degradation and its Pt impacts
degradation, and the
on long-term
interactions of Pt degradation with micro-scale transport resistance.
 PEMFC performance. Their simulation predictions revealed the cause and consequence
of non-uniform Pt degradation, the performance loss of low Pt-loading PEMFCs with Pt
Energies 2022, 15, 9247 degradation, and the interactions of Pt degradation with micro-scale transport12resistance. of 26
Moein-Jahromi et al. [118] presented a novel experiment-based algorithm to evalu-
ate the effect of cyclic load on CL performance loss. Their combined computational
model Moein-Jahromi
consists of a CL degradation
et al. model
[118] presented andexperiment-based
a novel an agglomeratealgorithm
CL performance
to evaluate model.
ThetheCL degradation
effect model
of cyclic load on CL predicts the ECA
performance loss.and agglomerate
Their size under any
combined computational given cy-
model
clicconsists of a CL degradation
load protocols model and
at various thermal andanRHagglomerate
operatingCL performance
conditions. model.
Then, The
the predicted
CL degradation
structural changesmodelof thepredicts
CL are the
usedECA and agglomerate
as input for the CL size under anymodel
agglomerate given to
cyclic
evaluate
load protocols at various thermal and RH operating conditions.
the performance loss the degraded CL may exhibit due to the cathode catalyst layer Then, the predicted
structural changes of the CL are used as input for the CL agglomerate model to evaluate
degradation and the Ostwald ripening. They stated that among the tested parameters,
the performance loss the degraded CL may exhibit due to the cathode catalyst layer
thedegradation
operating temperature
and the Ostwald wasripening.
found toTheybe the most
stated thatinfluential
among theparameter in raising the
tested parameters,
voltage
the operating temperature was found to be the most influential parameter in raising and
degradation rate under cyclic operation. In another study, Moein-Jahromi
Kermani [119]degradation
the voltage improved rate theirunder
model to forecast
cyclic operation.the In
aging process
another ofMoein-Jahromi
study, the fuel cell during
cyclic
and loading. As depicted
Kermani [119] improved intheir
Figure 9, their
model proposed
to forecast new process
the aging model involves
of the fuela cell
compre-
during cyclic loading. As depicted in Figure 9, their proposed
hensive three-dimensional PEMFC performance model coupled with a degradation new model involves a CL
comprehensive three-dimensional PEMFC performance model coupled with
model that is capable of calculating the ECA degradation, growth of Pt particles, and Pt a degradation
CL model in
dissolution that is capableInofaddition,
ionomer. calculating the ECA
based degradation,
on the numericalgrowth of aPtmulti-objective
results, particles, and op-
Pt dissolution in ionomer. In addition, based on the numerical results, a multi-objective
timization formula with different scenarios was designed to minimize the degradation
optimization formula with different scenarios was designed to minimize the degradation
rate
rateand
andmaximize
maximizethe the cell performance.
cell performance.

Figure
Figure 9. 9. (a) Diagram
(a) Diagram represents
represents combinations
combinations of of models,
models, (b)(b) Ostwald
Ostwald ripening
ripening procedure,and (c)
procedure,
effect of operating conditions on voltage performance during cycling load [119].[119].
and (c) effect of operating conditions on voltage performance during cycling load “Reprint-
“Reprinted/Reproduced
ed/Reproduced from Energy
from Energy Convers.
Convers. Manag.,231,
Manag., 231, Moein-Jahromi,
Moein-Jahromi,M.;M.; Kermani, M.J., M.J.,
Kermani,
Three-dimensional multiphase
Three-dimensional multiphase simulation
simulation and multi-objective
and optimization
multi-objective of PEM
optimization offuel
PEM cells degra-
fuel cells deg-
dation under automotive cyclic loads, 113837, Copyright (2021), with permission from Elsevier”.
radation under automotive cyclic loads, 113837, Copyright (2021), with permission from Elsevier”.
Gwak et al. [120] developed a microstructure CL model fully coupled with a three-
Gwak et macro-scale
dimensional al. [120] developed a microstructure
two-phase PEMFC CL model
model to explore fully transport
the oxygen coupled re-
with a
three-dimensional macro-scale two-phase PEMFC model to explore the oxygen transport
sistance in the cathode CL under different CL designs and operating conditions. Their
 Energies 2022, 15, x FOR PEER REVIEW 14 of 29

