Current Status, Research Trends, and Challenges

international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
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Current status, research trends, and challenges in

water electrolysis science and technology
S.A. Grigoriev a,*, V.N. Fateev a, D.G. Bessarabov b, P. Millet c

a
National Research Centre “Kurchatov Institute”, 1, Kurchatov Sq., Moscow, 123182, Russia
b
HySA Infrastructure Center of Competence, North-West University, Potchefstroom, 2520, South Africa
c
Universite Paris-Saclay, Institut de Chimie Moleculaire et des Materiaux d’Orsay, UMR CNRS 8182, 91405 Orsay,
France
highlights
Current status, research trends and challenges in water electrolysis are discussed.
Alkaline, proton exchange membrane and solid oxide electrolyzers are considered.
Electrochemical performances and limitations are presented and analyzed.
Cost components and several perspectives of future applications are reported.
Possible solutions for performance improvements are discussed.
article info abstract
Article history: Water electrolysis has various industrial applications. Over the past years, interest in water
Received 24 October 2019 electrolysis technologies has increased largely due to the renaissance of the nuclear-
Received in revised form hydrogen energy concept and also the prospect of the large-scale implementation of
12 March 2020 power plants based on renewable energy sources. The purpose of this paper is to present a
Accepted 13 March 2020 brief review of the state-of the-art in the field of water electrolysis science and technology,
Available online xxx including a description of the various water electrolysis technologies, and a discussion of
the associated challenges and opportunities. The three main types of water electrolyzers e
Keywords: alkaline, proton exchange membrane, and solid oxide e are considered and described.
Water electrolysis Their electrochemical performances and limitations are presented and analyzed. Some
Hydrogen production cost elements are also reported. Research trends in the field are discussed. Possible solu-
Nuclear-hydrogen energy tions for performance improvements are offered. The paper concludes with a discussion of
Renewables several perspectives in terms of future applications.
Energy storage © 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Power-to-X
Troostwijk in 1789 [1]. The electricity used in these experi-

Introduction ments was produced by an electrostatic machine and dis-
charged on gold electrodes in water. In 1800, Alessandro Volta
The first water electrolysis experiments were performed and applied his then recently invented voltaic pile to water elec-
reported by Jan Rudolph Deiman and Adriaan Paets van trolysis, but not much attention was paid to the results. In the
* Corresponding author.
E-mail addresses: sergey.grigoriev@outlook.com, grigoriev_sa@nrcki.ru (S.A. Grigoriev).
https://doi.org/10.1016/j.ijhydene.2020.03.109
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Grigoriev SA et al., Current status, research trends, and challenges in water electrolysis science and tech-
nology, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.03.109
2 international journal of hydrogen energy xxx (xxxx) xxx
same year, W. Nicholson and A. Carlisle carried out water and to develop solutions for distributed on-demand and on-
electrolysis experiments using copper electrodes (with oxide site generation [4,5].
formation at the anode), and a voltaic pile. A month later, J. There are various water electrolysis technologies available,
Ritter performed ‘real’ water electrolysis and was able to both on the laboratory scale and the industrial scale e they
collect oxygen and hydrogen gases separately (as reported by differ mainly in terms of the type of electrolyte used in the
Wetzels and Ritter [2]). Despite these promising early de- cells (Table 1). The three major types of water electrolyzers
velopments, the industrial application of water electrolysis now commercially available are an alkaline water electrolyzer
only began at the end of nineteenth century. By 1902, more (AWE), a proton exchange membrane cell (PEM), and a solid
than 400 electrolysis units (using alkaline electrolytes) were in oxide electrolysis cells (SOEC). The first two types are operated
operation [3]. There were many technical and engineering in near ambient temperature (NAT) conditions (usually from
reasons for this century-long delay, including the time ambient up to 90 C), whereas high-temperature SOECs are
required for the development of suitable direct current (DC) operated at temperatures typically between 700 and 950 C.
power sources. However, the development of efficient di- Several companies are currently providing series-produced
aphragms for the separation of the anode and cathode commercial electrolyzers of the alkaline and PEM types.
chambers was probably an even more challenging task. This is Small water electrolysis units (<10 kW) are used for gas
why, during the twentieth century, most technology im- chromatography, hydrogen welding, meteorology, or on-
provements were closely related to R&D on diaphragm demand hydrogen production on laboratory scale. Larger
membrane materials. units are used in metallurgy, pharmaceuticals, the food and
Today, hydrogen is an essential chemical agent for the beverage industry, glass and electronics production, and
production of ammonia, methanol, petroleum products, elsewhere. In the energy sector, hydrogen of electrolytic grade
various polymers, and many other compounds and materials. is used as a cooling medium for turbine generators and also in
Most of the hydrogen used in the industrial sector is currently bubble chambers of nuclear power plants. New applications
produced by steam reforming of fossil hydrocarbon (mainly (for example mobility) are appearing. The growing market for
methane), causing atmospheric pollution. Massive CO2 emis- electrolytic-grade hydrogen is driven by the need for the
sions into the atmosphere and the resulting impact on the storage of energy produced by renewable sources and nuclear
environment are calling for alternative solutions. To create a energy sources, improvement of smart-grid energy flexibility,
carbon-free and environment-friendly economy, it is consid- and the development of refueling stations for hydrogen
ered essential to use water electrolysis to produce hydrogen, vehicles.
Table 1 e Comparison of main water electrolysis technologies.

Types of water electrolyzers Alkaline PEM Solid Oxide
Technology status mature technology lab-scale, R&D
T range ( C) ambient - 120 700e1000
Electrolyte/pH 25-30 wt% (KOH)aq perfluorosulfonic acid Y2O3eZrO2, Sc2O3eZrO2,
MgOeZrO2, CaOeZrO2
Charge carrier OH Hþ O2e
Overall reaction H2O / H2 þ 1/2O2
Anode reaction 2OH / 1/2O2 þ H2O þ 2e H2O / 1/2O2 þ 2e þ 2Hþ O2 2e / 1/2O2
Cathode reaction 2H2О þ 2e / H2 þ 2OH 2Hþ þ 2e / H2 H2O þ 2e / H2 þ O2
Anode catalyst Ni2CoO4, LaeSreCoO3, Co3O4 Ir/Ru oxide (La,Sr)MnO3, (La,Sr)(Co,Fe)O3
Cathode catalyst nickel foam/Ni- stainless steel platinum Ni-YSZ or Ni-GDC Cermet
NieMo/ZrO2eTiO2
Separator asbestos, polysulfone-bonded polymer membrane ceramic
polyantimonic acid,
ZrO2 on polyphenylsulfone, NiO,
polysulfone impregnated with
Sb2O5 polyoxide
Sealant metallic synthetic rubber/fluoroeleastomer glass and vitro-ceramics
Current distributor Ni titanium ferritic stainless steel (Crofer APU)
Containment material nickel plated steel stainless steel stainless steel
P range (bar) 1e200 1e350 (700) 1e5
Conventional current 0.2e0.5 0e3 (up to 20) 0e2
density (A/cm2)
Efficiency (%) 60e80 80 100
(at i A/cm2/Ucell V/T C) 0.2e0.5/2.0/80 1.0/1.8/65 3.6/1.48/950
Capacity (Nm3/hour) 1e500 1e250 1
Durability (hours) 100,000 10,000e50,000 500e2000
H2O specification liquid >10 MU.cm steam
Load cycling medium good good
Stop/go cycling weak good weak
T cycling weak good weak
international journal of hydrogen energy xxx (xxxx) xxx 3
The extra energy of nuclear reactors could be used for the is a prerequisite to initiate the circulation of charge carriers
large-scale production of electrolytic-grade hydrogen, as an (electrons in the external power circuit and ions within the
alternative to the reforming of hydrocarbons. The develop- interpolar region). During electrolysis, the transfer of elec-
ment of the concept of so-called ‘nuclear-hydrogen power’ trons across each metal/electrolyte interface induces two
(the use of the energy generated by nuclear reactors) for large- different chemical redox processes, the sum of which is
scale hydrogen production from water, and the wider appli- equivalent to the water dissociation reaction. Water electrol-
cation of this hydrogen in industry, power generation, trans- ysis electrodes are particular in the sense that they both are
portation and domestic needs, commenced in the early 1970s gas-evolving electrodes. A cell separator that is permeable to
[6]. For example, the excess electric energy (in particular, that ions but impermeable to these gases is placed in the ionic
generated in off-peak hours) produced by a nuclear power phase, between the two electrodes, to prevent their sponta-
plant could be used for hydrogen production, storage, and neous recombination.
