i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3

Available online at www.sciencedirect.com

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journal homepage: www.elsevier.com/locate/he

Review Article

Influence of renewable energy power fluctuations

on water electrolysis for green hydrogen production

Hirokazu Kojima a,*, Kensaku Nagasawa b,**, Naoto Todoroki c,***,

Yoshikazu Ito d,****, Toshiaki Matsui e,*****, Ryo Nakajima f,******
a
Renewable Energy Research Center, National Institute of Advanced Industrial Science and Technology, 2-2-9
Machiikedai, Koriyama, Fukushima, 963-0298, Japan
b
Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, 240-
8501, Japan
c
Graduate School of Environmental Studies, Tohoku University, Sendai, 980-8579, Japan
d
Institute of Applied Physics, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, 305-
8573, Japan
e
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku,
Kyoto 615-8510, Japan
f
International Research Center for Hydrogen Energy, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka, 819-
0395, Japan

highlights graphical abstract

Renewable energy characteristics

significantly influence electrolyzer
performance.

Smoothing of photovoltaic and
wind power occurs in large-scale
power generation.

Degradation of electrode/mem-
brane was accelerated by poten-
tial/temperature changes.

Universal protocols for accelerated
degradation tests must be devel-
oped and shared.

The effects of direct input of
renewable energy on electrolyzers
must be studied.

* Corresponding author.
** Corresponding author.
*** Corresponding author.
**** Corresponding author.
***** Corresponding author.
****** Corresponding author.
E-mail addresses: hirokazu-kojima@aist.go.jp (H. Kojima), nagasawa-kensaku-st@ynu.ac.jp (K. Nagasawa), naoto.todoroki.b1@
tohoku.ac.jp (N. Todoroki), ito.yoshikazu.ga@u.tsukuba.ac.jp (Y. Ito), matsui@elech.kuic.kyoto-u.ac.jp (T. Matsui), ryo.nakajima.kyushu@
techno2050.com (R. Nakajima).
https://doi.org/10.1016/j.ijhydene.2022.11.018
0360-3199/© 2022 The Author(s). Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY
license (http://creativecommons.org/licenses/by/4.0/).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3 4573

article info abstract

Article history: The development of renewable energy technologies is essential to achieve carbon
Received 7 September 2022 neutrality. Hydrogen can be stably stored and transported in large quantities to maximize
Received in revised form power utilization. Detailed understanding of the characteristics and operating methods of
19 October 2022 water electrolysis technologies, in which naturally intermittent fluctuating power is used
Accepted 2 November 2022 directly, is required for green hydrogen production, because fluctuating power-driven
Available online 24 November 2022 water electrolysis processes significantly differ from industrial water electrolysis pro-
cesses driven by steady grid power. Thus, it is necessary to overcome several issues related
Keywords: to the direct use of fluctuating power. This article reviews the characteristics of fluctuating
Carbon neutrality power and its generation as well as the current status and issues related to the operation
Hydrogen conditions, water electrolyzer configuration, system requirements, stack/catalyst dura-
Renewable energy bility, and degradation mechanisms under the direct use of fluctuating power sources. It
Water electrolyzer also provides an accelerated degradation test protocol method for fair catalyst perfor-
Durability mance comparison and share of effective design directions. Finally, it discusses potential
challenges and recommendations for further improvements in water electrolyzer com-
ponents and systems suitable for practical use, suggesting that a breakthrough could be
realized toward the achievement of a sustainable hydrogen-based society.
© 2022 The Author(s). Published by Elsevier Ltd on behalf of Hydrogen Energy Publications
LLC. This is an open access article under the CC BY license (http://creativecommons.org/
licenses/by/4.0/).

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4573
Fluctuations in renewable energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4574
Photovoltaic power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4574
Wind power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4575
Hydrogen production systems using renewable energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4576
Power supply using renewable energy and electrolyzer durability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4577
Causes of water electrolyzer degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4577
Accelerated degradation test protocol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4578
Issues associated with water electrolyzers using renewable energy-based electric power . . . . . . . . . . . . . . . . . . . . . . . . . 4580
Issues associated with alkaline water electrolyzers using renewable energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4580
Issues associated with PEM water electrolyzers using renewable energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4583
Dynamic characteristics of SOECs using renewable energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4584
Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4587
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4588
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4588
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4588