Energies 2022, 15, 9247 13 of 26

resistance in the cathode CL under different CL designs and operating conditions. Their
developed model is displayed in Figure 10. The microscopic CL structural parameters
developed model is displayed
and compositions, as well as intheFigure 10. The microscopic
CL degradation CL structural
process including parameters
the growth of Ptand
na-
compositions,
noparticles and as well as Pt
active thesurface
CL degradation
area loss,process including the
were considered growth
in the of Pt nanopar-
microstructure CL
ticles
model.and active
They Pt surface
concluded thatarea loss,design
the CL were with
considered in the microstructure
low Pt loading might be easilyCL model.
degraded.
They concluded
Additionally, thatdemonstrated
they the CL design with
that low Pt loading
Pt particle growth might be easily
significantly degraded.
increases Ad-
the effec-
ditionally, they demonstrated that Pt particle growth significantly increases
tive oxygen diffusion path through the ionomer and water films, resulting in greater the effective
oxygen
oxygendiffusion
reductionpathandthrough the ionomer
lower voltage and water
performance. films, resulting
Moreover, in greater
their model wasoxygen
further
reduction
improvedand by lower
Ghasemi voltage
et al.performance.
[121] to considerMoreover, theirofmodel
the effects wastransport
electron further improved
in the CL
by GhasemiTheir
structure. et al.newly
[121] to consider model
developed the effects
was of electron
used transportand
to investigate in the CL structure.
compare the cell
Their newly developed
performance model
of the Pt/TiO 2/Cwas usedwith
catalyst to investigate and compare
the traditional the cell
Pt/C catalyst performance
under different
oflevels
the Pt/TiO /C catalyst with
of CL 2degradation. Theythe traditional
reported thatPt/C catalyst
although the under
usage different
of TiO2 aslevels of CL
Pt catalyst
degradation.
support was favorable for cell performance, the additional2electronic ohmic loss bywas
They reported that although the usage of TiO as Pt catalyst support the
favorable for cell
TiO2 particles performance,
could the under
be significant additional
high electronic ohmicoperating
current density loss by the TiO2 particles
conditions.
could be significant under high current density operating conditions.

Figure
Figure10.10.(a)
(a)Schematic
Schematicofofmicro-scale
micro-scaleoxygen
oxygenpermeation
permeationononagglomerate
agglomerate inincathode
cathode CL,
CL,(b)(b)
multi-
mul-
scale computational domains, (c) voltage losses for various CL designs and degradation
ti-scale computational domains, (c) voltage losses for various CL designs and degradation for pt for pt loading
ofloading
0.25 mg/cm 2
of 0.25, and
mg/cm (d)2,voltage
and (d)losses for various
voltage CLvarious
losses for designsCLanddesigns
degradation for pt loading
and degradation forofpt
0.05 mg/cm 2 [120]. “Reprinted/Reproduced from Int. from
J. Hydrogen Energy, 45, Gwak,
loading of 0.05 mg/cm 2 [120]. “Reprinted/Reproduced Int. J. Hydrogen Energy, 45,G.; Lee, G.;
Gwak, J.;
Lee, J.; Ghasemi,
Ghasemi, M.; Choi, M.;J.;Choi,
Lee, J.; Lee,Jang,
S.W.; S.W.;S.S.;
Jang,Ju,
S.S.;
H,Ju, H, Analyzing
Analyzing oxygenoxygen transport
transport resistance
resistance andand
Pt
Pt particle
particle growth
growth effect
effect in the
in the cathode
cathode catalyst
catalyst layer
layer ofof polymerelectrolyte
polymer electrolytefuel
fuelcells,
cells,13414–13427.,
13414–13427.,
Copyright(2020),
Copyright (2020),with
withpermission
permissionfrom fromElsevier”.
Elsevier”

