Gambou, Frank, et al.

“A Comprehensive Survey of Alkaline Electrolyzer Modeling:

Electrical Domain and Specific Electrolyte Conductivity”. Energies, vol. 15, nº 9,
maio de 2022, p. 3452. DOI.org (Crossref), https://doi.org/10.3390/en15093452.

energies
Review
A Comprehensive Survey of Alkaline Electrolyzer Modeling:
Electrical Domain and Specific Electrolyte Conductivity
Frank Gambou 1 , Damien Guilbert 1, * , Michel Zasadzinski 2 and Hugues Rafaralahy 2

1 Group of Research in Electrical Engineering of Nancy (GREEN), Université de Lorraine,

F-54000 Nancy, France; frank.gambou@univ-lorraine.fr
2 Research Center for Automatic Control of Nancy (CRAN), UMR CNRS 7039, Université de Lorraine,
F-54000 Nancy, France; michel.zasadzinski@univ-lorraine.fr (M.Z.); hugues.rafaralahy@univ-lorraine.fr (H.R.)
* Correspondence: damien.guilbert@univ-lorraine.fr; Tel.: +33-372-749-984

Abstract: Alkaline electrolyzers are the most widespread technology due to their maturity, low cost,
and large capacity in generating hydrogen. However, compared to proton exchange membrane
(PEM) electrolyzers, they request the use of potassium hydroxide (KOH) or sodium hydroxide
(NaOH) since the electrolyte relies on a liquid solution. For this reason, the performances of alkaline
electrolyzers are governed by the electrolyte concentration and operating temperature. Due to the
growing development of the water electrolysis process based on alkaline electrolyzers to generate
green hydrogen from renewable energy sources, the main purpose of this paper is to carry out a
comprehensive survey on alkaline electrolyzers, and more specifically about their electrical domain
and specific electrolytic conductivity. Besides, this survey will allow emphasizing the remaining key
issues from the modeling point of view.

Keywords: alkaline electrolyzer; hydrogen generation; modeling; dynamic operation; electrolyte conductivity

Citation: Gambou, F.; Guilbert, D.;

Zasadzinski, M.; Rafaralahy, H. A
Comprehensive Survey of Alkaline
Electrolyzer Modeling: Electrical
Domain and Specific Electrolyte
Conductivity. Energies 2022, 15, 3452.
https://doi.org/10.3390/en15093452
Academic Editor: Jin-Soo Park
Received: 4 April 2022
Accepted: 6 May 2022
Published: 9 May 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
1. Introduction
The recent report “Climate Change 2022” established by the intergovernmental panel
on climate change (IPCC) has concluded that climate change has been happening faster
than expected, mainly due to human activities [1]. Besides, the report has highlighted the
harmful effects of climate change such as temperature and water level increasing, health
issues, and reduction in the availability of water and food resources. To minimize the
effects of the climate change, the experts of IPCC have recommended replacing fossil
fuels with low-carbon energy sources such as nuclear, renewable energy sources (RES)
(e.g., hydroelectricity, wind, photovoltaic), and developing further carbon dioxide reduction
solutions (e.g., tree planting, carbon capture, storage, and use (CCSU)).
In this context to face climate change, hydrogen seems to be the best and most suitable
alternative for fossil-based energy sources since its consumption does not emit methane
and carbon dioxide, but produces only water [2,3]. This makes hydrogen one of the cleanest
fuels in the world and essential for achieving a pollution-free by 2050 according to the Eu-
ropean Union’s (EU) commitment. Unfortunately, its production is still largely dominated
by fossil fuels (specifically natural gas) [4–7]. Only a small amount is produced through the
water electrolysis process, which uses electricity to split water into hydrogen and oxygen.
To contribute to climate neutrality, hydrogen production must require electricity coming
from RES or nuclear [8]. As hydrogen is applied in various energy-intensive sectors such as
transport, industry, electricity, and buildings, it offers enormous solutions in the reduction
of greenhouse gas emissions [6,9]. For clean and efficient power generation, fuel cells can
be employed supplied by hydrogen and oxygen for which the reaction releases only heat
and water. There are several fuel cell technologies currently under development, each of
which presents its own benefits, limitations, and prospective applications. One of them,
the proton exchange membrane (PEM) fuel cell proposes a high-power density, a solid

Energies 2022, 15, 3452. https://doi.org/10.3390/en15093452 https://www.mdpi.com/journal/energies

Energies 2022, 15, 3452 2 of 20

polymer as an electrolyte, and low-temperature operation (around 80 ◦ C), enabling it to

start quickly and contributing to less deterioration of systems components (leading to better
durability) [10].
For this reason, the hydrogen strategy set by the EU is to install in Europe at least
6 GW of renewable hydrogen electrolyzers by 2024, and 40 GW by 2030 [7]. Hence, the goal
is to decrease greenhouse gas emissions by at least 55% by 2030.
Electrolyzers are electrochemical devices used to produce hydrogen through water
electrolysis. At the present moment, there are four electrolyzer technologies: alkaline
electrolyzer, PEM electrolyzer, solid oxide (SO) electrolyzer, and anion exchange membrane
(AEM) electrolyzer recently introduced in the literature to eliminate the weaknesses of
alkaline and PEM electrolyzers [8,11,12]. Only the two first technologies are commer-
cially available in the market and widely used; while the two remaining are still under
investigation since they are not enough mature to be accepted and employed in research
projects [12].
The alkaline electrolyzer technology has been used for over a century. Its principle
is based on the use of two electrodes immersed in an electrolyte solution of potassium
hydroxide (KOH) or sodium hydroxide (NaOH). A membrane called the diaphragm sep-
arates the two electrodes and allows the hydroxide ions (OH− ) to move from the cathode
to the anode [13,14]. In the literature, alkaline technology relying on an acidic electrolyte
has been introduced, highlighting the hydrogen evolution reaction (HER) performance to
make efficient, stable, and hydrogen evolution catalysts [15,16]. The advantage of this
technology is that the electrodes are made of cheaper catalysts such as cobalt, nickel,
or iron. Moreover, it has high durability and gas purity [11]. Unfortunately, it operates at
a low current density lying between 0.2 and 0.7 A·cm2 , making it less compact than PEM
electrolyzers. Furthermore, the production capacity dynamic range is set between 15 and
100%, which prevents alkaline electrolyzers from being fully exploited in RES operations.
Finally, the aqueous solution of the electrolyte (KOH or NaOH) leads up to regular checks
and maintenance to guarantee safe operations and the performance of the system [11].
The PEM electrolyzers were first developed in the 1960s to overcome some of the
disadvantages of the alkaline electrolyzer. They are composed of a solid polymer elec-
trolyte (SPE) separating the anode from the cathode and allowing protons (H+ ) to be
diffused from the anode to the cathode. The catalyst material on the anode and the
cathode side are, respectively, iridium and platinum, which are noble and expensive
materials [3]. On one hand, the main advantages of this technology over alkaline technol-
ogy are high current densities, low maintenance, and large production capacity dynamic
range (0–100%) [17]. On the other hand, the output hydrogen pressure is quite limited
(around 30 bar); whereas for alkaline electrolyzers, the pressure can go up to 200 bar at
the same rated power. Given that this technology has not yet reached a certain level of
maturity, its performances (e.g., specific energy consumption, hydrogen production rate,
lifespan) are below those met by alkaline electrolyzers. For this reason, this technology is
currently being investigated by researchers to compete from the performance point of
view with alkaline electrolyzers [18].
Recently, several review works have been reported for PEM electrolyzers. These re-
views deal with modeling aspects, novel components, cell failure mechanisms, and technol-
ogy [2,3,19–21]. On the other side, a few reviews can be found for alkaline electrolyzers.
In [11], the authors have focused their investigation on the technology while providing
research perspectives to enhance its performance and dissemination. In comparison, in [22],
the authors have reviewed and analyzed the coupling between alkaline electrolyzers and
RES (wind, solar); whereas in [23], the authors have analyzed the influence of the parame-
ters (e.g., geometry, electrolyte composition, electrocatalysts) on the efficiency of alkaline
electrolyzers. Relying on the current literature, the main goal of this paper is to review
alkaline electrolyzer modeling from the electrical domain point of view. Besides, given that
the alkaline electrolyzer performances are strongly linked with the specific electrolyte
conductivity of the aqueous solution, their modeling according to the temperature and
Energies 2022, 15, 3452 3 of 20

mass fraction of KOH or NaOH is considered in this review work. Hence, it allows bringing
out the remaining key issues from the modeling point of view.
It is important to point out that electrolyzer modeling is crucial to predict their behav-
iors in static and dynamic conditions for simulation purposes when connecting with wind
turbines, photovoltaic panels, and power grids. Besides, electrolyzers are coupled with
power conditioning systems such as AC-DC and DC-DC converters to manage their opera-
tion. The knowledge of their modeling allows designing fit, robust, efficient controllers to
optimize the operation of the electrolyzers from the energy efficiency point of view. Finally,
the modeling has also the purpose to optimally design alkaline electrolyzers by considering
the parameters affecting their energy efficiency [23].
The paper is divided into four sections. After reviewing alkaline and PEM tech-
nologies while highlighting the reported review works on both technologies, Section 2
summarizes the principle of operation, features, and static and dynamic operations
of alkaline electrolyzers and a comparison is provided with PEM electrolyzer technol-
ogy. Then, in the third section, a detailed synthesis of alkaline electrolyzer modeling
including electrical domain and specific electrolyte conductivity is provided. Finally,
in Section 4, a conclusion is provided enabling giving the remaining key issues for alkaline
electrolyzer modeling.