sustainable society, it is necessary to employ renewable

Introduction
Carbon-neutral initiatives intended to reduce greenhouse gas
emissions to zero by 2050 are being conducted worldwide [1,2].
The main sources of global CO2 emissions are power genera-
tion (40%), industrial activities (23%), and transportation (23%),
with the remaining 14% coming from other areas [3]. Various
initiatives have been suggested to reduce these emissions. For
instance, several scenarios in the energy sector are being
considered to increase the contribution of renewable energy
sources [4] such as hydropower, wind power, solar power,
geothermal power, wave and tidal power, and biomass power
to the total energy generated by ~90%, of which ~70% will be
provided by photovoltaic and wind power [5]. To achieve a
energy-based systems instead of fossil fuel-derived energy-
based systems [6e11].
Photovoltaic and wind power generation depends on the
weather, and large quantitative and temporal discrepancies
exist between the available power supply and demand. Thus,
maximizing the utilization of renewable energy currently re-
quires grid power adjustments with energy storage technol-
ogy. Moreover, as renewable energy has a naturally
intermittent character with highly uneven spatial distribu-
tion, establishing a means of energy transport to balance en-
ergy demand and supply areas is of great importance.
The electric power generated by renewable energy can be
stored using flywheels, water pumps, storage batteries,
4574 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
chemical substances (e.g., energy carriers), etc. The appro-
priate means of storage depends on the energy storage period
and amount, and storage batteries are generally employed to
balance power changes over short periods of time. However,
constructing large-scale plants for storage battery production
involves high costs, and some disadvantages such as the un-
suitability of batteries for long-term energy storage have been
identified. Meanwhile, hydrogen can be stably stored and
transported in large quantities in the form of liquid hydrogen
or other energy carriers such as ammonia and organic hy-
drides [12e18]. With these advantages, the importance of
hydrogen energy in achieving a carbon-neutral society is
increasingly being recognized, and hydrogen energy technol-
ogies manage the balance of power changes more effectively
than storage battery technologies [8].
Hydrogen is classified based on the production method and
process, such as steam reforming [19], water electrolysis,
biomass gasification [20], thermochemical hydrogen produc-
tion [21,22], or photocatalysis [23e28]. For example, gray
hydrogen is produced by emitting CO2 from fossil fuels; blue
hydrogen emits CO2 during the production process but sub-
sequently recovers and stores it in the ground; and green
hydrogen is produced by renewable energy-driven water
electrolysis [8,29]. In particular, water electrolysis for green
hydrogen has been an important technology for producing
renewable hydrogen along with fuel cells (FCs) [30e32].
Water electrolysis can be classified as alkaline water elec-
trolysis (AWE) [33e36], polymer electrolyte membrane water
electrolysis (PEMWE) [37e41], solid oxide electrolysis [40,42,43]
and others (anion exchange membrane water electrolysis
(AEMWE) [38,44e46] and protonic ceramic electrolysis cell
(PCEC) [47,48]). AWE can easily be scaled up by employing salt
electrolysis technologies. Many of the electrodes are not
precious metals and are relatively inexpensive. However, this
conventional system is not designed to be operated by
combining fluctuating power sources, and its performance
progressively degrades when the power supply is switched off
[49]. PEMWE is relatively resistant to fluctuating power and
shows less performance degradation with switch on/off ac-
tions than AWE. Thus, it is beneficial in operations with fluc-
tuating power [41]. However, precious metal electrode
catalysts and other components in PEM water electrolyzers
prevent worldwide popularization of this technique because of
cost and reserves issues. Solid oxide electrolysis cells (SOECs)
are expected to have high electrolytic efficiencies owing to
their low theoretical electrolysis voltages, although the current
technical maturity of SOECs is lower than those of AWE and
PEMWE. In addition, SOECs are promising for use in synthetic
fuel production through co-electrolysis [50]. Given such vary-
ing features, the appropriate water electrolysis technology
must be selected according to the intended purpose.
The production of hydrogen using fluctuating power is ex-
pected to be a low-cost hydrogen production method and dif-
fers significantly from industrial hydrogen production using
steady grid power. For example, the electrolyzer temperature
repeatedly changes from low to high under fluctuating power
operation. Thus, a thermally stable stack/cell is necessary.
Moreover, starting and stopping the operation of a water
electrolyzer could lead to degradation of its components. In
this way, these differences cause many new problems, which
are not considered in industrial processes. Furthermore,
photovoltaic/wind power rarely satisfies the requirements of
electrolyzer operation. Therefore, the system must be
compelled to operate under a wide fluctuating power range.
This review summarizes the characteristics of fluctuating
power for operation/system restrictions, effective operation
methods and configurations/components of water electro-
lyzers, system requirements and durability, catalyst degra-
dation, and universal electrolyzer performance evaluation to
clarify the issues related to fluctuating power operation.
Further, it describes the current achievements and potential
challenges related to water electrolyzers to promote the
realization of a hydrogen-based society.
Fluctuations in renewable energy
Photovoltaic and wind power generation are accessible
power generation modalities, although the amount of electric
power fluctuates strongly depending on the location and
weather conditions. To investigate appropriate system con-
figurations and operating conditions, it is necessary to un-
derstand both the naturally intermittent power fluctuation
patterns in photovoltaic and wind power generation and the
influences of fluctuations that accelerate performance
degradation of water electrolyzers, because these fluctuation
patterns do not follow Gaussian distributions [51] and are
fairly complicated. This section introduces the characteris-
tics of photovoltaic and wind power generation that have
been identified to date.
Photovoltaic power
The amount of photovoltaic power generation has been pre-
dicted based on weather forecasts [52,53]. Weather is classi-
fied according to the three (four) representative patterns of
“sunny,” “cloudy,” and “rainy” [53] (or “light rain” and “heavy
rain” [54]). Analyses of changes in very stable solar radiation
(sunny) on the time scale of minutes result in high electric
power generation and low solar radiation fluctuation rates of
<50 W/(m2 min), whereas analyses of changes in highly un-
stable solar radiation (cloudy) result in low electric power
generation and large solar radiation fluctuation rates of
>150 W/(m2 min) [55]. Understanding these representative
patterns, which can be divided by day, is important for pre-
dicting the amount of photovoltaic power generation and
reducing their loads on grid power. Recent attempts to classify
such patterns by machine-learning-based clustering using the
time-series data of power generation have been reported. For
example, several researchers have described the effects on
clustering the multiple daily patterns of photovoltaic power
generation time-series data by utilizing cluster approaches/
numbers [56], analysis of sample entropy [57], and analysis
using fractal dimensions [58]. Indeed, a pattern was obtained
from sites (a) and (b) in Fig. 1 by representative pattern clas-
sification. In the mostly sunny case, Class 1 is an easily pre-
dictable pattern in which the amount of photovoltaic power
generation is the highest during the day. In the mostly cloudy
case, Class 3 produces a high load on the grid power due to the
large fluctuations and could decrease water electrolysis
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
Fig. 1 e Examples of days belonging to the three classes at
sites (a) and (b) for various patterns (Classes 1e3). Adapted
with permission from Ref. [58]. Copyright 2005, Springer
Nature.
performance. These classifications will accelerate the utili-
zation of water electrolyzers in photovoltaic power
generation.
A smoothing effect that can reduce the range of fluctuations
in photovoltaic power generation has been reported by
combining the generation from multiple areas. In previous
studies, bundling nine points within a 3 km range as a short
distance example decreased the amplitude in sunny cases,
even decreasing the amplitude by more than 50% in cloudy
cases [59]. As a long-distance example, the smoothing effect
was observed from a large number of power plants scattered
over 1000 km and the amplitude of fluctuations decreased with
increasing number of power plants [60]. These effects were
also observed in photovoltaic power plants located 6e360 km
apart [61] and in 1.4 MW and 9.5 MW photovoltaic power plants
[62]. These findings indicate that increasing the number and
scale of photovoltaic power plants could decrease the ampli-
tude of fluctuations in photovoltaic power generation.
Wind power
Wind power generation is significantly affected by wind
speed. Whereas a proportional relationship exists between
4575
solar radiation and the amount of power generation, wind
power generation does not exhibit a proportional relation-
ship between wind speed and the amount of power gener-
ation. The process is more complicated than the
photovoltaic power process. For example, the wind speed
and direction as well as the generation amount vary
significantly over time [63]. The generation pattern also
fluctuates, depending on not only daily wind fluctuations,
but also the season [64]. Thus, wind power generation
modeling has been undertaken to achieve detailed pre-
dictions [65,66]. In addition, a wind farm model that con-
siders the spatial variations of turbulence, effects of
turbulence generated by the windmills themselves, and in-
teractions of these factors is necessary [67]. Although wind
speed time-series data have been compared and classified
using clustering methods to elucidate these factors [68], no
clear classification of fluctuation patterns is available at
present because the characteristics of power generation
depend on the inertia of wind turbine, implemented yaw
and pitch angle control, and so on. These power generation
units differ from photovoltaic power generation units and
become the keys to understand the pattern classification.
The amplitude of the fluctuations generated by multiple
wind turbines was reduced when the generation of 16 wind
turbines was combined under the assumption that short-
term fluctuations occurred in a probabilistic manner [69].
The investigation of multiple wind speed data measured at
six points within a range of 1e2 km (Fig. 2) [70] demonstrated
that a smoothing effect occurred for rapid fluctuations,
whereas almost no smoothing effects were observed for
fluctuations over time scales of more than 10 min. Analyses
of wind power generation data measured from 16 points
located over 100 km apart demonstrated the smoothing ef-
fect, which was also observed on short time scales of less
than 10 min even at longer distances [71]. Moreover, a
smoothing effect was observed for fluctuations shorter than
10 min in the cases of wind power generation at up to 24
plants at locations up to 130 km apart [72] and offshore wind
power generation at two plants with 80 and 72 wind turbines
[73]. These results indicate that the smoothing effect works
effectively if the time scale is within 10 min, even over long
distances.
Fig. 2 e Power spectral densities of the outputs of multiple
wind turbines for comparison between a single point and
sum of six points. Adapted with permission from Ref. [70].
Copyright 2004, Wiley.
4576 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3

Photovoltaic and wind power generation are strongly

steam conversion 27%, 2000 h

affected by the weather over time and fluctuate irregularly.
Photovoltaic power generation patterns can be classified,

TSP-1 (Haldor Topsøe)

whereas wind power generation patterns cannot at present.

