Hindawi

International Journal of Energy Research

Volume 2023, Article ID 3183108, 23 pages
https://doi.org/10.1155/2023/3183108

Review Article
A Review of Accelerated Stress Tests for Enhancing MEA
Durability in PEM Water Electrolysis Cells

Eveline Kuhnert , Viktor Hacker , and Merit Bodner

Institute of Chemical Engineering and Environmental Technology, Graz University of Technology, Inffeldgasse 25/C, 8010,
Graz, Austria

Correspondence should be addressed to Eveline Kuhnert; eveline.kuhnert@tugraz.at

Received 26 September 2022; Revised 28 November 2022; Accepted 29 November 2022; Published 4 February 2023

Academic Editor: Palaniappan Subramanian

Copyright © 2023 Eveline Kuhnert et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.

During the past decades, a significant amount of excellent scientific results has been generated in the field of polymer electrolyte
membrane water electrolysis (PEMWE). Compared to current state-of-the-art technologies, PEMWE offers the opportunity to
produce green hydrogen with zero carbon emissions. However, the membrane electrode assembly (MEA), whose price is still
high for a rather limited lifetime, needs further improvement in terms of performance, cost, and durability. In order to
efficiently process novel materials, accelerated stress tests (ASTs) can be implemented to provoke and investigate cell ageing
processes and assess failure modes under real-life conditions. In this review, the different accelerated stressors of the main
components of the MEA are discussed, and recent publications of ASTs in the study of PEMWE cell durability are
summarized. Furthermore, a concise review of the degradation mechanisms for the individual MEA components depicted in
recent publications is presented. The different aspects identified in this review serve as a roadmap to further advance the
durability of novel stack materials.

1. Introduction
In the efforts to create a renewable and sustainable energy
supply chain, hydrogen plays a key role. It can be produced
from various feedstocks, stored, and efficiently transformed
back into energy through fuel cells or be used in the chemi-
cal industry. However, the current hydrogen production
(i.e., approximately 70 Mt/a) is limited compared to, for
example, the annual global energy demand in the transport
sector alone, which amounts to roughly 1012 Mt/a hydrogen
equivalent (neglecting efficiency losses) in 2020. Further-
more, the vast majority of hydrogen is produced from natu-
ral gas and coal [1]. Combined with the increasing need to
efficiently store energy from renewable sources (e.g., wind,
solar, water, and tidal), electrolysis is capable of contributing
a valuable share to filling this gap. Among the available elec-
trolysis technologies, polymer electrolyte membrane water
electrolysis (PEMWE) is –up to date– the most capable of
coping with the relatively dynamic energy supply pattern
renewable sources exhibit [2]. PEMWEs have a quoted life-
time of 60.000 to 100.000 hours [3] and can achieve current
densities of >3 A cm–2, with commercial offerings at 1–
3 A cm–2 [3–5]. Yet this relatively new and emerging tech-
nology faces several challenges. Improved understanding of
the performance, cost, and durability trade-offs under pre-
dicted future dynamic operating modes using CO2-free elec-
tricity is necessary to meet the hydrogen shot clean
hydrogen cost target of $1/kg H2 by 2030 (and an interim
target of $2/kg H2 by 2025) [6]. Furthermore, new materials
are slow to make their way into actual products, as qualifica-
tion and validation are time-consuming processes with little
harmonization in testing procedures [5]. The examination
and understanding of performance losses will become even
more critical with a shift to low-cost applications and inter-
mittent power sources [7, 8].
Another well-known key issue of PEMWE is the scalabil-
ity from microscopic phenomena in laboratory cells to stack
or system level [9]. Different measurement set-ups and cell
geometries influence the measurement results and their
reproducibility. A variety of MEA materials and preparation
2 International Journal of Energy Research
methods exist, that additionally influence their comparabil-
ity. Therefore, it is important to introduce harmonized test-
ing procedures to rate the comparability of different cell sizes
assembled with similar materials.
In PEM fuel cells (PEMFC), the reverse process of
PEMWE, accelerated stress tests (ASTs) have experienced
much attention, as they are capable of accelerating the devel-
opment and increasing the understanding of lifetime-
limiting mechanisms [7]. The principle of an AST is to apply
different degradation accelerating stressors, either via in situ
testing or ex situ measurements, to project the durability of
the whole cell or a desired component. In order to design
ASTs for PEMWE that are capable of portraying real-life rel-
evant ageing, a fundamental understanding of dominating
degradation mechanisms as well as their dependency on
stressors during operation is critical. Degradation mecha-
nisms in PEMWEs are primarily dominated by irreversible
efficiency losses. Reversible degradation has been reported
as well, although it is understood to a far lesser extent [8].
Problems related to the higher voltage in PEMWEs are per-
formance degradation and material deterioration and bring
a challenge for their durability. Prolonged use under certain
operation conditions can lower the electrochemical stability
and accelerate the degradation of the materials. The most
critical components in the PEMWE cell are represented by
the membrane electrode assembly (MEA). A typical MEA
is composed of a polymer electrolyte membrane (PEM),
two catalyst layers (CLs), a carbon-based gas diffusion layer
(GDL) on the cathode side, and a metal-based porous trans-
port layer (PTL) on the anode side of the cell. Figure 1 shows
a schematic of the components in a PEMWE cell and the
half-cell reactions at the anodic and cathodic compartment.
At the anode, the oxygen evolution reaction (OER) takes
place where water is electrochemically split into oxygen
(O2), electrons (e–), and protons (H+). These protons diffuse
through a proton-conducting membrane to the cathode side,
where they are recombined with electrons to evolve as gas-
eous hydrogen (H2). On the cathode, platinum (Pt) is pre-
dominantly used as catalyst, whereas on the anode-side
iridium (Ir) is typically used for the OER due to its relatively
high activity and stability [10–13].
PEMs, such as those used in electrolysis cells, are typi-
cally made from perfluorosulfonic acid (PFSA) polymers
such as Nafion™ with a thickness of about 100 μm. Efforts
are being made to develop cheaper and more durable mem-
branes with higher proton conductivity. However, as of now,
developments in one direction typically limit the perfor-
mance in other directions as compared to commercial mem-
branes [14]. The PTLs act as current collectors and are
located between the current collecting flow field and the
reactive sites in the CL. The GDL on the cathode side of
the catalyst coated membrane (CCM) consists of a standard
carbon cloth. On the anode side of the CCM, metallic mate-
rials like Ti-based meshes are used as PTLs due to the high
potential of the OER.
Extensive reviews of the durability and degradation
mechanisms of PEMWE cells and its components exist.
For instance, Feng et al. [8] presented a comprehensive
review on the degradation mechanisms of key components
in PEMWE and summarized the alleviating strategies.
Khatib et al. [15] recently published a summary of the deg-
radation of components in PEMWE and investigated the
effects of degradation on the overall performance of the elec-
trolyzer. Shirvanian and Berkel [16] introduced a survey of
PEMWE status and reviewed state-of-the-art components
and limitations in performance and durability. In other
recent publications, the focus was set on specific compo-
nents in the PEMWE, such as electrocatalysts [17, 18],
membranes [19–21], PTLs [22–24], and BPPs [25]. Further-
more, EU-harmonized protocols for testing of several low-
temperature water electrolysis systems are summarized in
Joint Research Centre (JRC) reports by the Fuel Cells and
Hydrogen Joint Undertaking (FCH JU) [26–29]. A summary
of some articles related to the field of PEMWE degradation
is given in Table 1.
These works provide a general overview of potential deg-
radation mechanisms and testing procedures in PEMWE;
however, to the authors’ knowledge, no comprehensive
reviews on AST strategies for PEMWE exist so far. For
PEMFCs, a technology facing similar challenges, various
AST protocols at component stack and system level have
already been reviewed [30–32]. In this review, aspects of
degradation and durability of the key components of the
PEMWE are brought in context with their individual accel-
erating conditions, aiming to gather the information neces-
sary for the qualification and evaluation of state-of-the-art
and novel materials for PEMWE. The accelerating factors
responsible for PEMWE performance decay are summarized
for the membrane, catalysts, and diffusion media (GDL and
PTL), respectively. Finally, AST protocols for lifetime pre-
diction based on the functional properties of the materials
and operational conditions are discussed for the individual
components.
2. Membrane Degradation and
Accelerated Stressors
Due to the simultaneous presence of hydrogen on one side
and pure oxygen on the other side, gas separation is critical
for the safe operation of an electrolyzer. The state-of-the-art
materials used to separate the gaseous reaction products
(oxygen and hydrogen) are PFSA-based polymer mem-
branes (Nafion™). Nafion™ comprises of a PTFE backbone
with sulfonic acid end-groups that provide protonic conduc-
tivity (Figure 2) [16]. Historically, Nafion™ membranes are
identified with a three-digit number in which the first two
digits refer to the equivalent weight and the third digit refers
to the membrane thickness in 25.4 μm-units (e.g., Nafion™
115: equivalent weight = 1100 and thickness = 127 μm).
Applying thick electrolytic membranes to PEMWE cells
improve the physical and chemical durability and reduce
safety risks in the system [33]. However, the driving needs
to reduce the overall transport resistance results in increas-
ingly thinner PFSA membranes which tend to accelerate
gas crossover in PEMWE cells [20].
Regarding long-term performance, the PFSA membrane
is the weakest component in PEMWE systems, as perfor-
mance deterioration is mostly attributed to membrane
International Journal of Energy Research 3

Membrane Carbon GDL

PTL
BPP

Anode: H2O → 2H+ + ½ O2 + 2e−

O2 out H2 out Cathode: 2H+ + 2e− → H2

Overall reaction: 2H2O → H2 + ½ O2

H2O in

Pt-Catalyst
Ir-Catalyst

Figure 1: Schematic illustration of PEM water electrolysis (PEMWE).

Table 1: Highlighted publications related to PEM water electrolyzer degradation and standardized testing.

Technology Topic Article type Ref.

PEMWE Degradation of key components Review [8, 15, 16]
PEMWE Mitigation strategies Review [8]
PEMWE Catalyst properties Review [17, 18, 21]
PEMWE Membrane properties Review [19, 20]
PEMWE Porous transport layer (PTL) properties Review [22–24]
PEMWE Bipolar plate (BPP) properties Review [25]
PEMFC Durability test protocols Review [30, 31]
PEMWE, AWE, and AEMWE EU-harmonized test procedures for water electrolysis Report [27–29]
PEMWE, AWE, and AEMWE EU-harmonized protocols for electrolyzer testing Protocol [26]

(CF2 CF2)X (CF CF2) Table 2: Reactions involving free radicals in PEM membranes [36].
N
Rate
(OCF2 CF) O (CF2 CF2) SO3–H+ # Reaction
constant
CF3 1 HO• + Rf CF2 COOH ⟶ products <106 M-1 s-1
• −7
2 H2 O2 ⟶ 2HO 1:2 · 10 s-1
Figure 2: Chemical structure of Nafion™, x∗ 6.5.
3 HO• + H2 O2 ⟶ HOO• + H2 O 2:7 · 107 M-1 s-1
4 HOO• + H2 O2 ⟶ HO• + H2 O + O2 <1 M-1 s-1
pollution or chemical degradation [8]. Apart from Nafion™, • •
5 HO + H2 ⟶ H + H2 O 4:3 · 107 M-1 s-1
a few other membranes can be used in hydrogen produc-
• •
tion processes [34]. For instance, polybenzimidazoles 6 H + O2 ⟶ HOO 1:2 · 10 10
M-1 s-1
(PBI), sulfonated polyether ether ketones (SPEEK), polyox- 7 2HOO• ⟶ H2 O2 + O2 8:6 · 105 M-1 s-1
adiazole, polysulfone (PSF), or polyimides have recently
8 Fe2+ + H2 O2 + H+ ⟶ Fe3+ + HO• + H2 O 63 M-1 s-1
been considered as cheaper and more effective alternatives
in membrane-based electrolytic systems [34].