then re-electrification (electrochemical combustion in a fuel Water (either liquid or vapor) is supplied to the cell and
cell (FC)) on demand [7,8]. Thus, a so-called hydrogen cycle or water/hydrogen þ water/oxygen mixtures are separately
hydrogen battery could be used for load shifting of nuclear collected at the exhaust. The gas production rate can be
power plants, thereby eliminating the inefficient unloading accurately adjusted to process requirements by stacking, in
mode of operation; this, in turn, could maintain nuclear series, the appropriate number of cells. The resulting assem-
generating costs at a level that conforms to nominal load [9]. bly of cells is called a stack. The stack itself is included in the
Likewise, hydrogen energy storage could be implemented balance-of-plant (BoP), a number of ancillary equipment items
in power plants based on renewables [10] as well as the so- used to operate the water electrolysis unit at nominal tem-
called ‘Internet of Energy’ concept a new tendency in perature and pressure conditions and to deliver gaseous H2
smart-grid development that combines information and en- and O2 with the necessary levels of purity and dryness,
ergy (the terms Energy Internet, I-Energy, Internet of Decen- determined by downstream applications.
tralized Energy, Transactive Energy, Energy Cloud, and Fig. 1 provides an overview of a typical PEM process flow-
FREEDM Systems are also used) [11]. Hydrogen is a flexible sheet with key functions [12]. The electrolysis stack is fed by
energy vector. Because of its versatility, electrolysis could be an AC/DC power conversion system. After purification, feed
efficiently integrated with so-called Power-to-X technologies water is periodically pumped into the anodic circuit. Water is
(X ¼ gas, heat, mobility, etc.). circulated through the anodic chambers to fuel the reaction
The aim of this paper is to review the state-of-the-art, and remove the excess heat.
research trends, challenges, and opportunities associated At the cell level, there are two main factors applicable to
with water electrolysis technologies. Specific aspects and ad- the selection of cell components: the pH of the electrolyte
vantages of an AWE, PEM water electrolyzers, and SOECs are (either a liquid or a solid ion-conducting medium) and the
discussed with regards to the above-mentioned applications, operating temperature. The most developed technologies
in particular the use of renewable (transient) and nuclear available on the market operate at temperatures close to
(stationary) power sources. ambient temperature (from ambient up to 100 C). Currently,
there are three main technologies available on the market.
From a historical perspective, AWE is the oldest and more
General features of water electrolysis cells mature one. Later, in the 1960s, membranes made of proton-
conducting ionomers became commercially available, lead-
Thermodynamic analysis of the water splitting reaction ing to the development of the so-called PEM water electrolysis
shows that this is a nonspontaneous transformation over an technology. In the 1980s, high-temperature cells (700e1000 C)
extended range of operating temperatures and pressures of based on oxygen-ion-conducting ceramics were developed.
practical interest for industrial applications. The sign of the Some other cell concepts are also currently under develop-
Gibbs free energy change of the reaction becomes negative at ment and are emerging: (i) an elevated temperature (up to
temperatures of at least 2000 K (1 bar), and tempera- 350 C) proton-conducting polymer cell; (ii) an alkaline poly-
tures > 4000 K are required to obtain a hydrogen yield of 50% mer water electrolysis cell (25e100 C), and (iii) a cell with
only. The design of reactors that could be used for the thermal proton-conducting ceramics (300e600 C). As a result, it can be
dissociation of water, operating under such harsh conditions, expected that electrolytes covering a wide range of tempera-
and the design of devices (e.g., membranes) that could be used tures of interest will one day be available and that different
to successfully separate the resulting H2/O2 gas mixtures are technologies will become available for different applications
both very challenging tasks, which have not yet been over- and different operating conditions.
come. This is why electrochemical reactors are appropriate; There are basically three different types of water electrol-
they can be used to split water in NAT conditions. ysis cells: (i) the gap-cells (there is a gap distance between the
A water electrolysis cell is a galvanic chain with two electrodes and the cell separator); (ii) the zero-gap cell (porous
metallic electrodes (one anode and one cathode) placed face- electrodes are pressed against the cell separator); (iii) the PEM
to-face and separated by a thin layer of an ion-conducting cell (the electrolyte is confined in a thin layer that acts as
material. An external DC power source is used to adjust the electrolyte and cell separator at the same time). Alkaline cells
Fermi level of each electrode and bracket the two energy levels with the gap-cell design are limited in the maximum oper-
of the two redox couples (H2O/O2 and H2/H2O) involved in the ating current density to a few hundreds of mA/cm2 because of
water dissociation reaction. This difference is directly pro- gas screening effects appearing during gas production at
portional to the Gibbs free energy change of the reaction. This higher current densities. In 1967 the zero-gap design was
Fig. 1 e PEM water electrolysis process flowsheet [12].
introduced for alkaline electrolyzers [13]. The zero-gap design and gas bubbles, various alternative diaphragm materials
entails the electrodes (anode and cathode) both being in have been developed as alternatives. For example, inorganic
physical contact with the membrane, resulting in a compact ion-exchange-type membranes IMET® (Fig. 2) are used by
cell arrangements. Zero-gap design allows gases and liquids to Hydrogenics Corporation (formerly Stuart Energy) in HyS-
be transported to and from the electrodes by utilizing various TAT™ modular electrolyzers [15]; the purity of hydrogen
shapes of separators, such as a screen/grid or a perforated produced using this technology is >99.999%. Other companies
metal electrode, or by making the electrodes porous [14]. In are now also developing and producing AWEs, e.g., NEL (Nor-
PEM or high temperature water electrolysis cells, the gas way), MacPhy (France), ErreDue (Italy), Enapter (Italy), and
production is realized at the rear of the cell, not inside the some others.
interpolar region. This is a very efficient cell design which More recently, polymer membranes with hydroxyl ion
allows operation at several A/cm2. It should be noted that conductivity have appeared [16]. Some anion-exchange
whereas mass transport limitations exist (gas transport to the membranes are thermally very stable (in particular, those
reaction sites), there is no such limitations (gas transport based on poly (vinyl alcohol)) and they can potentially be used
away from the reaction site or liquid water transport to the for the electrolysis of water vapor, above the temperature of
anodic reaction sites) in PEM water electrolysis cells. In a high
temperature cell, steam transport to the reaction sites is
usually not a problem. In water electrolysis cells, there is no
specific overvoltage related to gas bubble nucleation and
growth, the rate-determining step being the charge transfer at
each interface.