Average 0.24 A/cm2,

750 or 800 (unclear)
Some smoothing effects in photovoltaic and wind power

SOEC

90% H2O/10% H2
generation have been confirmed by the scaling-up of genera-

Wind power
tion plants and bundling of the electric power generation
produced from the multiple plants.

7.5 (kW)
Project

[79]
110
75
e

e
e
Hydrogen production systems using renewable
energy

Photovoltaic power

water electrolyzer
GenHy®1000 PEM
Hydrogen production using fluctuating power requires
exploration of the best combinations according to the fluctu-
ating power source, presence or absence of storage batteries,

Project

[76,77]
use of an on- or off-grid system, and water electrolysis

250
1.0
12

90
method employed. This section introduces operation exam-

e
e

e
e
e
ples and the requirements of and restrictions on water elec-
trolysis using fluctuating power.

Photovoltaic power
The specifications and operating conditions of stack-

Table 1 e Specifications and test conditions for hydrogen production by electrolyzers using renewable energy.

Deionized water
HOGEN®RE PEM
based electrolyzers with simulated fluctuating power sour-

PEMWE

Commercial

electrolyzer
ces are summarized in Table 1 [74e79]. The electrolyzers and

1.1 A/cm2,
0.5 or 1.0

51e55  C
14,000 h,
cells mentioned are either commercially available or were

5 (Max)

>99.9
produced by demonstration projects and consume 10 kW of

[75]
6.6

75
e
e

e
power or less. In our survey, the number of reports
mentioning PEMWE was higher than that mentioning AWE,
and photovoltaic power use was major, whereas wind power
Photovoltaic power

use was minor [78]. In these papers, fluctuating power

E1050 PEM water

Deionized water
1.50e5.00 (Ca),
sources, their outputs, and electrolysis efficiencies were re-

0.15e0.25 (An)
Commercial

electrolyzer

ported. However, these articles only reported the follow-

80 (HHV)
ability of fluctuating power or changes in device performance
under varying temperatures or stack pressures. Very few
0.97

[74]
4.6

33
69

70
e

e
results on SOECs using fluctuating power on stacks have
been published. More importantly, some parameters such as
hydrogen gas purity and electrolysis efficiency have not been
HySTAT® alkaline
water electrolyzer

reported; thus, it is not possible to compare fairly the elec-

Wind emulator

trolyzer performances among the methods (see non-reported

30 wt% KOH
Commercial

74e83 (LHV)
AWE

terms in Table 1).

2.5 (Max)

Water electrolysis is an endothermic reaction, but a

>99.8

[78]
300

voltage higher than the theoretical electrolysis voltage is

4.9

22

65
e

necessary owing to the overpotential and ohmic loss. Indeed,

a 1 Nm3/h commercial water electrolyzer (Hydrogenics HyS-
TAT®) increases the electrolyzer temperature over time [80],
Power consumption (kWh/Nm3-H2)

even when using steady grid power. The electrolyzer char-

H2 production rate (Nm3-H2/h)

acteristics were further investigated using simulated wind

power generation [78]. The transient operation resulted in
considerable temperature increases with high power gener-
Experimental details
Hydrogen purity (%)

ation and temperature decreases with low power generation

Number of stacks

Temperature ( C)
Electrolyzer/cell

(Fig. 3). In addition, the crossover of the generated gas caused

Pressure (MPa)
Cell area (cm2)
Power source

Efficiency (%)

safety issues. The crossover gas (i.e., oxygen in hydrogen and

Reactant

hydrogen in oxygen) reached relatively high concentrations

when the amount of gas generated decreased with low power
generation (because the amount of hydrogen gas generated
was mostly determined by the current) (Fig. 3). Thus, the
fluctuations changed the electrolyzer state and generated gas
Conditions

Production

purity [81]. Moreover, a minimum power load restriction of

Durability

Reference

40% of the rated current was imposed during operation on an

Device

alkaline water electrolyzer without auxiliary equipment. In-

vestigations when falling below the minimum power load on
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3 4577

Fig. 3 e Simulation results for experimental wind power in an alkaline electrolyzer. (a) Evolution of the reference current
(iE,ref), current supplied to the electrolyzer (iE), voltage at the electrolytic module terminals (vE), and operating temperature (T)
and pressure (P) over time. (b) Evolution of the hydrogen flow (fH2), hydrogen transferred to the oxygen current (HTO), and
oxygen transferred to the hydrogen current (OTH) over time. Adapted with permission from Ref. [81]. Copyright 2013,
Elsevier.

alkaline water electrolyzers have been conducted to deter-

mine whether forcibly continuous operation is possible or
not to utilize renewable energy as much as possible [82]. The
results showed that 20 min operation was allowed and that
the number of operation stops of a water electrolyzer using
photovoltaic power could be halved. Thus, the energy effi-
ciency could be improved by an additional 6.3%. Further-
more, an investigation of the breakdown of electric power
consumption was conducted in a 60 kW PEM water electro-
lyzer using photovoltaic/wind power [83]. Among the auxil-
iary equipment in the system, a pressure swing adsorption
dehumidification unit exhibited the highest energy loss
(release of hydrogen gas), followed by the loss (power con-
sumption) in the auxiliary equipment and alternating cur-
rent/direct current (AC/DC) conversion units. These losses
led to a sharp decrease in water electrolysis efficiency
although the small amount of electric power (where the
rated current dropped below 50%) can be employed, and
fluctuating operations bring similar situations to electro-
lyzers. Thus, it is necessary to understand the different
abilities to support such fluctuation operations by clarifying
the factors determining such abilities, including cell struc-
tures and combinations with auxiliary equipment.
Photovoltaic and wind-power-based operation requires an
understanding of the operating conditions considering time
changes in stack/cell temperature, gas pressure, gas purity,
and amount of hydrogen gas generated, in addition to changes
in current and voltage. The range of input electric power is
limited, and its operation must be stopped when an insuffi-
cient amount of fluctuating power is available. Thus, concerns
related to the loss of opportunities to utilize renewable energy
and degradation of electrolyzer performance have been
raised. Decreases in the efficiency of hydrogen purification
devices when using small amounts of electric power have also
been observed, and the combination of auxiliary equipment in
the system has a major impact on the overall hydrogen pro-
duction efficiency.
Power supply using renewable energy and
electrolyzer durability
Photovoltaic and wind power generation exist in various time
cycles and output power fluctuation ranges. With these
characteristics, electrolyzer operation suffers from several
issues. For example, fluctuating power causes electrode
degradation due to sudden changes in electrode potential. In
particular, large potential changes are caused by the reverse
current generated when operation is stopped, which signifi-
cantly degrades the electrode performance of the electrolyzer
[84]. This section introduces catalyst degradation evaluation
methods by considering the factors causing degradations in
various water electrolysis methods and the potential fluctu-
ations caused by fluctuating power.
Causes of water electrolyzer degradation
Industrial water electrolyzers are bipolar-type electrolyzers
composed of multiple unit cells connected in series. A reverse
current originates from an electromotive force owing to
reverse reactions, in which the catalysts oxidized at the anode
and reduced at the cathode during electrolysis return to their
original chemical states during shutdown; the current flowing
in the closed circuit through a manifold connected to each
chamber is the reverse current [85,86] (Fig. 4). This reverse
current is often generated using photovoltaic or wind power
generation. The electrode degradation can be intentionally
prevented by flowing an arbitrary low protection current
during shutdown [87,88]. However, this method requires an
additional power supply to produce a protection current.
Therefore, a robust electrode that does not require a protec-
tion current must be developed.
Uchino et al. analyzed the reverse current by using
bipolar-type alkaline water electrolyzers [85,89] and
explained the characteristics of the reverse current in terms
4578 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3