2.1. Membrane Degradation Mechanisms. In this section, the
supposed degradation mechanisms refer to PFSA mem-
branes, unless otherwise stated. Apart from safety and oper-
ating issues, one issue that affects the stability of the
membrane and thus accelerates chemical degradation is the
crossover of gases. The crossover of product gases (hydrogen
and oxygen) can result in the formation of hydrogen perox-
ide or radicals at the catalysts [16, 35]. An overview of the
reactions involving free radicals in PEM membranes as pre-
sented by Gubler et al. [36] is given in Table 2.
The reactions 1-8 that are listed in Table 2 show that the
hydroxyl radical is the most aggressive intermediate as its
reaction with carboxylic end-groups in the main chain of
the PFSA ionomer can lead to a gradual “unzipping” of the
PFSA main chain (reaction 1) [37]. Primary sources of
HO•, which leads to the chain scission, are the slow homol-
ysis of H2O2 (reaction 2) and the Fenton reaction (reaction 8).
At high concentrations of H2O2, the “quenching of” HO•
becomes significant (reaction 3). The reaction of HOO• with
H2O2 is thus a source of HO• at high concentrations of
4 International Journal of Energy Research
Table 3: Performance of different Nafion™ membranes in PEM technology [43, 44]. The thicknesses are listed at begin of testing (BoT) and
end of testing (EoT), and the degradation rate is given in mV h–1.
Thickness BoT Thickness EoT Degradation
Operating conditions
(μm) (μm) (mV h–1)
NR211 25.4 7.5 0.26
NR212 44 14 0.18 AST under idle conditions
N115 124 78 0.09
N117 179 142 0.09
H2O2 (reaction 4). Hydrogen radicals are produced in the
reaction of H2 with HO• (reaction 5) that are further con-
verted into hydroperoxyl radicals (HOO•) in reaction 6. In
reaction 8, highly reactive hydroxyl radicals (HO•) are formed
through the produced H2O2. This reaction is also known as
the so-called Fenton’s reaction and strongly catalyzed by
Fe2+-ions [38]. If no ferrous iron-ion impurities are present,
HOO• mainly decays via disproportionation (reaction 7)
[36]. The radical attack of the perfluorinated backbone and
perfluorosulfonic side chains of the PEM can cause degrada-
tion resulting in fluoride and sulphur release and thinning of
the membrane [8]. The proposed reaction is as follows:
ðCF2 Þj COOH + 2OH• ⟶ ðCF2 Þj−1 COOH + CO2 + 2HF:
ð1Þ
In reaction 9, the carboxylic acid end-groups of the PEM
membrane react with two hydroxyl radicals. As a result, two
HF molecules are released and one CO2 and one CF2 molecule
are formed [39]. Therefore, in durability tests, the fluoride-ion
release rate (FRR) of the PEM electrolyzer exhaust can be seen
as indicator for the rate of chemical degradation of the
membrane.
Another degradation mechanism that poses a critical
safety issue is the diffusion of evolved gases (H2 and O2) in
water through the membrane to the opposite compartment
of the electrolyzer [40]. This phenomenon is driven by dif-
ferences in the dissolved gas concentrations in the liquid
water phases across the membrane [19, 40, 41].
The membrane thickness strongly correlates with the gas
crossover and therefore affects the lifetime of the electroly-
zer. Although very thin membranes offer a reduced trans-
port resistance, they cannot guarantee safe operation due
to higher diffusion of H2 and O2 through the PFSA mem-
brane. Therefore, relative thick membranes (120–200 μm)
like Nafion™ 115 and Nafion™ 117 are used in PEMWE to
avoid the crossover of gases [42]. An overview of the perfor-
mance of different PFSA membranes in respect to their
thickness from comparable PEMFC studies [43, 44] is pre-
sented in Table 3.
The major reason for the larger performance decay for
thin membranes can be explained by higher permeation
effects across the MEA. However, thicker membranes exhibit
a higher thickness loss, as they have more material to
degrade [43]. Chemical degradation processes like mem-
brane thinning or pinhole formation can increase the overall
permeation and subsequently reduce the efficiency of the
Research findings Ref.
The performance of thin membranes
[43, 44]
for 1000 h degrades much faster
PEMWE [20]. Furthermore, enhanced operation conditions
like high temperature [45–47], current density [40, 46], and
operation pressure [48–50] lead to an increase of the gas-
crossover rate. High-pressure operation results in significant
stress on the membrane, and the differential pressure in par-
ticular favors permeation. Therefore, the high-operation
pressure that is targeted in PEMWE requires the use of
thicker materials, because high pressure driven by the pres-
sure gradient increases the probability of H2 or O2 gas diffu-
sion across the membrane [14, 25, 42].
Additional stress may originate from preexisting defects
and foreign objects introduced during manufacturing or
from components such as the PTLs and current collectors.
Punctures, tears, and cracks are known to function as start-
ing points for further degradation, which inevitably result in
a reduced lifetime. In the presence of pure and usually pres-
surized oxygen, the thereby posed risk is, however, a multi-
tude higher than in, e.g., fuel cells, where typically ambient
air is fed. Even though the combustion of hydrogen and oxy-
gen is in the presence of catalyst favored over explosion in
the case of crossover between the electrodes, severe destruc-
tion of the materials can occur rapidly [51, 52]. Therefore, a
sufficient water supply to the anode is necessary to prevent
hot spots and local drying of the membrane [51].
2.2. Accelerated Stressors for Membrane Degradation
2.2.1. Hydration Conditions and Elevated Temperature.
Compared to PEMFC, where the membrane has to be
humidified by gases, the PEMWE membrane is in contact
with liquid water during the whole electrolyzer operation
[14, 19]. Several researchers found, that drying at elevated
temperatures (>100°C) has a negative impact on the pro-
tonic conductivity and the water-uptake properties of PEM
membranes [53, 54]. The water-uptake properties are
affected by the irreversible reorganization of the membrane
structure, and any decrease in water-uptake results in the
degradation of the proton conductivity [19]. During electro-
lyzer operation, the water not only functions as reactant but
also is used for cooling purposes. Consequently, water flow-
rate and temperature are important parameters that should
not be neglected. These findings agree with a study by
Selamet et al. [55], where the effect of water flowrate on
the performance of a 10-cell PEM electrolyzer stack
(100 cm−2 active area MEAs) is investigated. The PEMWE
stack is operated in a range of flowrates from 750
to1500 mL/min at 1.35 A cm−2 for 2000 hours. According
to the authors, the flowrate has no major influence on the
International Journal of Energy Research
performance of the PEM electrolyzer. However, if the flow-
rate of water is too low, the cell temperature rises uncon-
trollably, which affects the efficiency of the PEMWE.
Therefore, the flow rate is generally chosen for cooling pur-
poses at an operating current density [55]. The researchers
also tested the influence of other parameters during
PEMWE operation and found that the operating tempera-
ture is the most important factor affecting the performance.
At high operating temperatures, the activation barrier is
lowered, which results in enhanced membrane properties
like faster reaction kinetics, improved mass transport
(MT), and higher conductivity [55].
Temperatures above 90°C accelerate the rapid degrada-
tion of the membrane, and the increase of chemical degrada-
tion has reported to be directly proportional to the
temperature increase [56]. According to Kusoglu and Weber
[20], the thermal decomposition of the PFSA ionomer
occurs in three stages:
(1) Loss of (residual) water (from 100 to 200 ± 20°C),
ending with breakup of H3O+ and protonation of
SO3 to SO3H as well as partial decomposition of S
O3 H ⟶ SO2 + • OH close to 200°C
(2) Cleavage of the C–S bond (280 ± 30°C to 400 ± 20°C)
resulting in sulfonate-group degradation ending with
oxidation of the side-chain terminus, and
(3) The final decomposition (oxidation) of the perfluori-
nated matrix (400 ± 20°C to 600 ± 40°C) [20]
Therefore, PEMWE operation at higher temperatures
of above 90°C can limit the lifetime of the membrane sig-
nificantly. According to Frensch et al. [57], a temperature
increase from 60 to 80°C results in a moderate increase
of the degradation rate from 1.2 to 3.0 μV h−1, while
operating at 90°C has a significantly more detrimental
effect of 183.8 μV h−1. Furthermore, operation at elevated
temperatures significantly increases the FRR and mem-
brane thinning over time. Chandesris et al. [35] devel-
oped a model that investigates the oxygen crossover and
temperature-induced membrane degradation in PEMWE.
The authors revealed that the lifetime of an electrolyzer
cell is significantly decreased at high temperatures. Only
8.700 h operation at 353 K were necessary to thin 50%
of the membrane [35].
2.2.2. OCV. It has been reported that idle or open-circuit
voltage (OCV) conditions cause largely uniform degradation
across the MEA active area in PEMFC and accordingly lead
to near uniform thinning of the membrane [30]. Singh et al.
[58] showed that in situ hold at OCV causes chemical degra-
dation of PEMFC membranes. The results were verified via
infrared (IR) and scanning electron microscopy (SEM)
images that show that the pure chemical membrane degra-
dation proceeds generally uniform across the whole active
region of MEA. Therefore, in situ hold at OCV is the
accepted means to accelerate membrane chemical degrada-
tion of PEM cells, while the change of OCV is a useful index
to evaluate the membrane health, because the OCV
5
decreases with the increase of gas permeability caused by
membrane thinning, crack, and pinhole development [58, 59].
Cationic contamination has been reported as an accel-
erating factor for membrane degradation. While improp-
erly treated, feed water is the major cause of PEMWE
failures in this field [60, 61]. Weiß et al. [62] demon-
strated the ion exchange of metal impurities into the
membrane/ionomer phase during an OCV-AST. The cor-
rosion processes at low potentials resulted in the forma-
tion of metal cations which not only reduced the
membrane/ionomer conductivity but also increased the
high-frequency resistance (HFR) through the displacement
of protons in the ionomeric membrane [62].
2.2.3. Load Cycling and Constant Current Operation.
Another lifetime-limiting factor for membrane ageing in
PEMWE is the operating current. Chandesris et al. [35]
highlighted the impact of current density on the chemical
degradation rate in PEMWE membranes. They investigated
chemical membrane degradation in a 25 cm2 single cell set-
up at various temperatures and current densities. According
to the researchers, at low-current densities, two competing
HO• radical-consuming reactions take place: a first reaction
that requires hydrogen peroxide, and the second reaction
that accelerates the membrane attack. As the peroxide con-
centration is quite high at low current densities, the first
reaction becomes predominant, and the degradation rate is
reduced. High-current density operation results in a
decrease of the degradation rate, since the molar percentage
of oxygen at the cathode is reduced, and peroxide and free
radicals are formed [35].
These trends in low-current density operation have
also been confirmed by more recent research conducted
by Li et al. [63]. The researchers designed AST protocols
comprising of dynamic load profiles of 0–0.5 A cm−2 and
1.2–2 A cm−2, respectively. The experiments revealed that
low-current cycling had a far greater influence on the volt-
age degradation, whereas the ohmic resistance decreased
significantly during the high-load cycles, which could
imply membrane thinning and failure.
In a recent study, Fouda-Onana et al. [64] measured the
FRR as indicator for the membrane state-of-health. The
researchers performed in situ measurements of PEMWE
single cells that consisted of an alternating current profile
between 0 and 1 A cm-2. A set of electrochemical measure-
ments was performed at the end of each current sequence
to measure the performance deterioration of the cell. The
researchers additionally investigated the effect of tempera-
ture on the MEA. Therefore, the same ageing test (load
cycling between 0 and 1 A cm–2) was carried out on a
MEA at 60°C and at 80°C. The FRR shows an extremum
between 0.2 and 0.4 A cm–2. The extremum can be
explained by the mentioned competitive reaction between
radical (HO•) formations and the two reactions that con-
sume those radicals. In contrast to ageing at 60°C, ageing
at 80°C has a more severe impact on the membrane ageing
(see Table 4). The FRR shows a 5-fold increase at 80°C
compared to that one measured at 60°C (operation at
1 A cm-2). These findings indicate that the temperature has
6 International Journal of Energy Research
Table 4: Fluoride release rate (FRR) in μg (F–)/h/cm2 from the
cathode water exhaust during ageing tests at 60°C and 80°C,
adapted from [64].
0.2 A cm–2 0.4 A cm–2 1 A cm-2
°
Ageing at 60 C 0.5 0.5 0.3
Ageing at 80 C °
1.3∗ 2.2∗ 1.5∗
∗
: mean values.
much more severe effect on the membrane degradation
than the operating current [64].
Lettenmeier et al. [65] performed a study on the degra-
dation mechanisms of a commercially available 8-cell
120 cm2 stack electrolyzer. The researchers designed a proto-
col of measurements comprising of three setpoints (T1–T3).
After an initial activation for 300 h, at nominal condition
setpoint with 2 A cm−2 was applied for more than 400 h
(T1). Thereafter, the electrolyzer operated dynamically for
50 h between 2 A cm−2 and 0.15 A cm−2 (T2). At setpoint
(T3), the electrolyzer was operated at 4 A cm−2 for 250 h.
Operation at high current densities resulted in a reduction
of the ohmic drops, while longer operation gradually deacti-
vated the anode. After the test sequences, the researchers
performed ex situ measurements of the MEAs (SEM and
AFM) and water resin (XPS). The results indicate that the
loss of ionomer and catalyst material in the anode is depen-
dent on the set current [65]. Interestingly, no lowering of the
performance of the PEM electrolyzer was observed over
time, despite the degradation of the MEA components that
was reported [65].
2.2.4. Fenton’s Test. Fenton’s reagent is commonly used to
study the ex situ chemical degradation of membranes in
PEMFC research [30]. Although PEMWE is the reverse
technology of PEMFC, the degradation mechanisms of the
membrane are the same, since the state-of-the-art mem-
brane material used in both technologies is Nafion™. In gen-
eral, Fenton’s test is carried out in a solution of hydrogen
peroxide (H2O2) with ferrous iron (Fe2+ ions) as a catalyst:
Fe2+ + H2 O2 + ⟶ Fe3+ + OH• + OH− : ð2Þ
It is commonly agreed that trace Fe2+ or other contami-
nants accelerate the membrane attack in the presence of
H2O2 [38]. In practice, these metallic impurities come from
the balance of plant [8]. The interaction of Fe2+ ions with the
PEMWE system is not well documented, i.e., the ions may
cross the membrane, stay within it, or be flushed out at
one of the outlets. The radicals formed through the Fenton’s
reaction attack the membrane and produce further radicals,
such as R-CF2 in the case of Nafion™ [38]. A systematic
investigation of the degradation of Nafion™ membranes
using two variations of Fenton’s accelerated ageing experi-
ments was conducted by Kundu et al. [66]. A solution
method where Fe2+ ions and peroxide exist together in solu-
tion prior to the addition of Nafion™, and an exchange
method where Nafion™ in the Fe2+ form is exposed to
hydrogen peroxide. Figure 3 shows a comparison of the sur-
face morphologies of Nafion™ membranes after exposure to
Fenton’s reagent by two different test methods (solution and
exchange method).
A modelling framework for PEM degradation in elec-
trolysis mode was simulated by Frensch et al. [38]. The
researchers developed a Fenton model in which all major
involved electrochemical reactions were visualized. Addi-
tionally, experiments were performed that revealed a high
dependence of the FRR on the interaction of hydrogen per-
oxide and Fe impurities in the system. The iron impurities
were found to catalyze the reaction, while hydrogen peroxide
is necessary for the formation of destructive hydroxyl radi-
cals [38]. Further studies showed that Fenton-like metal
catalysts can replace Fe2+ ions to produce OH• radicals
[67, 68]. Laconti et al. [69] proposed an order for the rate
of chemical degradation caused by common contaminants:
Fe2+ > > Cu2+ > > TiO2+ > Co2+ > Pt2+ > Ni2+, where Fe2+
has the highest impact on the degradation rate and Ni2+
the lowest. In state-of-the-art PEMWE cells, titanium is the
material of choice for anodic components such as BPPs
and PTL [38].
2.3. Summary Membrane Degradation. The Nafion™ mem-
brane represents a core component of the MEA. Membrane
failure is mainly accelerated by undesirable operation condi-
tions such as high temperature, OCV, and mechanical stress
and results in changes of thickness (membrane thinning)
and the formation of defects (e.g., cracks or perforation).
The deterioration of these parameters can be measured as
a result of the FRR, voltage drop, or changes in the HFR in
membrane specific failure analysis [59]. An overview of
membrane failure in lifetime tests is given in Table 5.
Other AST strategies than the experiments presented in
Table 5 exist focus on the mechanical degradation of the
membrane. For instance, Borgardt et al. [70] tested the influ-
ence of the clamping pressure on the performance of differ-
ent PEMWE cell designs. To minimize the negative impact
of membrane degradation on the cell performance, novel
approaches like the reinforcement or modification of mem-
branes exist. Although the reduction of membrane thickness
in PEMWE is an important route to achieve proper effi-
ciency at high-current density, thinner membranes can
bring the risk of an increase of gas crossover and therefore
compromise the mechanical stability of the MEA. Recently,
Siracusano et al. [71] demonstrated a reinforced short-side-
chain PTFE-based membrane that enables stable electrolysis
operation at 4 A cm−2. Still, at the present stage, novel mate-
rials to replace PFSA membranes need to undergo durability
studies for the evaluation of their long-term performance.
3. Catalyst Degradation and
Accelerated Stressors
The harsh operation conditions, especially at the anodic
side of the PEMWE, limit the choice of electrocatalysts to
a small range of precious metal compounds. For monome-
tallic catalysts during the OER, a link between the activity
and stability has been established in which the most active
oxides (Au ≪ Pt < Ir < Ru ≪ Os) show the lowest stability
International Journal of Energy Research 7

100 𝜇m 100 𝜇m

(a) (b)

Figure 3: Surface morphology of Nafion™ membranes subjected to Fenton’s reagent ASTs via (a) solution method 100x magnification and
(b) exchange method 100x magnification. Reprinted from [66] with permission from Elsevier.