Liuetetal.
Liu al.[122]
[122]built
builtaamathematical
mathematicalmodel modelbased
basedon onthe
thefinite
finiteelement
elementmethod
methodtoto
studythe
study theCLCL microstructure
microstructure changes
changes duedue to mechanical
to mechanical degradation
degradation (see Figure
(see Figure 11).
11). They
They mentioned
mentioned that thethat the swelling
swelling and shrinking
and shrinking in response
in response to the humidity
to the humidity and tem-
and temperature
perature variations
variations resulted inresulted
residual in residual
plastic plastic
strain, and strain, and the accumulation
the accumulation of strain
of this plastic this plastic
may
strainan
cause may cause andelamination
interfacial interfacial delamination
between thebetween
ionomertheandionomer
the Pt/Cand the Pt/C agglom-
agglomerates and
erates and
damage the damage
ionomerthe ionomer
under underoperation.
long-term long-term operation.
Energies
Energies2022,
2022,15,
15,x 9247
FOR PEER REVIEW 15 14
of of2926

Figure 11. (a) Schematic of the CL structure, (b) structure under the channel/land, (c) simplified
Figure 11. (a) Schematic of the CL structure, (b) structure under the channel/land, (c) simplified CL
CL microstructure, and (d) plastic strain distribution at the swelling and shrinking processes [122].
microstructure, and (d) plastic strain distribution at the swelling and shrinking processes [122].
“Reprinted/Reproduced
“Reprinted/Reproduced from fromJ. J. Power
Power Sources,
Sources, 512,
512, Liu,
Liu, J.;J.; Yin,
Yin, Y.;Y.;Zhang,
Zhang,J.;J.;Zhang,
Zhang,T.;T.;Zhang,
Zhang,X.;X.;
Chen, H., Mechanical degradation of catalyst layer under accelerated relative humidity cycling inina a
Chen, H., Mechanical degradation of catalyst layer under accelerated relative humidity cycling
polymerelectrolyte
polymer electrolytemembrane
membranefuel fuelcell,
cell,230487,
230487,Copyright
Copyright(2021),
(2021),with
withpermission
permissionfromfromElsevier”.
Elsevier”.

2.2.3. Brief Summary of CL Degradation Models

2.2.3. Brief Summary of CL Degradation Models
Generally speaking, the CL is the most expensive component of MEA, yet holding the
Generally speaking, the CL is the most expensive component of MEA, yet holding
key role in PEMFC performance and commercialization. The Pt-based catalysts commonly
the key role in PEMFC performance and commercialization. The Pt-based catalysts
used in CLs exhibit different chemical and mechanical degradation when used in PEMFCs.
commonly used in CLs exhibit different chemical and mechanical degradation when
In this regard, several numerical studies have been performed to improve their performance
used in PEMFCs. In this regard, several numerical studies have been performed to im-
and durability. A summary of the CL degradation models is provided in Table 2. With
prove their performance and durability. A summary of the CL degradation models is
respect to degradation modeling research, the degradation phenomena affecting the PEMFC
provided
performancein Table
were2. With respect
addressed usingtomicro-scale
degradation modeling models
agglomerate research, thecombined
that degradation
with
phenomena affecting the PEMFC performance were addressed using micro-scale
multi-dimensional transport and electrochemical performance PEMFC models. However, ag-
glomerate models that combined with multi-dimensional transport and electrochemical
there is still a need to develop the existing models to optimize and evaluate CLs with
performance PEMFC models.that
new materials/compositions However, there
can provide is still aperformance
enhanced need to develop the existing
and durability under
models to optimize and evaluate CLs with new materials/compositions that can
various dynamic loads and real operating conditions, which may require more efforts in provide
enhanced performance
coupling the and durability
current degradation modelsunder
with various dynamic
nano-scale models.loads and the
Besides, realF/T-induced
operating
conditions, which may require more efforts in coupling the current degradation
degradation was experimentally visualized [23,123–125], but the underlying mechanism modelsof
with nano-scale models. Besides, the F/T-induced degradation was experimentally
F/T-induced degradation and mitigation strategies in the CL structure is rarely discussed visu-
alized [23,123–125],
numerically [126]. but the underlying mechanism of F/T-induced degradation and
mitigation strategies in the CL structure is rarely discussed numerically [126].
Table 2. Summary for the CL degradation models.
Table 2. Summary for the CL degradation models.
Year of
Author/s
Author/s Year Publication
of Publication Degradation
DegradationMechanism/Model Description
Mechanism/Model Description
Pt degradation: Modeling of aging mechanisms in a
Franco and
Franco M.M.Tembely
and Tembely [102]
[102] 2007
2007 Pt degradation: Modeling of aging mechanisms in a PEMFC cathode
PEMFC cathode
Structural changes in CL: Modeling of CL microstructure changes
Rong F. et al. [95,114] 2008 Structural changes in CL: Modeling of CL microstructure
induced by load cycling
Rong F. et al. [95,114] 2008
Pt/C catalyst
changes degradation:
induced by loadModeling
cycling of Pt/C catalyst degradation
Bi and T. F. Fuller [103] 2008
processes using physics-based
Pt/C catalyst degradation: model
Modeling of Pt/C catalyst
Bi and T. F. Fuller [103] 2008 Pt Catalyst Degradation: Modeling of Pt Catalyst degradation using
T. Takeshita et al. [104] 2008 degradation
1D macro model
processes using physics-based model
Pt Catalyst Degradation: Modeling of Pt layer
Pt/C catalyst degradation: Effect of gradation in catalyst Catalyst
on
T. Takeshita
Poornesh K.K. et
et al. [111,113]
[104] 2008
2010
degradation usingbetween
interfacial strength 1D macro model and catalyst layer
membrane
Ionomer
Pt/C decomposition:
catalyst Modeling
degradation: Effectofofplatinum diffusion,
gradation in catalyst layer
Burlatsky
Poornesh K.K.S.F. et al.
et al. [127]
[111,113] 2011
2010 precipitation, and band formation in the membrane
on interfacial strength between membrane and catalyst layer
Burlatsky S.F. et al. [127] 2011 Ionomer decomposition: Modeling of platinum diffusion,
Energies 2022, 15, 9247 15 of 26