Fig. 4 e Conceptual diagram of a bipolar-type electrolyzer. Adapted with permission from Ref. [85]. Copyright 2018, The
Electrochemical Society of Japan.

Fig. 5 e Electrode system with anodes after electrolysis at 0.6 A/cm2 and 30  C for 1 h. (a) Experimental (solid lines) and
simulated (dashed lines) reverse currents generated at the bipolar plate (BP) as a function of the shutdown time. (b) Electrode
potentials of the BPs and end plates (EPs) as functions of the shutdown time. Adapted with permission from Ref. [49].
Copyright 2022, Elsevier.

of an equivalent circuit. The redox reactions on the surface of
the Ni electrode with respect to changes in potential during
reverse current generation were experimentally investigated.
Haleem et al. [49] assessed the relationship between the cell-
stacking position and reverse current generation as well as
changes in potential, using a four-cell bipolar-type alkaline
water electrolyzer. They found that electrode degradation
showed rapid changes in the anode and cathode potentials
during operation start-up (Fig. 5). Moreover, experiments
have revealed that an appropriate combination of anode and
cathode catalysts is important for the design of electrolyzers
with high durability.
Accelerated degradation test protocol
The reverse current is the main cause of decreased electrode
performance. Comparative assessment of the components
and test parameters and shortening of the test time to accel-
erate catalyst degradation are necessary. To achieve these
objectives, the development of an accelerated degradation
test (ADT) is required to evaluate the durability of electrolyzer
components under practical conditions. A protocol applicable
to FCs was recently proposed, and unified tests were imple-
mented [90]. The protocol targets automobiles, and its pattern
evaluates the start and stop operations and power-load-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
Fig. 6 e Schematic of a unit cycle of the accelerated
durability test protocol. Adapted with permission from
Ref. [84]. Copyright 2021, The Electrochemical Society of
Japan.
response durability by using either triangular or rectangular
potential patterns [91,92]. A protocol that combines variations
in cell/stack temperature, humidity, fuel gas, flow rate,
chamber pressure, and constant current has also been devised
[93]. Many reports using the protocol for catalysts durability
on FCs are available, and the universal protocol significantly
facilitates developments related to FCs. Such initiatives are
also necessary for water electrolysis. Thus far, many ADTs
have been reported on water electrolysis; however, as will be
discussed later, the test conditions have not been unified
among research groups, institutions, and companies. Conse-
quently, performance comparisons with other groups are
difficult. Furthermore, few reports proposing common pro-
tocols considering fluctuating power have been published
[84,95,96]. This section introduces these issues in the case of
fluctuating power operation.
An ADT protocol was described for the anode durability
testing of alkaline water electrolyzers considering fluctuating
power and assumed a bipolar electrolyzer [84]. A single cycle
of the anode test involved constant-current control during the
operation period and voltage control for reverse current
simulation [85,89] during the showdown period (Fig. 6),
enabling anode degradation evaluations of a NiCoOx electrode
to be conducted over 2000 cycles within approximately 70 h.
As the constant-current tests using the same electrode at
600 mA/cm2 did not exhibit degradation after over 900 h, the
protocol is useful for shortening the durability test time to at
least 1/10 in the presence of a reverse current under practical
conditions.
Alia et al. [94] investigated five basic patterns typified for
fluctuating power inputs (i.e., holding, triangular, square,
sawtooth up, and sawtooth down) in degradation evaluations
of PEM water electrolyzers and reported that the square and
sawtooth patterns accelerated electrode degradation. More-
over, the degradation tests using the triangular and square
patterns showed that the degradation behavior of the
4579
Fig. 7 e Protocols of an accelerated stress test (AST)
simulating an intermittent power supply to a PEM water
electrolyzer with periods of low and high current density
followed by an OCV (“OCV-AST,” black solid lines) and a
reference test that avoids the OCV (“reference test,” blue
dotted lines) by holding the potential at 1.3 V. (a) Current
profiles obtained during the first cycle of the OCV test. (b)
Associated potential profiles recorded at 80  C with
pcathode ¼ 1 MPa and panode ¼ 0.1 MPa while feeding water
at a rate of 5 mL/min into the anode compartment. Adapted
with permission from Ref. [95]. Copyright 2019, IOP
Publishing. (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version
of this article.)
electrolyzer over time was similar to those obtained using
wind and photovoltaic power inputs. Furthermore, Weib et al.
[95] proposed a protocol considering start and stop operations.
This protocol simulated operation and shutdown under con-
stant currents of 3 and 0.1 A/cm2 followed by an open circuit
voltage (OCV, 0 A/cm2) in a single cycle (Fig. 7). The protocol
showed that the OCV accelerated degradation and that
avoiding the OCV period was important for ensuring long-
term stability.
Widely recognized ADTs have not been established for
SOECs, and lifespan predictions are conducted exclusively
using long-term durability tests. The factors accelerating the
degradation of solid oxide fuel cells (SOFCs) have been clar-
ified to some extent, but no studies have focused on the
degradation acceleration of SOECs [96]. A few factors influ-
encing accelerated degradation have been investigated, but
such investigations have been limited to the evaluation of
the effects of high current densities and impurities, whereas
no progress on the appropriate selection of operating pa-
rameters leading to degradation has been achieved yet
€ nigshofer et al. created
[97,98]. In response to this problem, Ko
4580 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
Fig. 8 e Characteristic data for an alkaline water electrolyzer operated using photovoltaic cells during the day. Adapted with
permission from Ref. [100]. Copyright 1992, Elsevier.
a test protocol for accelerated degradation conditions [96,99].
SOECs were operated under various conditions to derive the
degradation rate, and the results were compared with those
in previous reports. The authors found that long-term per-
formance could be predicted after hundreds of hours of
operation, depending on conditions. A series of studies is
currently being conducted for electrolyte-supported cell
stacks, and it has been noted that the degradation mode
should change if the cell configuration and/or components
are changed.
Few reports using practical bipolar electrolyzers are avail-
able to investigate the effects of shutdown on catalyst
degradation and its mechanism using fluctuating power
sources. Moreover, although the reverse current phenomenon
directly affects electrode degradation, reports considering this
phenomenon are scarce. However, these studies contribute to
the commercialization of electrolyzers and play important
roles in establishing the practical applications and upscaling
of water electrolyzers for green hydrogen production.
Numerous protocols for ADTs considering fluctuating power
for AWE and PEMWE have recently been proposed, but these
protocols have not been widely implemented. For SOECs, ADT
protocols are only at the initial evaluation stage.
Issues associated with water electrolyzers using
renewable energy-based electric power
This section introduces demonstrations of renewable energy-
based fluctuating power-driven water electrolysis. Previous
scholars have reported unique characteristics and problems
that are not observed under steady grid power operation.
Thus, this section focuses on the issues related to different
types of water electrolyzers individually to expand the utili-
zation of fluctuating power.
Issues associated with alkaline water electrolyzers using
renewable energy
Reports on the electrolysis characteristics of alkaline water
electrolyzers using fluctuating power have been published,
but studies on the long-term durability of these systems under
fluctuating power inputs are extremely limited compared
with studies on PEM water electrolyzers. This subsection re-
views the degradation of catalysts under start and stop oper-
ations of alkaline water electrolyzers, which is the main cause
of electrolyzer performance degradation, and describes the
requirements for future developments.
In a verification test conducted in Stuttgart in 1989, a 10 kW
bipolar alkaline water electrolyzer was operated over a long
period of time using photovoltaic cells [100]. A maximum
output of approximately 500 mA/cm2 was achieved during
operation between 12:00 and 14:00 (solid line, ICU electrolyzer,
1 DC current) (Fig. 8). During this period, the amount of solar
radiation (dotted line, global insulation), as well as the elec-
trolyzer output, showed large fluctuations. The ability of the
system to operate despite changes in the amount of solar ra-
diation was also high. The electrolyzer was operated with
photovoltaic cells during the day and stopped with a protec-
tion current at night for approximately five months, and no
noticeable degradation of the electrolyzer performance or
electrodes was observed.
Nakajima et al. reported the short-term response of the cell
voltage under simulated wind power [101]. No delay in the cell
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3 4581