Alkaline water electrolysis
Hydrogen production by AWEs is now a well-established

technology and electrolysis installations up to the megawatt
(MW) scale of electric power are commercially available. AWE
cells use an aqueous solution of KOH as liquid electrolyte. One
of the key components of an alkaline electrolysis cell is the
diaphragm separator. Porous diaphragms based on asbestos
were used for many decades, until the mid-1970s, before being
banned due to health hazards. Because asbestos is a toxic Fig. 2 e Inorganic ion-exchange-type membranes IMET®
material and also because it is permeable to dissolved gases for alkaline water electrolysis. (Courtesy: Hydrogenics Co.)
water vaporization [17]. Most of the research activity in the electrolyzed, there is no ‘bubble evolution problem’; current
field is focused on the optimization of catalyst/electrode ma- densities up to 0.9 A/cm2 were achieved. Hydrogen obtained
terials [18]. To data, performances and durability are still was of high purity, suitable for application in low-temperature
rather low, but significant progress has already been made FCs. Rather good stability of the electrolysis parameters was
over the past few years and the concept is gaining mo- obtained. However, the water balance control of such a sys-
mentum. However, it will be difficult to achieve significant tem proved to be rather complicated (problems were similar to
improvements in this area since the modification or replace- those found in matrix-type alkaline FCs) and the commer-
ment of rather inexpensive and efficient alkaline electrolysis cialization of such electrolyzers will first require de-
materials (e.g., Ni, Fe) with more expensive ones is not an velopments (in particular, the sensors and control systems)
attractive option. [22]. Furthermore, it is noted that Centrotech has also devel-
A conventional (liquid electrolyte) AWE has some opera- oped concepts of laboratory electrolysis modules with tubular
tional limitations. In particular, the maximum current density design (Fig. 4).
is usually limited to <0.45 A/cm2. This is because at elevated Progress in cell design has led to more flexible AWE tech-
current densities the generated gas bubbles that tend to flow nology. This is important and useful, particularly when the
upwards along the electrode surface, due to gravity, can form cell/stack is powered by fluctuating renewable energy sources.
a continuous and nonconductive film of gas over the entire We now turn the focus to high-pressure electrolysis prob-
electrode surface. The resulting screening effect increases the lems. The well-known Nernst formula shows the relationship
energy consumption and also favors gas transport in both between the equilibrium electrolysis cell voltage, the partial
directions across the diaphragm. In modern AWE cells, the pressure of gases, and water activity in the electrolyte (when
electrodes are made of porous grids that are pressed against liquid water is used):
the diaphragm to minimize the distance and reduce the
1=2
parasite ohmic resistances. Such zero-gap configuration is RT PO2 PH2
E ¼ Eo þ ln
used to improve process efficiency [19]. By using advanced nF aH2 O
concepts, current densities of up to 2 A/cm2 [20] and pressures where Еo is the standard value of the equilibrium cell voltage
of up to 100 bar (see Fig. 3 [21]), and even 350 bar [22], can be (Еo ¼ 1.229 V at 25 C for liquid water), R is the absolute gas
achieved in AWE systems. constant, T is the absolute temperature, PO2 and PH2 (in atm)
Some interesting and unusual results on water vapor are the partial pressures of the reaction products, and aH2 O is
electrolysis involving the use of a filter-press-type alkaline the activity of water in the electrolyte.
battery with a porous diaphragm, and with an absorbed It is obvious from this equation that an increase in the gas
(matrix) electrolyte, were obtained by the Russian company pressure within the cell will increase the equilibrium voltage
Centrotech [23]. Using dynamic circulation of a hydrogen/ and therefore the energy consumption during electrolysis.
water gas mixture and water condensation in a porous dia- Such a decrease in efficiency is partially compensated for by a
phragm containing alkali, due to a temperature gradient, they decrease in gas bubbles size and a reduction in the gas
obtained a current density of 0.6 A/cm2 at 1.6 V, 95 С, and screening effects [24]. Of course, such an improvement is not
overall pressure 0.4 MPa. Since in such a cell the water vapor is obtained during the electrolysis of water vapor.
Fig. 3 e Mean cell voltage versus current density measured on the 5-cell AWE short stack at 80 C and different operating
pressures [21].
Fig. 4 e Alkaline-type water electrolysis laboratory unit with tubular modules. Hydrogen productivity of 16.5 l/h. Operating
pressure up to 16 bar. (Courtesy: RME “Centrotech”, Novouralsk, Russia.)
Currently, the capital cost of AWE systems could be esti- of perfluorosulfonic acid (PFSA) (1). One porous catalytic layer
mated as 900e1700 V/kW [25,26]. According to the targets for is placed on each side (2-20 ). The catalyst layers can be coated
2025 of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) directly onto the membrane or, alternatively, onto each of the
of the European Commission (EC) and the National Renewable two porous transport layers (3-30 ) placed against the MEA to
Energy Laboratory (NREL) of the U.S. Department of Energy favor homogenous distribution of current lines [27]. Liquid
(DOE), Capex (total system cost including power supply and water is pumped across both cathodic and anodic cell com-
installation costs) is estimated as 480 V/kW. partments (4-40 ) to feed the reaction on the anode side, and
also to extract the excess heat produced inside the cell during
operation. There is a quantitative relationship between the
Proton exchange membrane electrolysis water flow, the operating current density, and the maximum
cell DT (temperature difference between cell entrance and
Fig. 5 shows the cross-section of an elementary PEM water exhaust) [28]. H2 and O2 produced by the reactions are
electrolysis cell. This unit cell is quite compact (5e7 mm thick collected at the back of the porous transport layers, and the
in most cases), and delimited by two terminal end-plates (5- liquidegas biphasic mixtures are pumped to separators for
50 ), usually made of titanium. The membrane electrode as- gravimetric separation [29].
sembly (MEA) placed at the center is the core cell component Historically, the first PEM water electrolyzer was developed
where the water splitting takes place. It is usually made of a in 1966 by General Electric Co., within the framework of the
thin (90e200 mm thick) proton-conducting polymer membrane U.S. space program. It was associated with the invention of a
Fig. 5 e Schematic representation (cross-sectional view) of a PEM water electrolysis cell. 1 e PTFE-reinforced membrane, 2/2′
e catalytic layers, 3/3′ e porous transport layers, 4/4′ e spacers and flow disrupters, 5/5′ e end-plates [26].