2. Alkaline Electrolyser Technology

2.1. Operation and Characteristics
As pointed out in the introduction, among the four existing water technologies,
only two are available in the market such as alkaline, PEM; whereas SO and AEM are
still being investigated before widespread acceptance and dissemination [24,25]. In this
review work, alkaline water electrolysis technology is considered since it is currently
being employed in many research projects such as the development of carbon-free hy-
drogen production facilities supplied by renewable sources [26,27]. Similar to fuel cells,
electrolyzers performing the water electrolysis process are composed of an anode and
a cathode separated by an electrolyte. In the case of the alkaline electrolyzer, the elec-
trolyte is based on a liquid solution that may be potassium hydroxide (KOH) or sodium
hydroxide (NaOH) [11]. Generally, alkaline electrolyzer manufacturers prefer to use
KOH instead of NaOH since an aqueous solution with 25–30 wt.% KOH features a higher
specific electrolyte conductivity at a standard temperature range from 50 to 80 ◦ C [22].
The principle of operation of the alkaline water electrolysis is provided in Figure 1; while
the equations of the chemical reactions are given in Equations (1)–(3) below:

Anode : 2OH− → 1/ 2O2 + H2 O + 2e− (1)

Cathode : 2H2 O + 2e− → H2 + 2OH− (2)

Global : 2H2 O → 2H2 + O2 (3)
 Energies 2022, 15, x FOR PEER REVIEW 4 of 21
Energies 2022, 15, 3452 4 of 20