Table 5: Summary of ASTs for the evaluation of PEMWE membrane stability.

AST mode Operating conditions Research findings Ref.

Ex situ degradation Fenton’s reagent
Ex situ degradation Fenton’s reagent
Feed water flowrate between 750
Hydration conditions
and 1500 sccm
Operation at 1 A cm−2 for 80.700 h Membrane chemical degradation (fluoride emission and membrane
Thermal stress
at 353 K and for 380.500 h at 333 K
Cycling between OCV and operating
OCV-AST
potentials (up to 3 A cm−2)
Load cycling Current between 0 and 2 A cm−2
Dynamic load of 0–0.5 A cm−2 and
Load cycling
1.2–2 A cm-2 for 350 h
Constant current of 2 A cm−2 for 400 h High current density operation has no immediate negative effect
Constant current
and 4 A cm−2 for 250 h
Simulation of different constant current
High constant current −2
densities up to 10 A cm
Membrane weight loss over the testing time was over 20% of
[66]
the original weight and accompanied by fluoride release
The fluoride emission is highly dependent on the iron
[38]
concentration, which catalyzes the reaction
The water flowrate indirectly influences the performance because
[55]
it is also used for cooling purposes in the system
[35]
thinning) is strongly affected by the operating temperature
Cationic contamination of the membrane is a possible reason
[62]
for the increase of the high-frequency resistance (HFR)
The temperature was found to have a more critical effect
on the membrane degradation compared to the current [64]
density in PEMWE operation
Dynamic conditions may lower the cell performance by
[63]
accelerated membrane thinning effects
[65]
on the cell performance, although MEA components degrade
The current density has a minor effect on the degradation
rate. It follows a complex mechanism, and a maximum [35]
degradation rate is observed at quite low-current densities

(Au ≫ Pt > Ir > Ru ≫ Os) [61]. Therefore, the most popular
materials that are currently used for the OER in commer-
cial anodes are Ir-based and Ru-based electrocatalysts
[10–12, 72]. For the hydrogen-evolution reaction (HER)
that occurs on the cathode side of the PEMWE, carbon-
supported platinum (Pt/C) is recognized as the state-of-
the-art material [16]. The performance of the catalysts is
largely credited to the morphology, particle size, crystal
structure, and substrate materials [5]. Various material
combinations have been tested, especially for the OER to
reduce the amount of catalyst loading and enhance the sta-
bility of the materials. In this review, the focus is set on cat-
alysts that comprise of Pt-based metals as cathode and IrOx
as anode catalysts.
3.1. Catalyst Degradation Mechanisms. Catalyst degradation
occurs on both anode and cathode catalysts, whereas the fast
kinetics of the HER on widely used Pt catalysts in PEMWE
cathodes allow loading reduction down to 0.025 mg cm−2
and have a minor impact on the performance [73]. There-
fore, the main challenge remains the stability of the anode
catalyst. According to Spöri et al. [74], the degradation of
the CLs during the harsh PEMWE operating conditions
includes catalyst dissolution, catalyst migration and agglom-
eration, CL detachment, and support passivation [74]. Cata-
lyst degradation can also be related to the instability of the
PFSA membrane and PTLs. During long-term electrolyzer
operation, the instability of the PFSA-membrane highly
affects the anode and cathode CLs. Grigoriev et al. [60]
8 International Journal of Energy Research
reported membrane thinning during PEMWE long-term
operation as a result of interactions with oxidizing species
formed at the electrodes. The stability issue of the PTLs
has also been studied. According to Rakousky et al. [75],
the Ti in the PTL corrodes and causes contamination of
the anode CL, leading to a decrease in the anodic exchange
current density. In addition, a low-conductive Ti-oxide layer
is formed between the anode and the PTL that increases the
ohmic resistance of the cell [75, 76]. Other mechanisms for
catalyst degradation are related to mechanical damage (i.e.,
uneven contact pressure or improper membrane swelling).
For instance, bubble formation on the catalyst surface is
reported to induce particle loss or layer detachment and dis-
ruption of the catalyst-membrane interface [8].
3.1.1. Catalyst Agglomeration and Migration. Nanoparticles
(NPs) tend to agglomerate into bigger particles with respect
to time due to their high-specific surface energy [8, 15]. As a
result, the active catalyst area available for the electrochem-
ical reaction is reduced, resulting in a decrease of the
catalytic activity [77]. The interaction between catalyst
nanoparticles (NPs) is a common phenomenon in PEMFC,
and there are several mechanisms that are believed to drive
the Pt surface area loss with time: (i) coalescence via crystal
migration, (ii) growth via modified Ostwald ripening, and
(iii) reprecipitation at other nucleation sites [74, 78]. These
particle growth mechanisms may also be applied to
PEMWE, because changes in the morphology of the CLs like
migration, agglomeration, coalescence, or detachment of
catalyst NPs have been reported at the cathode and anode
during the long-term operation of PEMWE cells [8, 15,
79]. For instance, IrOx agglomeration is accelerated under
harsh operation conditions and contributes to the drop of
mass activity toward the OER [79]. Paciok et al. [80] showed
that the migration of Pt particles is correlated to the applied
overpotential at the cathode. In their study, XPS analysis
revealed that with a more negative overpotential, the hydro-
gen coverage rate of the Pt particles increases, which results
in a bigger gap between the Pt particles and the carbon sup-
port. Thus, the weakened Van der Waals forces allow an
increase of the mobility of Pt particles, which further results
in their agglomeration [80].
Yu et al. [81] confirmed that catalysts undergo degra-
dation through agglomeration during the long-term opera-
tion of PEMWE. Pt was profiled via EDX mapping, and
the results show the particle agglomeration and shape
transformation from spherical to dendritic. Additionally,
Claudel et al. [79] revealed that simulated PEMWE anode
operating conditions result in a loss of OER activity due to
the growth of catalyst particles and oxidation of species
along with the decrease in the number of individual NPs
concomitantly [79].
3.1.2. Dissolution of IrOx. Regardless of its high activity, dis-
solution of IrOx during the OER has been reported [82–84].
The dissolution rate enhances with an increase of potential,
and stable IrO2 starts to dilute at approximately 1.8 V [8].
Cherevko et al. [85] assume that dissolution processes at
high potentials are a consequence of the formation of one
Oxygen evolution Dissolution
½ O2 IrO2OH HIrO2 Ir(III)
Slow IrO2 (hydr.) Fast
Figure 4: Possible pathways of iridium dissolution during the
oxygen evolution reaction (OER) proposed by Cherevko et al. [85].
or several unstable Ir(III) complexes which rapidly dissolve
in an electrochemical process. The tentative mechanism, as
reported by the authors, is represented in the following
chemical reactions:
2IrO2 ðOHÞ + 2H2 O ⟶ 2IrðOHÞ3 + O2 ,
ð3Þ
2IrO2 ðOHÞ ⟶ 2HIrO2 :
The suggested mechanism for the OER is shown in
Figure 4. The whole pathway for the second reaction can
be rewritten as following:
HIrO2 ⟶ IrO2 + H+ + e− ,
IrO2 + H2 O ⟶ IrO2 ðOHÞ + H+ + e− , ð4Þ
2IrO2 ðOHÞ ⟶ 2HIrO2 + O2 :
Degradation of IrOx through the evolution of oxygen
from the lattice strongly depends on the structure and
morphology of the electrocatalyst [86]. While crystalline,
rutile-type iridium oxides are metallic conductors with a
high degree of stoichiometry; their amorphous counter-
parts are permeable to water and more vulnerable to cor-
rosion in the OER potential region [86, 87]. Kasian et al.
[83] found that lattice oxygen evolution may occur in both
materials; however, amorphous hydrous IrOx exhibits a
higher number of defects, and the porosity and the pres-
ence of -Ir(III)OOH- groups in the CL increase the prob-
ability of the formation of molecular oxygen from the
lattice and the dissolution of catalyst [83].
3.2. Accelerated Stressors for Catalyst Degradation
3.2.1. Start-Up/Shut-Down Cycling and OCV. Factors such as
operational currents and the frequency of changes in load,
temperature, and pressure make real-world operation of
PEMWEs challenging [88]. Many stressors are involved,
and coupling effects make it difficult to distinguish between
their impacts on material degradation [89]. According to
recent studies, AST profiles for the investigation of PEMWE
catalyst durability frequently mimic operation from renew-
able energy, like wind, solar, or water sources. In this case,
the fluctuating power supply results in PEMWE operation
between periods of hydrogen generation, when power is
available, and idle periods, where no electricity is supplied
(OCV) [73]. For instance, Weiß et al. [62] evaluated the cat-
alyst stability for such realistic operating conditions. The
International Journal of Energy Research
3 operation of a PEMWE for the first time. The researchers
3 A.cm–2geo.
i (A.cm–2geo.)
2
1 152 ng cm−2 or 0.005% of the total catalyst loading was lost
0.1 A.cm–2geo.
0 dynamic operation was observed by Alia et al. [90]. The
OCV-AST
Reference test
(a)
1.5
Ecell (V)
1.0
0.5
0.0
0 5 10 15 20
t (min)
OCV-AST
Reference test
(b)
Figure 5: Accelerated stress test (AST) profile imitating an
intermittent power supply during PEMWE. Current profiles (a)
and associated potential profiles (b) at 80°C during the first cycle
of the OCV-test. Adapted from [62] (CC BY 4.0).
proposed test protocol is shown in Figure 5. According to
the researchers, an AST that cycles between OCV and oper-
ating potential has a much severe effect on the degradation
rate compared to experiments where no OCV periods are
applied.
The study also revealed that IrOx can easily be reduced
to metallic Ir when IrOx-based MEAs are held at OCV.
Crossover H2 from the cathode side between ∼0 V and
∼1.6 V during the OCV-AST reduces the surface of the IrOx
catalyst at the anode to a state closer to less stable hydrous
IrOx [62]. Considering that hydrous IrOx is much more
likely to corrode in the OER potential region compared to
dry, crystalline IrOx, these results represent a critical degra-
dation mechanism in the study of PEMWE [86].
These findings are supported by a recent study con-
ducted by Rheinländer et al. [86]. The researchers have
tested events similar to operation interrupts in a PEMWE
cell at 80°C. The AST profile consisted of three steps: in
the first step, the cathode pressure was set to 5.5 bara and
a current of 1 A cm−2 was applied. In the second step, the
operation was interrupted by switching off the power supply,
waterflow, and cell heating on the anode side. In the third
step, the cell was held at OCV for 2 h in a transient period.
After these steps, the cell was restarted [86]. Dodwell et al.
9
[88] reported open-circuit Pt dissolution during intermittent
found that the underlying mechanism of Pt dissolution at
the cathode is similar to cathode degradation in PEMFCs,
where the passivation of catalyst surfaces gradually hinders
the Pt dissolution process. During a 90 h OCV, hold test
[88] in their study.
0 A.cm–2geo.
The effect of CL degradation at low catalyst loading and
researchers analyzed various test variables including the
stressor pattern/severity, the cycling frequency, and potential
ramping [90].
The dynamic operation leads to thinning of the Ir CLs
which significantly contributed to the overall durability loss
[90]. Life tests of an electrolysis cell that were carried out
by Grigoriev et al. [60] showed that current reversals can
occur during shut-down procedures in PEMWE. In these
shut-down periods, operation in FC mode is possible by
the consumption of the remaining electrolysis gases (H2
and O2). Consequently, Pt may be carried away from the
cathodic electrocatalytic layer into the membrane. The
decreased Pt concentration and the loss of cohesion of Pt
25 30 NPs result in a lowered activity of the cathodic CL. Besides
Pt, several other contaminants (Ti, Ir, Fe, Ni, and Si) from
feed water or, e.g., the corrosion of pipes that have lower
mobility compared to hydrogen is deposited in the mem-
brane’s near-cathode region, leading to an increase of the
electrolysis potential over the course of durability tests [60].
3.2.2. Load Cycling and Constant Current Operation. The
effect of constant current operation and load cycling on
catalyst degradation in PEMWE was studied by Rakousky
et al. [91]. The researchers investigated a PEMWE cell at
80°C and found that high-static current densities (up to
3 A cm−2) resulted in the largest performance losses.
Siracusano et al. [92] investigated PEMWE catalyst dissolu-
tion at high-current densities. Galvanostatic operation at
1 A cm−2 leads to a quite low-degradation rate of 5 μV h−1,
whereas operation at 3 A cm−2 caused a three-fold higher
degradation rate of 15 μV h−1 [92]. In particular, the anodic
dissolution of IrOx has been reported at high current den-
sities [14, 17, 30]. A case study involving anode dissolution
has been performed by Grigoriev et al. [93]. In order to
maintain a higher cell voltage and anode potential in their
degradation study, Pt was used as the electrocatalyst at both
anode and cathode CL. The researchers found that a corro-
sion process in the CL is the first MEA degradation mech-
anism followed by thinning of the Nafion™ membrane.
After 100 h of activation the current density was set to
1 A cm−2; afterwards, on/off galvanostatic cycles (between
0 and 1 A cm−2) for approximately 5500 h of operation were
applied. Additionally, SEM, TEM, and EDX analyses were
performed to detect the observed performance decay.
TEM pictures representing cross-sections of the anodic area
after the experiments are shown in Figure 6. The results
indicate that the dissolution and precipitation of anode cat-
alyst particles have a major impact on to the overall degra-
dation of the cell performance [93].
10
(a)
Figure 6: TEM micrographs of the cross-sectioned MEA 5500 h operation between 0 and 1 A cm . A 5 μm thick Pt layer is visible on (a). A
clear representation of Pt particles on the micrograph is presented in (b). Adapted from [93] with permission from Elsevier.
3.2.3. Potential Cycling. Potential cycling as an AST in
PEMWE durability studies has been analyzed by Brightman
et al. [94]. The researchers used a reference electrode to
study the catalyst degradation in an operating PEMWE.
The results revealed that the cathode contributes more to
changes in OCV than the anode during shut-down cycling.
The researchers also demonstrated that potential cycling
has a more severe effect on the catalyst durability than cur-
rent cycling. The Pt surface area barely decreased during
the current cycling procedure, whereas a significant loss of
the ECSA (electrochemically active surface area) was
observed during potential cycling. Therefore, potential
cycling can be considered as a useful AST for the evaluation
of catalyst stability in Pt-based cathode CLs in PEMWE [94].
In a recent study, Spöri et al. [95] presented a transient
ADT (accelerated degradation test) protocol for RDE tests
that consist of potential square-wave cycles between 0.05
and 2 V. Additionally, the researchers ran static CA (chron-
oamperometric) tests at the same potentials for comparison
reasons. A much higher electrode potential dependence of
catalyst dissolution was observed during the transient ADT
protocols compared to the static CA protocols [95]. In order
to verify the proposed ADTs for their applicability in
PEMWE systems, the researchers also ran PEMWE single
cell tests. Therefore, CCMs were subjected to (i) 24 h poten-
tiostatic operation at 1.75 V; (CCM-CA), (ii) 24 h power
cycling between 0 A cm−2 and a potential of 1.75 V (CCM-
PC), and (iii) 15.000 cycles between 0 and 1.75 V (CCM-
ADT) [95]. Figure 7 represents the ADT protocols (i)–(iii)
and the polarization curve during (iii) [95]. According to
Spöri et al. [95], transient fast potential cycling and static
International Journal of Energy Research
(b)
−2
experiments have a lower impact on the degradation in
single cell PEMWE measurements compared to the RDE
measurements in their study. This might be due to the
higher temperature of 80°C in CCM vs. ∼25°C in RDE
experiments and higher catalyst loading in CCMs. Still,
the researchers observed a higher degree of mass-activity
losses in transient compared to static CCM measurements.
Additionally, the results imply that static constant current
or constant potential stability measurements (CCM-CA)
are insufficient to test the catalyst stability of state-of-
the-art PEMWE applications [95].
3.2.4. Cationic Contamination. The accumulation of metallic
cations like Fe3+ [96], Cu2+ and Al3+ [97], Ca2+ [98], and
Na+ [99] in the MEA can range from being a contributing
factor to being the dominating mechanism in PEM electrol-
ysis performance degradation. The foreign cationic impuri-
ties may originate from impurities in stack component
materials, impurities of feed water, and other sources [96,
100]. According to Cheng et al. [100], even trace amounts
of impurities present in either fuel or air streams of PEMFCs
can have a severely poisoning effect on MEA components,
including the anode and cathode CL [100]. This effect is
anticipated to be identical, if not more severe in electrolyzer
operation if impurities enter the stack with the feed water.
The distribution of dissolved contaminants is promoted by
the over stoichiometric feed rate (λ > 4) of liquid water
[101] in PEMWE. Cationic contamination from Fe3+,
Cu2+, and Al3+ has been reported as a result from degrada-
tion of materials and corrosion of pipes in the system [96,
97]. Li et al. [102] investigated the effect of long-term
International Journal of Energy Research 11