Table 2. Cont.

Year of
Author/s Degradation Mechanism/Model Description
Publication
Pt/C degradation: Modeling the key role of platinum oxides using
Colombo E. et al. [128] 2011
transient and physical 2D model
Pt degradation: Modeling framework for surface area
S. G. Rinaldo et al. [105] 2012 loss and mass balance phenomena in supported Pt nanoparticle
catalysts
Pt degradation: Modeling of Pt nanoparticle dissolution and
E. F. Holby and D. Morgan [106] 2012
oxidation in PEMFCs
Pt degradation: Modeling the effects of coalescence/sintering of Pt
R. K. Ahluwalia et al. [107,108] 2014, 2013
particles on particle growth and ECSA loss
Pt degradation: Modeling of Pt degradation, Ostwald ripening on
Y. Li, K. Moriyama et al. [101] 2015 carbon support and Pt dissolution-re-precipitation through the
ionomer phase
Pt degradation: Modeling of transient platinum degradation under
Li Y. and C.Y. Wang [117] 2017
current cycling
Pt/C catalyst degradation: Modeling of ECSA degradation, Pt
Moein-Jahromi et al. [118,119] 2017, 2021 particle growth, the agglomerates via Ostwald ripening, and Pt mass
loading loss under cyclic load
Carbon corrosion: Modeling of the carbon support corrosion and
Randrianarizafy et al. [109] 2020
mitigation strategies through the use of a pseudo-3D model
Pt degradation: Modeling the oxygen transport resistance and Pt
Gwak G. et al. [120] 2020
particle growth effect in CL
Pt degradation: Investigating the usage of TiO2 as Pt catalyst support
Ghasemi M. et al. [121] 2021 under different degrees of CL aging using multi-scale two-phase
model
Structural changes in CL: Modeling the structural changes in CL
Chang Y. et al. [129] 2021
under humidity and thermal cycling
Mechanical degradation: Microstructure changes under accelerated
Liu et al. [122] 2021
relative humidity cycling
Pt degradation: Modeling of Pt degradation in the membrane
Weibo Zheng et al. [99] 2022 electrode assembly considering Pt mass loss and particle growth
mechanisms

