materials

Article
Study of the Durability of Membrane Electrode Assemblies in
Various Accelerated Stress Tests for Proton-Exchange Membrane
Water Electrolysis
Zhengquan Su 1,2 , Jun Liu 2, *, Pengfei Li 2 and Changhao Liang 2

1 Institute of Physical Science and Information Technology, Anhui University, Hefei 230601, China;
q21201318@stu.ahu.edu.cn
2 Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology,
Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China; pfli@issp.ac.cn (P.L.);
chliang@issp.ac.cn (C.L.)
* Correspondence: jliu@issp.ac.cn; Tel.: +86-55165591320; Tel./Fax: +86-55165591434

Abstract: In this work, we focus on the degradation of membrane electrode assemblies (MEAs) in
proton-exchange membrane water electrolysis (PEMWE) induced by different accelerated stress
tests (ASTs), including constant-current mode, square-wave mode, and solar photovoltaic mode. In
constant-current mode, at continuous testing for 600 h at 80 ◦ C, a degradation of operating voltage
increased by the enhanced current density from 22 µV/h (1 A/cm2 ) to 50 µV/h (3 A/cm2 ). In
square-wave mode, we found that in the narrow fluctuation range (1–2 A/cm2 ), the shorter step
time (2 s) generates a higher degradation rate of operating voltage, but in the wide fluctuation
range (1–3 A/cm2 ), the longer step time (22 s) induces a faster operating voltage rise. In the solar
photovoltaic mode, we used a simulation of 11 h sunshine duration containing multiple constant-
current and square-wave modes, which is closest to the actual application environment. Over 1400 h
ASTs, the solar photovoltaic mode lead to the most serious voltage rise of 87.7 µV/h. These results are
beneficial to understanding the durability of the PEM electrolyzer and optimizing the components of
MEAs, such as catalysts, membranes, and gas diffusion layers.

Citation: Su, Z.; Liu, J.; Li, P.; Liang, C. Keywords: accelerated stress tests; PEM water electrolysis; step time; square-wave; voltage rise;
Study of the Durability of Membrane membrane electrode assemblies
Electrode Assemblies in Various
Accelerated Stress Tests for
Proton-Exchange Membrane Water
Electrolysis. Materials 2024, 17, 1331. 1. Introduction
https://doi.org/10.3390/ma17061331
The extensive usage of fossil fuels has exacerbated environmental issues, intensifying
Academic Editors: Jiayuan Yu and the urgent need to develop alternative energy sources. In line with the swift progress
Junfeng Chen in wind and solar photovoltaic power installation, the development of suitable energy
storage solutions is imperative [1]. In a perfect scenario, the combination of water de-
Received: 24 February 2024
Revised: 11 March 2024
composition and renewable energy sources could offer a practical approach to converting
Accepted: 12 March 2024
excess energy into hydrogen, a promising solution for both renewable energy storage
Published: 14 March 2024 and fluctuation challenges [2–4]. Proton-exchange membrane water electrolysis (PEMWE)
stands out as a leading method for clean hydrogen production due to its compact design,
high efficiency, and operational flexibility, which enable its direct coupling with renewable
energy sources [5]. Nevertheless, the intermittency of and fluctuation in renewable energy
Copyright: © 2024 by the authors. sources can degrade the performance of proton-exchange membrane water electrolysers,
Licensee MDPI, Basel, Switzerland. potentially leading to increased voltage values in the electrolyzer [6]. Aiming at this issue,
This article is an open access article the challenge lies in effectively assessing durability under laboratory conditions and identi-
distributed under the terms and
fying the critical degradation parameters, particularly during dynamic operation, which is
conditions of the Creative Commons
not yet well understood [7,8].
Attribution (CC BY) license (https://
The operational lifespan of PEMWE have been the subject of numerous studies in
creativecommons.org/licenses/by/
the literature [9–14]. It has been well accepted that both constant-current (static) mode
4.0/).

Materials 2024, 17, 1331. https://doi.org/10.3390/ma17061331 https://www.mdpi.com/journal/materials