2.0 1.90

1.9 1.85
1.80
1.8
1.75
1.7 1.70
1.6 1.65
1.60
1.5
1.55
1.4 1.50
1.3 1.45
1.40
1.2
0 2 4 6 8 10 12 14 16 18 20 22 24
t (h)

Ecell

(a)
2.00 1.90
1.75 1.85
1.80
1.50
1.75
1.25 1.70
1.00 1.65
0.75 1.60
1.55
0.50
1.50
0.25 1.45
0.00 1.40
40 41 42 43 44 45 46
t (min)

Ecell

(b)
2.0 2.00

1.5 1.75

1.0 1.50

0.5 1.25

0.0 1.00

–0.5 0.75

–1.0 0.50

–1.5 0.25

–2.0 0.00
2535 2540 2545 2550 2555 2560
t (s)

Ecell

(c)

Figure 7: Continued.
12 International Journal of Energy Research

2.1
Standard loading CCM - NR-212 - 1.69 mglr cm–2
2.0 ADT 0.0 V - 1.75 V
Ecell: closed symbols
EiR: open symbols
1.9

1.8

Ecell (V)
1.7

1.6

1.5

1.4
0.0 0.5 1.0 1.5 2.0 2.5 3.0
jgeo. (A cm ) –2

2.5k 10.0k
5.0k 12.5k
7.5k 15.0k
(d)

Figure 7: Current voltage characteristics of the three ADT protocols: (a) CCM-CA, (b) CCM-PC, and (c) CCM-ADT with the
corresponding polarization curve (d). Reprinted from [95] (CC BY 4.0).

H+available H+ depleted region of CCL

½O2 + 2H+ + 2e− → H2O C + 2H2O → CO2 + 4H+ + 4e−

½ O2 + 2H+ + 2e− → H2O

Proton occupancy (𝛾H+)

Pt
Pt Ca2+
H+ H+ Ca2+
Pt Pt Pt
Pt Pt C
C Pt
H+ H+ Pt
Pt Pt C
Pt Pt
Ca2+ Pt Pt
Ca2+ Ca2+
+ + +
H H H
2+ Pt + Ca2+
Ca H
Pt Pt Pt
C
Pt Pt
C
Pt Pt
Pt Pt

PEM GDL →
0.0 Normalized distance from membrane 1.0

Figure 8: Hypothesized carbon corrosion process of the cathode CL in a PEMFC.

contamination with iron ions on the performance of a and associated performance breakdown can already occur
PEMWE single cell. The researchers observed a significant at low concentrations of 3 ppm Al3+ on the cathode side
performance decay in which the degradation rate reached [97]. Cathode CL thinning due to the accumulation of
to 128.9 μV h−1 after the 829 h contamination test [102]. In Ca2+ ions in PEMFC cells has been investigated by Banas
a more recent publication, Li et al. [97] investigated the effect et al. [103]. Results showed that the accumulation of Ca2+
of further cationic impurities (Fe3+, Cu2+, and Al3+ ions) in ions can lead to proton depletion in the cathode CL [97,
single PEMWE cells and found that all impurity ions have 103]. As a result, carbon corrosion can occur, which then
a severe impact on the cell performance. Cell poisoning accelerates cathode CL thinning (Figure 8) [97].
International Journal of Energy Research
As shown in Figure 8, foreign cations accumulate in the
cathode side due to the balance of migration and diffusion.
Lack of proton access accelerates the carbon corrosion [97].
On the cathode CL, the same state-of-the-art materials are
used in PEMWE and PEMFC cells. Therefore, the effect
of cationic impurities on the performance of the PEMWE
cell is expected to be even more detrimental due to the
higher potentials [97]. The contamination effect of Na+
on PEMWE has been studied by Zhang et al. [104]. Differ-
ent poisoning modes (anode poisoning and cathode poi-
soning) were compared, and the results imply that Na+
poisoning has a more severe effect on the anodic than on
the cathodic cell components. In the experiments, the
anode potential increased by about 0.160 V because protons
were replaced by Na+ ions at the anode and membrane
with increasing cell voltage. At the cathode, the potential
decreased with decreasing proton concentration [104].
Generally, reactions (5) and (6) occur at anode and cathode
in PEMWE systems. However, if there are not enough pro-
tons for reaction (6), the reaction (7) takes place at the
cathode. As a result, the cathode potential declines signifi-
cantly due to the lack of protons. Additionally, Na+ ions
and OH− can enter the feed water, which increases the
pH at the cathode compartment [104].
Anode : H2 O ⟶ 2H+ + ½O2 + 2e−  φ0 = 1:229 V,
ð5Þ
Cathode : 2H+ + 2e− ⟶ H2  φ0 = 0:000 V, ð6Þ
Cathode : 2H2 O + 2e− ⟶ H2 + 2OH−  φ0 = −0:828 V:
ð7Þ
3.3. Summary Catalyst Degradation. The main failure
modes for catalyst degradation, primarily OCV, dynamic
operation, load cycling, and cationic contamination can be
identified by various AST methods. Considering the fact
that during the lifetime of an electrolyzer operation inter-
rupts can be expected to occur frequently, AST profiles that
represent realistic operation conditions are needed. In
Table 6 a summary of lifetime tests for PEMWE catalysts,
including test protocols simulating an intermittent power
supply, are presented.
Coupling of an electrolyzer unit with fluctuating renew-
able energy sources results in intermittent operation with
idle periods when no power is available and hydrogen gener-
ation, when enough current is supplied [62]. This recurring
transition between reducing and oxidizing conditions signif-
icantly affects the performance of the PEMWE system [62].
According to the currently understood decay mechanisms,
the sluggish kinetics and instability of the OER catalyst
materials constitute an obstacle toward commercialization
of PEMWE technology [16]. Therefore, current research
focuses on lowering the Ir loading and improving the degra-
dation resistance [105–107]. In particular, understanding the
degradation mechanism on the catalyst surface during OER
is a cornerstone in the development of novel catalysts for
13
PEMWE, since the state-of-the-art Ir-based anode materials
are still affected by the harsh reaction environment [108].
4. PTL/GDL Degradation and
Accelerated Stressors
In PEMFCs, usually carbon materials are used as current
collectors on anode and cathode side (GDL). Due to the
harsh conditions on the anode in PEMWEs, carbon mate-
rials are in most cases only used on the cathode, where
hydrogen is formed. The carbon corrosion and consumption
due to the high potential of the oxygen electrode result in the
rapid deterioration of interfacial contact, which has a major
impact on the performance and efficiency of the cell [109].
Therefore, metallic materials like Ti-based meshes, foams,
or sintered powders are usually used as PTLs at the anode
side of the electrolyzer. In this section, the term “GDL” is
used for the material on the cathode side, and the term
“PTL” is used for the material on the anode side of the elec-
trolyzer. In a recent review, Doan et al. [22] summarized
some of the state-of-the-art PTL and GDL materials used
in PEM technology (Table 7).
Currently, only a limited number of studies have focused
on the lifetime-limiting factors for the carbon-based GDL
and even less for the Ti-PTL on the anode side of the
PEMWE [30]. PTL/GDL degradation can generally be
divided into two groups: on the one hand, chemical degrada-
tion that is mainly caused by corrosion and on the other
hand, mechanical degradation that in most cases originates
from compression force, dissolution, and erosion by hydro-
thermal effects [8].
4.1. Gas Diffusion Layer Degradation Mechanisms. The GDL
is placed on the cathode side of the CCM between the cur-
rent collecting flow field and the reactive sites of the Pt cat-
alyst. It provides mechanical support to the MEA and is
responsible for the electron and gas transport to and from
the CL with minimum voltage, current, thermal, interfacial,
and fluidic losses [89]. Mechanical stress that results from
the high compression of the cell components strongly affects
the physical properties of the GDL. Carbon fibers can break
or even be displaced under compression, which can change
the structure morphology, and affect the current transport
and permeability of reactants [8, 122]. As a result, the
obstruction of diffusion pathways can lead to ineffective
gas transport or saturation of the pores, decreasing the over-
all performance of the cell [8]. Compared to the anode com-
partment, the cathodic overpotential (approximately 0.1 V
SHE) is insufficient to cause rapid carbon corrosion of the
GDL. Although carbon-based GDLs are used in the cathode
side of the cell, further research is needed to gain a better
understanding of the performance of these materials under
real-life conditions over time [14].
4.1.1. Accelerated Stressors for Gas Diffusion Layer
Degradation. In PEMFC research, various AST protocols
exist, targeting for instance the chemical or mechanical deg-
radation of the GDLs [123]. GDL degradation can occur
rapidly under accelerated conditions like immersion in
 14

Table 6: Summary of ASTs for the evaluation of PEMWE catalyst stability.

AST mode Operating conditions Research findings Ref.