5 of 21
Energies 2022, 15, x FOR PEER REVIEW 5 of 21
Energies 2022, 15, x FOR PEER REVIEW 5 of 21 5 of 21
Figure 1. Principle of operation of alkaline electrolyzers.
Energies 2022, 15, x FOR PEERFigure
REVIEW1. Principle of operation5 of
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alkaline electrolyzers. 5 of 21
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ayer
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 Energies 2022, 15, x FOR PEER REVIEW 5 of 21 5 of 21
Energies 2022, 15, 3452 5 of 21 5 of 20
Energies 2022, 15, x FOR PEER REVIEW 5 of 21 5 of 21
Energies 2022, 15, x FOR PEER REVIEW 5 of 21 5 of 21
trolyzers
n introduced in the 1960s to compete with alkaline have beentointroduced
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capacity is
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Energies
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platinum PEER
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aintenance,
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[3]. the
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to
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(>1000
Table catalysts
analysis of long-term
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electrolysis
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and
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with high
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of
ysis2. long-term
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with present
200 bar), and lifetime,
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specific and overscaling
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sis upthreats
[31].
consumption
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dynamic production
2. SWOT
PGM-based
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of view [3]. Onweaknesses,
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ysis
nt 2. They
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e use
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platinum)
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ysis with strengths,
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[28]. Besides,
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resources
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footprint 4.53 and
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ogen
5000
0–100%)   electrolyzers
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hydrogen of hydrogen
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ogenby
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nd production
nuclear plants coated
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Development
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Threats
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Finally,
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close
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to From
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recycling on
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alkaline (leading
papers,up
electrolyzers canto generate
a higher
alkaline and cost)
PEM
nd
ed
e,
g and
on the  Increase
current nuclear
catalyst of PGM
state-of-the-art resources
coating demands
by atomic
(research (leadinglayer
papers, up to a higher
deposition,
alkaline and and cost)
PEM due to the current market dissemination of PEM
acturers) [9,22,32],
ling hydrogen Table
facilities 3 summarizes
production
for PGM-based units the
hydrogen electrolyzer
main at features
very
catalysts assuming manufacturers)
high of alkaline
pressure
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to 200 barTableagainst 3 summarizes
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PEM main features
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at alkaline
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ding
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Table 3,state-of-the-art
[9,22,32], Table be catalyst
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that
rate the
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same
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porous
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from Table 3,state-of-the-art
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and
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ed
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ogen
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
[9,22,32],
Lack state-of-the-art
Table
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hydrogen summarizes(research
refueling the papers,
main
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features
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alkaline
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gies.
very From
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pressure 3,
Increase Table
it
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of 3PGM
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200 summarizes
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demands an the
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erate
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form at 30
700 bar
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Lack Enhancement of long-term stability, lifetime, and due to the current market the dissemination of PEM
g
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ower
e,
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NEL
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3 summarizes
be
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bar
company).
refueling
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that
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30
embedded
High-pressureat main
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in
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manufacturers)
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assuming can
power
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end-
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fuel cell
[9,22,32],
Table
of 2 electric
MW 3,
hydrogen Table
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vehicles
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3 summarizes
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be noted [33].
(FCEVs)
company). that
unitsalkaline
In
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High-pressure
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compressors
hydrogen
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alkaline
gen-
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ayer
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[9,22,32], Table up
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features of
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3, it can be supplied
noted thatby low-carbon
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gies.
very
ower
t issue From
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pressure 3,of-life
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is be noted
recycling
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ofstored
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erate electrolyzers
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hydrogen
production
200 barunder
company).
stored
electric against
of long-term
market
vehicles
refueling
plants
30at
High-pressure
gaseous bar the
dissemination
technology
supplied age
(FCEVs)
stations by
forsame
stability,
form is
tanks PEM
hydrogen
at
mature
[33].
close
renewable of electrolyzers
rated
lifetime,
700
toPEM
embedded
Inbar power
over
the any
and inand
produc-
PEM
in
case,ofelectrolyzers,
stor- 2 MW from
commercial fuel
hydrogen
NEL
thecell company).
best performance
electric
production
High-pressure
vehicles
units can
(FCEVs) hydrogen
be obtained
[33]. Insuch produc-
any case,
very
e,
g an
owerand
onend-
high
the
of 2 pressure
current
MW from (upNEL
scaling to
state-of-the-art 200 bar
company).
up single against
(research 30
High-pressure
cells atbar the
papers,
tion
(>1000 for
is
cm same
an PEM
2alkaline
hydrogen
) importantelectrolyzers
rated power
andproduc-PEM
issue of 2
sinceMW from
hydrogen NEL is company).
stored under High-pressure
gaseous form hydrogen
at 700 bar produc-
in stor-
t issue
equested
nd since
ed in commercial hydrogen
to meet fuel
electrolyzers
the
hydrogen is
cell stored
electric
high-pressure
production under
supplied gaseous
vehicles
byas low
requirements
units (FCEVs)
low-carbon form
specific
compressors of at
[33].700
energy
energy
FCEVs. In
are barany in stor-
case,
consumption,
sources
requested
Further- to high
meet hydrogen
the high-pressurevolume rate, and
requirements lifetime.of The
FCEVs. mainFurther-
ower ofsince
2 MW from nuclear
NEL resources High-pressure
company). tion is an hydrogen
important produc-
issue since hydrogen is stored
tacturers)
ed issue
equested
hnology
[9,22,32],
in commercial
isto 
hydrogen
meet
Lack
mature the Table
overof is
Dissemination
fuel cell 3 electric
stored
high-pressure
hydrogen
PEM
summarizes
under
ofvehicles
low the
gaseous
requirements
refueling
electrolyzers, drawbacks age
carbon main
(FCEVs)
stations
more,
the form
besttanks features
footprint
of at
[33].
close
since 700
embedded
FCEVs.
reported the
performance In ofany
bar
tohydrogen
the alkaline
in
Further-
concern
technology stor-
in
case,
can commercial
the
be low
is current
mature fueldensity
over cell
PEMelectric (upunder 0.7 gaseous
tovehicles
electrolyzers, A·cm the 2form
(FCEVs)
−best making at 700
[33].
performance Inbar
the anyin case,
elec- stor-
can be
e,
t
ogen
gies.
ed and
issue
inFromsince
commercialhydrogen
Table 3, it
fuel can is
cell
production stored
be noted
electric under
plants that gaseous
vehicles age
alkaline
supplied (FCEVs) form
tanks at
electrolyzers
compressors
byvolume [33].
renewable 700
embedded
In
are bar can
any in
requested stor-
in
gen-
case,commercial
to meet fuel
the cell electric
high-pressure vehicles
requirements (FCEVs) of [33].
FCEVs. In any case,
Further-
equested
hnology
ow istomature
specific meet the
over
hydrogen
energy high-pressure
PEM
consumption, production highrequirements
electrolyzers, trolyzer
units
hydrogenthe best
bulky)
obtained of such
Finally,
FCEVs.
performance
and as and
set
rate,
relying
Further-
low
and can
production be
specific
on life-
the to capacity dynamic range
energystate-of-the-art
current consumption, (limiting
high hydrogen
(research operating
papers, volume conditions
rate,andandPEM life-
ed specific
nd
very
hnology
ow inhigh
equested commercial
is pressure
to meet
mature
energy fuel
the(up
nuclear
over cell
to
PEM
consumption, electric
200
high-pressure bar
resources vehicles
against
electrolyzers,
high to 30
requirements
the(FCEVs)
compressors
bar
more,
generate
hydrogen best for of [33].
PEM
since FCEVs.
hydrogen).
volume the
performance Intechnology
are
rate, any
requested
electrolyzers
Further-
The
and case,
can be
system
life- is meet the
mature
efficiency overis high-pressure
PEM
assessed electrolyzers,
by requirements
considering the best
the ofalkaline
FCEVs.
performance
stack efficiencyFurther-
can be
awbacks
g on the reported concern the low
current state-of-the-art time.
current papers,
(research density
electrolyzer The (up main
alkaline to drawbacks
0.7and A·cm−2
manufacturers) PEM reported concern 3 the low current density (up to 0.7 A·cm−2
ow
ogen
equested
ower
hnology
awbacks of 2
is
specific to
MW meet
maturefrom
energy
reported the
over NELhigh-pressure
PEM
consumption,
concern company).
theelectrolyzers,
low high requirements
High-pressure
hydrogen
range
current more,
the best
obtained
and
density ofhydrogen
since
volume
the FCEVs.
such
losses
(up the
performanceto as
rate,
from
0.7 Further-
technology
produc-
low
and can
power
A·cm−2 be
specific
life- is[9,22,32],
mature
energy
electronics
Table
over PEM
consumption,
(around
summarizes
electrolyzers,
5%) high
with the
the
hydrogen
use the main
of best features
performance
volume
AC-DC
of alkaline
rate,
converters andcanlife-
be
lyzer bulky)
acturers) and setTable
[9,22,32], production 3 summarizes capacitythe making
dynamic
andmain PEM the
range
features electrolyzer
(limiting
of alkaline
technologies. bulky)
op-
From and 3,
Table setitproduction
can be noted capacity
that dynamic
alkaline range (limiting
electrolyzers can op-
gen-
nd
hnology
owtoissue isreported
since
specific mature
hydrogen
energy over PEM
is
consumption, stored electrolyzers,
under
high gaseous
hydrogenthe
time. best
obtained form performance
volume
The such
at 700
main as
rate,bar low
andin
drawbackscan be
specific
stor-
life- energy consumption, high hydrogen volume rate, and life-
awbacks
lyzer bulky) and 3,setconcern
itproduction the low such
current
capacity as
density
dynamic
erating Finally,
isthyristors (up
range
conditions relying
or
to 0.7
(limiting on
transistors-based
A·cm−2
to the reported
op-
generate current
hydrogen). concern
state-of-the-art
rectifiers [34,35].the low current
(research density
papers, (upby to
alkaline 0.7
andA·cm−2
PEM
gies.
owg
ed
generate
on
in
From
specific
the
hydrogen).
Table
energy
current
commercial
canThe
consumption,
state-of-the-art
fuel cell
besystem
noted
electric
efficiency
high
that alkaline
hydrogen
(research
vehicles erate
time.
assessed
papers,
(FCEVs)
electrolyzers
hydrogen
volume
The
by
main
alkaline
[33].
considering
rate,
In at can
very
and
drawbacks
and
any
gen-
highreported
life-
PEM
case, pressure (upThe
concern to 200 system
the bar
low
efficiency
against
current
is
30density
barassessed
for PEM
(up to
considering
electrolyzers
0.7 A·cm−2
awbacks
lyzer
orange
very bulky)
generate reported
and
hydrogen).
andpressure
high the lossesconcern
set(up production
The
fromto 200 the
system
power low
barcapacitycurrent
efficiency
electronics
against 30 density
making
electrolyzer
dynamic
is
the assessed
stack
(around
bar for (up
the
range
PEM5%) to
by
efficiency 0.7
electrolyzer
(limiting A·cm−2
manufacturers)
considering
with range
the
electrolyzers bulky)
use and
op-and[9,22,32], set
the losses production
Table 3power
fromcompany). capacity
summarizeselectronics dynamic
the main (around range
features (limiting
5%) with of alkaline op-
the use
awbacks
acturers)
equested reported
[9,22,32],
to meet concern
the Table 3 the
high-pressure low
summarizes current the
requirements at the
density
making
main same(up
the
features
of rated
FCEVs.to 0.7
of power
electrolyzer A·cm−2
alkaline
Further- of 2 MW
bulky) andfrom
set NEL
production capacityHigh-pressure
dynamic hydrogen
range produc-
(limiting op-
lyzer
orange bulky)
generate
ofand and set
hydrogen).
the losses production
The
from capacity
systemelectronics
power efficiency dynamic
erating
and
of PEM
is(around
assessed
AC-DC range
conditions
5%) (limiting
technologies.
bywith to
considering
converters the op-
generate
From
use
such hydrogen).
Table 3, itor
as thyristors The
can system efficiency
be noted that alkaline is assessed
electrolyzersby considering
can gen-
ers
ower
gies.
hnology
such
go generate
lyzer on From
the
as
bulky)
is
thyristors
2 current
MW
and
Table
mature
from
set
3, it
over
or
NEL transistors-based
state-of-the-art
production
can PEM
company).
be noted (research
capacity
that
electrolyzers,
rectifiers
High-pressuretion
papers,
dynamic
erating
alkaline
the bestis [34,35].
an hydrogen
important
alkaline
range
conditions
electrolyzers
performance and
(limiting
produc-
to
can issue
PEM
can op-
generate
gen-
be since hydrogen The
hydrogen). istransistors-based
stored
system under
efficiency
rectifiers
gaseous is form [34,35].
assessed at 700
by bar in stor-
considering
ers range
suchand
tacturers)
issue since hydrogen).
the losses or
as thyristors
hydrogen The
from system
power
istransistors-based
stored efficiency
electronics
under is(around
the
erate
rectifiers
gaseous assessed
stack
formhydrogen5%)
[34,35].
at bywith
efficiency
700 considering
at very
bar range
the
in use
stor- andpressure
high the losses (up fromto 200 power bar electronics
against 30 bar (around
for PEM 5%)electrolyzers
with the use
ow
ers orange
very generate
high
specific
such and
as
[9,22,32],
hydrogen).
pressure
energy
the losses
thyristors
Table
(up The
to
consumption,
from
or
3power
summarizes
system
200 barhigh
transistors-based efficiency
against 30age
the
hydrogen
electronics of
at main
is
the
bar
(around
rectifiers
tanks
assessed
stack
AC-DC
the for features
volume
samePEM5%)
[34,35].
embedded
by
efficiency ofpower
considering
range
electrolyzers
rate,
ratedwith
converters andthe
in
alkaline commercial
life-
use
such ofand
as
2 the losses
thyristors
MW from
fuelfrom
or
NEL
cell power
electricelectronics
transistors-based
company).
vehicles (FCEVs) (around
rectifiers
High-pressure
[33].
5%) with
[34,35].
hydrogen
In any thecase,
produc-use
ed
gies. in commercial
From Table 3,fuel
it cancell beelectric
noted vehicles
that alkaline(FCEVs)
compressors [33].
electrolyzers In
are any
requested
can case,
gen- to meet the high-pressure requirements of FCEVs. Further-
range
ower
awbacks
ers suchofand the losses
2reported
as MW from from
NEL
concern power
company).
the low electronics
High-pressure
current of (around
AC-DC
density 5%)
hydrogen
(up towith
converters the
0.7 produc-
A·cm−2 usesince
such as thyristors oristransistors-based rectifiers [34,35].
equested
very high tothyristors
meet the or transistors-based
high-pressure rectifiers
requirements tion
more,
is an [34,35].
ofPEM
since
important
FCEVs.
the
issue
Further-
technology
hydrogen stored under gaseous
is mature over PEM electrolyzers, the best performance can be
form at 700 bar in stor-
ers
lyzer such
t issue aspressure
since
bulky) and set(up
thyristors
hydrogen oris to
production 200 barunder
transistors-based
stored against
capacity 30
gaseous bar
rectifiers
dynamic
age for
form
tanks [34,35].
at
range 700 electrolyzers
bar
(limiting
embeddedcan in stor-
op-
in becommercial fuel cell electric vehicles (FCEVs) [33]. In any case,
hnology
ower of is
2 MWmaturefrom over NEL PEM electrolyzers, the best
obtained performance
such as anylow specific energy consumption, high hydrogen volume rate, and life-
ed in commercial
o generate hydrogen).fuel cellcompany).
The system High-pressure
electric efficiency
vehicles (FCEVs)
is assessed
compressors hydrogen
[33]. byareIn produc-
considering
requestedcase, to meet the high-pressure requirements of FCEVs. Further-
owtrangespecific
issue and
since energy
hydrogen consumption,
is stored high hydrogen time. volume
The main rate, and
drawbacks life- reported concern the low current density (up to 0.7 A·cm−2
equested tothe
meet the from
losses powerunder
high-pressure gaseous
requirements
electronics form
(around ofatFCEVs.
5%) 700 barFurther-
with in stor-
the use is mature over
awbacks reported concern the low current more, density
making
since
(up the
to 0.7technology
the electrolyzer A·cm−2 PEM electrolyzers, the best performance can be
bulky) and set production capacity dynamic range (limiting op-
Energies 2022, 15, x FOR PEER REVIEW 6 of 21