2.3. GDL
Both the anode and cathode GDLs are critical components of PEMFCs. They not only
provide mechanical support for other fuel cell components, but also control the reactants,
water, and charge transportation; thus, they play an important role in determining the
fuel cell performance [130]. The GDL has essential functions in the PEMFC, which are
transporting the reactant gas supplied by the flow channels to the CLs, conducting the
electrons with low resistance, and removing the generated water from the membrane to
the flow channel. The GDL is a thin layer, known as a carbon-based porous material layer,
composed of (randomly) oriented carbon fibers covered by a hydrophobic agent, commonly
PTFE [8,131,132].
Such a unique structure also makes it more vulnerable to compression than other
cell components under clamping and cyclic compressions. The GDL changes its physical
structure as well as initial compressive behavior, which deteriorates its functions and
reduces cell performance [111,133]. In addition, most of the critical material parameters in
terms of performance, such as electrical and thermal conductivities, gas permeability, and
diffusivity, rely on the compressive behavior of GDLs [134,135]. In addition, it was reported
that under some operational and environmental conditions such as after 11,000 h operation
and under subfreezing operating temperatures [136], the GDL surface hydrophilicity
noticeably changes, causing the development of wettability and maximizing the mass
transport resistance [137]. Even though most of the published modeling studies have
focused on the effects of GDL properties on the PEMFC performance, very little attention
has been paid to the degradation mechanisms of the GDL.
Energies 2022, 15, 9247 16 of 26

2.3.1. Degradation Mechanisms

The degradation phenomena in the GDL mainly target the carbon fibers and/or the
PTFE.
Consequently, these GDL degradation phenomena under different cell operating
conditions can generally result in physical damage, such as the mechanical degradation
caused by compressive clamping systems and ice formation, fiber breakage, and mechan-
ical/chemical carbon corrosion, or wettability changes due to the surface oxidation and
PTFE loss.
Although carbon oxidation is unlikely to occur with the appearance of Pt in the
GDL/CL interface due to platinum dissolution after long-time operation [33], the carbon
oxidation in the microscopic layer of the GDL was observed using subsequent fuel cell
testing [138]. It was found that the carbon oxidation of the MPL results in reducing the mass
transport, water management ability, and conductivity of the GDL, but the quantitative
correlation between the carbon oxidation and degradation rate has not yet been proposed.
On the other hand, the mechanical stress generated by the stacking pressure may lead
to plastic deformation and high stress points at the membrane and GDL [139]. These
structural changes in the GDL mostly influence the contact pressure distributions under
the channel and land areas of the flow field [140].

2.3.2. Degradation Modeling

The loss of hydrophobicity due to PTFE loss was reported to decrease the cell perfor-
mance. As plotted in Figure 12, Pauchet et al. [141] proposed a numerical approach that
combines pore network modeling and performance modeling to investigate the effects of
hydrophobicity loss on the GDL properties, particularly the gas diffusion coefficient. They
attempted to provide more explanations for the experimentally measured performance
degradation rate induced by hydrophobicity loss in GDLs. Their approach was based
on calculating the gas diffusion coefficient first via the pore network model, considering
the effect of the change in wettability as a function of the hydrophobicity loss. Then, the
gas diffusion coefficient was used as input to the performance model to simulate the elec-
trical performance of the cell. They showed that the performance losses induced by the
hydrophobicity loss captured by the computational model were comparable to the ones
measured by the experimental degradation tests. They revealed that the degradation of the
GDL causes a non-linear drop in the electrical performance of the PEMFC. Furthermore,
their results showed that the hydrophobicity loss of the GDL increased the non-uniformity
of the current density distributions between the inlet and outlet regions. Based on their
predicted results, they stated that a fully hydrophobic GDL could be fully hydrophilic in
roughly 2000 h. Seidenberger et al. [142] investigated the impact of PTFE degradation on
the water accumulation behavior within the GDL using a three-dimensional Monte Carlo
model. Different PTFE coverage ratios were explored. They reported decreasing the PTFE
coverage results in increasing the water content and forming larger water clusters. They
also mentioned that upon the PTFE being reduced to a certain value of 55%, the formation
of very large water clusters occurs and covers the entire area of the GDL, which in turn
could significantly accelerate the ageing of the GDL.
Generally speaking, applying an exceedingly large compressive force on the GDL
raises the mechanical degradation index of the GDL component, which might result in
damage to the GDL and the uneven distribution of the contact pressure, and affect the fuel
cell performance and structure. Several numerical studies have investigated the impact of
the mechanical degradation induced by compressive pressure on fuel cell performance un-
der non-proper compact systems [143]. Ozden and Tari [144] conducted a parametric study
using a series of CFD simulations to investigate the influence of degradation on the perfor-
mance of PEMFCs. Based on their study, it was concluded that the membrane degradation
is the least effective factor in terms of fuel cell degradation, followed by the CL and GDL.
The impact of non-homogeneous GDL compression on the GDL properties [145,146], con-
tact resistance [147], GDL structure [148], local performance and lifetime [149,150], has been
Energies 2022, 15, 9247 17 of 26