Cycling between OCV and operating potentials leads to Ir dissolution
OCV-AST Cycling between OCV and operating potentials (up to 3 A cm−2) [62]
and an increased contact resistance between the electrode and the PTL
Succession of on/off galvanostatic cycles (ranging between 0 A corrosion process in the CL is the first MEA degradation mechanism
OCV-AST [93]
and 1 A cm−2) followed by thinning of the Nafion™ membrane
5 cm−2 electrolyzer is switched from average duty point Operation transients during PEMWE can induce conversion of IrO2 in
OCV-AST [86]
(1 A cm−2) to idle mode (OCV) the anode CL into a more hydrous form
−2
1 h 1 A cm pre-OCV followed by OCV for 72 h and 1 h During operation, the Pt dissolution is constant, whereas at idle periods,
OCV hold test [88]
operation at 1 A cm−2 post-OCV the Pt dissolution depends on the potential and duration of OCV
4000 h life tests (6 h operation everyday (shut-down over night When the electrolysis cell is switched off, current reversal and operation
Shut-down procedures [60]
and for weekends and holidays) in FC mode can cause degradation of the cathode CL
Evaluation of various stressor profiles (potential hold, triangle/ Less severe performance losses are reported for wind and solar AST
Dynamic operation [90]
square wave, and Sawtooth up/down profiles) models compared to triangle and square-wave potential cycling
2 A cm−2 up to 1100 h, 2.5 A cm−2 up to 1450 h, and 3 A cm−2 The performance stability is independent on the operation mode—there
High and elevated current [91]
up to 1940 h is no difference between constant and dynamic current density operation
Cell operation at 3 A cm−2 shows three times increase of corrosion rate
Constant current Operation at 3 A cm−2 for 1000 h [92]
compared to operation at 1 A cm−2
1000 square-wave cycles with a 30 s hold a period between Potential cycling is a more severe test of catalyst durability than current
Potential cycling [94]
1.75 V and 0.3 V cycling
An enhanced electrode potential dependence of catalyst dissolution was
Transient operation Square-wave cycles between 0.05 V and 2 V [95]
observed in transient compared to static ADT protocols
+
Anode poisoning: 1000 mL 0.05 mol L−1 Na2SO4 to anode and Na contaminants in the anode compartment have more severe effects
Na+ contamination 1000 mL DI water to cathode; operation at 0.5 A cm−2 on the cell performance than the contamination of cathode feed in [104]
(cathode poisoning v. v.) PEMWE
2+ Soaking PEMFC CCMs in cationic solution of 0.9 mM of CaSO4 Contaminated CCM had significant and uniform CL thinning caused by
Ca contamination in PEMFC [103]
and 29.1 mM of H2SO4 carbon mass loss by a carbon oxidation mechanism
3+ Solution containing 1 ppm Fe3+ fed to a single cell for ~800 h at
Fe contamination The cell performance degrades severely with 1 ppm Fe3+ contamination [102]
0.5 A cm−2
Fe3+ ions have a higher degrading effect than Cu2+ ions. Al3+ ion
Contaminated feed solution containing 5 ppm of Fe2(SO4)3,
Fe3+, Cu2+, and Al3+ contaminations poisoning results in severe cathode CL degradation even at low [97]
CuSO4, or Al2(SO4)3 in DI water, respectively
concentration of 3 ppm
International Journal of Energy Research
International Journal of Energy Research
Table 7: Summary of some PTL/GDL materials used in PEM
technology [22].
PTL/GDL material PEMWE PEMFC
Titanium material
Iridium coated PTL [110]
Titanium powder [111–113]
Titanium fiber [112]
Titanium felt [114]
Carbon material
Carbon cloth [115, 116]
Carbon fiber paper [115, 117]
Carbon felt [115]
IrO2 deposited on carbon paper [118]
Other metals material
Stainless steel [119]
Copper foil [119–121]
H2O2 solution or subjection to cyclic or static compression
tests. H2O2 is a strong oxidizing agent and can cause severe
degradation across most PEMWE components. Several stud-
ies have reported GDL performance loss after H2O2 immer-
sion tests, and the MPL was found to be even more open to
attack from the oxidizing species [124, 125]. For instance,
Liu et al. [125] performed a carbon corrosion test in H2O2
solution and analyzed the effect of a MPL on commercial
carbon-based GDLs. For a pristine GDL with MPL at
2.5 A cm−2, the potential decreased by 59% and an increased
water content of up to 44% was observed [125].
The GDL is the component with the highest porosity in
the PEMWE, and its cellular structure leaves it vulnerable to
structural changes and permanent degradation under
mechanical stress [123, 126]. In the study of Chun et al.
[127], the mechanical durability of different GDLs with
commercial and home-made crack-free MPL has been tested
in a dummy cell without CL and only air supply to avoid
electrochemical degradation. The results imply that the
mechanical degradation during long-term operation can be
significantly reduced by the preparation of crack-free MPL
[127]. Dotelli et al. [128] investigated the effect of compres-
sion pressure on the GDL, when the assembly of GDLs and
CCMs was compressed to 30% and 50% of its initial thick-
ness. The higher compression ratio at 50% resulted in a
reduced cell performance. This effect was partially mitigated
when the operating temperature was raised to 80°C. The
presence of the MPL in the carbon cloth resulted in a
reduced contact resistance and therefore proved extremely
beneficial for the operations, especially at high current den-
sity [128]. Radhakrishnan and Haridoss [129] performed
five compression cycles on a Toray carbon paper GDL at
two different pressure setpoints (1.4 MPa and 3.4 MPa).
The cyclic compression experiments resulted in changes in
the structure like cracks of fibers and a decreased porosity
and hydrophobicity. Furthermore, a gradual loss of PTFE
was observed in course of the experiments. The elevated
15
pressure experiments at 3.4 MPa showed a more severe effect
during the initial cycles [123, 129].
4.2. Porous Transport Layer Degradation Mechanisms. The
PTL, which is located between the anode CL and flow
field, is responsible for the transport of the reactant water
and removal of the produced oxygen gas in the PEMWE
cell. Furthermore, it acts as a current collector to ensure
stable electrochemical performance [24]. Generally, mate-
rials like Ti powders, foams, films, or meshes are used as
PTL in PEMWE cells [130]. The metal-based PTLs can
undergo hydrogen embrittlement or surface passivation
and are therefore often coated with precious metals such
as platinum or gold with obvious effects on the capital
costs. The resistance for hydrogen embrittlement is given
by Lu and Srinivasan [131] and follows the following
order Ti = Ta > Nb > Zr > graphite (with Ti and Ta being
the most prone to hydrogen embrittlement and graphite
as the least) [131].
PTL properties like surface roughness have lately
received much attention because of the effect on the Ir-
based anode CL which is in close contact with the PTL mate-
rial [22]. The formation and growth of oxygen bubbles
inside the PTL pores of the anode of a PEMWE cell can
block active catalyst sites and decrease the effective ECSA.
Approaches exist which aim to reduce the MT losses by
modification of the PTL morphology to decrease the number
of coalescence host sites [132]. The choice of PTL material
influences the performance of PEMWE, for example, for sin-
tered Ti powder, the morphology and surface properties can
be the most important factors, while porosity is the most
important factor for thin/tunable Ti films (TT PTL) [24].
4.2.1. Accelerated Stressors for Porous Transport Layer
Degradation. Borgardt et al. [111] investigated the effect of
pressure on the mechanical properties of Ti PTLs. In situ
and ex situ durability tests were carried out on PTLs made
from two differently shaped powders. Samples made of
spherical powder were in a porosity range of 10–33%, while
samples of irregular-shaped powder were in the range of 10–
55%. According to the researchers, high porosity and thin
thickness lower the physical stability of the PTL but exhibit
high durability under high pressure. Furthermore, a porosity
of at least 25% and 500 μm thickness enabled the PTL to
resist 50 bar differential pressure [111]. Pushkarev et al.
[133] investigated MEA combinations of different PTLs in
PEMWE single cells. The PTL structure had only a minor
impact on the activation and ohmic overpotential. However,
at current densities of 2 A cm−2 and higher, structure-
dependent MT losses were reduced due to the higher volume
of void phase and flow pore size. According to the
researchers, PTLs with low porosity and small pore size
could be responsible for MT limitations due to the worsened
contact between the flow field channels and the PTL. In
Figure 9, two SEM images of PTLs with different bulk poros-
ities tested in this study are shown [133].
Passivation that has been reported on the anode side of
the PEMWE for Ti-based BPPs will also influence the Ti-
PTL if not coated with a protective layer [89]. A study
16
(a)
Figure 9: Initial SEM images of a PTL with bulk porosity of 51.9% (a) and 25.4% (b). Reprinted from [133] with permission from Elsevier.
Table 8: Investigated operation modes in a PEM water electrolysis
degradation study. Fresh cell assemblies were used for each
experiment, and a break-in of at least 500 h was performed. All
cycling tests were performed at 80°C. From [57] with permission
from Elsevier.
Operation mode (name) Test condition
Constant current at 80 (cc) 2.0 A cm−2
Constant voltage at 60 (T60) 2.0 V
Constant voltage at 80 (T80) 2.0 V
Constant voltage at 90 (T90) 2.0 V
100 s current cycling (cyc100s) 0−2.0 A cm−2, 100 s dwell time
10 s current cycling (cyc100s) 0−2.0 A cm−2, 10 s dwell time
Solar PV profile (solar) 0−2.0 A cm−2, 60 s dwell time
performed by Rakousky et al. [75] shows a performance loss
at constant current density (2 A cm−2) during long-term
operation of a PEMWE due to semiconducting TiOx that is
formed on the anode Ti-PTL. Coating of the Ti-PTLs with
Pt achieved a substantially reduced degradation rate of only
12 μV h−1, compared to 194 μV h−1 when no coating was
applied [75].
The passivation of Ti components in PEMWEs was also
observed in lifetime studies performed by Frensch et al. [57].
They investigated several MEAs with the same specifications
for 500 h at different operation modes, including variations
in the operating temperature and different current cycling
modes (Table 8). Titanium-sintered PTLs (1 mm, 30%
porosity) were used on the cathode and anode sides, respec-
tively. In an attempt to separate the total ohmic resistance
into its components, the researchers identified the passiv-
ation of the Ti-PTL and the accompanying positive effect
of MEA adjustments as main PTL contributions [57].
Although the use of corrosion-resistant coatings for PTL
materials is advantageous for long-term PEMWE operation,
it makes small scale research hardware expensive and diffi-
cult to source and is hardly sustainable in industrial applica-
tions. Despite the fact that carbon materials are generally not
used in anodic PTLs, several studies approve the use of
International Journal of Energy Research
(b)
cheaper, more abundant materials like carbon fibers in short
term experiments [24].
Results from Young et al. [134] show that the stability of
conventional carbon-based fuel cell GDLs is sufficient for
cell-conditioning and break-in procedures as well as the ini-
tial characterization of PEMWE cells [134]. The perfor-
mance of the carbon-based materials was tested in a 10 h
cell-conditioning procedure followed by twelve polarization
curve measurements (2.5 h each). Allowable operation of
40 h was reported that includes 15 h of operation between
2 V and 3 V [134]. Becker et al. [135] designed PEMWE sin-
gle cell tests for anode PTLs made out of carbon-coated
316 L stainless steel. The substituted material was tested in
situ for 30 days at 2 A cm−2 and potentials up to 1.2 V vs.
RHE [135]. These results show that Ti-based PTLs are not
necessarily required for initial performance characterization
procedures in PEMWE.
4.3. Summary PTL/GDL Degradation. Studies on the impact
of different PTL/GDL materials on PEMWE performance
are still under investigation, and the high cost of titanium
is still a limiting factor that makes the development of
commercialized materials challenging. To date, no effective
characterization protocols exist for PEMWE, although
much attention has been paid to the design and screening
of PEMWE materials more recently. In Table 9, some of
the available studies performed on GDL durability are
summarized.
According to the currently understood decay mecha-
nisms in GDLs, effects such as carbon corrosion and CL
interaction under compression lead to a performance decay
during PEMWE operation. Successful mitigation strategies
so far have relied on scarce and expensive metal coatings
that contribute to the already high capital cost. To date, only
a limited number of degradation protocols for the PTL on
the anodic side of the electrolyzer exist. Some of the available
lifetime tests for PTL degradation are listed in Table 10.
Recently, great promise for PTL design optimization has
been shown by Stiber et al. [136]. The researchers presented
a PTL for PEMWE that enables operation at up to 6 A cm−2,
90°C, and 90 bar H2 output pressure. The PTL consisted of a
International Journal of Energy Research 17

Table 9: Summary of ASTs for the evaluation of GDL stability in PEM technology.

AST mode Operating conditions Research findings Ref.

Mechanical degradation in a PEMFC dummy
Mechanical degradation
cell for 28 days at 65°C
Mechanical compression of GDLs to 30% and
Static compression 50% of its initial thickness at 60°C and 80°C,
respectively
Compression of GDL samples between a pair of
Cyclic compression graphite plates, which are sandwiched between
aluminum end plates at 1.7 MPa and 3.4 MPa
Submersion of pristine GDLs in a 35 wt% H2O2 Water accumulation within the GDL is attributed
Accelerated carbon corrosion solution at 90°C for 12 h and further soaking in to the loss of MPL hydrophobicity caused by a
DI water for 24 h
Puddle-shaped defects decrease the performance
[127]
due to water accumulation
A higher compression ratio results in lower cell
performance. Introduction of a MPL onto the
[128]
carbon cloth is extremely beneficial for the
operation, especially at high current density
The impact of cyclic compression on the
hydrophobicity of the GDL is seen to be
[129]
significantly higher than that reported elsewhere
due to electrochemical effects
[125]
carbon-corrosion-based degradation mechanism

Table 10: Summary of ASTs for the evaluation of PTL stability in PEMWEs.

AST mode Operating conditions Research findings Ref.