Fig. 9 e Cell voltage response as a function of a simulated wind power-generated current pattern in (a) medium and (b) large
water electrolyzers. Adapted with permission from Ref. [101]. Copyright 2017, IOP Publishing.

voltage (red line) with respect to the input current (black line)
was observed in either the (a) medium or (b) large electrolyzers
(Fig. 9). Moreover, no changes in cell voltage were observed
during the test periods (medium: 3 h, large: 1 h), indicating the
ability to follow large power fluctuations without start and stop
operations. Gandia et al. tested the responses of a 5 kW elec-
trolyzer (Hydrogenics, HySTAT) using a similar simulated wind
power. The authors found that the electrolysis current closely
followed the input power during the 14 h test [78]. The oxygen
concentration in hydrogen was consistently maintained at low
levels of 0.02e0.03 vol%, and the hydrogen concentration in
oxygen changed according to the fluctuating power but did not
exceed 0.2 vol%. These results indicate that an alkaline water
electrolyzer can reasonably operate safely even during non-
stop fluctuating power operation.
Divisek et al. conducted a durability test of an electrolyzer Fig. 10 e Electrode potential stability of a Raney nickel
simulating the use of photovoltaic cells with downtime at anode (top) and cathode (bottom) during a simulated day/
night. In this test, electrolysis was conducted for 10 h each day night cycle with continuous (A) and discontinuous
at a constant current density of 400 mA/cm2; then, the elec- operation (B). Adapted with permission from Ref. [87].
trolyzer was shut down for 14 h. This process was repeated Copyright 1990, Elsevier.
over a total period of 15,700 h (Fig. 10) [87]. The results showed
that the potentials of both electrodes hardly changed during and stop operations [109e114]. However, the “Stability Test
continuous operation without any downtime (A), but the Protocol” column clearly shows that the conditions are not
overpotentials of both electrodes increased each time during unified. Thus, fair comparisons using ADTs are difficult.
start and stop operation (B), with progressive degradation of Moreover, developing a catalyst that is resistant to chemical
the electrode performance due to the reverse current. degradation against the reverse current, as well as physical
Developing electrode and catalyst materials with high degradation such as detachment caused by this chemical
reverse-current resistance is important because the perfor- degradation is challenging. To overcome these issues, by
mance degrades due to the reverse current. However, most of adding a small amount of manganese as a sacrificial oxidation
these studies on electrode catalysts have not considered the element to cobalt phosphate-based catalysts for the hydrogen
start and stop operations. For example, some potential cycle evolution reaction (HER), oxidation-caused degradation can be
tests have not incorporated the oxidation of the catalysts at the suppressed [109]. Regarding the oxygen evolution reaction
cathode (e.g., from 0.4 to 0 V vs. reversible hydrogen elec- (OER) catalysts, the addition of Co(OH)2 nanosheets, which
trode, RHE) [102e104] or the reduction reaction of the oxide/ exhibit a self-repairing effect on nickel electrodes, to the
hydroxide (catalyst) at the anode (e.g., 1.0e1.7 V vs. RHE) electrolytes has also been proposed [110]. These methods are
[105e108]. Table 2 shows examples of catalyst durability expected to improve the catalyst durability under start and
evaluations based on ADT protocols that have considered start stop operations.
4582 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3

Table 2 e Protocols for stability tests simulating the effects of renewable energy power fluctuations on the HER and OER
catalysts of alkaline water electrolyzers and the corresponding experimental data.
Reaction Stability test protocol Catalyst Electrolyte Temperature Current hinitial hend (mV) Ref.
( C) density (mV)
for h
(mA/cm2)
HER 200 mA/cm2, 1 h e OCP, 1 h: 50 MnnCo1enPx 1 M KOH 25 100 105 195 [109]
cycles
0.4e0.5 V, 0.5 V/s, Co-ns/Ni 7 M KOH e 100 68 64 [110]
CV, 40,000 cycles
0.25e0.4 V, 5 mV/s, NiFe/CP 1 M KOH RT 100 245 265 [111]
LSV, 3000 scans
300 mA/cm2, 30 mine0.074 V, Raney Ni 30% KOH 70 300 277 557 [112]
60 s, 33 cycles
OER 0.5e1.8 V, 1 V/s, CV, 60,000 cycles Co-ns/Ni 7 M KOH e 100 350 360 [110]
0.5e1.8 V, 1 V/s, CV 20,000 cycles NiFe-HyOx/ 7 M KOH 20 100 267 262 [113]
316SS
0e240 mA/cm2, Ni0.9Fe0.1Co2O4/Ni 1 M KOH 22 240 563 583 [114]
1 mA/s, CV, 2000 cycles
600 mA/cm2 for 3 se0.3 V for 3 s, NiCoOx/Ni 7 M KOH 25 100 420 600 [84]
2000 cycles