Materials 2024, 17, 1331 2 of 13

and square-wave (dynamic) mode may lead to performance degradation. The overall
performance degradation of an electrolyzer mainly comes from the degradation of the
MEA, which results from two sources: the proton-exchange membrane and the catalyst. A
proton-exchange membrane could degrade or become contaminated, which would result in
degradation of the electrolytic performance. Membrane degradation is divided into three
categories: mechanical, chemical, and thermal degradation. Of these, chemical and thermal
degradation are more affected by fluctuations in the power supply. In the anode of an elec-
trolyzer, water undergoes an oxidation reaction, and H2 O2 or hydroxyl radicals generated
through the two-electron reaction pathway attack the hydrocarbon chain segments of the
perfluorinated sulfonic acid membrane, causing the membrane to degrade [10]. When faced
with fluctuating conditions, the uneven distribution of current in the catalyst layer produces
a local hot area that causes uneven heating of the proton-exchange membrane, resulting in
membrane expansion or deformation, and at the same time, the small amount of hydrogen
and oxygen that passes through the membrane reacts with exothermic heat [15], which also
produces a local hot area, thus accelerating the degradation reaction of the membrane. And
catalyst degradation can be further categorized into redeposition, Ostwald ripening, and
coalescence degradation [16,17]. In the constant-current mode, when operating at a current
density of 3 A/cm2 for 1000 h, it was observed that the corrosion rate at 3 A/cm2 was
triple that at 1 A/cm2 [18]. Chandesris et al. [19] have discovered that variations in current
density had a negligible impact on attenuation under constant-current test conditions
of 10 A/cm2 . However, this constant-current operation does not accurately reflect the
actual conditions of PEMWE application. Li et al. [20,21] have conducted experiments with
low-current fluctuations ranging from 0 to 0.5 A/cm2 and 1.2 to 2 A/cm2 , demonstrating
that low-current cycling had a more significant effect on voltage degradation, and that a
reduction in ohmic losses under high-current cycling indicated membrane thinning and
failure. Rakousky [22,23] and Fouda-Onana [24] have attributed the degradation to the
oxidation of the porous titanium plate, which serves as a transport layer, as well as the
thinning of the polymeric membrane. Rakousky et al. [25] have investigated PEMWE with
five different current density fluctuation curves and identified varying degrees of degra-
dation. Steffen et al. [26] have systematically examined the impact of different dynamic
modes on the degradation of PEMWE, finding that faster current cycling enhanced the
overall performance over a test duration of 500 h. Despite this, the precise degradation
mechanisms [27–32] that impact their performance remain largely unexplained. Further-
more, there is ongoing ambiguity regarding the differential influence of various current
modes, such as the dynamic rate of the current on the degradation rates.
As the MEA production process continues to advance, performance and stability have
been improved, and in order to assess the stability of the new MEA, it is necessary to run it
for a longer period of time, which undoubtedly greatly increases the time cost. For MEAs
with excellent stability performance, it is more difficult to observe the performance in the
later period of the test, so some extreme test conditions are needed to accelerate the aging
of MEA, so that the MEA can reach the state in the later period of the test in a relatively
shorter period of time. Aiming at this issue, we have designed three acceleration schemes
in the hope of finding the factor that causes the rapid degradation of MEA performance in
electrolyzer. The three acceleration schemes are constant-current mode for 600 h, square-
wave mode for 600 h, and simulating solar PV mode over 1400 h, which are used in this
work to investigate the effects of current density, fluctuation range, and step time on the
voltage rise of a PEM electrolyzer. Corresponding EIS investigations were performed to
explain the very reason for the degradation rate of MEAs.

2. Experimental
2.1. Membrane Electrode Assemblies and Test Bench Setup
The membrane electrode assemblies (MEAs) were provided by Anhui Contango New
Energy Technology Co., Ltd. (Hefei, China), where Pt/C with a loading of 0.5 mg/cm2
and Ir black with a loading of 1.0 mg/cm2 were used as cathode catalysts and anode
Materials 2024, 17, 1331 3 of 13

catalysts, respectively. The PEM membrane with a thickness of 120 µm (DM6321A) was
from Dongyue Future Hydrogen Energy Co., Ltd. (Zibo, China) Carbon paper (TGP-H-
60, Toray, Tokyo, Japan) with a thickness of 0.18 mm was employed as the cathode gas
diffusion layer (GDL), and Pt-coated porous sintered titanium was used as the anode
GDL. The cathode end-plate had serpentine-shaped flow fields and the anode end-plate
had dotted flow fields. The effective active area of the MEA in all the experiments was
30.624 cm2 (5.80 cm × 5.28 cm). The single-cell electrolyzer was secured with screws and
nuts, and the amount of compression was set at 2.7 MPa for this experiment. The structure
of the electrolyser used in this experiment is shown schematically in Figure S1. The single-
cell electrolyzer was connected to a 6 mm inner diameter water flow line, and a pump
continuously supplied deionized water to the PEMWE at a flow rate of 100 mL/min to
circulate the deionized water between the tank and the PEMWE anode and replenish the
tank with deionized water at regular intervals in order to minimize the adverse effects
of the decrease in water on the membrane electrodes as a result of the increase in the
concentration of ions. A variety of current switching processes were implemented on the
PEMWE system with a temperature of 80 ◦ C for durability test.