reported in the literature considering varied numerical approaches. Nitta et al. [135,149,151]
investigated the influence of clamping pressure on GDL thermal conductivity and contact
resistance. They reported that the thermal conductivity of the GDL is independent of
clamping force. They also stated that the thermal contact resistance declines and correlates
non-linearly with the applied compressive pressure. Recently, Yan et al. [152] studied the
influence of GDL compression on the performance of PEMFC stacks. They stated that the
maximum power output of the stack is obtained over a clamping pressure range of 1.5 to
3.5 MPa. In addition, their results reported that the case with clamping pressure of 1.5 MPa
achieved the best voltage consistency. Atyabi et al. [153] examined the GDL compression
effect on PEMFC performance using a single-channel cell; their simulation considered the
effect of electrical and thermal resistances. They concluded that the performance of the
fuel cell improved up to the pressure of 4.5 MPa, where the maximum temperature rise
was found at the clamping pressure of 2.5 MPa. Li et al. [154] explored the inhomogeneous
GDL deformation impact on the performance of a serpentine-channel PEMFC by using a
coupling approach; the best overall performance was found at the clamping pressure of
1 MPa. Besides, they suggested that the appreciate assembly force could be controlled in
the range of 0.5–1.5 MPa to ensure an improved net power of the cell and satisfy a proper
level of the required pressure head for the pump. Robert et al. [155] showed that the cell
power production dramatically increased when the compressive stress was applied. Also,
they reported that a higher compression ratio improved the thermal management and the
hydration of the cell. Taymaz et al. [156] proposed that pressure values in a range18ofof0.5
Energies 2022, 15, x FOR PEER REVIEW 29
to 1.0 MPa were the optimum ones when considering the electrical properties of fuel cell
components.

Figure 12. (a)(a)

Figure 12. Chart
Chart of PNM/PN
of PNM/PN approach,
approach, (b) Performance
(b) Performance degradation
degradation for a non-linear
for a non-linear PTFE loss
PTFE
with time, (c) Performance degradation for a linear PTFE loss with time with
loss with time, (c) Performance degradation for a linear PTFE loss [141].time [141].
“Reprint-
“Reprinted/Reproduced
ed/Reproduced from Int. J. Hydrogen Energy, 37, Pauchet, J.; Prat, M.; Schott, P.; Kuttanikkad,Kut-
from Int. J. Hydrogen Energy, 37, Pauchet, J.; Prat, M.; Schott, P.; S.P.,
Performance
tanikkad, S.P., loss of protonloss
Performance exchange membrane
of proton exchange fuel cell due fuel
membrane to hydrophobicity loss in gas diffu-
cell due to hydrophobicity loss
sion
in gaslayer: Analysis
diffusion layer:byAnalysis
multiscale approach combining
by multiscale pore network
approach combining poreand performance
network modelling,
and performance
1628–1641, Copyright ( 2012), with permission from Elsevier”.
modelling, 1628–1641, Copyright (2012), with permission from Elsevier”.

Generally
Ice speaking,
formation applying
may cause directan exceedingly
damage to thelarge compressive
physical structureforce
of theonGDL
the GDL
(See
raises the
Figure 13).mechanical
Therefore, itdegradation indexperformance
can cause severe of the GDL loss.
component, which
Since cold startmight result
operation is in
a
crucial
damage issue for the
to the GDL development of PEMFC
and the uneven technology
distribution [157–159],
of the contact the cold start
pressure, andmodels
affect are
the
fuel cell performance and structure. Several numerical studies have investigated the
impact of the mechanical degradation induced by compressive pressure on fuel cell
performance under non-proper compact systems [143]. Ozden and Tari [144] conducted a
parametric study using a series of CFD simulations to investigate the influence of deg-
Energies 2022, 15, 9247 18 of 26