Furthermore, due to their high maneuverability, rapid start/

stop and control response capabilities [29,31] PEM water
electrolyzers are also suited for Smart Home [34] and Internet
of Energy [11] technologies. The energy required to split water
in such cells lies in the range 3.9e4.0 kW*h/Nm3 at 1 A/cm2.
PEM electrolysis can produce pressurized H2/O2 gases at
pressures up to 350 bar directly in self-pressurized electrolysis
stacks [35], a technique that excludes further compression for
storage or transportation, with a decrease in the capital and
operating costs. For example, the high-pressure electrolysis
stacks developed by National Research Centre (NRC) “Kurch-
Fig. 6 e PEM electrolysis stack with operating pressure up atov Institute” (Figs. 6 and 7) can be used for charging standard
to 200 bar (NRC “Kurchatov Institute”, Moscow, Russia). gas cylinders. It is notable that operation of PEM stacks at
pressures up to only several tens of bars enables us to reduce
energy consumption for electrolysis [24]. This is useful, to
sulfonated polystyrene ion-exchange electrolyte membrane
exclude the most energy-demanding first compression stage
by W. Thomas Grubb in the early 1950s [30]. The most widely
(from 0 to ca. 30e50 bar) of multistage mechanical hydrogen
used PFSA and commercially available membranes are sold
compressors. Compared with piston-type compressors, an
under various brand names: Nafion®, Fumapem®, Flemion®,
economy of the electric power of 600 kW*h/t of hydrogen is
and Aciplex®. Due to their cost, they have been used mainly
obtained, by increasing the operating pressure from 20 to
for oxygen generation in anaerobic conditions, mainly for
60 bar.
underwater and space applications. Over the last decade, civil
For low temperature water electrolysis the gas evolution
applications related to the production of hydrogen as a clean
(gas bubbles production) plays a rather important role. It has
energy vector have led to the development of MW-scale sys-
some well-known positive influence on the process as pro-
tems. PEM water electrolyzers have demonstrated several key
vides an electrolyte flow along the electrolysis cell and cooling
advantages compared with other water electrolysis technol-
of the electrodes and a membrane/diaphragm (see for
ogies: a high load flexibility and the ability to provide grid
example [36e38]). But a negative influence of these gas bub-
balancing services [31]. For example, the largest SILYZER 300
bles is more important as they are screening the electrode
system, developed by Siemens AG, demonstrates a full range
surfaces, increasing the reactions overvoltages, increasing the
(0e100%) load dynamics in 10%/s and a minimum load 5%
electrolyte resistance and limiting current density [39,40].
[32]. PEM electrolyzers enable us to achieve quite high current
Such effects are less important in case of PEM electrolysis
densities (up to 10 A/cm2 [28]) and hydrogen purity (up to
where gas evolution takes part only on the “back side” of the
99.9999% [33]), and can be optimally integrated into e-mobility
electrodes (opposite to the membrane) and gases are not
and e-fuel paradigms via the Power-to-X technologies.
reducing the volume of the electrolyte fraction between the
Fig. 7 e Mean cell voltage U and power costs W versus current density i measured on the 8-cell PEM stack at 85 C and
different operating pressures (data of NRC “Kurchatov Institute”, Moscow, Russia).
electrodes and its conductivity. Though the screening of the current density to about 0.5$102 А/сm2, and even more, with a
electrocatalyst surface and blocking of the porous electrode further pressure increase [55]. All these effects will obviously
(current collector) pores in PEM electrolysis cell also may decrease the current efficiency and/or gas purity, especially at
result in mass transfer losses and decrease of a current den- operating current densities of several hundreds of mA/cm2
sity, especially at relatively large currents (ca. > 1 A/cm2). An and/or when frequent startestop cycles are applied (operation
increase in pressure, temperature or water flow rate reduces with renewable energy systems) and a further increase in
such losses [41]. These results are in a good agreement with the pressure in the electrolysis cells will make the energy ef-
the data of Fig. 7. In case of conventional alkaline water ficiency of the electrolysis process even poorer. It should be
electrolysis cell the influence of gas bubbles on an electrolyte noted here that an increased pressure (and also temperature)
resistivity becomes critical at lower current density [42,43] and may lead to an accelerated membrane/diaphragm degrada-
together with other factors it limits a practical current density tion, as has been established for Nafion® [56,57].
at a level of 0.45 A/cm2. Certainly, optimization of electrodes Despite the fact that an increased electrolysis pressure
and a cell geometry, and application of hydrophilic electrodes does have beneficial effects, for example, a reduction of the
may give some positive results [43,44]. Also, application of energy consumption for hydrogen compression, in view of
surfactants or magnetic field may be useful for separation of downstream process storage and a reduction of the water
gas bubbles from an electrode surface and an overvoltage vapor content in hydrogen an important aspect that will
decrease [44e46]. But from authors point of view, the best reduce the energy cost related to hydrogen drying for storage
solution of the problem in case of an alkaline electrolysis is a and transportation there are some important limitations for
zero-gap design [43] like in case of a PEM electrolysis cell. a high-pressure operation. In particular, when the extra cost
In AWE and PEM water electrolysis cells, the cell separators required for high-pressure equipment (pumps, valves, etc.)
(the diaphragm and the polymer membrane) are not 100% gas and possible safety problems are taken into account, it is
proof. There are several microscopic phenomena that occur, impractical to develop pressurized water electrolyzers
tending to reduce the faradaic efficiency of these cells [47]. The capable of operating above 200e300 bar.
situation can be analyzed by calculating the value of the The technology is already commercially available at the
parasitic current densities associated with these different ef- multi-MW scale (Fig. 8), but several improvements are still
fects. The first effect is due to the diffusion of hydrogen from needed to bring the cost of electrolytic hydrogen down to the 5
the cathodic to the anodic cell compartment. According to the V/kg range of interest for mobility applications in European
Fick equation, the rate of gas diffusion through a membrane/ countries. To reach this goal, one existing challenge that
diaphragm is proportional to the partial pressure of this gas. needs to be overcome is the replacement of electrocatalysts
Therefore, when the operating pressure is increased, there is containing platinum group metals (PGMs) [58,59] by non-noble
an immediate impact on cross-permeation phenomena and (e.g. using transition metals or their oxides) electrocatalysts.
gas purity. The situation is similar in liquid electrolytes Currently, the cost share of PGMs is less than a few % at sys-
(AWEs) or in polymers (PEM technology). The diffusion coef- tem level but the large-scale deployment of the technology in
ficient of hydrogen at 80 С is equal to 2.2$105 cm2/s in a the frame of the energy transition will require, sooner or later,
Nafion® membrane [48], to 0.7e1.0$104 cm2/s in water [49,50], the use of much cheaper materials. In addition to cost, the
and to 1.9$105 cm2/s in 30% mass aqueous KОН solution [34], high sensitivity of platinum to trace amounts of mineral and
but up to 10 times smaller when a diaphragm is used [51], and organic impurities found in the feed water [60] is also calling
several orders more (0.92 cm2/s) in the gas phase [52]. At an for alternatives. Also, the type of iridium oxide used for the
operating pressure of 100 bar, assuming a zero hydrogen oxygen evolution reaction (OER) has a significant impact on
concentration in the anode compartment (i.e., total and activity and durability of electrocatalytic layer [58] and alter-
instantaneous oxidation of cross-permeating hydrogen by native solutions are needed there as well. To reduce the cost of
oxygen), the hydrogen flow through a 200-mm thick alkali so- PGMs, there are two main options: (i) the reduction of PGM
lution or Nafion® membrane will be up to 107 mol*cm2/s
(this is equivalent to a current density of up to 20 mA/cm2).