Table 3. Summary of features for alkaline and PEM water electrolysis technologies.
Energies 2022, 15, 3452 6 of 20
Specification Alkaline Electrolyzer PEM Electrolyzer
Electrolyte 25–30% KOH aqueous solution Solid polymer
Cell temperature
Table 3. Summary of features for alkaline and PEM water 60–80 °C
electrolysis technologies. 50–80 °C
Gas purity 99.999% 99.999%
Specification PressureAlkaline Electrolyzer 1–200 bar PEM Electrolyzer 1–50 bar
Electrolyte Current25–30%
densityKOH aqueous solution0.2–0.7 A·cm−² Solid polymer 0.6–2.0 A·cm−²
Cell temperature 60–80 ◦C 50–80 ◦C
Cell voltage 1.5–2.6 V 1.4–2.3 V
Gas purity 99.999% 99.999%
Pressure
Cell voltage efficiency (LHV 1, HHV
1–200 bar 1–50 bar 57–83%
2)
58–77%
Current density 0.2–0.7 A·cm− 2 0.6–2.0 A·cm−2
Cell voltage Stack voltage 1.5–2.6 V 18–522 V 1.4–2.3 V 4–125 V
Cell voltage efficiency (LHV 1 , HHV 2 ) Stack Current 58–77% 60–5250 A 57–83% 9–75 A
Stack voltage 18–522 V 4–125 V
System efficiency 55–73% 55–75%
Stack Current 60–5250 A 9–75 A
System efficiency Specific energy consumption at
55–73% 55–75%
3.8–4.4 kWh·Nm−3 4.53–7.3 kWh·Nm−3
Specific energy consumption at stack stack 3.8–4.4 kWh·Nm−3 4.53–7.3 kWh·Nm−3
Production capacity dynamic Production
range capacity dynamic range
15–100% 15–100% 0–100% 0–100%
Cell area Cell area ≤4 m2 ≤4 m² ≤300 m2 ≤300 m²
Hydrogen production rate 1.5–3880 Nm3 ·h−1 0.22–5000 Nm3 ·h−1
Hydrogen production rate 1.5–3880 Nm3·h−1 0.22–5000 Nm3·h−1
Hydrogen volume rate Up to 8374 kg/24 h Up to 10786 kg/24 h
Lifetime stack Hydrogen volume
<90,000 hrate Up to 8374 kg/24 h
(more than 10 years) Up to
<60,000 h 10786 kg/24 h
Lifetime stack <90,000 h (more than 10 years) 35,000–80,000<60,000
h h
Lifetime system incl. maintenance 20 + years
(around 935,000–80,000
years) h
Lifetime system incl. maintenance 20 + years
1 Lower heating value (around 120 MJ·kg−1 ), 2 Higher heating value (around 142 MJ·kg−(around
1 ). 9 years)
1 Lower heating value (around 120 MJ·kg−1), 2: Higher heating value (around 142 MJ·kg−1).
2.2. Static and Dynamic Operation
2.2. Static
Beforeand Dynamic Operation
reviewing the electrical domain modeling of alkaline electrolyzers in the
next Before
section,reviewing the electrical
it is crucial to show domain modeling
their static of alkaline
and dynamic electrolyzers in the
characterization. next
Hence,
section,
an it is crucial
experimental testtobench
showhastheir static
been and dynamic
realized characterization.
at the GREEN laboratory,Hence,
IUT deanLongwy
experi-
(Cosnes-et-Romain,
mental test bench has France), to perform
been realized static
at the and dynamic
GREEN testsIUT
laboratory, on de
a single
Longwycell (France),
alkaline
electrolyzer as shown
to perform static in Figure
and dynamic 2. onThe
tests technical
a single specifications
cell alkaline of the
electrolyzer as electrolyzer are
shown in Figure
summarized
2. The technicalin Table 4.
specifications of the electrolyzer are summarized in Table 4.

Figure2.
Figure 2. Experimental
Experimental test
test bench
bench for
for static
static and
and dynamic
dynamictests.
tests.
Energies 2022, 15, x FOR PEER REVIEW 7 of 21

Energies 2022, 15, 3452 7 of 20

Table 4. Technical specification of the studied alkaline electrolyzer.

Table 4. Technical specification of the studied alkaline
Parameters electrolyzer.
Value Unit
RatedParameters
electrical power 150
Value W
Unit
Operating voltage range 1.6–2.6 V
Rated electrical power 150 W
Current
Operating range
voltage range 0–45
1.6–2.6 AV
Delivery output
Currenthydrogen
range pressure 0.1–10.5
0–45 Bar
A
Delivery output hydrogen
Hydrogen pressure
purity 0.1–10.5
99.999 Bar
%
Hydrogen purity 99.999
Cells number 1 -%
Cells number 1 -
Hydrogen volume
Hydrogen volume range
range 0–310
0–310 mL·
mLmin
−1
·min−1
Electrolyte
Electrolyte 32% weightKOH
32% weight KOH --

The realized experimental test bench includes the following devices: (1) a single-cell
The realized experimental test bench includes the following devices: (1) a single-cell al-
alkaline electrolyzer, (2) a 4-channel oscilloscope, (3) a DC power supply, (4) a laptop en-
kaline electrolyzer, (2) a 4-channel oscilloscope, (3) a DC power supply, (4) a laptop enabling
abling the control of the DC power supply for static and dynamic tests purposes, (5) a
the control of the DC power supply for static and dynamic tests purposes, (5) a voltage
voltage
probe toprobe
acquire to acquire
the cell the cell voltage
voltage of the electrolyzer,
of the electrolyzer, (6) a current
(6) a current probe toprobe to measure
measure the cell
the cell current of the electrolyzer, and (7) an isolated transformer
current of the electrolyzer, and (7) an isolated transformer to eliminate the interference to eliminate the inter-
ference
and noise andfromnoise thefrom
powerthegrid.
power Togrid.
enableTotheenable
goodthe good operation
operation of the single-cell
of the single-cell alkaline
alkaline electrolyzer, 1000 mL of distilled water has been
electrolyzer, 1000 mL of distilled water has been mixed with 32% weight KOH mixed with 32% weight KOH as
as requested
requested by the electrolyzer
by the electrolyzer manufacturer.manufacturer.
When theWhen the lye
lye liquid hasliquid
been has
fullybeen fullyitmelted,
melted, has beenit
has been put in a tank to supply the alkaline electrolyzer. Besides, the
put in a tank to supply the alkaline electrolyzer. Besides, the KOH purity is 85%. Once the KOH purity is 85%.
Once the hydrogen
hydrogen is generated, is generated,
it is storedit in
is stored in metalstorage
metal hydride hydridetanks
storage
(nottanks
shown(not
in shown
Figure in
2),
Figure 2), enabling meeting safety recommendations
enabling meeting safety recommendations for hydrogen storage. for hydrogen storage.
First
First ofof all,
all, the
the static
static characterization
characterization of of the
the single-cell
single-cell alkaline
alkaline electrolyzer
electrolyzer isis de-
de-
picted
picted inin Figure
Figure 3. 3. This
This characterization
characterization allows
allows emphasizing
emphasizing the the two
two main
main overvoltage
overvoltage
regions,
regions, thethe first
first from
from 00 to
to 22 A
A (activation
(activation region),
region), andand the
the second
second from
from 22 to
to 45
45 AA (ohmic
(ohmic
region).
region). The
Thereversible
reversiblevoltage
voltageatatzero-current
zero-currentisisroughly
roughlyequalequaltoto1.6
1.6V.V.The
Theohmic
ohmicover-
over-
voltage is influenced by different parameters such as the electrical
voltage is influenced by different parameters such as the electrical conductivity of both conductivity of both
electrodes (i.e., anode
electrodes (i.e., anodeand andcathode),
cathode),the the specific
specific electrolyte
electrolyte conductivity,
conductivity, distances
distances be-
between
tween the electrodes,
the electrodes, and hydrogen
and hydrogen and oxygen
and oxygen bubbles bubbles that cover
that cover some some
parts parts
of theof the sur-
surface of
face of the electrodes.
the electrodes.

Figure 3.
Figure Static characterization
3. Static characterization of
of the
the studied
studied alkaline
alkaline electrolyzer.
electrolyzer.