2.2. Electrochemical Measurements

Electrochemical impedance spectroscopy (EIS) measurements were performed in
yhr constant-current mode at a frequency range between 10 kHz and 1 Hz. The cyclic
voltammetry curve was measured at a scan rate of 0.01 V/s over a voltage range of
0.05–1.3 V. More detailed experimental procedures of this investigation are displayed in
Figure S2. The durability experimental tests were performed by a computer-controlled
DC power supply, temperature probe, voltmeter, impedance meter, and electrochemical
workstation, which contained the following steps:
(1) Activation process: Before the performance test, an activation procedure was applied
to the electrolyzer using ITECH’s DC power supply IT-M3110 (ITECH, Nanjing,
China) to provide current, and it was carried out in the following order: 0.2 A/cm2
for 1 h, 1 A/cm2 for 1 h, 2 V for 0.5 h, 1.7 V for 2 h, and 2 V for 0.5 h.
(2) Accelerated stress tests (ASTs): Three types of ASTs were performed. The first one
was the constant-current mode test at 1 A/cm2 , 2 A/cm2 , and 3 A/cm2 ; The second
was square-wave mode tests fluctuating in the range of 1–2 A/cm2 and 1–3 A/cm2 ; a
cycle of the square-wave mode consisted of two parts, a current-holding part and a
current-change part. In this investigation, the current-holding part was used for 28 s
dwell time, while the current-varying part was used for different step times (2 s, 12 s,
and 22 s). The last AST simulated a solar fluctuation, using the power generated in
Qinghai, China, during 13 h of sunshine on a day in June 2022. Detailed parameters of
the ASTs are displayed in Table 1, and the corresponding test waveforms are shown
in Figure 1a–d.

Table 1. Investigated operation modes. Each AST was kept running under the same test conditions
for 600 h, except the solar PV profile which was running for 1430 h.

Operation Mode Test Condition Mode of Change (Name)

1 A/cm2 (C1)
Constant current 600 h, 80 ◦ C 2 A/cm2 (C2)
3 A/cm2 (C3)
1~2 A/cm2 2 s step time (N02)
Narrow square wave 28 s dwell time 12 s step time (N12)
600 h, 80 ◦ C 22 s step time (N22)
1~3 A/cm2 2 s step time (W02)
Wide square wave 28 s dwell time 12 s step time (W12)
600 h, 80 ◦ C 22 s step time (W22)

Solar photovoltaic mode 0~3 A/cm2 Simulating fluctuation (Solar)

1540 h, 80 ◦ C
 1~3 A/cm2 2 s step time (W02)
Wide square wave 28 s dwell time 12 s step time (W12)
600 h, 80 °C 22 s step time (W22)
0~3 A/cm2
Materials 2024, 17, 1331 Solar photovoltaic mode Simulating fluctuation
4 of 13 (Solar)
1540 h, 80 °C

The AST 2
Figure 1.
Figure 1. The ASTwaveforms
waveforms used in this
used investigation.
in this (a) The
investigation. (a)1,The
2, and 3 A/cm
1, 2, and 3 A/cmconstant-current
2 constant-current

density mode
mode tests. 2
density tests.(b)
(b)Narrow
Narrow square-wave
square-wave mode test with
mode fluctuations
test with in the range
fluctuations in theofrange
1–2 A/cm
of 1–2. A/cm2.
(c)Wide
Wide square-wave
square-wave mode test with fluctuations in theinrange of 1–3of A/cm 2 . (d) Simulating solar PVsolar PV
(c) mode test with fluctuations the range 1–3 A/cm 2. (d) Simulating

fluctuation mode within a current density range of 0–3 A/cm 2.

fluctuation mode within a current density range of 0–3 A/cm . 2

3. Results and Discussion

3. Results and Discussion
This section compares the degradation in different operation modes; however, in order
Thisunderstand
to better section compares the degradation
the dynamic in different
mode of operation of the operation
grid servicemodes; however,
and discuss the in or-
der to better
impact understand
of transient changes the dynamic
in PV mode of on
power generation operation of the the
the electrolyzer, grid service
analysis and discuss
focuses
on the
the discussion
impact of the AST,
of transient whichinhas
changes PVfaster
powerdegradation rates:
generation onN02
the and W22. Although,
electrolyzer, the analysis
none of them decay as fast as Solar, and the degradation rates for each
focuses on the discussion of the AST, which has faster degradation rates: AST are shown in W22.
N02 and
Table 2. none of them decay as fast as Solar, and the degradation rates for each AST are
Although,
shown
Table 2.in Table 2. rate analyses for different ASTs used in this investigation.
Degradation