Fig. 11 e Long-term development of cell voltage under different operation modes: (a) constant current of 1 A/cm2, (b)
alternating operation at 2 and 1 A/cm2 for 6 h at each current, (c) alternating operation at 2 and 0 A/cm2 for 6 h at each
current, and (d) alternating operation at 2 and 0 A/cm2 for 10 min at each current. Adapted with permission from Ref. [115].
Copyright 2017, Elsevier.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
The use of fluctuating power led to electrode performance
degradation owing to the reverse current, resulting in a
prominent increase in cell voltage. Frequent input with rela-
tively small power fluctuation ranges without start and stop
operations did not produce performance degradation, though
only a few cases have been reported. Therefore, developing
electrodes and catalysts with high durability during start and
stop operations is necessary. At present, however, no uni-
versal evaluation of electrodes and catalysts is available.
Thus, comparative investigations are difficult, and improve-
ment guidelines cannot be shared worldwide.
Issues associated with PEM water electrolyzers using
renewable energy
This section describes the effects of power and cell tempera-
ture fluctuations on PEMWE. Previous research on the start
and stop operations on a single-cell PEM water electrolyzer
has been reported [115,116]. Major performance degradation
was clearly observed in durability tests with fluctuating
power, particularly in tests in which constant currents of 1
and 2 A/cm2 were exchanged every 6 h or constant currents of
0 and 2 A/cm2 were exchanged every 10 min (Fig. 11). Such
degradation could be attributed to an increase in the contact
resistance of the titanium porous transport layer (PTL) and
degradation of the cathode catalyst (e.g., increases in particle
size and agglomeration). Conversely, performance degrada-
tion was not observed under a constant current of 1 A/cm2
(i.e., steady grid power) or during switching between constant
currents of 0 and 2 A/cm2 every 6 h (i.e., intermittent operation
over 6 h). These findings indicate that PEMWE can proceed
steadily when using steady grid power and photovoltaic
power.
The effects of cell temperature changes have been inves-
tigated using a single-cell PEM water electrolyzer. Experi-
ments in which the fluctuating current was set to 0e3 A/cm2
and the variable temperature was set to 25e80  C (Fig. 12)
revealed no significant performance degradation for more
than 210 h during a current and temperature change test [117].
However, other researchers have reported that the cell
Fig. 12 e Temperature and current cycling of a PEMWE
membrane electrode assembly. The test protocol is shown
in the inset. Platinum loading: 0.1 mg/cm2; IrRuOx loading:
0.4 mg/cm2. Adapted with permission from Ref. [117].
Copyright 2020, Elsevier.
4583
Fig. 13 e Solar photovoltaic load tests showing system
power consumption versus control signal. Adapted with
permission from Ref. [83]. Copyright 2020, Elsevier.
temperature influences the decomposition of Nafion mem-
branes. Therefore, the temperature fluctuations should be
also considered in ADT protocols [118,119].
A 60 kW PEM water electrolyzer was used in a study con-
ducted at the University of California [83]. An electric power
profile simulating the photovoltaic and wind power genera-
tion data was input into the PEM water electrolyzer (65 cells,
catalyst layer area: 214 cm2) for performance evaluation. In
the case of photovoltaic power generation (Fig. 13), the
amount of hydrogen produced in the summer was more than
twice that produced in the winter. Moreover, the power
generated by sunlight in the winter fell below the minimum
power load on some days, even throughout the day, suggest-
ing that the electrolyzer must stop operation on these days. In
the case of wind power generation (Fig. 14), unlike photovol-
taic power generation, a longer period of time during which no
electric power was generated was observed, and the power
fluctuations were complicated. The profiles of photovoltaic
and wind power generation showed that the maximum power
fluctuation change rates after 1 s were ~100%. Thus, consid-
ering the minimum power load, the necessity of devising a
system that utilizes fluctuating power not only at the stack
level, but also at the level of the entire water electrolysis
system level and on a time scale of seconds was highlighted.
Several issues have been encountered when upscaling PEM
water electrolyzers. First, the amounts of precious metals
used for the electrolyzer increase with upscaling. The Inter-
national Energy Agency [120] stated that 300 kg of platinum
and 700 kg of iridium per gigawatt of the catalyst are required
for PEMWE. To decrease the cost, it has been attempted to
decrease the required amount of iridium oxide (IrO2) catalyst
by improving the catalyst coating method on Nafion mem-
branes, such as by adding IrO2 nanofibers between the anode
PTL and Nafion membrane [121]. This strategy could increase
the catalyst utilization area and successfully reduced the
amount of catalyst required to one-sixth of the conventional
amount without decreasing the electrolytic performance.
Second, numerous issues have been identified in 100-kW-
class PEM water electrolyzers. Nafion membranes experience
increased heterogeneities due to the pressure [122], heat
generation [123], and current [124] inside the electrolyzer,
particularly when the electrolyzer is upscaled, resulting in
4584 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
Fig. 14 e Wind load tests conducted over 3 weeks showing system power consumption versus control signal. Adapted with
permission from Ref. [83]. Copyright 2020, Elsevier.
Fig. 15 e Photograph of a membrane electrode assembly
after the PEMWE test. Adapted with permission from
Ref. [125]. Copyright 2012, Elsevier.
local damage; the accumulation of this damage has been re-
ported to create holes in Nafion membranes, possibly leading
to explosion (Fig. 15) [125]. Using renewable-energy-based
fluctuating power can cause sudden power fluctuations and
is believed to increase the heterogeneities described above,
possibly promoting the degradation of Nafion membranes.
Whether a PEM water electrolyzer using fluctuating power
can be effectively operated without degradation is important.
With an appropriate understanding of the operating condi-
tions that do and do not accelerate degradation under fluc-
tuating power operations, the overall hydrogen production
efficiency should be able to be improved. Moreover, it is
necessary to develop new technology to reduce the amounts
of precious metals used and the corresponding costs and to
control the membrane damage to consider heterogeneities in
the electrolyzer.
Dynamic characteristics of SOECs using renewable energy
SOECs are required to have lifetimes of 5e10 years, and related
development research has been actively conducted. However,
the technical maturity of SOECs is lower than that of SOFCs,
and further improvements in performance and durability are
needed for their commercialization (Table 3). In 2012, a Julich
circular anode-supported SOFC was used for steam electrol-
ysis for 9 kh under the conditions of an 80% humidified gas
supply, 780  C, and 1 A/cm2 [126]. The degradation rate was
3.8%/kh for the entire test period and 1.7%/kh over a 3600 h
incident-free period. In contract, the durability of cells has
recently been improved. For example, a commercially avail-
able circular electrolyte support-type cell was used to conduct
steam electrolysis for over 20 kh while feeding 75% humidified
hydrogen at approximately 850  C and 0.9 A/cm2; a major
improvement in degradation rate to 0.57%/kh was observed in
this system [127]. The same cell was reported to have a
degradation rate of 0.53%/kh or less even after operating for 21
kh (0.6 A/cm2) when the temperature was reduced to
approximately 780  C [128]. When a cathode-supported cell
(anode-supported cell in FC mode) was used in a short-stack
test, a voltage degradation rate of only approximately 0.6%/
kh was observed for an operating time of 20 kh under the
conditions of 50% humidified hydrogen supply, 700e800  C,
and 0.5 A/cm2 [129]. Most durability evaluations of steam
electrolysis or co-electrolysis are conducted in steady-state
operating environments (i.e., ones with constant current and
voltage), and the parameters set in these tests include tem-
perature, gas composition, current density, and voltage
[130e133]. Post-mortem analysis of various electrodes has
also been conducted, revealing that Ni coarsening, Ni migra-
tion, and percolation loss were the main factors influencing
degradation in nickel-yttria-stabilized zirconia (Ni-YSZ) fuel
electrodes [134e137]. The oxygen electrode may be degraded
Table 3 e Examples of SOEC cell configurations, operating conditions, and degradation rates.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
Cell configuration Operating condition Voltage Reference
 degradation/kh
Cathode Electrolyte Interlayer Anode Support Electrode Temperature/ C Current Mode Gas Fuel/steam Duration
area/cm2 density utilization
Ni-YSZ YSZ GDC LSCF Electrolyte 45 780 1 A/cm2 Const. 80% 36% 9 kh 3.8% (40 mV) [126]
current humidified H2
Ni-GDC 6Sc1CeSZ GDC LSCF Electrolyte 45 ~850 0.9 A/cm2 Const. 75% 51% >20 kh 0.57% (7.4 mV) [127]
current humidified H2
Ni-GDC 10Sc1CeSZ GDC LSCF Electrolyte 45 ~780 0.6 A/cm2 Const. 75% 50% 21 kh 0.53% (7 mV) [128]
current humidified H2
Ni-YSZ YSZ GDC LSCF Cathode 80 700e800 0.5 A/cm2 Const. 50% 50% 20 kh ~0.6% [129]
current humidified H2
Ni-YSZ YSZ LSCF-GDC Cathode 45 ~700 On: 0.4 A/cm2, Const. 70% e 0.6 kh 5% (70 mV) [142]
off: 0 or current, humidified H2
0.02 A/cm2 on-off
cycle
Ni-YSZ YSZ GDC LSC-GDC/LSC Cathode 100 700 On: 0.6 A/cm2, Const. 90% e >2 kh 2% (24 mV) [144]
off: 0 A/cm2 current, humidified H2
on-off
cycle
Ni-GDC 3YSZ GDC LSCF Electrolyte 45 ~850 On: 0.7 A/cm2, On-off 75% e 2.7 kh 0.4% (5 mV) [145]
off: 0.07 A/cm2 cycle, humidified H2 (on-off) þ 5.8 kh
Const. (const. current)
current
Ni-YSZ YSZ GDC LSC-GDC Cathode 80 750 <0.5 A/cm2 Wind 20e90％ e 1 kh 0.8% [146]
power humidified H2,
CO2eH2OeH2
Ni-YSZ 800 <0.75 A/cm2 Wind 90% 9 kh [79]
power humidified H2