After performing a static characterization of the alkaline electrolyzer, dynamic tests

After performing a static characterization of the alkaline electrolyzer, dynamic tests
have been carried out. Rise and falling current steps (from 20 to 40 A, and inversely) have
have been carried out. Rise and falling current steps (from 20 to 40 A, and inversely) have
been applied to the single-cell alkaline electrolyzer. The results are shown in Figure 4.
been applied to the single-cell alkaline electrolyzer. The results are shown in Figure 4. It
It can be noted that the single-cell alkaline electrolyzer responds quickly when changing
can be noted that the single-cell alkaline electrolyzer responds quickly when changing
operating conditions. Indeed, in both cases, the steady-state cell voltage operation is
operating conditions. Indeed, in both cases, the steady-state cell voltage operation is
reached in 0.24 ms. Both tests demonstrate that the specific electrolyte conductivity is
suitable to meet dynamic performance, as required when connecting alkaline electrolyzers
to intermittent green energy sources such as RES [36].
Energies 2022, 15, x FOR PEER REVIEW 8 of 21

Energies 2022, 15, 3452
reached in 0.24 ms. Both tests demonstrate that the specific electrolyte conductivity is suit-
able to meet dynamic performance, as required when connecting alkaline electrolyzers to
reached in 0.24 ms. Both tests demonstrate that the specific electrolyte conductivity is suit-
intermittent green energy sources such as RES [36]. 8 of 20
able to meet dynamic performance, as required when connecting alkaline electrolyzers to
intermittent green energy sources such as RES [36].

Figure 4. Dynamic test with a rise current step from 20 to 40 A (Ch1 and Ch3) and a falling current
step from 40 to 20 A (Ch2 and Ch4).
Figure4.4.Dynamic
Figure Dynamictesttestwith
withaarise
risecurrent
currentstep
stepfrom
from20
20to
to40
40AA(Ch1
(Ch1and
andCh3)
Ch3)and
andaafalling
fallingcurrent
current
step from 40
step Finally,to
from 40 to 20
20AA (Ch2
(Ch2and
andCh4).
Ch4).
a test with dynamic solicitations has been performed to highlight the perfor-
mance of theastudied
Finally, test with alkaline
dynamic electrolyzer.
solicitations This
hastest includes
been performeda risetocurrent stepthe
highlight (from 20
perfor-
Finally, a test with dynamic solicitations has been performed to highlight the perfor-
to 45 A) at 9 s, then a falling current step (from 45 to 10 A) at 32 s, and finally
mance of the studied alkaline electrolyzer. This test includes a rise current step (from 20 to a rise current
mance of the studied alkaline electrolyzer. This test includes a rise current step (from 20
step
45 A)(from
at 9 s, 10
thento a30 A) atcurrent
falling 70 s asstep
illustrated
(from 45intoFigure
10 A) at5.32Ins,conclusion,
and finally adynamic perfor-
rise current step
to 45 A) at 9 s, then a falling current step (from 45 to 10 A) at 32 s, and finally a rise current
mances
(from 10are met
to 30 A)when
at 70 the
s asalkaline electrolyzer
illustrated in Figure is
5. solicited by sudden
In conclusion, dynamic operating conditions
performances are
step (from 10 to 30 A) at 70 s as illustrated in Figure 5. In conclusion, dynamic perfor-
change.
met when the alkaline electrolyzer is solicited by sudden operating conditions change.
mances are met when the alkaline electrolyzer is solicited by sudden operating conditions
change.

Figure 5.
Figure Tests with
5. Tests with dynamic
dynamic solicitations.
solicitations.

3. Electrical Domain Modeling

3.Figure 5. Tests
Electrical with dynamic
Domain solicitations.
Modeling
Over the last decades, the modeling of alkaline electrolyzers has attracted a lot of
Over theDomain
investigation
3. Electrical last researchers
from decades, the
Modeling to modeling
develop the ofuse
alkaline
of thiselectrolyzers
technology athas attracted
a large a lot of
scale powered
investigation
by RES. from
However, researchers to develop the use of this technology at a large scale pow-
Over the last as mentioned
decades, in the introduction,
the modeling of alkalinealkaline electrolyzers
electrolyzers have received
has attracted a lot of
less modeling investigation than PEM electrolyzers. This difference may be explained by
investigation from researchers to develop the use of this technology at a large scale pow-
the benefits of using PEM electrolyzers over alkaline electrolyzers from the high current
density, low maintenance, and large partial load range point of view. Besides, compared to
PEM electrolyzers, no review works have been reported in the literature regarding alkaline
electrolyzers modeling. Only three reviews can be found, dealing with the technology,
its coupling with RES, and the effects of the parameters on the energy efficiency. Given that
Energies 2022, 15, 3452 9 of 20

this review work is focused on electrical domain modeling, this section has been split into
three main parts: semi-empirical, empirical, and dynamic modeling. This section aims at
providing valuable information and guidelines to industrials, researchers, and students to
model alkaline electrolyzers from the electrical domain point of view.

3.1. Static Modeling

3.1.1. Introduction
First of all, the performance of the alkaline electrolyzer is linked to its polarization
curve as shown in Figure 3. From Figure 3, the higher the current, the higher the cell voltage
due to the overvoltages. At zero-current, the cell voltage is equal to the reversible voltage
Vrev . At very low currents (up to 2 A), the activation overvoltages (anode and cathode) are
preponderant, while from 2 A and above, the ohmic region is predominant. The reversible
voltage, the activation, and the ohmic overvoltages depend strongly on the temperature,
gas pressures, and the electrical conductivity of both electrodes (i.e., anode and cathode),
the specific electrolyte conductivity, distances between the electrodes, and hydrogen and
oxygen bubbles that envelops some areas of the surface of the electrodes. Hence, the cell
voltage Vcell of the alkaline electrolyzer can be expressed by the general expression in
Equation (4) below:
Vcell = Vrev + ηohm + ηact,a + ηact,c (4)
where Vrev (V) is the reversible voltage, η ohm (V) is the ohmic overvoltage, η act,a (V) and
η act,c (V) are, respectively, the activation overvoltage at the anode and the cathode.
In the next subsections, the semi-empirical, empirical, and dynamic modeling is
detailed and analyzed.

3.1.2. Semi-Empirical Modeling

Several semi-empirical equations for alkaline electrolyzers have been used to model
the current-voltage curve. One of the most used semi-empirical models was first described
by Ulleberg [37]. The model combines thermodynamics, kinetics, and resistive effects of
the electrolyzer. The basic form of the current-voltage curve is given in Equation (5) [22,37]:
     
iel iel
Vcell = Vrev + r · + s· log t· +1 (5)
Aelec Aelec

where Vrev (V) is the reversible voltage, the second term is the ohmic overvoltage defined
by its parameter r (Ω m2 ) and the last term represents the activation overvoltage defined by
the parameters s (V) and t (m2 A−1 ). The current absorbed by the electrolyzer is represented
by iel (A), while Aelec (m2 ) stands for the cell electrode area. The term iel /Aelec (A m−2 ) is
the current density that can be replaced by j (A m−2 ).
Based on the article Ref. [38], the performance of the alkaline electrolyzer highly
depends on its operating temperature. Therefore, to improve the above semi-empirical
model, the temperature effect must be considered. As reported in Ref. [39], only the two
parameters r and t depend on the temperature while the parameter s is usually assumed
to be constant. Considering the electrolyzer operating temperature, Ulleberg’s model in
Equation (5) can be modified as expressed in the following Equation (6):
  
t2 t3
Vcell = Vrev + (r1 + r2 ·θ )· j + s· log t1 + + 2 · j + 1 (6)
θ θ

where θ (◦ C) is the operating temperature, r1 (Ω m2 ) and r2 (Ω m2 ◦ C−1 ) reflect ohmic losses,

t1 (m2 A−1 ), t2 (m2 A−1 ◦ C) and t3 (m2 A−1 ◦ C2 ) are related to the activation overvoltages
and j (A m−2 ) is the current density [22].
Energies 2022, 15, 3452 10 of 20

Gas pressure also influences the performance of the alkaline electrolyzer [22,38]. Con-
sidering also the gas pressure P (bar), the above Ulleberg’s equation can be expressed in
Equation (7) as:
  
t2 t3
Vcell = Vrev + [(r1 + δ1 ) + r2 ·θ + δ2 · P]· j + s· log t1 + + 2 · j + 1 (7)
θ θ

Equation (7) introduces new empirical parameters δ1 (Ω m2 ) and δ2 (Ω m2 bar−1 ),

which are related to the linear change in the ohmic overvoltage.
Many authors have demonstrated that the distance electrode-diaphragm d (mm) [40]
and the electrolyte molarity concentration M (mol L−1 ) have a significant influence on the
alkaline electrolyzer performances. The ohmic losses depend on the electrode-diaphragm
distance d and the electrolyte molarity concentration M. To obtain an accurate equation for
the current-voltage curve, these two new parameters must be examined. Thus, the resulting
semi-empirical model is given by Equation (8) below:

· θ + p2 M + p3 M 2 + q2 · d · j +
 
Vcell = Vrev +h(r1 + p1 + q
1 ) + r2 i
t2 t3 (8)
s· log t1 + θ + θ2
·j + 1

where p1 (Ω m2 ), p2 (Ω m2 mol−1 L), and p3 (Ω m2 mol−2 L2 ) represent the ohmic drops

due to the electrolyte concentration, q1 (Ω m2 ) and q2 (Ω m2 mm−1 ) represent the ohmic
losses due to the electrode-diaphragm distance.
To determine the different parameters in Equations (6)–(8), experimental data are
compared to the model through the use of a numerical regression method mainly based on
least square algorithms [41–43]. Relying on previous works carried out to determine the
parameters of the models (6)–(8), Table 5 has been made to summarize the values of the
different parameters.