Durability tests under a load of up Highly porous samples (>30%) exhibit brittle behavior.
Ex situ and in situ
to 300 bar in ex situ and up to Samples with low sintering temperature cannot [111]
pressure tests
50 bar in in situ tests guarantee sufficient fatigue strength
Passivation of the anode Ti-PTL results in an increased
Constant current operation of
Constant current ohmic cell resistance. Pt-coated PTL reduces [75]
2 A cm−2 for 1000 h
degradation by 89%
Longevity test of Carbon-based PTL material sets are sufficient for
40 h operation between 2 V and 3 V [134]
carbon materials initial PEMWE performance characterization
Ex situ corrosion testing at 70 °C for 2.5 h
Longevity test of Substitution of Pt-Ti with cheaper PTL materials
in acidic environment, and in situ
carbon-coated shows potential for significant cost savings in [135]
degradation testing for 30 days
steel materials PEMWE stack design
at 2 A cm−2
Various operation Mitigation strategies are necessary to prevent Ti
See Table 8 [57]
modes/MEA passivation from reducing the cell’s efficiency

Ti porous-sintered layer (PSL) with a low-cost Ti mesh.
Interestingly, this approach did not require a flow field in
the BPP [136]. Other studies suggest that traditional
carbon-based GDL materials are sufficient for electrolyzer
initial performance assessments [134, 137]. To facilitate
low-cost PTL material and component screening and devel-
opment, standardized procedures for various types of mate-
rials and experimental designs are required [24].
5. Concluding Remarks
This document reviews and summarizes different AST
protocols in PEMWE technology with a focus on the mem-
brane electrode assembly. The component specific stressors
under different operating conditions are outlined for the
PFSA-membrane, catalyst layers, and GDL and PTL,
respectively. Regarding material deterioration in catalyst
degradation research, the current focus is set on the disso-
lution of the Ir-catalyst during the OER, whereas on the
cathode-side Pt/C corrosion is a major issue, particularly
during the dynamic operation of the PEMWE. The PFSA-
membrane and ionomer degrade when the electrolyzer
operates at elevated temperatures and at OCV. For the
Ti-based PTL, surface corrosion and passivation are of con-
cern. This is triggered by the high current density operation
of the PEMWE, and once a passive film is formed on the
surface, the contact resistance increases and the perfor-
mance declines. A precious metal coating is therefore com-
monly applied to protect the PTL from corrosion and
passivation of the metal surface. To conclude, novel mate-
rials and cell components for PEMWE are still slow to
make their way into the market due to the limited access
to standardized test equipment and procedures and the
high cost of precious metal components. The implementa-
tion of AST protocols has been successful to some extent;
however, a harmonized database needs to be created to
move technology from lab scale to commercial deployment.
This complementary investigation of accelerated stressors
in PEMWE cells provides a basis for the development of
a variety of ASTs, which can help the research community
to quickly assess component durability and efficiently pro-
cess novel materials.
18 International Journal of Energy Research