Table 2. Degradation AST for different

Test Mode rate analyses Degradation Rateused in thisImpact
ASTs on Degradation
investigation.
C1 22. 7 µV/h @ 1 A/cm2 High current density would
Constant-current
Test Mode mode C2
AST Degradation Rate
26.1 µV/h @ 2 A/cm2 Impact on Degradation
accelerate degradation.
C3 50.0 µV/h @ 3 A/cm2
C1 22. 7 µV/h @ 1 A/cm 2
Constant-current High2 current density would accelerate deg-
32.5 µV/h @ 1 A/cm
C2 26.1N02
µV/h 47.3
@ 2µV/h
A/cm@ 22 A/cm2
mode
Narrow square-wave mode Fluctuates inradation.
the range of 1–2 A/cm2 ,
C3 50.0 µV/h
N12 @ 3
27.1 A/cm
µV/h @ 21 A/cm2 decreasing step time of current
(1–2 A/cm2 ) 36.6 µV/h @ 22 A/cm2 would accelerate degradation.
32.5 µV/h @ 1 A/cm
N02 21.7 µV/h @ 1 A/cm2
47.3N22
µV/h 24.9
@ 2µV/h
A/cm 2
@ 2 A/cm2
Narrow square- Fluctuates in the range of 1–2 A/cm2, de-
27.1 µV/h @ 1
27.9 A/cm
µV/h @ 21 A/cm2
wave mode N12 W02
@ 23 creasing
A/cm2 step time of current would2 acceler-
36.6 µV/h 46.2
@ 2µV/h
A/cm Fluctuates in the range of 1–3 A/cm ,
(1–2
Wide A/cm 2) mode
square-wave 29.8 µV/h @ 21 A/cm2 atestep
increasing degradation.
time of current would
(1–3 A/cm2 ) 21.7 µV/h 52.7
W12 @ 1µV/h
A/cm@ 3 A/cm 2 accelerate degradation, but there
N22 seems to be an upper limit.
24.9 µV/h 36.7
@ 2µV/h
A/cm 2
@ 1 A/cm2
W22
52.8 µV/h @ 3 A/cm2
39.7 µV/h @ 1 A/cm2 Near 2–3 A/cm2 , increasing step
Simulating solar mode Solar 52.4 µV/h @ 2 A/cm2 time, the maximum degradation
87.7 µV/h @ 3 A/cm2 rate occurs.
 Solar 52.4 µV/h @ 2 A/cm2
mode maximum degradation rate occurs.
87.7 µV/h @ 3 A/cm2

Materials 2024, 17, 1331

3.1. PEMWE Performance Change
5 of 13
This investigation is divided into three modes: constant current, square wave,
simulated solar. In the 600 h test time of this experiment, except for the existence of
3.1. PEMWEenhancement
formance Performance Change
at the beginning of the test, the voltage gradually increases w
timeThis investigation is divided into three modes: constant current, square wave, and
thereafter.
simulated
Figure solar. In thethat
2 shows 600 the
h test time of thisrates
degradation experiment, exceptmodes
of different for theareexistence
obviouslyof differ
performance enhancement at the beginning of the test, the voltage gradually increases with
Figure 2a shows the degradation pattern in the constant-current mode, and the three fi
time thereafter.
linesFigure
show2theshowsdegradation rates of the
that the degradation ratesthree constant
of different modescurrents. Consistent
are obviously with comm
different.
sense,2a
Figure a shows
higherthecurrent leadspattern
degradation to a greater degradation rate.
in the constant-current mode, Figure
and the2b shows
three fittedthe relat
ship between the degradation rate and the step time for different square-wave fluc
lines show the degradation rates of the three constant currents. Consistent with common
sense,
tions,aandhigher
thecurrent leads to abetween
relationship greater degradation rate. Figure
the degradation rate2band
showsthethe relationship
step time appears t
between the degradation rate and the step time for different square-wave fluctuations, and
different for the wide and narrow square-wave tests. The plots of the voltage with tim
the relationship between the degradation rate and the step time appears to be different
different
for the wide square-wave tests are compared,
and narrow square-wave as shown
tests. The plots in Figure
of the voltage withS3. Briefly,
time the degrada
in different
square-wave tests are compared, as shown in Figure S3. Briefly, the degradation ratedependin
rate is linearly correlated with the step time, although this trend changes is
whether
linearly a narrow
correlated orthe
with wide
stepsquare-wave
time, althoughtest this is used.
trend Increasing
changes dependingthe on
step time in the w
whether
asquare-wave
narrow or wide testsquare-wave test is used.
would accelerate Increasingconversely,
degradation; the step timeincreasing
in the widethe square-
step time in
wave
narrow testsquare-wave
would accelerate degradation;
test would slow conversely, increasing
degradation. the step
Figure time in the narrow
2c demonstrates that the lar
square-wave test would slow degradation. Figure 2c demonstrates that the largest increase
increase in voltage in this investigation is solar. And the data for all sets of voltage
in voltage in this investigation is solar. And the data for all sets of voltage over time are
time are
shown shownS1–S4.
in Tables in Tables S1–S4.

Figure2.2.(a)
Figure (a)Voltage
Voltagechange at different
change constant-current
at different density, and
constant-current the slope
density, andofthe
theslope
fitted of
linethe fitted
represents
represents average degradation rate. (b) The relationship between degradation rateinand step
average degradation rate. (b) The relationship between degradation rate and step time
narrow and and
in narrow widewide
square-wave tests. (c)tests.
square-wave Voltage
(c)rise in solarrise
Voltage at different
in solarcurrent densities.
at different current densities.
More information could be derived from Figure 3a–c, as after AST, the degradation
rate at the larger current was always greater than the degradation at the smaller current.
The degradation rate follows a different pattern from the current step time for different
square-wave modes. In the wide square-wave mode, the degradation rate of W02 increased
from 46.2 µV/h to 52.7 µV/h with W12, continued to increase the current step time W22,
and then degradation rate reached a maximum value of 52.8 µV/h calculated at 3 A/cm2 .
The rate of degradation increased with the increase in the current step time. In contrast, the
 rate at the larger current was always greater than the degradation at the smaller current.
The degradation rate follows a different pattern from the current step time for different
square-wave modes. In the wide square-wave mode, the degradation rate of W02 in-
creased from 46.2 µV/h to 52.7 µV/h with W12, continued to increase the current step time
Materials 2024, 17, 1331 W22, and then degradation rate reached a maximum value of 52.8 µV/h calculated at 3
6 of 13
A/cm . The rate of degradation increased with the increase in the current step time. In
2