Table 5. Parameters for the calculation of the cell voltage for Equations (6)–(8).

Parameter Equation (6) [22,37] Equation (7) [22,38] Equation (8) [40] Unit
r1 8.05 × 10−5 4.45153 × 10−5 3.53855 × 10−4 Ω m2
r2 −2.5 × 10−7 6.88874 × 10−9 −3.02150 × 10−6 Ω m2 ◦ C−1
s 0.185 0.33824 2.2396 × 10−1 V
t1 1.002 −0.01539 5.13093 m2 A−1
t2 8.424 2.00181 −2.40447 × 102 m2 ◦ C A−1
t3 247.3 15.24178 5.99576 × 103 m2 ◦ C2 A−1
δ1 - −3.12996 × 10−6 - Ω m2
δ2 - 4.47137 × 10−7 - Ω m2 bar−1
p1 - - 3.410251 × 10−4 Ω m2
p2 - - −7.489577 × 10−5 Ω m2 mol−1 L
p3 - - 3.916035 × 10−6 Ω m2 mol−2 L2
q1 - - −1.576117 × 10−4 Ω m2
q2 - - 1.576117 × 10−5 Ω m2 mm−1

In [22,37,38,40], the authors have shown curves on which the experimental results and
the results predicted by the models are very close, but, except for [40] where the average
error obtained using Equation (8) is less than 0.8%, there is no numerical values associated
with the analysis on these errors. Considering the experimental results and the predicted
behavior of the electrolyzer, one can conjecture that the proposed classes of models are
valid in different operating modes, especially when coupling with intermittent sources
such as wind turbines and photovoltaic panels to investigate hydrogen production systems.
Energies 2022, 15, 3452 11 of 20

Finally, considering that all the cells in the alkaline electrolyzer have the same physical
performance and behavior, then the electrolyzer total voltage (Vel ) is equal to the cell voltage
(Vcell ) multiplied by the number of cells of the stack Ncell as reported in Equation (9) below:

Vel = Ncell ·Vcell (9)

In the next subsection, empirical models are reported and detailed.

3.1.3. Empirical Modeling

As reported in the literature, the main electrical expression of the cell voltage Vcell
including the different voltages is given by Equation (10) [22,44]:

Vcell = Vrev + ( R a + Rc + Rele + Rmem )·iel + ηact,a + ηact,c (10)

where Vrev (V) is the reversible voltage, Ra (Ω) and Rc (Ω) are ohmic resistances, respectively,
related to the conductivity of the electrodes (anode and cathode), Rele (Ω) represents the
ohmic loss due to the electrolyte conductivity, Rmem (Ω) stands for the membrane ohmic
resistance, η act,a (V) and η act,c (V) are, respectively, the activation overvoltage at the anode
and the cathode.
In this subsection, the expressions of the reversible voltage and the different overvolt-
ages (activation and ohmic) are provided and studied.

Reversible Potential
The reversible potential is defined as a required voltage that is just needed to start the
electrolysis reaction. Its value is directly related to the Gibbs energy ∆G (J mol−1 ) defined
in Equation (11) below [19,22,37]:

∆G = ∆H − T ·∆S (11)

where ∆H (J mol−1 ) is the change in enthalpy, ∆S (J mol−1 ◦ K−1 ) the change in entropy,
and T (◦ K) the temperature.
The reversible potential Vrev is the ratio of the Gibbs energy ∆G to the product of Fara-
day’s constant F and the number of exchanged electrons n, as given in Equation (12) below:

∆G ∆H − T ·∆S
Vrev = = (12)
n· F n· F
The change in enthalpy ∆H is also related to the thermoneutral cell voltage Vth by the
following Equation (13):
∆H ∆G + T ·∆S
Vth = = (13)
n· F n· F
Given that the number of electrons n = 2 (see chemical reactions, Equations (1)–(3)) and
the Faraday’s constant F = 96,485 C mol−1 , at standard conditions (T = 298.15 ◦ K, pressure of
1 bar), the values of the enthalpy ∆H and the entropy ∆S are given as: ∆H = 285.84 kJ mol−1 ,
∆S = 0.1631 kJ mol−1 ◦ K−1 . At these conditions, the reversible potential and the thermoneu-
tral cell voltage are, respectively, given by: Vrev,0 = 1.23 V and Vth,0 = 1.48 V.
At other operating conditions, the reversible potential Vrev (V) is determined using
Nernst’s equation in Equation (14) as reported in articles [40,45,46]:

( P − Pv,KOH )3/ 2
!
R· T
Vrev = Vrev,0,T + · ln (14)
n· F α H2 O

where Vrev,0,T (V) is the reversible potential at a given condition (i.e., temperature and
pressure), R = 8.315 J K−1 mol−1 the universal gas constant, T (◦ K) the temperature, n the
number of electrons, F (C mol−1 ) the Faraday’s constant, P (bar) the gas pressure, Pv,KOH
Energies 2022, 15, 3452 12 of 20

(bar) the vapor pressures, and α H2 O is the water activity of the electrolyte solution based
on KOH.
The reversible potential Vrev,0,T (V) can be assessed as a function of temperature T (◦ K)
in Equation (15) as reported in articles [45–48]:

Vrev,0,T = 1.5184 − 1.5421·10−3 · T + 9.523·10−5 · T · ln( T ) + 9.84·10−8 · T 2 (15)

The vapor pressures of the KOH solution Pv,KOH (bar) is calculated using the following
Equation (16) as reported in [45]:



Pv,KOH = exp 2.302· a + b· ln Pv,H2 O (16)

where a and b are coefficients that depend on the KOH molality m (mol kg−1 ) as given in
Equations (17) and (18) below, and Pv,H2 O (bar) is the vapor pressure of pure water, which is
expressed as a function of the temperature T (◦ K) in Equation (19) as reported in [45]:

a = −0.0151·m − 1.6788·10−3 ·m2 + 2.2588·10−5 ·m3 (17)

b = 1 − 1.2062·10−3 ·m + 5.6024·10−4 ·m2 − 7.8228·10−6 ·m3 (18)

 
7699.68 −3
Pv,H2 O = exp 81.6179 − − 10.9· ln T + 9.5891·10 · T (19)
T
In Equation (20), the water activity αH2 O of the electrolyte solution based on KOH is ex-
pressed as a function of the temperature T (◦ K) and the molality concentration m (mol kg−1 )
as reported in [45]:

!
2 3.177·m − 2.131·m2
α H2 O = exp −0.05192·m + 0.003302·m + (20)
T

Equations (15)–(20) are valid for pressure ranging from 1 to 200 bar, temperature
between 273.15 to 523.15 ◦ K, and the molality concentration ranging from 2 to 18 mol kg−1 .

Activation Overpotential
The activation overvoltages starting the water electrolysis process at the anode η act,a
and at the cathode η act,c can be evaluated using the Butler–Volmer equations (or Tafel’s
approximations) in Equations (21) and (22) as reported in articles [44,47].

R· T
 
ja
ηact,a = 2.3· · log (21)
αa · F j0,a

R· T
 
jc
ηact,c = 2.3· · log (22)
αc · F j0,c
where αa and αc are, respectively, the charge transfer coefficients at the anode and the cathode,
ja (mA cm−2 ) and jc (mA cm−2 ) are the current densities of the electrodes, j0,a (mA cm−2 ) and
j0,c (mA cm−2 ) are the exchange current densities of the electrodes.
Based on the physical and electrical behavior of the Hydrogen Research Institute (HRI)
alkaline electrolyzer reported in [44], the physical models of the current densities (j0,a and
j0,c ) as a function of temperature T (◦ K) are given in Equations (23) and (24):

j0,a = 30.4 − 0.206· T + 0.00035· T 2 (23)

j0,c = 13.72491 − 0.09055· T + 0.09055· T 2 (24)

Energies 2022, 15, 3452 13 of 20

The charge transfer coefficients (αa and αc ) of the HRI electrolyzer as a function of
temperature T (◦ K) are given in Equations (25) and (26) as reported in [44]:

α a = 0.0675 + 0.00095· T (25)

αc = 0.1175 + 0.00095· T (26)

Ohmic Overpotential
Alkaline electrolyzers are made of different elements. Each element is modeled as
electrical resistance. The total ohmic resistance of the electrolyzer can be expressed in
Equation (27) as reported in articles [44,49]:

Rtotal = R a + Rc + Rele + Rmem (27)

where Ra (Ω) and Rc (Ω) are the anode and the cathode resistances, Rele (Ω) the resistance
of the electrolyte (KOH or NaOH), and Rmem (Ω) the resistance of the membrane.
a. Electrodes
Electrodes in alkaline electrolyzer can either be cobalt, nickel, or iron. Most of the
electrodes are made of nickel because of their stability [11]. Electrodes resistances depend
on their conductivity and their geometry as reported in the article [44]. Therefore, the resis-
tances at the anode Ra and the cathode Rc of electrodes made of nickel (Ni) are given in
Equations (28) and (29) as reported in [44]:
 