essential for studying successful operation and F/T-induced degradation [160,161]. Several
models were developed to examine and improve the PEMFC performance under freezing
operating temperatures [162–166]. Oszcipok et al. [136] stated that formed liquid water
would freeze in the GDL pores before reaching the gas flow channels. They also indicated
that the variation of hydrophobicity of the GDL after F/T cycling mainly influenced the
cathode GDL. Furthermore, they found that, after repeated F/T cycles, the hydrophilic
and hydrophobic network structure could be damaged by the F/T-induced stress. Yang
et al. [167] investigated the effect of MEA design on the ice/water distributions and out-
put performance of cold startup operation by changing the contact angle of the micro
porous layer (MPL); they considered different surrounding heat transfer coefficients, design
Energies 2022, 15, x FOR PEER REVIEW 2
parameters, and structural properties in their analysis. They found that weakening the
hydrophobicity of the GDL enhanced the water removal in the MPL, hence preventing the
MPL from water-flooding.

Figure 13. GDL/MPL degradation during F/T cycles [29,168]. Scanning electron microscopy (SEM)
Figure 13. GDL/MPL degradation during F/T cycles [29,168]. Scanning electron microscopy
images of the single and double-layer GDLs: (a,c) surface morphology of the single-layer GDL before
images of the single and double-layer GDLs: (a) and (c) surface morphology of the singl
and on completionGDL of before
60 F-T and
cycles,
on respectively;
completion of(b,d) surface
60 F-T morphology
cycles, of the
respectively; double-layer
(b) and (d) surfaceGDL
morphology
before and on completion of 60 F-T cycles, respectively. “Reprinted/Reproduced from J. Power
double-layer GDL before and on completion of 60 F-T cycles, respectively. “Reprinted/Repro
Sources, 513, Pan, Y.; Wang,
from H.;Sources,
J. Power Brandon, N.P.,
513, GasY.;diffusion
Pan, layer
Wang, H.; degradation
Brandon, N.P., in proton
Gas exchange
diffusion layer degrada
proton
membrane fuel cells: exchange membrane
Mechanisms, fuel cells:
characterization Mechanisms,
techniques characterization
and modelling techniques
approaches, 230560, and mod
Copyright (2021),approaches, 230560,
with permission Copyright
from (2021), with permission from Elsevier”.
Elsevier”.

Interesting models that have

Interesting the potential
models to investigate
that have different
the potential effects of GDL
to investigate degra-effects of
different
dation were developed by Shimpalee et al. [169], Zhu et al. [170], and Gao et al.
degradation were developed by Shimpalee et al. [169], Zhu et al. [170], [171]. Theirand Gao
models described the detailed GDL structure to improve the mass transport and achieve
[171]. Their models described the detailed GDL structure to improve the mass tran
the high performance of PEMFCs.
and achieve the highTheir approachof
performance used a co-simulation
PEMFCs. technique
Their approach usedthat
a co-simu
couples the commonly
techniqueused
thatmacro-scale CFD modelused
couples the commonly and macro-scale
micro-scale MBL model and
CFD model for the
micro-scale
model for the GDL component. Their simulation results more descriptively predict
transports of reactants gases and water inside the GDL microstructure of PEMFCs
compared to the predictions from macro-scale PEMFCs, particularly the liquid satu
and temperature inside the GDL. That might potentially enhance the understand
Energies 2022, 15, 9247 19 of 26

GDL component. Their simulation results more descriptively predicted the transports of
reactants gases and water inside the GDL microstructure of PEMFCs when compared to
the predictions from macro-scale PEMFCs, particularly the liquid saturation and tempera-
ture inside the GDL. That might potentially enhance the understanding of the transport
mechanism and result in enhancement in the mass and heat transport inside the PEMFC.
Most of the existing models that address the GDL focus on the resultant changes
induced by GDL degradation, while PEMFC models that directly discuss or model GDL
degradation evolution during PEMFC operation are relatively limited. A summary of
GDL degradation models is provided in Table 3. Also, some modeling studies have
attempted to elucidate and establish some link between GDL degradation and performance
decay. Several models that describe the effects of mechanical degradation induced by
compression or F/T have been proposed, but most of these models did not describe the
damage accumulation due to degradation. Furthermore, the chemical- and electrochemical-
induced degradation in the GDL that captures the chemical oxidation, PTFE loss, material
dissolution, and chemical carbon corrosion are not well established yet. It can be concluded
that despite the great efforts that have been carried out to develop a more durable GDL,
the link between the degradation mechanism, transport properties, GDL structural and
physical properties, and operating conditions is not clearly understood. In addition, several
studies highlighted the degradation modes separately, meaning that the contribution of
each kind of degradation mode to overall GDL degradation is not quantified yet.