4585
4586 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
owing to oxygen evolution reaction [138,139]. However, this
degradation depends on the cell structure and composition.
The effects of impurities in the steam on performance and
durability have also been investigated [132,140].
Few studies on fluctuating input power supplies that
correspond to the renewable energy power generation status
are available. Understanding SOEC operation with input fluc-
tuations from a thermal perspective is essential [141]. For
example, the thermo-neutral potential at 700  C is approxi-
mately 1.28 V. Thus, if an SOEC is operated at a voltage higher
than 1.28 V, then the reaction will become exothermic; if
operated at a lower voltage, then the reaction will become
endothermic. Therefore, when ceramics are the main cell
components, as is the case for cathode-supported cells, a cell
surface temperature distribution exceeding 10  C/cm could
lead to an increased risk of damage [142]. The cell material and
configuration also play roles in this damage. Metal-supported
cells are expected to be able to handle rapid thermal cycles
and to tolerate temperature distributions of 100  C/cm or
higher [143]. Therefore, the cell durability toward the temper-
ature distribution will be greatly improved, and the flexibility
of operating conditions in response to input fluctuations could
increase.
Cell characteristics during on/off operation under simu-
lated fluctuating inputs have been reported. Such switching
tests can be used to clarify the load profiles that are actually
required, and long-term stability can be predicted. Petipas
et al., for example, used a commercially available circular
anode-supported SOFC to investigate the possibility of cell
damage due to on/off operation and whether a minimum
current must be passed to protect the cell [142]. The authors
conducted steady operation under thermo-neutral conditions,
as well as under 1800 square-wave (i.e., the current width and
switching interval were changed over a total time of 140 h)
current inputs, over a 600 h period. In this case, the current was
set to a value near the thermo-neutral point, even during
square-wave operation. According to the results, the cell was
degraded regardless of the operating conditions (5%/kh), and
the degradation phenomenon unique to the on/off operation of
SOECs was not observed. The cell temperature difference be-
tween the current passing and open circuit states was in the
range of 10  C or less, which is not a condition that would lead
to mechanical failure. Furthermore, no minimum current
input was required. Fu et al. used a stack equipped with five
hydrogen-electrode supported cells to conduct 2 kh of steady
operation at 700  C, followed by short-term fluctuating opera-
tion (i.e., 756 on/off operations, two load time patterns) [144].
Fig. 16 shows the voltages and stack temperatures obtained
during fluctuating operation. In these tests, a current lower
than the thermo-neutral potential was applied. The results
indicated that the temperature fluctuation was limited to less
than 10  C, even in the stack. One cell behaved differently
during the test owing to unstable electrical contact, but the
degradation rate excluding this one poorly performing cell was
2%/kh. Therefore, the authors concluded that no significant
degradation could be observed under fluctuating operation.
Schefold et al. used an electrolyte-supported cell to
conduct a 8.7 kh test, including a combination of 80,000 on/off
operation (2.7 kh) at approximately 850  C and steady opera-
tion (5.8 kh) [145]. The degradation rate was low, at only 0.4%/
Fig. 16 e Enlarged view of slow cycling operation. Adapted
with permission from Ref. [144]. Copyright 2014, Wiley.
kh; no overall signs of electrochemical degradation were
noted; and no impact of the cycle test was found. The degra-
dation rate under fluctuating operation was slightly lower
than that under continuous operation [127], but this differ-
ence was mainly attributed to the experimental conditions
rather than differences in operation mode. The results above
reveal that the degradation mode unique to on/off operation
does not occur in single cells or stacks, which suggests that
this type of cell can be applied to SOECs using fluctuating
renewable energy.
There have been reports on the simulation of actual fluc-
tuating renewable energy inputs. In Denmark, tests were
conducted using Haldor Topsøe A/S cells under the assump-
tion that these cells would absorb 100% of the electric power
generated by wind power [79]. The researchers used wind
power generation data collected in 5 min intervals in
December, which showed the largest amount of electric power
generation over the year, to analyze the cell behavior when a
gaseous mixture of 10% H2e90% H2O was supplied to a single
cell at 800  C. No issues were found with the load-following
capability, and stable operation was confirmed over the
course of 9 kh, indicating that the wind power generation
profile did not affect cell degradation. The cell lifetime was
estimated to be at least 2 years. Similar tests have also been
conducted using a 75 cell stack, which was controlled so that
the maximum current was 0.5 A/cm2 and the average current
was 0.24 A/cm2. Fluctuations observed over 2 months were
implemented in this test, but no degradation that was unique
to this operation mode was confirmed. Note that the cells were
operated at the thermo-neutral potential or lower in each test.
Rao et al. conducted SOEC stack durability tests to produce
syngas under wind power generation fluctuations [146].
Similar to the above report, the authors used wind power
generation data obtained from wind farms on Bornholm Is-
land, Denmark [146] and conducted stack tests by repeating the
24 h data over 1 kh (Fig. 17). A co-electrolysis test was con-
ducted at 750  C using a stack in which six DTU Energy anode-
supported cells were assembled into a stack with SOLIDpower.
The ohmic resistance obtained during the 1 kh operating
period was constant and showed no issues, slight degradation
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
Fig. 17 e (a) Evolution of voltage as a function of time
during durability testing in co-electrolysis mode at 750  C;
(b) enlarged view from 420 to 470 h in (a). Adapted with
permission from Ref. [146]. Copyright 2020, Elsevier.
was observed in the anode, and the voltage degradation was as
low as 0.8%/kh. As the experiment was a co-electrolysis test, a
current value relative to the thermo-neutral point was not set,
but the upper limit of the current was set within the range in
which degradation could be suppressed [79]. Analysis of the
distribution of relaxation time suggested degradation, prob-
ably related to the triple-phase boundary reaction process of
the fuel electrode, but this degradation was not recognized as
an issue. This test demonstrated that synthetic methane could
be produced by passing the syngas generated in the co-