1 La
Ra = (28)
σNi Sa
 
1 Lc
Rc = (29)
σNi Sc
where La (cm) and Lc (cm) are, respectively, the anode and the cathode thickness, Sa (cm2 )
and Sc (cm2 ) are the electrode cross-sections, and σNi (S cm−1 ) is the conductivity of an
electrode made of nickel.
As reported in the article [44], the conductivity σNi can be calculated as a function of
temperature T (◦ K) using the following Equation (30):

σNi = 6000000 − 279650· T + 532· T 2 − 0.38057· T 3 (30)

b. Electrolytes
The alkaline electrolysis reaction generates bubbles from hydrogen and oxygen gases,
thus the electrolyte resistance Rele in Equation (31) is the sum of the bubble-free electrolyte
resistance Rele,bf and the resistance due to bubbles Rele,b as reported in articles [44,50]:

Rele = Rele,b f + Rele,b (31)

In articles [44,50], the formula used to calculate the bubble-free electrolyte resistance
Rele,bf is given in Equation (32) below:
 
1 d a,m dc,m
Rele,b f = + (32)
σb f Sa Sc

where da,m (cm) and dc,m (cm) are, respectively, the anode-membrane and the cathode-
membrane distances, Sa (cm2 ) and Sc (cm2 ) are the anode and cathode cross-sections and
σbf (S m−1 ) is the bubble-free electrolyte conductivity.
Energies 2022, 15, 3452 14 of 20

The bubble-free conductivity σbf can be determined as a function of the electrolyte

molarity concentration M (mol L−1 ) and the temperature T (◦ K) as reported in [44,47,51]
according to Equation (33) below:

σb f = −204.1· M − 0.28·
M2 + 0.5332·( M· T ) + 20720· M

T + 0.1043· M
3
(33)
−0.00003· M2 · T 2

The Equation (33) can also be expressed according to the temperature and KOH mass
fractions. Since it is an important issue in this review paper, it is analyzed and detailed in
the next subsection.
The resistance Rele,b due to bubbles in the electrolyte is given in Equation (34) as
reported in the article [44]:
!
1
Rele,b = Rele,b f · −1 (34)
(1 − ε )3 / 2

where ε is a coefficient that depends on the effective electrode surface Seff (cm2 ) and the
nominal electrode surface S (cm2 ) as given in Equation (35):

Se f f
 
ε = 1− (35)
S

c. Membrane
As reported in [44], the HRI electrolyzer membrane resistance made of Zirfon material
of 0.5 mm thickness is given in Equation (36) as:

0.060 + 80· exp( T / 50)

Rmem = (36)
10000·Smem

where Smem (cm2 ) is the membrane surface, T (◦ K) is the temperature.

After analyzing the semi-empirical and empirical models, the next subsection allows
introducing the dynamic modeling of alkaline electrolyzers that has to be considered when
coupling them with intermittent energy sources.

3.2. Dynamic Modeling

Compared to static modeling, dynamic modeling of alkaline electrolyzers has received
fewer investigations from researchers. Indeed, over the last decade, only two papers have
considered dynamic issues when modeling alkaline electrolyzers [45,52]. First of all, in [45],
the authors have proposed an equivalent electrical circuit to model both static and dynamic
behaviors of this electrolyzer. This equivalent electrical circuit for one cell is shown in
Figure 6. It is composed of the following components linked to the previous analysis
reported in this section:
1. A DC source, Vrev , represents the reversible voltage (located on the cathode side where
the hydrogen is generated).
2. A current source (iact,a or iact,c ) connected in parallel with a capacitor Ca or CC modeling
the activation overvoltage and especially the well-known double-layer effect between
the electrode (anode or cathode) and the electrolyte.
3. Four resistors Ra , Rc , Rmem , and Rele model, respectively, the anode, cathode, mem-
brane, and electrolyte.

Energies 2022, 15, 3452
1. A DC source, Vrev, represents the reversible voltage (located on the cathode side
where the hydrogen is generated).
2. A current source (iact,a or iact,c) connected in parallel with a capacitor Ca or CC modeling
the activation overvoltage and especially the well-known double-layer effect be-
tween the electrode (anode or cathode) and the electrolyte.
3. Four resistors Ra, Rc, Rmem, and Rele model, respectively, the anode, cathode, mem- 15 of 20
brane, and electrolyte.

Figure
Figure 6.
6. Equivalent
Equivalentelectrical
electricalcircuit
circuit modeling
modeling both
both static
static and
and dynamic
dynamic behaviors
behaviors for
for one
one cell.
cell.

Both current
Both currentsources
sources(i(i and
act,a
act,a iact,ci)act,c
and of)theof electrical
the electrical
circuitcircuit
enableenable replicating
replicating the
the acti-
vation phenomena for the anode and the cathode. These sources can be modeled as aa
activation phenomena for the anode and the cathode. These sources can be modeled as
function of
function of their
their activation
activation overvoltages
overvoltages (η (ηact,a andηηact,c
act,aand act,c), ),relying
relyingon onaafit
fitTafel
Tafel expression
expression
provided below valid for the whole stack of
provided below valid for the whole stack of the electrolyzer [45]:the electrolyzer [45]:

 
     ηact,a,el 
i act,a Aelec,a (sact ,el )
ηact,a,el = Ncell ·ηact,a = s a · log t a ·  i  + 1 ⇒ iact,a = Aelecta,a · 10 sa Ncell  − 1 (37)
a · N
, acell

 act,a ,el = N cell  act,a = sa  log t a   Aact ,a

elec,a  + 1  iact,a =  10 − 1 (37)
  Aelec,a 
  iact,c   Aelec,c  ( sc · N ) 

t a
 ηact,c,el 
ηact,c,el = Ncell ·ηact,c = sc · log tc · + 1 ⇒ i act,c = · 10 cell − 1 (38)
Aelec,c tc

    given
where ta and tc are the temperature-dependent overvoltage coefficients
 i A  
act,c , el  below:
 
 act,c ,el = N cell  act,c = sc  log tc   act,c  +t1a2 ta3iact,c = elec,c  10 sc Ncell  − 1 (38)
 ta A=electa1,c +
 θ  + θ 2 tc   (39)
 
tc2 t
where ta and tc are the temperature-dependent + c32
tc = tc1 + overvoltage coefficients given below: (40)
θ θ
Energies 2022, 15, x FOR PEER REVIEW 16 of 21
where θ (◦ C) is the operating temperature, ta 22 At−a13), ta2 (m2 A−1 ◦ C), ta3 (m2 A−1 ◦ C2 )
t = t +
ta1 (m + 2 (39)
and tc1 (m2 A−1 ), tc2 (m2 A−1 ◦ C), tc3 (m2 A−1◦ C2 )are parameters related, respectively,
a a1

to the activation overvoltage at the anode and the cathode side.

The
The equivalent electrical circuit
circuit(Figure
(Figure6)6)can tccan be simplified as as depicted in Figure 7
equivalent electrical 2 betsimplified depicted in Figure 7 [52].
[52]. In this circuit, the activation t
branch = t at + the + c3
cathode side (i and C ) has been (40)
ne-
 side  2 (iact,c and
act,c C
In this circuit, the activation branch at the cathode c c 1 CC ) has been neglected
glected
since itssince its overpotential
overpotential is lower is lower
than the than the overpotential
overpotential at theatanode
the anode side [19].
side [19]. Be-
Besides,
sides,
where in [52],
in [52],θa(°C) a first
firstisvalue value
the operating of the capacitance
temperature,
of the capacitance has
hastbeen been provided,
a1 (m provided,
2 A ), ta2 (mequal
−1 2 equal
A °C),
−1 to
to 15 15
ta3mF.mF.
(m This
2 This
A °C
−1 value
2 ) and
value is
is
c1 much
tmuch
(m2 A lower
lower than
−1), tc2 (m
than 2 Athose
−1 °C),reported
those Afor
tc3 (m2 for
reported −1 °C
PEMPEM2) are electrolyzers
parameters
electrolyzers [53]. Indeed,
related,
[53]. Indeed, forfor PEM
respectively,
PEM electrolyz-
to the acti-
electrolyzers,
ers, capacitance
vation overvoltage
capacitance values values from
at the
from to 369toFand
3anode 69 Fthe
have have been
cathode
been reportedreported according
side.according to thetooperating
the operating con-
conditions.
ditions. Based on the dynamic tests provided in Figures 4 and
Based on the dynamic tests provided in Figures 4 and 5, alkaline electrolyzers can respond 5, alkaline electrolyzers can
respond quickly to sudden operating conditions changes.
quickly to sudden operating conditions changes. This analysis can explain the small This analysis can explain the
small value of the capacitance for this electrolyzer technology,
value of the capacitance for this electrolyzer technology, whereas, for PEM electrolyzers, whereas, for PEM electro-
lyzers, the dynamics
the dynamics met are met are meaningful.
more more meaningful. Hence, Hence, the values
the values of capacitance
of capacitance are higher
are higher than
than alkaline
alkaline electrolyzers.
electrolyzers.