Literature does report on some solutions that reduce the
hydrogen cross-over in PEM water electrolysis cells [53]. Some
local pressure increase, and the oversaturation of the elec-
trolyte by hydrogen, which additionally increases hydrogen
flow, may take place at the electrodes, especially at high
current density [51,52,54].
A second phenomenon that contributes to gas cross-
permeation is that hydrogen (oxygen) solubility in water in-
creases with pressure and, as a result, there is an increase in
hydrogen (oxygen) transport through the membrane/dia-
phragm, with water molecules hydrating the ions (oxygen
transport with hydrated hydrogen ions when Nafion® is used).
Such a transport leads to the recombination of oxygen and
hydrogen at the electrode surface and decreases the current Fig. 8 e Overview of the PEM water electrolysis hall of the
efficiency. When the cell is operated at a current density of 1 EnergiePark at Mainz, Germany (Courtesy: Siemens AG,
A/cm2 and at 30 bar, such effects induce a reduction in the reproduced from Refs. [26].)
loadings; (ii) their replacement by alternative materials. On considerably (by up to 50%) at low current densities (up to 0.3
the hydrogen side, progress in PEM fuel cell technology has led A/cm2). Besides ethanol, sulfur dioxide (sulfurous anhydride)
to carbon-supported Pt nanoparticles of excellent activity: and some organic compounds, such as methanol and formic
they can be used directly at the cathode of PEM water elec- acid, in particular, can be used as depolarizing agents [75].
trolysis cells. Another option is to replace Pt by palladium [59] Depolarized electrolysis systems are applied in thermo-
but of course the cost benefit is limited, if any. Regarding non- chemical cycles used for hydrogen production. Among a
PGM materials, promising backup solutions are emerging, number of thermochemical cycles, the sulfur-based cycles,
inspired by natural hydrogenases. Quite diverse compounds specifically the sulfur iodine and the hybrid sulfur (HyS) cy-
such as porphyrins on graphite paste [61], phthalocyanine cles, seem most favorable [76,77]. The HyS cycle requires a
[62], MoSx species (either in the form of amorphous polymers high-temperature step (involving the heat from a nuclear
or MoS2crystallites) [63], have shown promising HER proper- reactor), where sulfuric acid (H2SO4) is decomposed to SO2,
ties, but not convincingly in strong acidic media. Molecular H2O, and O2. Subsequently, the oxygen is removed as a
complexes of transition metals such as Co, Ni or Fe cla- product, whereas the SO2 and H2O are fed to the PEM elec-
throchelates have been more specifically studied for applica- trolyzer where they are converted to H2 and H2SO4 [76]. It is
tion at the cathode of PEM water electrolysis cells. They have notable that the same PEM membranes can be used to develop
demonstrated acceptable HER activity levels [64,65] and can be sister technologies, such as in electrochemical hydrogen
implemented directly in PEM water electrolysis cells [66]. For compressors [78].
best-performing materials, a 50 mV additional overvoltage is Hydrogen pressure up to 14500 psi (ca. 1000 bar) has been
required at 1 A/cm2 compared to Pt but they are significantly achieved in one step by electrochemical compression this
less sensitive to poisoning. world record was set by HyET from the Netherlands in 2011
On the OER side, where large operating potentials [79,80]. A multistage electrochemical hydrogen compressor
(1.8e2.0 V) are reached, the situation is even more challenging incorporating several MEAs in series can be used to reach
and alternative are scarce. IrO2 loadings can be reduced down higher pressures. Energy costs for hydrogen compression by
to the 0.5 mg/cm2 range [67], but on the long-term, the activity an electrochemical method are less than for traditional me-
of MEAs is also reduced. A compromise has to be found be- chanical compression. In particular, specific energy con-
tween large loadings and better durability but larger cost, sumption at 3000 psi (ca. 207 bar) and current density 2.2 A/
versus lower loadings and less durability. Several attempts cm2 is < 5 kW*h/kg H2 [81]. The use of electrochemical
have been made to develop appropriate electron-conducting hydrogen compressors in hydrogen refueling stations has
metal oxides that could be used as a supporting substrate been proposed to pressurize hydrogen gas for storage. They
for IrO2 nanoparticles, for example fluorine-doped IrO2, SnO2, have also been applied in new refrigeration systems, to pres-
NbO2 solid solutions [68] or antimony-doped SnO2 [69]. In spite surize hydrogen for absorption into metal hydrides or to
of these efforts, there is no convincing alternative to unsup- pressurize other working fluids [80].
ported IrO2 up to now. Credible non-PGM alternatives are There is currently a move to increase the productivity of
currently not available. PEM electrolysis systems up to tens of MWs, due to the need to
Despite their remarkable properties, PFSA materials with produce huge volumes of hydrogen, using the energy of large-
long or short side chains (used as membrane materials in PEM scale renewables-based power plants. In particular, Siemens
water electrolysis cells) are, to some extent, one of the AG has developed the largest PEM production line base on
weakest parts of the PEM cell. Various polymer degradation their SILYZER 300 technology (17.5 MW rated power) that uses
mechanisms have already been identified and reported in the wind and solar energy to produce up to 2000 kg hydrogen per
literature [70]. Membrane thinning (the result of membrane hour [32]. Commercially available large-scale PEM electrolysis
chemical modification during operation) is one of them [71]. systems are offered by Are vaH2Gen (France), ITM Power (UK),
Water freezing in sub-zero operating temperature environ- Hydrogenics (Canada) (Fig. 9), Proton On-Site (USA) (Fig. 10),
ments is another, in some specific cases (e.g., the application Giner (USA), NEL (Norway), and other companies (Table 2).
of PEM electrolyzers with power plants based on renewable Thus, analysis of the situation that prevails for PEM water
energy sources in northern and high-mountain regions electrolysis systems allows us to conclude that there are
[72,73]). This problem could be overcome by electrolyzing currently two main trends: an increase in specific productivity
waterealcohol solutions instead of pure water at the startup and operating pressure of the system. Many experts predict a
of the electrolysis system [74]. For example, during a cold start progressive shift from alkaline to PEM water electrolysis sys-
period of limited duration, a solution of ethanol in water is tems over a period of 10 years (2020e2030) since PEM is the
supplied to the electrolysis stack and the DC power is turned preferred water electrolysis technology for operation with
on. The cell temperature then gradually increases due to in- renewables [82].