Table 3. Summary for the GDL degradation models.

Year of
Authors Model Description
Publication
Modeling of the effect of hydrophobicity loss
Pauchet J. et al. [141] 2012
of GDL on performance of a PEMFC
PTFE degradation: Modeling of water
Seidenberger K. et al. [142] 2012 distribution and PTFE degradation
mechanisms in PEMFCs
Modeling the effective transport properties
Bosomoiu M. et al. [172] 2015
for fresh GDL vs. aged GDL.
Modeling the microstructure morphology of
Zhang Z. et al. [148] 2020
carbon paper-type GDL using FEM model
Simulation approach combining a pore-scale
Zhu L. et al. [170] 2021 model and lattice Boltzmann method for
GDL to study the compression effect

3. Conclusions
Prior to the commercialization of PEMFCs, the lifetime and failure mechanisms of the
MEA components should be thoroughly investigated because the current understanding of
these mechanisms is insufficient. Long real-time degradation tests and the high-cost chal-
lenges of identifying the main participating parameters via experimental techniques make
degradation modeling of great interest for some scientists in academia and industry. This
paper is dedicated to reviewing the modeling of degradation phenomena in the different
components of MEA in PEMFCs. First, chemical, mechanical, and thermal degradation
mechanisms in the proton exchange membrane are discussed. Also, the related membrane
degradation models are presented. Furthermore, recent degradation modeling studies of
porous layers, namely CL and GDL, are reported. Moreover, a brief summary of the future
direction and research gaps and challenges that may be needed for the development of a
more durable MEA are summarized.
Regarding membrane degradation models, it is found that the degradation mecha-
nisms in the membrane are assumed to exist separately, which is inaccurate. Therefore, the
review suggests the development of a unified degradation model that involves hydrogen
peroxide and hydroxyl radical formation and considers the unzipping mechanism of the
main membrane backbone and the cleaving of the sulfonic acid side chains that cause con-
Energies 2022, 15, 9247 20 of 26

ductivity loss, which would provide valuable information on understanding the membrane
chemical degradation mechanisms. Similarly, a unified model for membrane mechanical
degradation that includes clamping stresses, humidity cycling, and vibration excitations is
required to provide a better understanding of membrane mechanical degradation mecha-
nisms. With respect to CL degradation modeling research, the degradation phenomena
affecting the PEMFC performance were addressed using micro-scale agglomerate models
that combined with multi-dimensional transport and electrochemical performance PEMFC
models. However, there is still a need to develop the existing models to optimize and evalu-
ate CLs with new materials/compositions, which may require more efforts in coupling the
current degradation models with nano-scale models. Besides, the F/T-induced degradation
was experimentally visualized, but the underlying mechanism of F/T-induced degradation
and mitigation strategies in the CL structure are rarely discussed numerically.
In addition, most of the existing models that address the GDL focus on the resultant
changes induced by GDL degradation, while PEMFC models that directly discuss or
model GDL degradation evolution or damage accumulation during PEMFC operation are
relatively limited. Furthermore, the chemical- and electrochemical-induced degradation in
the GDL that capture the chemical oxidation, PTFE loss, material dissolution, and chemical
carbon corrosion are not well established yet. Lastly, several studies highlighted the
degradation modes separately, meaning that the contribution of each kind of degradation
mode on overall GDL degradation is not quantified yet.

Author Contributions: Conceptualization, A.M.D., L.W. and F.J.; methodology, A.M.D. and L.W.;
formal analysis, J.G.; investigation, A.M.D., L.W. and B.T.H.; resources, F.J.; visualization, J.G. and
B.T.H.; writing—original draft preparation, A.M.D., L.W. and B.T.H.; writing—review and editing,
F.J. All authors have read and agreed to the published version of the manuscript.
Funding: Financial support received from the National Natural Science Foundation of China
(52006226), CAS-VPST Silk Road Science Fund (182344KYSB20210007), Guangzhou Science and
Technology Plan (202102020356), and our industrial partner, Zhongheng Shangneng (Chongqing)
New Energy Technology Co., Ltd., is gratefully acknowledged.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: The authors declare no conflict of interest.

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