contrast, the degradation rate decreased with the increasing step time in the narrow
square-mode test.decreased
degradation rate The speculation
with theofincreasing
this phenomenon
step timeisinthat in the narrow
the narrow square-wave
square-mode test.
mode, low current
The speculation of would produce less
this phenomenon impact,
is that in theand the main
narrow influencing
square-wave factor
mode, of degra-
low current
wouldwould
dation producebe less
the impact, and the
rapid change inmain influencing
current; factorinofthe
meanwhile, degradation would be mode,
wide square-wave the
rapid change in current; meanwhile, in the wide square-wave mode, it would
it would be exposed to higher currents for longer time, the main influencing factor would be exposed
betothe
higher
highcurrents
current,forandlonger time, theofmain
the degree influencing
impact of the highfactor wouldwould
current be the be
high current,
greater than
and the degree of impact of the high current would be greater than the current
the current switching process, which explains the increase in the current step time accom- switching
process,
panied bywhich explains
an increase inthe
theincrease in the
decay rate. current step
Therefore, thistime accompanied
leads by anobtained
the fastest AST increase from
in
the decay rate. Therefore, this leads the fastest AST obtained from the square-wave mode
the square-wave mode to be W22.
to be W22.

C3′ s(a)
Figure3.3.C3′s
Figure (a)polarization
polarization curves
curves at different
differenttimes,
times,(b)
(b)EIS
EISover
overtime, and
time, (c)(c)
and CVCV
plots changes
plots changes
before
beforeand
andafter
afterAST.
AST.

Theconstant-current
constant-current mode 2
The mode test
testwas
wasused
usedtotoallow
allowthe
theelectrolyzer
electrolyzerto run at 1atA/cm
to run 1 A/cm, 2,
2 A/cm 2 , and 3 A/cm2 for 600 h. Polarization curves and EIS were recorded periodically
2 A/cm , and 3 A/cm for 600 h. Polarization curves and EIS were recorded periodically to
2 2
to analyze the degradation pattern. Figure 2a indicates that the fastest AST in the constant-
analyze the degradation pattern. Figure 2a indicates that the fastest AST in the constant-
current mode is C3, and Figure 3 shows the electrochemical tests during the test period.
current mode is C3, and Figure 3 shows the electrochemical tests during the test period.
Figures S4 and S5 show the difference between the fresh MEA and the MEA after running
Figures S4 and S5 show the difference between the fresh MEA and the MEA after running
at a constant-current density of 3 A/cm2 for 600 h, where more cracks and bumps were
atobserved
a constant-current density of 3 A/cm 2 for 600 h, where more cracks and bumps were
on the surface of the anode catalyst layer by using SEM. Additionally, the content
observed on
after EDS showed the surface of the
a change anode
in the catalyst
elemental layermainly
content, by using SEM. Additionally,
a decrease the of
in the percentage con-
tent after EDS showed a change in the elemental content, mainly a decrease
Ir from 86.62% to 81.71%, an increase in O from 7.79% to 10.45%, and in increase in F from in the per-
centage of Ir from 86.62% to 81.71%, an increase in O from 7.79% to 10.45%,
5.59% to 7.84%. A similar situation occurred with the square-wave mode test and the solar and in increase
inphotovoltaic
F from 5.59% to ASTs,
mode 7.84%.asAshown
similarin situation occurred
Figures S6–S8 (N02, with the square-wave
W22, and solar). The CVmodecurvestest
and the solar
in Figure S9, photovoltaic
observed from mode ASTs,(0ash),
the initial shown in Figures
intermediate S6–S8
state (N02,
(200 and W22,
400 andfinal
h), and solar).
(600 h) states, show a larger recession in AST at W22, which is consistent with the larger
increase in measured voltage.
The IV curve in Figure 3a shows that in the part of the current density that is less
than 0.5 A/cm2 , the polarization curve basically does not change with time, indicating
that the electrolyzer performance is stable and less affected by test condition. However, in
Materials 2024, 17, 1331 7 of 13