ternal dissipations. When the nominal temperature is Finally, we would like to mention the fact that there are
reached, the ethanol solution is replaced with deionized water also unconventional approaches to improving PEM (and
and the nominal mode of system operation can commence. alkaline) electrolysis efficiency that could lead to innovative
Of course, the energy required for the production of short-term developments. For example, application of a cen-
hydrogen depends on the hydrogenated compounds supplied trifugal force during electrolysis [83], ultrasonic (resonance)
to the cell. Anodic depolarization can be achieved by replacing impact [84e88], application of an additional UV water treat-
water with another hydrogen-containing reactant. In the ment [89,90], influence of magnetic fields [91e93], gravita-
abovementioned case of electrochemical conversion of an tional field [94], and so on. At first sight, such approaches are
aqueous ethanol solution, the cell potential decreases potentially interesting and could lead to some improvements
in efficiency (e.g., they could decrease the energy of water

molecule bonds or accelerate gas bubble removal from the
electrocatalyst surfaces). However, the total energy require-
ment (DG) of the water dissociation reaction will remain un-
changed at constant T,P conditions, and, in most cases, the
implementation of such innovative approaches will require
more energy than what can be saved. The benefit, if any,
might be limited, except if a free energy source can be used. It
is therefore hardly possible to expect any real industrial
progress in electrolysis using such approaches.
For various reasons, the Capex of PEM technology
(1700e2500 V/kW for 300e500 kW systems) is still higher than
the Capex of alkaline technology (900e1700 V/kW for 300
kWe5 MW systems) [25,26]. The majority of experts believe in
a shift from incumbent AWE to PEM systems as the preferred
technology over the period 2020e2030 for electrolysis in-
Fig. 9 e PEM electrolysis stacks. (Courtesy: Hydrogenics Co.) stallations coupled to power plants based on renewable en-
ergy sources [25]. According to the US DOE and European FCH
JU roadmaps, the Capex of PEM electrolysis technology should
be reduced in the short term from ~2000 V/kW down to ~1400
V/kW for systems at the 1 MW/200 Nm3/h scale, with an ul-
timate goal of ~700 V/kW in 2020 (DOE Hydrogen and Fuel
Cells Program 2014). For large systems, the Opex are cost
predominant, and the cost of a kilowatt hour (kWh) of elec-
tricity alone dictates the cost of hydrogen. A target cost for on-
site delivery is 4e5 V/kg. In some favorable cases (e.g., grid
regulation service for which the electricity cost is zero or even
negative), water electrolysis can compete directly with steam
reforming.
Solid oxide electrolysis
Thermodynamic analysis of the water splitting reaction

shows that the Gibbs free energy change of the reaction (and
hence the equilibrium cell voltage, also called the counter-
electromotive force) decreases when the cell temperature is
increased [95]. It therefore seems rather attractive to split
water at elevated temperatures, typically in the 800e1000 C
range [96]. For example, an equilibrium voltage of only 0.85 V
is required to electrolyze water vapor at 800 C, under 1 bar
pressure [97]. The energy balance is obtained by providing
high-temperature heat as the necessary complementary
amount of energy. Besides a reduction (by approximately one
third) in the specific electrical energy consumption, another
Fig. 10 e PEM electrolysis stack with hydrogen productivity
benefit is that, at such temperatures, any kinetic limitations
2 m3/h and operating pressure 30 bar (Courtesy: Proton
related to reactant/product transportation and the electro-
Onsite Inc.).
chemical reaction itself are minor, and efficiencies close to
Table 2 e Comparison of the main performances of typical PEM electrolyzers produced by different companies.
Manufacturer Country of origin Capacity range Capacity range Pressure Energy consumption
(kgH2/h) (Nm3H2/h) (bar) range (kW*h/kgH2)
Siemens Germany 100e2000 1000e22 400 1e35 45e65
NEL Norway 3e350 30e4000 1e30 47e55
Proton Onsite USA
Hydrogenics Canada 0.5e450 4e5000 1e8 55
ITM-Power UK 10e170 110e1900 1e20 45e60
AREVAH2Gen France 0.5e35 5e400 1e45 45e55
Ginner USA 3e20 30e200 1e40 e
Fig. 11 e Temperature dependence of the main thermodynamic parameters of water electrolysis [95].
100% can be reached at current densities of practical interest definition of such standards as was done earlier for NAT water
(~1 A/cm2). All these characteristics contribute to making such electrolysis [102].
a concept very promising for hydrogen production and elec- From the material viewpoint, oxygen-ion-conducting ce-
tricity storage [98]. ramics are used as solid membranes and hence this type of
High-temperature steam electrolysis in a SOEC has the cell is usually referred to as a SOEC. Fig. 12 shows a schematic
potential to offer high efficiency. The total energy demand for diagram of a SOEC. Two thin electrodes are placed on each
water splitting is lower in the vapor phase than in the liquid side of the ceramic membrane and the circulation of water
phase, and the energy for vaporization can be provided ther- vapor and the collection of gases is organized by using cell
mally within the SOEC system, rather than electrically separators equipped with flow fields, also called in-
(Fig. 11). terconnects. Water vapor is supplied to the hydrogen side and
Water electrolyzers operating in NAT conditions produce pure oxygen is collected on the other side. Fig. 13 shows a
low-temperature heat (40e70 C), which is of limited interest multistack solid oxide water electrolysis (SOWE) unit, which,
and value. The energy content is very low and such heat can during operation, is covered by an insulated hood for homo-
be used for heating purposes only, when the electrolyzers are geneous heating at the target temperature.
operated in cold environments. In warm environments, stack Cell sealing is a challenging task; however, there are re-
cooling might be a limiting factor that dictates the maximum ports on pressurized cells operating at pressures up to 8 bar
operating current density. This is why this heat is usually not [103]. From a historical perspective, the development of SOEC
taken into account when calculating the efficiency of such water electrolysis began in the USA, in the 1970s, at General
electrolyzers [99]. Electric and Brookhaven National Laboratory, followed by at
The situation is different for solid oxide electrolyzers Dornier in Germany, and some research centers in USSR
operating in the 700e900 C range. In such cells, the thermo- [104,105]. The most popular electrolyte material was a stabi-
neutral voltage is reached at somewhat elevated current lized zirconium dioxide with oxygen ion conductivity. The
densities (several hundreds of mA/cm2) [26]. Therefore, the first article describing such a concept was published in 1980
cells are frequently operated in the endothermic current [106]. In recent years, SOEC has attracted increasing interest
density range when heat is available [100]. In the exothermic due to the significant progress made in the sister solid oxide
mode, because of the high energy value of the heat produced, fuel cell (SOFC) technology and the increasing interest in
the extra heat could be taken into account. Usually the heat of carbon-neutral energy scenarios [107]. SOECs are typically
hydrogen and oxygen is used to produce high-temperature operated in the 700e900 C temperature range. Since a sig-
water vapor via counterflow heat exchangers. An example of nificant amount (ca. one third) of the energy required for water
heat integration and optimization is reported in literature vapor splitting can be supplied to the cell as heat, it is foreseen
[101]. To date, there is no standard available in the literature to that SOEC plants will be coupled to a high-temperature ther-
calculate the process efficiency by taking such heat into ac- mal source, in particular, a high-temperature gas-cooled re-
count. The European Commission is actively supporting the actors (HTHRs) [7]. HTHR is a rather new type (Generation IV)
of environment-friendly nuclear power reactor with several
Fig. 12 e Schematic of a SOEC cell showing the internal components.