Abbreviations mechanical stress and surface passivation. (Supplementary

Materials)
AEMWE: Anion exchange membrane water electrolyzer
ADT: Accelerated degradation test References
AST: Accelerated stress test
AWE: Alkaline water electrolyzer [1] International Energy Agency, “The future of hydrogen-
BPP: Bipolar plate seizing today’s opportunitiesReport prepared by the IEA for
CA: Chronoamperometric the G20, JapanAccessed: Jul. 02, 2022 https://www.iea.org/
CCM: Catalyst coated membrane reports/the-future-of-hydrogen.
CL: Catalyst layer [2] U. Babic, M. Suermann, F. N. Büchi, L. Gubler, and T. J.
DI: Deionized Schmidt, “Critical review—identifying critical gaps for poly-
ECSA: Electrochemically active surface area mer electrolyte water electrolysis development,” Journal of
FRR: Fluoride release rate the Electrochemical Society, vol. 164, no. 4, pp. F387–F399,
GDBL: Gas diffusion backing layer 2017.
GDL: Gas diffusion layer [3] A. Buttler and H. Spliethoff, “Current status of water electrol-
HER: Hydrogen evolution reaction ysis for energy storage, grid balancing and sector coupling via
power-to-gas and power-to-liquids: a review,” Renewable and
HFR: High frequency resistance
Sustainable Energy Reviews, vol. 82, pp. 2440–2454, 2018.
MEA: Membrane electrode assembly
MPL: Microporous layer [4] S. Shiva Kumar and V. Himabindu, “Hydrogen production
by PEM water electrolysis - a review,” Materials Science for
MT: Mass transfer
Energy Technologies, vol. 2, no. 3, pp. 442–454, 2019.
NP: Nanoparticle
[5] T. Wang, X. Cao, and L. Jiao, “PEM water electrolysis for
OCV: Open circuit voltage
hydrogen production: fundamentals, advances, and pros-
OER: Oxygen evolution reaction pects,” Carb Neutrality, vol. 1, no. 1, p. 21, 2022.
PBI: Polybenzimidazoles
[6] Office of Energy Efficiency & Renewable Energy, “DOE
PEMFC: Proton exchange membrane fuel cell
research focuses on overcoming challenges in hydrogen pro-
PEMWE: Polymer electrolyte water electrolysis duction,” Access: Aug. 26, 2022. https://www.energy.gov/
PFSA: Perfluorosulfonic acid eere/fuelcells/hydrogen-production-electrolysis.
PSF: Polysulfone [7] K. Ayers, “The potential of proton exchange membrane-
PTL: Porous transport layer based electrolysis technology,” Current Opinion in Electro-
SEM: Scanning electron microscopy chemistry, vol. 18, pp. 9–15, 2019.
SOEC: Solid oxides electrolysis cell [8] Q. Feng, X.−. Z. Yuan, G. Liu et al., “A review of proton
SPEEK: Sulfonated polyether ether ketones. exchange membrane water electrolysis on degradation mech-
anisms and mitigation strategies,” Journal of Power Sources,
Data Availability vol. 366, pp. 33–55, 2017.
[9] C. Immerz, M. Paidar, G. Papakonstantinou et al., “Effect of
The data that support the findings of this study are available the MEA design on the performance of PEMWE single cells
within the article. with different sizes,” Journal of Applied Electrochemistry,
vol. 48, no. 6, pp. 701–711, 2018.
Conflicts of Interest [10] H. Kim, J. Kim, J. Kim et al., “Dendritic gold-supported irid-
ium/iridium oxide ultra-low loading electrodes for high-
The authors declare that they have no conflicts of interest. performance proton exchange membrane water electrolyzer,”
Applied Catalysis B: Environmental, vol. 283, article 119596,
Acknowledgments 2021.
[11] A. Hartig-Weiss, M. Miller, H. Beyer et al., “Iridium oxide
The financial support by the Austrian Research Promotion
catalyst supported on antimony-doped tin oxide for high
Agency (FFG) through the 8th call of “COMET-Projects” oxygen evolution reaction activity in acidic media,” ACS
is gratefully acknowledged. Applied Nano Materials, vol. 3, no. 3, pp. 2185–2196, 2020.
[12] S. Chatterjee, X. Peng, S. Intikhab et al., “Nanoporous iridium
Supplementary Materials nanosheets for polymer electrolyte membrane electrolysis,”
Advanced Energy Materials, vol. 11, no. 34, article 2101438,
“Graphical Abstract”: membrane electrode assembly (MEA) 2021.
accelerated stressors responsible for degradation of PEM
[13] G. C. da Silva, K. J. J. Mayrhofer, E. A. Ticianelli, and
water electrolysis cells. A series of complex mechanical, S. Cherevko, “Dissolution stability: the major challenge in
chemical, and thermal stressors is responsible for MEA fail- the regenerative fuel cells bifunctional catalysis,” Journal of
ure during PEMWE operation. At the membrane, thinning the Electrochemical Society, vol. 165, no. 16, pp. F1376–
processes and pinhole formation can occur as a result from F1384, 2018.
interactions with oxidizing species formed at the electrodes. [14] M. Carmo, D. L. Fritz, J. Mergel, and D. Stolten, “A compre-
Catalyst accelerated stressors are carbon corrosion, Ostwald hensive review on PEM water electrolysis,” International
ripening, and agglomeration/dissolution processes. The gas Journal of Hydrogen Energy, vol. 38, no. 12, pp. 4901–4934,
diffusion media (GDL and PTL) are mainly affected by 2013.
International Journal of Energy Research
[15] F. N. Khatib, T. Wilberforce, O. Ijaodola et al., “Material deg-
radation of components in polymer electrolyte membrane
(PEM) electrolytic cell and mitigation mechanisms: a review,”
Renewable and Sustainable Energy Reviews, vol. 111, pp. 1–
14, 2019.
[16] P. Shirvanian and F. van Berkel, “Novel components in pro-
ton exchange membrane (PEM) water electrolyzers
(PEMWE): status, challenges and future needs. A mini
review,” Electrochemistry Communications, vol. 114, article
106704, 2020.
[17] S. Cherevko, “Stability and dissolution of electrocatalysts:
building the bridge between model and "real world" systems,”
Current Opinion in Electrochemistry, vol. 8, pp. 118–125,
2018.
[18] C. V. Pham, D. Escalera-López, K. Mayrhofer, S. Cherevko,
and S. Thiele, “Essentials of high performance water electro-
lyzers–from catalyst layer materials to electrode engineering,”
Advanced Energy Materials, vol. 11, no. 44, article 2101998,
2021.
[19] H. Ito, T. Maeda, A. Nakano, and H. Takenaka, “Properties of
Nafion membranes under PEM water electrolysis condi-
tions,” International Journal of Hydrogen Energy, vol. 36,
no. 17, pp. 10527–10540, 2011.
[20] A. Kusoglu and A. Z. Weber, “New insights into perfluori-
nated sulfonic-acid ionomers,” Chemical Reviews, vol. 117,
no. 3, pp. 987–1104, 2017.
[21] K. Ayers, “High efficiency PEM water electrolysis: enabled by
advanced catalysts, membranes, and processes,” Current
Opinion in Chemical Engineering, vol. 33, article 100719,
2021.
[22] T. L. Doan, H. E. Lee, S. S. H. Shah et al., “A review of the
porous transport layer in polymer electrolyte membrane
water electrolysis,” International Journal of Energy Research,
vol. 45, no. 10, pp. 14207–14220, 2021.
[23] C. H. Lee, R. Banerjee, F. Arbabi, J. Hinebaugh, and
A. Bazylak, “Porous transport layer related mass transport
losses in polymer electrolyte membrane electrolysis: a
review,” in ASME 2016 14th International Conference on
Nanochannels, Microchannels, and Minichannels, pp. 1–11,
Washington, DC, USA, 2016.
[24] X.-Z. Yuan, N. Shaigan, C. Song et al., “The porous transport
layer in proton exchange membrane water electrolysis: per-
spectives on a complex component,” Sustainable Energy &
Fuels, vol. 6, no. 8, pp. 1824–1853, 2022.
[25] H. Teuku, I. Alshami, J. Goh, M. S. Masdar, and K. S. Loh,
“Review on bipolar plates for low-temperature polymer
electrolyte membrane water electrolyzer,” International
Journal of Energy Research, vol. 45, no. 15, pp. 20583–
20600, 2021.
[26] G. Tsotridis and A. Pilenga, EU Harmonized Protocols for
Testing of Low Temperature Water Electrolysis, Publications
Office of the European Union, Luxembourg, 2021.
[27] T. Malkow, A. Pilenga, and G. Tsotridis, EU Harmonised Test
Procedure: Electrochemical Impedance Spectroscopy for Water
Electrolysis Cells, Publications Office, 2018.
[28] T. Malkow, EU Harmonised Cyclic Voltammetry Test Method
for Low-Temperature Water Electrolysis Single Cells, Publica-
tions Office, 2018.
[29] T. Malkow, EU Harmonised Polarisation Curve Test Method
for Low-Temperature Water Electrolysis, Publications Office,
2018.
19
[30] S. Zhang, X. Yuan, H. Wang et al., “A review of accelerated
stress tests of MEA durability in PEM fuel cells,” Interna-
tional Journal of Hydrogen Energy, vol. 34, no. 1, pp. 388–
404, 2009.
[31] R. Petrone, D. Hissel, M. C. Péra, D. Chamagne, and
R. Gouriveau, “Accelerated stress test procedures for PEM
fuel cells under actual load constraints: state-of-art and pro-
posals,” International Journal of Hydrogen Energy, vol. 40,
no. 36, pp. 12489–12505, 2015.
[32] X.-Z. Yuan, H. Li, S. Zhang, J. Martin, and H. Wang, “A
review of polymer electrolyte membrane fuel cell durability
test protocols,” Journal of Power Sources, vol. 196, no. 22,
pp. 9107–9116, 2011.
[33] S. Y. Baek, J. Y. Lee, T. K. Lee, H. J. Kim, and S. Y. Lee, “Asym-
metric porous membranes with improving mass transfer for
proton exchange membrane water electrolysis (PEMWE),”
ECS Meeting Abstracts, vol. MA2020-02, no. 38, pp. 2485–
2485, 2020.
[34] M. F. Ahmad Kamaroddin, N. Sabli, T. A. Tuan Abdullah
et al., “Membrane-based electrolysis for hydrogen produc-
tion: a review,” Membranes, vol. 11, no. 11, p. 810, 2021.
[35] M. Chandesris, V. Médeau, N. Guillet, S. Chelghoum,
D. Thoby, and F. Fouda-Onana, “Numerical modelling of
membrane degradation in PEM water electrolyzer: influence
of the temperature and current density,” International Jour-
nal of Hydrogen Energy, vol. 40, pp. 1–8, 2015.
[36] L. Gubler, S. M. Dockheer, and W. H. Koppenol, “Radicals in
fuel cell membranes: mechanisms of formation and ionomer
attack,” ECS Transactions, vol. 41, no. 1, pp. 1431–1439,
2011.
[37] D. Curtin, R. Lousenberg, T. Henry, P. Tangeman, and
M. Tisack, “Chemical Degradation of Perfluorinated Sulfonic
Acid Membranes,” in Polymer Electrolyte Fuel Cell Durabil-
ity, Power Sources, pp. 57–69, Springer, 2004.
[38] S. H. Frensch, G. Serre, F. Fouda-Onana et al., “Impact of iron
and hydrogen peroxide on membrane degradation for poly-
mer electrolyte membrane water electrolysis: computational
and experimental investigation on fluoride emission,” Jour-
nal of Power Sources, vol. 420, pp. 54–62, 2019.
[39] P. Marocco, K. Sundseth, T. Aarhaug et al., “Online measure-
ments of fluoride ions in proton exchange membrane water
electrolysis through ion chromatography,” Journal of Power
Sources, vol. 483, article 229179, 2021.
[40] A. Martin, P. Trinke, B. Bensmann, and R. Hanke-Rauschen-
bach, “Hydrogen crossover in PEM water electrolysis at cur-
rent densities up to 10 a cm−2,” Journal of the Electrochemical
Society, vol. 169, no. 9, article 094507, 2022.
[41] P. Trinke, G. P. Keeley, M. Carmo, B. Bensmann, and
R. Hanke-Rauschenbach, “Elucidating the effect of mass
transport resistances on hydrogen crossover and cell perfor-
mance in PEM water electrolyzers by varying the cathode
ionomer content,” Journal of the Electrochemical Society,
vol. 166, no. 8, pp. F465–F471, 2019.
[42] P. Holzapfel, M. Bühler, C. van Pham et al., “Directly coated
membrane electrode assemblies for proton exchange mem-
brane water electrolysis,” Electrochemistry Communications,
vol. 110, article 106640, 2020.
[43] X.-Z. Yuan, S. Zhang, S. Ban et al., “Degradation of a PEM
fuel cell stack with Nafion® membranes of different thick-
nesses. Part II: ex situ diagnosis,” Journal of Power Sources,
vol. 205, pp. 324–334, 2012.
20
[44] X.-Z. Yuan, S. Zhang, H. Wang et al., “Degradation of a poly-
mer exchange membrane fuel cell stack with Nafion® mem-
branes of different thicknesses: part I. in situ diagnosis,”
Journal of Power Sources, vol. 195, no. 22, pp. 7594–7599,
2010.
[45] M. Schalenbach, M. A. Hoeh, J. T. Gostick, W. Lueke, and
D. Stolten, “Gas permeation through Nafion. Part 2: resistor
network model,” Journal of Physical Chemistry C, vol. 119,
no. 45, pp. 25156–25169, 2015.
[46] P. Trinke, B. Bensmann, and R. Hanke-Rauschenbach, “Cur-
rent density effect on hydrogen permeation in PEM water
electrolyzers,” International Journal of Hydrogen Energy,
vol. 42, no. 21, pp. 14355–14366, 2017.
[47] S. S. Kocha, J. Deliang Yang, and J. S. Yi, “Characterization of
gas crossover and its implications in PEM fuel cells,” AICHE
Journal, vol. 52, no. 5, pp. 1916–1925, 2006.
[48] A. Martin, P. Trinke, M. Stähler et al., “The effect of cell com-
pression and cathode pressure on hydrogen crossover in
PEM water electrolysis,” Journal of the Electrochemical Soci-
ety, vol. 169, no. 1, article 014502, 2022.
[49] D. Ye, Z. Tu, Y. Yu et al., “Hydrogen permeation across
super-thin membrane and the burning limitation in low-
temperature proton exchange membrane fuel cell,” Interna-
tional Journal of Energy Research, vol. 38, no. 9, pp. 1181–
1191, 2014.
[50] P. Trinke, B. Bensmann, S. Reichstein, R. Hanke-Rauschen-
bach, and K. Sundmacher, “Impact of pressure and tempera-
ture on hydrogen permeation in PEM water electrolyzers
operated at asymmetric pressure conditions,” ECS Transac-
tions, vol. 75, no. 14, pp. 1081–1094, 2016.
[51] P. Millet, A. Ranjbari, F. de Guglielmo, S. A. Grigoriev, and
F. Auprêtre, “Cell failure mechanisms in PEM water electro-
lyzers,” International Journal of Hydrogen Energy, vol. 37,
no. 22, pp. 17478–17487, 2012.
[52] M. Bodner, C. Hochenauer, and V. Hacker, “Effect of pinhole
location on degradation in polymer electrolyte fuel cells,”
Journal of Power Sources, vol. 295, pp. 336–348, 2015.
[53] R. W. Kopitzke, C. A. Linkous, H. R. Anderson, and G. L.
Nelson, “Conductivity and water uptake of aromatic-based
proton exchange membrane electrolytes,” Journal of the Elec-
trochemical Society, vol. 147, no. 5, p. 1677, 2000.
[54] M. Doyle, M. E. Lewittes, M. G. Roelofs, S. A. Perusich, and
R. E. Lowrey, “Relationship between ionic conductivity of
perfluorinated ionomeric membranes and nonaqueous sol-
vent properties,” Journal of Membrane Science, vol. 184,
no. 2, pp. 257–273, 2001.
[55] Ö. F. Selamet, M. C. Acar, M. D. Mat, and Y. Kaplan, “Effects
of operating parameters on the performance of a high-
pressure proton exchange membrane electrolyzer,” Interna-
tional Journal of Energy Research, vol. 37, no. 5, pp. 457–
467, 2013.
[56] G. S. Ogumerem and E. N. Pistikopoulos, “Parametric opti-
mization and control for a smart proton exchange membrane
water electrolysis (PEMWE) system,” Journal of Process Con-
trol, vol. 91, pp. 37–49, 2020.
[57] S. H. Frensch, F. Fouda-Onana, G. Serre, D. Thoby, S. S.
Araya, and S. K. Kær, “Influence of the operation mode on
PEM water electrolysis degradation,” International Journal
of Hydrogen Energy, vol. 44, no. 57, pp. 29889–29898, 2019.
[58] Y. Singh, F. P. Orfino, M. Dutta, and E. Kjeang, “3D failure
analysis of pure mechanical and pure chemical degradation
International Journal of Energy Research
in fuel cell membranes,” Journal of the Electrochemical Soci-
ety, vol. 164, no. 13, pp. F1331–F1341, 2017.
[59] Y. Xing, H. Li, and G. Avgouropoulos, “Research progress of
proton exchange membrane failure and mitigation strate-
gies,” Materials, vol. 14, no. 10, p. 2591, 2021.
[60] S. A. Grigoriev, D. G. Bessarabov, and V. N. Fateev, “Degra-
dation mechanisms of MEA characteristics during water elec-
trolysis in solid polymer electrolyte cells,” Russian Journal of
Electrochemistry, vol. 53, no. 3, pp. 318–323, 2017.
[61] N. Danilovic, R. Subbaraman, K. C. Chang et al., “Activity–
stability trends for the oxygen evolution reaction on mono-
metallic oxides in acidic environments,” Journal of Physical
Chemistry Letters, vol. 5, no. 14, pp. 2474–2478, 2014.
[62] A. Weiß, A. Siebel, M. Bernt, T.-H. Shen, V. Tileli, and H. A.
Gasteiger, “Impact of intermittent operation on lifetime and
performance of a PEM water electrolyzer,” Journal of the
Electrochemical Society, vol. 166, no. 8, pp. F487–F497, 2019.
[63] N. Li, S. S. Araya, and S. K. Kær, “Investigating low and high
load cycling tests as accelerated stress tests for proton
exchange membrane water electrolysis,” Electrochimica Acta,
vol. 370, article 137748, 2021.
[64] F. Fouda-Onana, M. Chandesris, V. Médeau, S. Chelghoum,
D. Thoby, and N. Guillet, “Investigation on the degradation
of MEAs for PEM water electrolysers part I: effects of testing
conditions on MEA performances and membrane proper-
ties,” International Journal of Hydrogen Energy, vol. 41,
no. 38, pp. 16627–16636, 2016.
[65] P. Lettenmeier, R. Wang, R. Abouatallah et al., “Durable
membrane electrode assemblies for proton exchange mem-
brane electrolyzer systems operating at high current densi-
ties,” Electrochimica Acta, vol. 210, pp. 502–511, 2016.
[66] S. Kundu, L. C. Simon, and M. W. Fowler, “Comparison of
two accelerated Nafion™ degradation experiments,” Polymer
Degradation and Stability, vol. 93, no. 1, pp. 214–224, 2008.
[67] S. Goldstein, D. Meyerstein, and G. Czapski, “The Fenton
reagents,” Free Radical Biology and Medicine, vol. 15, no. 4,
pp. 435–445, 1993.
[68] Z. Liu, T. Wang, X. Yu, Z. Geng, Y. Sang, and H. Liu, “In situ
alternative switching between Ti4+ and Ti3+ driven by H2O2
in TiO2 nanostructures: mechanism of pseudo-Fenton reac-
tion,” Materials Chemistry Frontiers, vol. 1, no. 10,
pp. 1989–1994, 2017.
[69] A. Laconti, H. Liu, C. Mittelsteadt, and R. McDonald, “Poly-
mer electrolyte membrane degradation mechanisms in fuel
cells - findings over the past 30 years and comparison with
electrolyzers,” ECS Transactions, vol. 1, no. 8, pp. 199–219,
2006.
[70] E. Borgardt, L. Giesenberg, M. Reska et al., “Impact of clamp-
ing pressure and stress relaxation on the performance of dif-
ferent polymer electrolyte membrane water electrolysis cell
designs,” International Journal of Hydrogen Energy, vol. 44,
no. 42, pp. 23556–23567, 2019.
[71] S. Siracusano, F. Pantò, S. Tonella, C. Oldani, and A. S. Aricò,
“Reinforced short-side-chain Aquivion® membrane for pro-
ton exchange membrane water electrolysis,” International
Journal of Hydrogen Energy, vol. 47, no. 35, pp. 15557–
15570, 2022.
[72] J. Shan, T. Ling, K. Davey, Y. Zheng, and S. Qiao, “Transition-
metal-doped RuIr bifunctional nanocrystals for overall water
splitting in acidic environments,” Advanced Materials,
vol. 31, no. 17, article 1900510, 2019.
International Journal of Energy Research
[73] M. Bernt, A. Siebel, and H. A. Gasteiger, “Analysis of voltage
losses in PEM water electrolyzers with low platinum group
metal loadings,” Journal of the Electrochemical Society,
vol. 165, no. 5, pp. F305–F314, 2018.
[74] C. Spöri, J. T. H. Kwan, A. Bonakdarpour, D. P. Wilkinson,
and P. Strasser, “The stability challenges of oxygen evolving
catalysts: towards a common fundamental understanding
and mitigation of catalyst degradation,” Angewandte Chemie,
International Edition, vol. 56, no. 22, pp. 5994–6021, 2017.
[75] C. Rakousky, U. Reimer, K. Wippermann, M. Carmo,
W. Lueke, and D. Stolten, “An analysis of degradation phe-
nomena in polymer electrolyte membrane water electrolysis,”
Journal of Power Sources, vol. 326, pp. 120–128, 2016.
[76] C. Rakousky, U. Reimer, K. Wippermann et al., “Polymer
electrolyte membrane water electrolysis: restraining degrada-
tion in the presence of fluctuating power,” Journal of Power
Sources, vol. 342, pp. 38–47, 2017.
[77] P. Paciok, C. Rakousky, and C. Marcelo, “Sensivity analysis of
a PEM electrolyser cathode with respect to the platinum and
Nafion loading,” ECS Meeting Abstracts, vol. MA2015-01,
no. 26, 2015.
[78] S. Shrestha, Y. Liu, and W. E. Mustain, “Electrocatalytic activ-
ity and stability of Pt clusters on state-of-the-art supports: a
review,” Catalysis Reviews, vol. 53, no. 3, pp. 256–336, 2011.
[79] F. Claudel, L. Dubau, G. Berthomé et al., “Degradation mech-
anisms of oxygen evolution reaction electrocatalysts: a com-
bined identical-location transmission electron microscopy
and X-ray photoelectron spectroscopy study,” ACS Catalysis,
vol. 9, no. 5, pp. 4688–4698, 2019.
[80] P. Paciok, M. Carmo, W. Lüke, M. Heggen, and D. Stolten,
“Investigation of Pt/C catalysts using identical location trans-
mission electron microscopy under PEM electrolysis condi-
tions,” ECS Meeting Abstracts, vol. MA2016-02, no. 38, 2016.
[81] H. Yu, L. Bonville, J. Jankovic, and R. Maric, “Microscopic
insights on the degradation of a PEM water electrolyzer with
ultra-low catalyst loading,” Applied Catalysis B: Environmen-
tal, vol. 260, article 118194, 2020.
[82] J. Knöppel, M. Möckl, D. Escalera-López et al., “On the limi-
tations in assessing stability of oxygen evolution catalysts
using aqueous model electrochemical cells,” Nature Commu-
nications, vol. 12, no. 1, p. 2231, 2021.
[83] O. Kasian, S. Geiger, T. Li et al., “Degradation of iridium oxi-
desviaoxygen evolution from the lattice: correlating atomic
scale structure with reaction mechanisms,” Energy & Envi-
ronmental Science, vol. 12, no. 12, pp. 3548–3555, 2019.
[84] T. Naito, T. Shinagawa, T. Nishimoto, and K. Takanabe,
“Recent advances in understanding oxygen evolution reac-
tion mechanisms over iridium oxide,” Inorganic Chemistry
Frontiers, vol. 8, no. 11, pp. 2900–2917, 2021.
[85] S. Cherevko, S. Geiger, O. Kasian, A. Mingers, and K. J. J.
Mayrhofer, “Oxygen evolution activity and stability of irid-
ium in acidic media. Part 2. - electrochemically grown
hydrous iridium oxide,” Journal of Electroanalytical Chemis-
try, vol. 774, pp. 102–110, 2016.
[86] P. J. Rheinländer and J. Durst, “Transformation of the OER-
active IrOxspecies under transient operation conditions in
PEM water electrolysis,” Journal of the Electrochemical Soci-
ety, vol. 168, no. 2, article 024511, 2021.
[87] V. Pfeifer, T. E. Jones, J. J. Velasco Vélez et al., “The electronic
structure of iridium and its oxides,” Surface and Interface
Analysis, vol. 48, no. 5, pp. 261–273, 2016.
21
[88] J. Dodwell, M. Maier, J. Majasan et al., “Open-circuit dissolu-
tion of platinum from the cathode in polymer electrolyte
membrane water electrolysers,” Journal of Power Sources,
vol. 498, article 229937, 2021.
[89] P. Aßmann, A. S. Gago, P. Gazdzicki, K. A. Friedrich, and
M. Wark, “Toward developing accelerated stress tests for
proton exchange membrane electrolyzers,” Current Opinion
in Electrochemistry, vol. 21, pp. 225–233, 2020.
[90] S. M. Alia, S. Stariha, and R. L. Borup, “Electrolyzer durability
at low catalyst loading and with dynamic operation,” Journal
of the Electrochemical Society, vol. 166, no. 15, pp. F1164–
F1172, 2019.
[91] C. Rakousky, G. P. Keeley, K. Wippermann, M. Carmo, and
D. Stolten, “The stability challenge on the pathway to high-
current-density polymer electrolyte membrane water electro-
lyzers,” Electrochimica Acta, vol. 278, pp. 324–331, 2018.
[92] S. Siracusano, N. Hodnik, P. Jovanovic et al., “New insights
into the stability of a high performance nanostructured cata-
lyst for sustainable water electrolysis,” Nano Energy, vol. 40,
pp. 618–632, 2017.
[93] S. A. Grigoriev, K. A. Dzhus, D. G. Bessarabov, and P. Millet,
“Failure of PEM water electrolysis cells: case study involving
anode dissolution and membrane thinning,” International
Journal of Hydrogen Energy, vol. 39, no. 35, pp. 20440–
20446, 2014.
[94] E. Brightman, J. Dodwell, N. van Dijk, and G. Hinds, “In situ
characterisation of PEM water electrolysers using a novel ref-
erence electrode,” Electrochemistry Communications, vol. 52,
pp. 1–4, 2015.
[95] C. Spöri, C. Brand, M. Kroschel, and P. Strasser, “Accelerated
degradation protocols for iridium-based oxygen evolving cat-
alysts in water splitting devices,” Journal of the Electrochemi-
cal Society, vol. 168, no. 3, article 034508, 2021.
[96] X. Wang, L. Zhang, G. Li, G. Zhang, Z.-G. Shao, and B. Yi,
“The influence of ferric ion contamination on the solid poly-
mer electrolyte water electrolysis performance,” Electrochi-
mica Acta, vol. 158, pp. 253–257, 2015.
[97] N. Li, S. S. Araya, X. Cui, and S. K. Kær, “The effects of cat-
ionic impurities on the performance of proton exchange
membrane water electrolyzer,” Journal of Power Sources,
vol. 473, article 228617, 2020.
[98] A. Uddin, J. Park, U. Pasaogullari, and L. J. Bonville, “Cation
contamination in polymer electrolyte fuel cells: impacts,
mechanisms, and mitigation,” ECS Meeting Abstracts, vol. -
MA2015-03, no. 3, 2015.
[99] E. Price, “Durability and degradation issues in PEM electrol-
ysis cells and its components,” Johnson Matthey Technology
Review, vol. 61, no. 1, pp. 47–51, 2017.
[100] X. Cheng, Z. Shi, N. Glass et al., “A review of PEM hydrogen
fuel cell contamination: impacts, mechanisms, and mitiga-
tion,” Journal of Power Sources, vol. 165, no. 2, pp. 739–756,
2007.
[101] H. Sato, H. Matsushima, M. Ueda, and H. Ito, “Effect of water
stoichiometry on deuterium isotope separation by anion
exchange membrane water electrolysis,” International Jour-
nal of Hydrogen Energy, vol. 46, no. 68, pp. 33689–33695,
2021.
[102] N. Li, S. S. Araya, and S. K. Kær, “Long-term contamination
effect of iron ions on cell performance degradation of proton
exchange membrane water electrolyser,” Journal of Power
Sources, vol. 434, article 226755, 2019.
22
[103] C. J. Banas, M. A. Uddin, J. Park, L. J. Bonville, and
U. Pasaogullari, “Thinning of cathode catalyst layer in poly-
mer electrolyte fuel cells due to foreign cation contamina-
tion,” Journal of the Electrochemical Society, vol. 165, no. 6,
pp. F3015–F3023, 2018.
[104] L. Zhang, X. Jie, Z.-G. Shao, Z.-M. Zhou, G. Xiao, and B. Yi,
“The influence of sodium ion on the solid polymer electrolyte
water electrolysis,” International Journal of Hydrogen Energy,
vol. 37, no. 2, pp. 1321–1325, 2012.
[105] D. Kulkarni, A. Huynh, P. Satjaritanun et al., “Elucidating
effects of catalyst loadings and porous transport layer mor-
phologies on operation of proton exchange membrane water
electrolyzers,” Applied Catalysis B: Environmental, vol. 308,
article 121213, 2022.
[106] Y. N. Regmi, E. Tzanetopoulos, G. Zeng et al., “Supported
oxygen evolution catalysts by design: toward lower precious
metal loading and improved conductivity in proton exchange
membrane water electrolyzers,” ACS Catalysis, vol. 10, no. 21,
pp. 13125–13135, 2020.
[107] E. Cruz Ortiz, F. Hegge, M. Breitwieser, and S. Vierrath,
“Improving the performance of proton exchange membrane
water electrolyzers with low Ir-loaded anodes by adding
PEDOT: PSS as electrically conductive binder,” RSC
Advances, vol. 10, no. 62, pp. 37923–37927, 2020.
[108] O. Kasian, J.-P. Grote, S. Geiger, S. Cherevko, and K. J. J.
Mayrhofer, “The common intermediates of oxygen evolution
and dissolution reactions during water electrolysis on irid-
ium,” Angewandte Chemie, International Edition, vol. 57,
no. 9, pp. 2488–2491, 2018.
[109] S. Steen and F.-Y. Zhang, “Optimization of gas diffusion
layers with high-corrosion resistance for PEMWE,” ECS
Meeting Abstracts, vol. MA2014-01, no. 14, 2014.
[110] C. Liu, M. Carmo, G. Bender et al., “Performance enhance-
ment of PEM electrolyzers through iridium-coated titanium
porous transport layers,” Electrochemistry Communications,
vol. 97, pp. 96–99, 2018.
[111] E. Borgardt, O. Panchenko, F. J. Hackemüller et al., “Mechan-
ical characterization and durability of sintered porous trans-
port layers for polymer electrolyte membrane electrolysis,”
Journal of Power Sources, vol. 374, pp. 84–91, 2018.
[112] O. Panchenko, E. Borgardt, W. Zwaygardt et al., “In-situ two-
phase flow investigation of different porous transport layer
for a polymer electrolyte membrane (PEM) electrolyzer with
neutron spectroscopy,” Journal of Power Sources, vol. 390,
pp. 108–115, 2018.
[113] J. Mo, R. R. Dehoff, W. H. Peter, T. J. Toops, J. B. Green, and
F.-Y. Zhang, “Additive manufacturing of liquid/gas diffusion
layers for low-cost and high- efficiency hydrogen produc-
tion,” International Journal of Hydrogen Energy, vol. 41,
no. 4, pp. 3128–3135, 2016.
[114] C. M. Hwang, M. Ishida, H. Ito et al., “Influence of properties
of gas diffusion layers on the performance of polymer
electrolyte-based unitized reversible fuel cells,” International
Journal of Hydrogen Energy, vol. 36, no. 2, pp. 1740–1753,
2011.
[115] S. Escribano, J.-F. Blachot, J. Ethève, A. Morin, and
R. Mosdale, “Characterization of PEMFCs gas diffusion
layers properties,” Journal of Power Sources, vol. 156, no. 1,
pp. 8–13, 2006.
[116] V. Mishra, F. Yang, and R. Pitchumani, “Measurement and
prediction of electrical contact resistance between gas diffu-
sion layers and bipolar plate for applications to PEM fuel
International Journal of Energy Research
cells,” Journal of Fuel Cell Science and Technology, vol. 1,
no. 1, pp. 2–9, 2004.
[117] P. M. Wilde, M. Mändle, M. Murata, and N. Berg, “Structural
and physical properties of GDL and GDL/BPP combinations
and their influence on PEMFC performance,” Fuel Cells,
vol. 4, no. 3, pp. 180–184, 2004.
[118] S. Song, H. Zhang, X. Ma, Z.-G. Shao, Y. Zhang, and B. Yi,
“Bifunctional oxygen electrode with corrosion-resistive gas
diffusion layer for unitized regenerative fuel cell,” Electro-
chemistry Communications, vol. 8, no. 3, pp. 399–405, 2006.
[119] G. Chen, H. Zhang, H. Zhong, and H. Ma, “Gas diffusion
layer with titanium carbide for a unitized regenerative fuel
cell,” Electrochimica Acta, vol. 55, no. 28, pp. 8801–8807,
2010.
[120] F.-Y. Zhang, S. G. Advani, and A. K. Prasad, “Performance of
a metallic gas diffusion layer for PEM fuel cells,” Journal of
Power Sources, vol. 176, no. 1, pp. 293–298, 2008.
[121] F.-Y. Zhang, A. K. Prasad, and S. G. Advani, “Investigation of
a copper etching technique to fabricate metallic gas diffusion
media,” Journal of Micromechanics and Microengineering,
vol. 16, no. 11, pp. N23–N27, 2006.
[122] F. Lapicque, M. Belhadj, C. Bonnet, J. Pauchet, and
Y. Thomas, “A critical review on gas diffusion micro and
macroporous layers degradations for improved membrane
fuel cell durability,” Journal of Power Sources, vol. 336,
pp. 40–53, 2016.
[123] Y. Pan, H. Wang, and N. P. Brandon, “Gas diffusion layer
degradation in proton exchange membrane fuel cells: mecha-
nisms, characterization techniques and modelling
approaches,” Journal of Power Sources, vol. 513, article
230560, 2021.
[124] M. G. George, H. Liu, D. Muirhead et al., “Accelerated degra-
dation of polymer electrolyte membrane fuel cell gas diffu-
sion layers,” Journal of the Electrochemical Society, vol. 164,
no. 7, pp. F714–F721, 2017.
[125] H. Liu, M. G. George, N. Ge et al., “Microporous layer degra-
dation in polymer electrolyte membrane fuel cells,” Journal of
the Electrochemical Society, vol. 165, no. 6, pp. F3271–F3280,
2018.
[126] A. M. Dafalla and F. Jiang, “Stresses and their impacts on pro-
ton exchange membrane fuel cells: a review,” International
Journal of Hydrogen Energy, vol. 43, no. 4, pp. 2327–2348,
2018.
[127] J. H. Chun, D. H. Jo, S. G. Kim, S. H. Park, C. H. Lee, and S. H.
Kim, “Improvement of the mechanical durability of micro
porous layer in a proton exchange membrane fuel cell by
elimination of surface cracks,” Renewable Energy, vol. 48,
pp. 35–41, 2012.
[128] G. Dotelli, L. Omati, P. Gallo Stampino, P. Grassini, and
D. Brivio, “Investigation of gas diffusion layer compression
by electrochemical impedance spectroscopy on running poly-
mer electrolyte membrane fuel cells,” Journal of Power
Sources, vol. 196, no. 21, pp. 8955–8966, 2011.
[129] V. Radhakrishnan and P. Haridoss, “Effect of cyclic compres-
sion on structure and properties of a gas diffusion layer used
in PEM fuel cells,” International Journal of Hydrogen Energy,
vol. 35, no. 20, pp. 11107–11118, 2010.
[130] J. O. Majasan, F. Iacoviello, J. I. S. Cho et al., “Correlative
study of microstructure and performance for porous trans-
port layers in polymer electrolyte membrane water electroly-
sers by X-ray computed tomography and electrochemical
International Journal of Energy Research 23