the region of higher current density, the voltage gradually increases with time. Although
during the early part of this investigation the magnitude of voltage values increased and
decreased at times, all the values showed a pattern of degradation after 600 h of AST.
Figure 3b shows the Nyquist plot of the EIS spectrum at 0.2 A/cm2 ; the high-frequency
impedance decreases in the early part of AST and then increases, which is consistent with
the voltage decrease in the polarization curve in the early part of the AST. The initial and
final CV curves of the fastest AST for the constant-current mode are shown in Figure 3c.
Usually, the area under the CV curve represents the amount of redox charge involved in
the electrochemical reaction. The capacitance current will be less than the initial current,
and this is a result of the lower performance of the electrolyzer; the same change has been
observed in previous studies [33,34]. The average oxidation and reduction currents of the
electrolyzer decreased after the durability test, the catalytic performance decreased, and
the degradation was evident in the electrochemical characterization tests.
Figure 4 shows the degradation of the three ASTs in wide square-wave mode, with
the average degradation rate calculated every 100 h for a total of 600 h of degradation.
The average degradation rate at different times of the wide square mode can be seen
from Figure 4a–c, except for the 100 h at the beginning of the experiment. Due to other
factors, W12 has a faster degradation in the same fluctuation range, and then all of the
wide square-wave modes satisfy the pattern that the degradation rate and the current
step time are positively correlated. Passivation of Ti tends to occur at high potentials
because when the titanium capacitive is passivated and an oxide layer is formed on the
surface, the oxide layer prevents the transfer of electrons and ions, leading to an increase in
electrolytic resistance, which in turn requires a higher voltage to maintain a certain current
density [35,36]. This will increase the energy consumption and voltage of the electrolysis
process. After the titanium plate passivates to a certain degree, the surface oxide layer will
not be significantly thickened by the high voltage; that is, the titanium plate reaches a more
stable state due to the existence of the surface oxide layer, which enhances the corrosion
resistance and electrochemical stability of the titanium plate at the expense of part of the
electrode efficiency to obtain the property of long-term stability. However, since this part
of the change occurs inside the electrolyzer, there is no study that can accurately describe
the mechanism of the change. Some relevant studies have shown that it is possible to
plate a layer of titanium plate with a good conductivity line and electrocatalytic activity
Pt, the purpose of which is to artificially inhibit the oxidation of the titanium plate and
protect the Ti substrate from corrosion passivation with the Pt layer, which can reduce
the electrolysis voltage to a certain extent and improve the performance of the electrolytic
water by enhancing the stability of the components.

3.2. Analyzing the Evolution of Resistance

As can be seen in Figure 5b, an impedance spectrum can be described by two semi-
circles, which correspond to the two R-C models in Figure 5a and are referred to as the
high-frequency arc RHF and the low-frequency arc RLF , whose centers are below the real axis.
This indicates the presence of non-ideal capacitive behavior [37,38]. The high-frequency in-
tercept on the real axis represents the total ohmic resistance of the electrolyzer, mainly from
the electrical or ionic conductive elements, which corresponds to Rohm in the equivalent
circuit model. The difference between the low-frequency and high-frequency intercepts of
Rohm in the plot is defined as the polarization resistance (Rp ). The shape and magnitude of
the impedance spectrum of the electrolytic bath significantly change with current density.
When the current density is high enough, the polarization resistance (RHF + RLF ) becomes
small and the impedance becomes mainly ohmic. The literature suggests that the effect
of the cathode process is responsible for RHF [39]. On the other hand, the anode process
(OER) corresponds to RLF . Since the analysis of impedance at low currents is of practical in-
terest because of the possibility of partial-load operation in grid-balancing services and the
phenomena observed at small current densities mainly reflect the behavior of the catalyst,
comparatively, the AC impedance at high current densities is not very useful.
Materials 2024, 17, x FOR PEER REVIEW 8 of 14
Materials 2024, 17, 1331 8 of 13

Figure
Materials 2024, 17, x FOR PEER Average degradation rate at 1 A/cm2 and 3 A/cm2 for (a) W02, (b) W12, and (c) W22 with
4. REVIEW 9 of 14
Figure
time in4.wide
Average degradation
square rate at 1 A/cm
mode. (d) Comparison of theand
2 3 A/cm2 for
degradation (a) W02,
of three ASTs(b)
at 1W12,
A/cmand
2 in(c) W22 with
wide
time in wide mode.
square-wave square mode. (d) Comparison of the degradation of three ASTs at 1 A/cm2 in wide
square-wave mode.