unique features, in particular, the ability to produce heat at application of electrolyte layers on electrolyte/electrode sur-
temperatures > 1000 C and with a high level of safety faces [110e120]. Many attempts have been made to create
[108,109]. SOFCs and electrolyzers operating at lower temperatures
Several companies and research centers are currently (450e700 C), but without real practical success thus far [121].
working on SOEC developments, for example, the European Hence, for SOECs, the main electrolyte material is still zirco-
Institute for Energy Research (Karlsruhe, Germany), Risø Na- nium dioxide stabilized by yttrium oxide or some similar
tional Laboratory (Denmark), Institute of Science and Tech- oxides.
nology for Ceramics (ISTEC-CNR; Italy), Sunfire (Germany) To date, SOEC systems is the least developed electrolysis
(Fig. 14), Sylfen (France), and others. SOEC development and technology. It is not yet commercialized, but these systems
improvements rely mainly on SOFC developments; most have been developed, and demonstrated on laboratory and
materials and technologies developed for FCs can be used for experimental plant scale [122]. There are some companies
electrolyzers. The main research activities are devoted to the that are currently aiming to bring this technology to market.
quest for new electrolytes (oxygen and proton conductors and Despite a list of significant advantages, there is a list of
even electrolytes with a mixed ion/electron conductivity) and drawbacks that limit market applications. Common problems
electrode materials, development of new technologies for thin of SOECs and SOFCs are a rather long turn-on and turn-off
electrolyte films production (due to high resistivity of oxygen- procedure due to the difference in thermal expansion co-
ion-conducting ceramics) and electrode layers, or the efficients of components, and a rather rapid degradation (up
to several percent over 1000 h) because of the high-
Fig. 13 e Multistack solid oxide water electrolysis unit. Fig. 14 e Solid oxide water electrolysis stack developed by
(Source: Ceramatec, Inc.) Sunfire. (courtesy: Sunfire GmbH)
temperature interdiffusion of the cell (stack) components and temperatures involved there are no kinetic limitations with
poisoning by the corrosion products of construction materials most suitable materials (electrode compositions). Such elec-
[123,124]. Another problem is due to the low conductivity of trode compositions must provide a mixed ion/electron con-
ion-conducting ceramics, requiring elevated temperatures ductivity and have a similar thermal expansion coefficient to
(>800 C), were corrosion management is more challenging that of a solid electrolyte. Certainly, interdiffusion of the
and lifespans are reduced. The problem has been partly solved components of the electrode compositions and the electrolyte
by developing cathode-supported or anode-supported thin must be low. In particular, for a stabilized ZrO2 electrolyte, a
ceramic membranes. The possibility of operating SOEC cells at nickel zirconia cermet is rather suitable for the cathode;
elevated pressure for the direct storage of hydrogen also re- furthermore, a lanthanum strontium manganite is also suit-
mains limited due to the difficulty in developing high- able [133,134]. Several solid electrolytes with oxygen
temperature cell gaskets (usually glasses) soft enough for and proton conductivity are currently under devel-
gas proof cells but viscous enough to sustain significant opmentdoptimal compositions must be determined for each
pressure differences. Backup solutions (the SOEC cell/stack type of electrolyte [135].
can be placed in a pressurized container and operated under In the case of low-temperature electrolysis, the electro-
small in/out pressure differences) have been proposed and catalysis issues are significantly more important. The latest
used, but of course the extra cost resulting from such an research and development, mainly in the field of the alkaline
approach does not solve the problem in a cost-effective way electrolysis, is well described in a very recent review (2018)
and the solution cannot be easily extrapolated to large stacks. [18]. In alkaline medium, the electrochemical stability of the
Another problem arises from the fact that the oxygen pro- electrocatalysts is not very critical, and different metals (e.g.,
duced on the anode side at such elevated temperatures is very Ni) may be used as electrodes [19,21]. Pt-based electrocatalysts
corrosive and it can rapidly degrade the cell components. The do still attract attention as they provide higher activity,
solution to this problem is usually air dilution, but this adds especially in terms of hydrogen evolution, and higher stabil-
additional energy costs and complexity to the BoP. ity. The following have been investigated and found to have
Regarding future developments, solid oxide cells have two high electrocatalytic activity: a PteCo alloy deposited on car-
additional features of interest. At the temperature of opera- bon, PtePd, PteMo, PteCe, PteSm and PteHo alloys, amongst
tion, both half-cell reactions are fully reversible. Since SOEC others.
and SOFC cells have similar designs, and use similar materials However, the main research activity is focused on Ni, Co,
and cell components, they can be operated reversibly and Fe, and Mo alloys [18]. To achieve a decrease in electrocatalyst
used as regenerative FC/electrolyzer systems [125e127]. It loading, particular attention has been paid to catalysts on
should also be stressed here that in such high-temperature different carriers, such as carbon; different carbides, for
cells, it is not only possible to electrolyze steam (H2O / example WC, W2C, and Mo2C; and oxides, e.g., TiO2 nanobelts
H2 þ O2) but also carbon dioxide (CO2 / CO þ O2) when CO2 is [136]. Here it should be emphasized that the difference in
supplied to the cathode. When both carbon dioxide and water electrocatalytic activity of most of the electrocatalysts
vapor are supplied to the cathode, co-electrolysis can take mentioned above (this section) is not very large, and that the
place (CO2 þ H2O / CO þ H2 þ O2) and a syn-gas (CO þ H2) is lifespan and cost are becoming increasingly important, from
produced at the cathode and oxygen at the anode. However, the practical point of view. It is for this reason that we expect
this process is complicated by an additional cathode reaction that different alloys of the base metals, on different carriers,
(H2O þ CO / H2 þ CO2) [128,129]. will find wide practical application in the future.