Simplifiedequivalent
Figure7.7.Simplified
Figure equivalent electrical
electrical circuit
circuit modeling
modeling both
both static
static andand dynamic
dynamic behaviors
behaviors for
for one
cell.
one cell.

Like static modeling, dynamic modeling requests experimental data to determine the
parameters of the equivalent electrical circuit shown in Figures 6 and 7. It is important to
point out that this type of modeling is strongly influenced by the operating variables such
Energies 2022, 15, 3452 16 of 20

Like static modeling, dynamic modeling requests experimental data to determine the
parameters of the equivalent electrical circuit shown in Figures 6 and 7. It is important to
point out that this type of modeling is strongly influenced by the operating variables such as
the current, the temperature, and gas pressure. Indeed, as highlighted in previous work [54],
the electrolyzer behavior strongly differs according to the operating conditions. For this
reason, the parameters of the model cannot be supposed constant, but variables to ensure
the reliability of the model in recreating the behavior of the electrolyzer in agreement with
the operating conditions. Relying on the electrical equations retrieved from the equivalent
electrical circuit and the experimental data, different modeling approaches can be adopted
such as regression analysis to assess the parameters of the model [55,56]. Such an approach
enables obtaining good fitting but other methods that are also attractive can be employed,
such as genetic or Levenberg–Marquardt algorithm.
Finally, on one hand, the main advantage of dynamic modeling over static modeling is
the reliability in reproducing the dynamic behavior of alkaline electrolyzer when it is sup-
plied by dynamic sources such as wind turbines or solar panels [54]. Besides, high modeling
reliability can be obtained by taking into account different operating parameters (current,
temperature, and gas pressure). This modeling is a powerful tool to develop efficient,
robust, and suitable controllers considering dynamic operating conditions, which is not
possible considering only static modeling [57]. On the other hand, the main drawback com-
pared to static modeling is the determination of the parameters of the model since they are
considered variable to enhance the reliability of the model. In other words, this modeling
requests a lot of experimental data and the use of different approaches to determine the
parameters of the model. Moreover, the design of controllers is more complex due to the
use of an equivalent electrical circuit [55].

3.3. Specific Electrolyte Conductivity

The specific electrolyte conductivity for KOH and NaOH is given in Equations (41)
and (42). Equation (41) is valid for temperature T (◦ K) ranging from 258.15 to 373.15 ◦ K
and KOH mass fraction wKOH between 0.15 and 0.45, while Equation (42) is suitable for
temperatures θ (◦ C) between 25 and 50 ◦ C and NaOH mass fraction wNaOH from 0.08 to
0.25 as reported in the article [22]. The parameters needed to calculate these conductivities
are listed in Table 6.

σKOH = K1 ·(100·wKOH ) + K2 · T + K3 · T 2 + K4 · T ·(100·wKOH )+

(100·wKOH ) (41)
K5 · T 2 ·(100·wKOH )K6 + K7 · (100·wT ) + K8 · T
KOH

σNaOH = K1 + K2 ·θ + K3 ·w3NaOH + K4 ·w2NaOH + K5 ·w NaOH (42)

Table 6. Parameters for the calculation of the specific electrolyte conductivities of KOH and NaOH
solutions by Equations (41) and (42) [22].

Parameter Equation (41) Unit Equation (42) Unit

K1 27.9844803 S m−1 −45.7 S m−1
K2 −0.924129482 S m−1 K−1 1.02 S m−1 ◦ C−1
K3 −0.0149660371 S m−1 K−2 3200 S m−1
K4 −0.0905209551 S m−1 K−1 −2990 S m−1
K5 0.0114933252 S m−1 K−2 784 S m−1
K6 0.1765 - - -
K7 6.96648518 S m−1 K−1 - -
K8 −2898.15658 S m−1 K - -

Relying on the Equations (41) and (42) and the parameters of both equations reported
in Table 6, the specific electrolyte conductivity of KOH and NaOH has been plotted ac-
cording to the mass fraction w as shown in Figure 8. Besides, two temperatures have been
considered, 25 and 50 ◦ C.
 K7 6.96648518 S m−1 K−1 - -
K8 −2898.15658 S m−1 K - -

Relying on the Equations (41) and (42) and the parameters of both equations reported
Energies 2022, 15, 3452 in Table 6, the specific electrolyte conductivity of KOH and NaOH has been plotted ac-
17 of 20
cording to the mass fraction w as shown in Figure 8. Besides, two temperatures have been
considered, 25 and 50 °C.

Figure 8.
Figure Specificelectrolyte
8. Specific electrolyteconductivity
conductivityforfor liquid
liquid solutions
solutions based
based on on either
either KOHKOH or NaOH
or NaOH ac-
according to the mass fraction of the solution.
cording to the mass fraction of the solution.

Based on
Based on Figure
Figure 8,
8,one
onecan
cannote
notethat
thatfor
foralkaline electrolyzers
alkaline with
electrolyzers KOH
with KOH liquid solution,
liquid solu-
tion, the specific electrolyte conductivity is higher compared to alkaline electrolyzersNaOH
the specific electrolyte conductivity is higher compared to alkaline electrolyzers with with
solution.
NaOH Indeed,
solution. as it has
Indeed, as itbeen demonstrated
has been demonstratedin previous papers
in previous [18,42],
papers thethe
[18,42], specific
spe-
electrolyte conductivity of KOH is optimal for mass fractions between 25 and 35 wt.%
cific electrolyte conductivity of KOH is optimal for mass fractions between 25 and 35 wt.%
and a temperature range from 50 to 80 ◦ C. The use of a liquid solution based on NaOH
offers a cheaper option than KOH but features a lower specific electrolyte conductivity.
For example, at 50 ◦ C, the maximum specific electrolyte conductivity of KOH is equal
to 95 S·m−1 , whereas for NaOH the conductivity is equal to 65 S·m−1 . By comparison,
at 25 ◦ C, both specific electrolyte conductivities have decreased, 63 S·m−1 for KOH and
42 S·m−1 for NaOH. Furthermore, it is important to point out that the specific electrolyte
conductivity of NaOH is optimal for lower mass fractions between 15 and 25 wt.% and
temperatures between 50 and 80 ◦ C. In summary, KOH liquid solution features a specific
electrolyte conductivity between 46 and 50% higher than NaOH liquid solution at their
optimal mass fractions.

4. Conclusions
The purpose of this paper was to review alkaline electrolyzer technology and its mod-
eling from the electrical domain and specific electrolyte conductivity points of view. It has
been emphasized that modeling of this electrolyzer technology has received less interest
from researchers compared to PEM electrolyzers. However, alkaline electrolyzers feature
several benefits in terms of cost due to cheaper catalysts, high lifespan, gas purity, hydrogen
production capacity, and low specific energy consumption. However, this technology still
suffers from having limited current density and production capacity range and requesting
frequent maintenance due to the use of an aqueous electrolyte solution.
Since this technology is quite mature, several perspectives are considered such as the
increase in the use of non-precious metals combined with nickel material to enhance the
performance, the design in spacing electrodes to optimize hydrogen production, and the
dissemination of low carbon footprint hydrogen production plants supplied by renewable
and nuclear resources.
Besides, as demonstrated in this paper, alkaline electrolyzers can respond quickly to
dynamic solicitations and are consequently suitable to be coupled with renewable energy
sources such as wind turbine conversion systems. The literature review focused on the
electrical domain modeling has enabled to bring out the lacks. Indeed, static modeling
has been widely investigated, but dynamic modeling has not been thoroughly analyzed
Energies 2022, 15, 3452 18 of 20

considering that only two papers have been published on this issue. Over static modeling,
dynamic modeling enables enhancing the reliability in reproducing the dynamic behavior
of alkaline electrolyzer when it is supplied by dynamic energy sources. Furthermore,
high modeling efficiency can be reached by taking into consideration different operating
parameters (current, temperature, and gas pressure). This modeling is a powerful tool to
design efficient and fit controllers considering dynamic operating conditions, which is not
possible considering only static modeling. On the other side, compared to static modeling,
the determination of the parameters of the model can be complex since they are considered
variable to increase the reliability of the model.
Hence, further research investigations are requested to bring new knowledge of
alkaline electrolyzer behaviors supplied by dynamic sources and to model these behaviors
according to the operating conditions by the development of equivalent electrical circuits
and the use of different approaches to determine their parameters.

Author Contributions: Conceptualization, F.G., D.G., M.Z. and H.R.; methodology, F.G. and D.G.;
validation, F.G. and D.G.; investigation, F.G. and D.G.; writing—original draft preparation, F.G.
and D.G.; writing—review and editing, F.G. and D.G. All authors have read and agreed to the
published version of the manuscript.
Funding: The experimental hydrogen platform presented in this paper has been realized thanks to
the financial support of the IUT of Longwy, CRAN, and GREEN research laboratories.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due to their current utilization for future
works involving the authors of this paper.
Acknowledgments: The authors would like to express their gratitude to the executive team of IUT of
Longwy, CRAN, and GREEN research laboratories for their constant support in developing fruitful
cooperation between CRAN and GREEN research teams from the IUT of Longwy campus.
Conflicts of Interest: The authors declare no conflict of interest.

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