3.2. Analyzing the Evolution of Resistance

As can be seen in Figure 5b, an impedance spectrum can be described by two semi-
circles, which correspond to the two R-C models in Figure 5a and are referred to as the
high-frequency arc RHF and the low-frequency arc RLF, whose centers are below the real
axis. This indicates the presence of non-ideal capacitive behavior [37,38]. The high-fre-
quency intercept on the real axis represents the total ohmic resistance of the electrolyzer,
mainly from the electrical or ionic conductive elements, which corresponds to Rohm in the
equivalent circuit model. The difference between the low-frequency and high-frequency
intercepts of Rohm in the plot is defined as the polarization resistance (Rp). The shape and
magnitude of the impedance spectrum of the electrolytic bath significantly change with
current density. When the current density is high enough, the polarization resistance (RHF
+Figure
RLF) becomes small
Figure
5. (a) Equivalent and
5. (a) the impedance
Equivalent
circuit model circuit (b)becomes
model
[40] and and (b)mainly
[40] measured
EIS ohmic.
EISatmeasured
different at Thedensities.
different
current literature suggests
current densities.
that the effect of the cathode process is responsible for RHF [39]. On the other hand, the
anodeThe process The loss
loss of(OER)
performance of performance
corresponds to RisLF.categorized
is categorized into
Since the into
reversible reversible
loss
analysis and loss and irreversible
ofirreversible
impedance loss, itloss, and
and currents
at low
has been it
shown has been
that shown
allowing that
the allowing
electrolyzerthe electrolyzer
to dwell timeto dwell
(zero time (zero
current)
is of practical interest because of the possibility of partial-load operation in grid-balancing current)
for a for a
sufficient sufficient
period of time period
couldof time could
restore somerestore some
of the of the reversible
reversible loss [41].lossIn[41]. In addition
addition to reversible loss,
to reversible
services and the phenomena observed at small current densities mainly reflect the behav-
destructive
loss, destructive degradation
degradation of theofcatalyst
the catalyst occurs,
occurs, whichwhich results
results in anin an increase
increase ininthe
the polari-
ior of the catalyst,
polarization zation
comparatively,
resistance,
resistance, known known the AC impedance
as irreversible
as irreversible loss. loss.
Apart
atfrom
Aparthigh
from current
the the
effect
densities
effect of the
of the
is not very
catalyst,
catalyst, other
useful.
other factorsfactors that contribute
that contribute to the to voltage
the voltage increase
increase include
include thethedecline
declineininindividual
individual compo-
components nents
in thein the electrolyzer.
electrolyzer.
The relevantindicates
The relevant literature literaturethat
indicates that the changes
the changes in electrolyzer
in electrolyzer performance
performance can can be
explained by the changes in the proton exchange membrane and
be explained by the changes in the proton exchange membrane and PTL, and the effect PTL, and the effect of
PTL is mainly a negative effect due to surface corrosion and the passivation of the Ti plate,
but there may also be other effects on non-ohmic resistance. The common method used
today is the Nyquist plot, where the high-frequency impedance represents the total ohmic
impedance. In this investigation, the high-frequency impedance was analyzed to under-
stand the change in ohmic impedance of the membrane electrodes in different ASTs.
 Materials 2024, 17, 1331 9 of 13

of PTL is mainly a negative effect due to surface corrosion and the passivation of the Ti
plate, but there may also be other effects on non-ohmic resistance. The common method
used today is the Nyquist plot, where the high-frequency impedance represents the total
ohmic impedance. In this investigation, the high-frequency impedance was analyzed to
understand the change in ohmic impedance of the membrane electrodes in different ASTs.
Figure 6 shows the percentage rate of change in high-frequency impedance with time,
at a current density of 2 A/cm2 . In this investigation design of ASTs, a slight decrease
in high-frequency impedance at the beginning of the test can be observed. We speculate
that it is the insufficient activation process that produces this phenomenon, so all the first
100 h are regarded as the activation time in the impedance calculation process; thereafter,
the increase in high-frequency impedance was mainly due to the effect of the titanium
plate [18,25]. By analyzing the graphs as the ohmic resistance increases, the degradation
rate due to a combination of influences other than the titanium plate can be obtained. The
total degradation rate was extracted from the polarization curve, except for first 100 h at
2 A/cm2+ , and HFR increasing was used to calculate the degradation from the titanium
plate, which was subtracted to obtain the non-ohmic degradation. From Figure 7, although
the pattern of total degradation rate versus current step time varied with square-wave
mode, evidently, as the step time increases, the degradation rate due to ohmic impedance,
i.e., the negative impact of corrosion and passivation on the performance of the titanium
Materials 2024, 17, x FOR PEER REVIEW decreases. This was probably due to the shorter residual time of oxygen within the
plate, 10
electrode operation during cyclic operation. This is also the reason suggested earlier as a
reason for lower local membrane dehydration of the proton membrane dehydration.

Figure6.6.Percentage
Figure Percentage change rate in
change HFR
rate in over
HFRtime
overfortime
(a) constant-current mode, (b) narrow
for (a) constant-current mode,square-
(b) narrow sq
wave
wavemode,
mode, (c)(c)
wide square-wave
wide mode,mode,
square-wave and (d)and
solar.
(d) solar.
Materials 2024, 17, 1331 10 of 13

Figure 7. Separation of the impact of ohmic resistance on the voltage degradation rate at 2.0 A/cm2 .
The total degradation rate was extracted from IV curves at different times.