characterization,” International Journal of Hydrogen Energy,

vol. 44, no. 36, pp. 19519–19532, 2019.
[131] P. W. T. Lu and S. Srinivasan, “Advances in water electrolysis
technology with emphasis on use of the solid polymer elec-
trolyte,” Journal of Applied Electrochemistry, vol. 9, no. 3,
pp. 269–283, 1979.
[132] A. Nouri-Khorasani, E. Tabu Ojong, T. Smolinka, and D. P.
Wilkinson, “Model of oxygen bubbles and performance
impact in the porous transport layer of PEM water electroly-
sis cells,” International Journal of Hydrogen Energy, vol. 42,
no. 48, pp. 28665–28680, 2017.
[133] A. S. Pushkarev, I. V. Pushkareva, M. A. Solovyev et al., “On
the influence of porous transport layers parameters on the per-
formances of polymer electrolyte membrane water electrolysis
cells,” Electrochimica Acta, vol. 399, article 139436, 2021.
[134] J. L. Young, Z. Kang, F. Ganci, S. Madachy, and G. Bender,
“PEM electrolyzer characterization with carbon-based hard-
ware and material sets,” Electrochemistry Communications,
vol. 124, article 106941, 2021.
[135] H. Becker, E. J. F. Dickinson, X. Lu et al., “Assessing potential
profiles in water electrolysers to minimise titanium use,”
Energy & Environmental Science, vol. 15, no. 6, pp. 2508–
2518, 2022.
[136] S. Stiber, H. Balzer, A. Wierhake et al., “Porous transport
layers for proton exchange membrane electrolysis under
extreme conditions of current density, temperature, and pres-
sure,” Advanced Energy Materials, vol. 11, no. 33, article
2100630, 2021.
[137] J. Schröder, V. A. Mints, A. Bornet et al., “The gas diffusion
electrode setup as straightforward testing device for proton
exchange membrane water electrolyzer catalysts,” JACS Au,
vol. 1, no. 3, pp. 247–251, 2021.