electrolyzer through a catalytic reactor.
The performance and degradation rate of SOECs have been
improved, and determining whether the degradation phe-
nomena observed during testing is due to the cell configura-
tion or operation mode has become feasible. A degradation
phenomenon unique to the operation mode was not
confirmed in the reports above, even when a fluctuating input
power supply simulating renewable energy was used, as long
as operation was performed within a potential range that did
not exceed the thermo-neutral point. These results confirm
that SOECs are quite robust.
Conclusions and outlook
The development of technologies that can introduce large
amounts of renewable energy is essential to achieve carbon
neutrality, and it is crucial to share hydrogen production
technology that makes maximum the use of naturally
4587
intermittent renewable energy sources and its related issues.
The amount of power generated by photovoltaic and wind
power sources fluctuates irregularly, and the characteristics of
these power fluctuations are carefully analyzed to utilize
renewable energy. A smoothing effect of reducing the power
fluctuation range on photovoltaic and wind power has been
verified with the scaling-up of electric power generation or
bundling of the electric power produced at multiple locations.
However, the operating conditions under fluctuating power,
compatibility of different water electrolysis methods, and
techniques for evaluating water electrolyzer performance and
durability have not yet been connected with each other. Thus,
the effects of power fluctuations on water electrolysis are not
yet understood, and fluctuation patterns that cause electro-
lyzer performance degradation should be comprehensively
investigated.
Producing hydrogen through water electrolysis using fluc-
tuating power does not involve simply inputting fluctuating
power into the electrolyzer, whereas electrolyzers require
fluctuating operation that follows changes in the electrolyzer
environment over time. In other words, inputs of fluctuating
currents into an electrolyzer change not only the voltage of
the electrolyzer, but also its temperature and gas pressure, gas
purity, and gas generation amount over time. Therefore,
durability of the entire system against the changes must be
ensured. Moreover, considering operational restrictions such
as minimum power loads, the electrolyzer must stop oper-
ating when the electric power falls below the operation range.
During shutdown, renewable energy cannot be utilized,
decreasing the overall energy utilization efficiency. In addi-
tion, even if low power load operation is feasible, energy is
consumed during the operation in the system, including in the
auxiliary equipment, and the overall efficiency decreases
significantly. Therefore, the development of a water electro-
lyzer with expanded operating conditions as well as the
design of an electrolyzer system appropriately combined with
auxiliary equipment is important.
AWE results in severe catalyst degradation owing to the
reverse current in start and stop operations. Thus, electric
power generation in large-scale photovoltaic and wind power
plants, where smoothing effects can be expected, could be the
main application prospect. However, start and stop operations
are inevitable, and electrodes and catalysts highly resistant to
these operations need to be developed.
PEMWE, in contrast to AWE, can be operated under low
power loads with fluctuating power. However, precious metal
catalysts lead to high costs. Moreover, performance degrada-
tion under specific operations has been reported. Thus, tech-
nological developments that enable the requisite amounts of
precious-metal catalysts to be decreased without decreasing
the performance or lifetime of the electrolyzer are required.
Furthermore, the development of membranes that can resist
uneven pressures or local heat as well as cell configurations to
decrease such heterogeneities for the scaling-up of electro-
lyzers are important.
SOECs have been proven to be robust against power fluc-
tuations at the small-scale cell and stack levels, but their
operation is limited to ranges below the thermo-neutral point.
Further expansion of the operating range requires the devel-
opment of metal-support-type cells and stacks that are highly
4588 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 4 5 7 2 e4 5 9 3
adaptable to thermal cycles and are resistant to thermal
shock, which is necessary to utilize power fluctuations beyond
the thermo-neutral point.
Various initiatives, from basic laboratory-scale in-
vestigations to practical demonstrations, have been imple-
mented on water electrolysis using fluctuating power. We
understand that crucial issues that differ from those observed
using steady grid power have emerged under fluctuating
operation and that catalyst degradation occurs quickly under
sudden power fluctuations. However, compared with world-
wide initiatives in FC communities, comprehensive initiatives
in entire water electrolysis communities are insufficient. In
particular, at present, we cannot share universal ADT pro-
tocols simulating actual electrolyzer environments under
fluctuating power operation and experimental data and
practical knowledge to clarify the performance degradation
mechanism of each component. To accelerate the develop-
ment of highly effective and durable electrolyzers for green
hydrogen production, we propose utilizing universal ADT
protocols and sharing a common foundational technology and
experimental results to evaluate the performances of elec-
trolyzer components universally. Simultaneously, it is
necessary to clarify the power fluctuation patterns for effec-
tive electrolyzer operation, detailed changes in the physical
parameters, and which factors accelerate and do not accel-
erate degradation. Moreover, the differences between the
degradation factors at the laboratory and practical demon-
stration scales should be clarified, and highly efficient and
durable methods of electrolyzer operation should be estab-
lished subsequently. Finally, we should utilize this shared
knowledge and experience for the further development of
water electrolyzers by improving universal test protocols that
can simulate plant-sized electrolyzers in laboratories and
fluctuating power on the plant level.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
We thank Prof. Kazunari Sasaki at Kyushu University,
Research Advisor Ko Sakata at the Institute of Applied Energy,
Director Takashi Shimazu at Toyota Central R&D Labs., Inc.,
Dr. Hideyuki Takagi at National Institute of Advanced Indus-
trial Science and Technology, Dr. Hirohide Furutani at Na-
tional Institute of Advanced Industrial Science and
Technology, Prof. Ryuji Matsuhashi at the University of Tokyo,
Prof. Shigenori Mitsushima at Yokohama National University
for their valuable advice. This work was supported by the
Toyota Mobility Foundation (TMF).
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