Compared with the previous ASTs in this investigation, the ohmic impedance follows
the same law of becoming smaller and then increasing. Because the durability test time is
long for 1430 h, and the ohmic impedance decrease was observed in the first 100 h, which
indicates that the passivation of the Ti plate was basically stable, the decrease in the ohmic
value in the early part of the investigation was caused by the incomplete activation process.
The degradation rates shown in Figure 6a are consistent with common sense, and high
current will promote degradation. C1 is special, as the final high-frequency impedance
has a very small reduction compared to the start, indicating that the influence of C1 on the
titanium plate is small. Alongside this, the membrane and the titanium plate bring about
the effect to counteract each other, so the 1 A/cm2 current mode is not able to accelerate
degradation. Figure 6b,c shows the percentage change in high-frequency impedance in
the square-wave mode, and larger changes occur in the wide square-wave mode, affected
by high current. Meanwhile, Figure 6d illustrates that solar simulation would cause more
severe corrosion and passivation of the titanium plates, in the form of increased high-
frequency impedance.
Figure 7 shows that the separation of voltage degradation rate and the phenomenon of
high-frequency impedance decrease exist in the first 100 h of each AST, indicating that the
electrolyzer has not reached a stable state; consequently, it is not included in the calculation
of the degradation rate separation. Thereafter, the high-frequency impedance continues
to increase, implying that the titanium plate is gradually corroding and passivating. In-
terestingly, different from the law of total degradation rate, the voltage degradation due
to ohmic resistance decreases when increasing the step time. The speculation of this phe-
nomenon is that the gas produced from the catalyst layer is not discharged in time under
the case of rapid current change and remains in the GDL; thus, the insufficient exchange of
substances increases the impedance value, which ultimately leads to irreversible damage
to the membrane electrodes.

4. Conclusions
In summary, we investigated the impact of different AST conditions on an electrolyzer’s
performance, including constant-current, square-wave, and simulate photovoltaic fluctua-
tions, by collecting polarization curves and electrochemical impedance spectroscopy data,
offering comprehensive insights into the electrolyzer’s performance dynamics.
In the constant-current density mode tests, a consistent consensus was that the higher
current density yields higher degradation rates of the operating voltage compared to

1
Materials 2024, 17, 1331 11 of 13

the instances involving lower current densities. The square-wave measurements lead to
two counter trends: within a narrow fluctuation range (1–2 A/cm2 ), the short step time (2 s)
exhibits a higher degradation rate compared to the long step times (12 and 22 s). However,
within a wide fluctuation range (1–3 A/cm2 ), the trend is inverse. The degradation rate
associated with the current step time of 22 s was observed to be higher than those of the
2 and 12 s. For the simulating solar test, which consists of multiple constant-current density
and square-wave modes, the investigations indicate that a high current density and long
step time would lead to the most serious degradation rate compared with other ASTs.
Our investigation offers valuable insights into accelerating test efficiency and un-
derstanding service life by elucidating the intricate relationship between current-related
parameters and electrolyzer performance degradation. Understanding these factors makes
it possible to balance research with the design and operation of PEM electrolysis systems
to improve overall performance and reliability. Consequently, when executing ASTs that
encompass high-current conditions, meticulous consideration and balance of all component
responses become imperative. This equilibrium is crucial due to the interconnected nature
of the system components.

Supplementary Materials: The following supporting information can be downloaded at: https://www.
mdpi.com/article/10.3390/ma17061331/s1. Figure S1. A graphical outline of accelerated stress tests.
Figure S2. (a) Schematic diagram of the structure and (b) exploded view of the electrolyzer used
in the investigation. Figure S3. Degradation rate of narrow square wave mode in (a) 1 A/cm2 and
(b) 2 A/cm2 , and degradation rate in (c) 1 A/cm2 and (d) 3 A/cm2 for wide square wave mode, the
slope k represents the degradation rate. Figure S4. (a) High and (b) low magnification SEM images
and (c–f) EDS mappings of the fresh MEA used in this investigation. Figure S5. (a) High and (b) low
magnification SEM images and (c–f) EDS mappings of the MEA after constant current mode AST
C3. Figure S6. (a) High and (b) low magnification SEM images and (c–f) EDS mappings of the MEA
after narrow square wave mode AST N02. Figure S7. (a) High and (b) low magnification SEM images
and (c–f) EDS mappings of the MEA after wide square wave mode AST W22. Figure S8. (a) High
and (b) low magnification SEM images and (c–f) EDS mappings of the MEA after solar photovoltaic
mode AST. Figure S9. CV curves over time in (a) constant current density mode AST C3, (b) narrow
square wave mode AST N02 and (c) wide square wave mode AST W22. Table S1. Voltage at different
times in constant current test. Table S2. Voltage in 1 A/cm2 and 2 A/cm2 at different times in narrow
square wave mode test. Table S3. Voltage in 1 A/cm2 and 3 A/cm2 at different times in wide square
wave mode test. Table S4. Voltage at different times in Simulating solar fluctuation test.
Author Contributions: Methodology, P.L.; Software, P.L.; Validation, C.L.; Investigation, Z.S.; Data
curation, Z.S.; Writing—original draft, Z.S.; Writing—review & editing, J.L.; Project administration,
C.L.; Funding acquisition, J.L. and C.L. All authors have read and agreed to the published version of
the manuscript.
Funding: This work was financially supported by the National Natural Science Foundation of China
(NSFC, 51971211, 52071313), the Youth Innovation Promotion Association of CAS (2017483), the
HFIPS Director’s Fund (YZJJ202102, YZJJKX202202, YZJJ-GGZX-2022-01), and the Plan for Anhui
Major Provincial Science & Technology Project (Grants 2021d05050006).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Data are contained within the article and Supplementary Materials.
Conflicts of Interest: The authors declare no conflict of interest.

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