In the near future, it is likely that SOEC developments will For PEM electrolysis, the electrocatalysis issue is more
follow SOFC developments. The large-scale deployment of the critical because the acidic properties of the PEMs result in the
technology coupled to high-temperature nuclear reactors is electrocatalysts having stability problems; here, mainly
however only a long-term perspective. Smaller systems could precious metals and precious-metal-based compositions (al-
find applications more rapidly, even when high-temperature loys) are used. For the cathode, Pt is still is the best catalyst for
heat is not available. SOEC technology could be used for oxy- use in acidic media. Some Pt alloys, in particular, PtePd and
gen production in long-distance human missions, e.g., the PteNi, sometimes demonstrate even higher activity, but here
exploration of Mars (where the atmosphere contains much the structure of the catalyst particles may play a very impor-
CO2) or other planets [130,131]. Such a project, the Mars Oxy- tant role [137e140].
gen In-Situ Resource Utilization Experiment, MOXIE [132], is In efforts to achieve a decrease in precious metals loading,
under development by NASA. At present, the capital cost of electrocatalysts on carbon carriers (carbon black, carbon
electrolysis installations based on SOECs is significantly nanotubes and nanofibers, graphene, etc.) have been found to
higher than for the alkaline and PEM systems: 2000e4000 be very efficient (as in case of PEM FCs) [26]. Several re-
V/kW [25,26]. However, over the period until 2030, many ex- searchers have also carried out investigations into electro-
perts see the costs dropping to the level of 500e1000 V/kW catalysts without precious metals [141e146]. The suitability of
[25]. an organic electrocatalyst, more specifically, poly (3,4-
ethylenedioxythiophene), for hydrogen production has been
reported [147]. However, the activity and stability of such
Electrocatalysis of water electrolysis cathodes is lower and as the precious metal loading on the
cathode is relatively small in comparison with an anode
In the case of high-temperature electrolysis, there is no real (about 0.1 mg/cm2) it is not too important from practical point
problem with electrocatalysis since at the very high of view.
The main problem pertaining to PEM electrolysis is the From this plot, the main characteristics, strengths, and
anode electrocatalysts. The anode overvoltage is rather high weaknesses of the three main technologies can be easily
and the electrocatalyst durability may determine the lifespan identified. Conventional alkaline cells can be operated close to
of the electrolysis stack. It is well known that, as anode elec- 100 C because the high KOH concentration increases the
trocatalyst for PEM electrolysis, Ru (Ru dioxide) is the most boiling point of the electrolyte. However, the kinetics is not
active, but it is not sufficiently stable [26]. The best electro- always optimized and the cell resistance (resulting from cell
catalysts for an anode (besides RuO) are Ir and Ir-based com- materials, and also from the gas production and related
positions [58]. Carbon carriers are not sufficiently stable as screening effects) is large. As a result, the cell voltage and the
anode electrocatalysts. In efforts to achieve an increase in the specific energy consumption tend to increase rapidly, and the
carrier conductivity, doped oxide carriers (TiO2, SnO2, and maximum operating current density is limited to a few hun-
others) are under development [148e152]. Such catalysts on dreds of mA/cm2. The cells can be pressurized, but the man-
carriers do have slightly higher activity, but the catalyst layer agement of pressure differences between both sides is not a
parameters are deteriorated (due to an increase in the re- simple matter and potentially dangerous. The technology
sistivity); their effective lifespan remains unproven. For here is the least expensive of the three technologies, in terms
adequate electrolysis cell parameters, the amount of Ir- of Capex (700e800 V/kW), and is well suited for operations
containing electrocatalyst could be rather small; however, where high power density and compacity are not required,
for an acceptable lifespan, a catalyst loading of ~1e2 mg/cm2 and preferably for operation in stationary conditions.
is required. Any further decrease in catalyst loading is under The situation for PEM water electrolysis is quite different,
the question. despite the fact that the E is the same. PGM electrocatalysts,
and the thin (<200 mm thick) and highly conducting protonic
membrane, make the kinetics much more efficient. The cell is
Performance comparison more compact and can be operated in the multi-A/cm2 range
with good efficiency. It is also highly flexible, and the tech-
The performances of water electrolysis cells can be compared nology can be used to provide grid services [31]. PEM cells have
by plotting their currentevoltage curves (ieV curves), been used for decades for oxygen generation in underwater
measured on typical cells. Orders of magnitude are shown in conditions, but it is civilian applications for hydrogen pro-
Fig. 15. The size of the cells and the operating conditions are duction that are driving developments. PEM cells can be
representative of those used in the industry. For PEM and operated under pressure (commonly up to 80 bars) and also
alkaline cells (operation in NAT conditions in aqueous media), under a pressure difference. This is an advantage, for several
a standard water electrolysis voltage E of 1.23 V is required to reasons: the compression cost of hydrogen is reduced, the
initiate the reaction. For SOECs, an E of only 0.85 V is required. management of the oxygen that is released to the atmosphere
A scale showing the specific energy consumption, expressed is made simpler and safer, and the BoP is simpler. However,
in kW*h of electricity per kg H2, is included on the right-hand the technology is still expensive (in the 1000e1500 V/kW
side. range). Efforts are underway to upscale (>MW scale) and
reduce costs.
Fig. 15 e Comparison of typical ieV curves measured on alkaline, PEM and SOEC water electrolysis cells.
Regarding SOECs, the standard water electrolysis voltage E announced plans to build ‘Woven City’, a ‘prototype city of the
is much lower, for thermodynamics reasons (as discussed future’ powered by a combination of solar energy, geothermal
earlier). The high level of reversibility makes the efficiency energy, and hydrogen technologies [162].
much higher. The slope of the ieV curve is mostly dictated by The European Commission set up the European Hydrogen
the conductivity of the ceramic (not the charge transfer re- Valleys Partnership in efforts to accelerate the shift towards
action). At elevated current density, mass transport limita- large-scale multiapplication hydrogen projects [163]. A
tions are observed due to the kinetics of water vapor transport ‘Hydrogen Valley’ can be defined as a geographical area city,
to the reaction sites, especially when the operating pressure is region, island, or industrial site where several hydrogen
low. This technology is much more expensive than the other applications are combined together into an integrated
two (>2000 V/kW) and, furthermore, it is not as developed in hydrogen ecosystem that consumes a significant amount of
terms of size, productivity, and commercial availability. hydrogen. A Hydrogen Valley should ideally cover the entire
hydrogen value chain (production, storage, distribution, and
final use). The National Research Centre “Kurchatov Institute”
Future outlook and water electrolyzers of the (Russia), with the support from the Ministry of Science and
next generation Higher Education of the Russian Federation, is developing
emerging technologies of decentralized power generation
Water electrolysis science and technology are facing several based on a diversified approach (Fig. 16). Application of elec-
challenging tasks. The objective of most R&D activities is to trochemical energy storage and a generation system (based on
increase the operating current density (to reduce the Capex) water electrolyzers, hydrogen accumulators, and FCs) allows
and at the same time, to improve efficiency (to reduce the one to smooth the daily, monthly, and seasonal irregularity of
Opex). Simultaneously, it is necessary to optimize existing energy supply to remote customers.
systems (electrolyzer þ hydrogen compressor) so that high- The effective application of water electrolyzers will include
pressure hydrogen (700 bar is required for mobility applica- their integration with nuclear power plants, which improves
tions) can be delivered on site in a cost-efficient and safety- the plant maneuverability [9]. At night off-peak hours, low-
satisfying way. In most applications, the target product of priced energy of a nuclear power plant could be utilized for
water electrolysis is pressurized hydrogen; oxygen is a by- water electrolysis, with further accumulation of electrolytic-
product, usually released to the atmosphere. Hence, there is grade gases in the storage system. In the hours of peak elec-
an interest to develop systems operating in so-called ‘asym- trical load, accumulated gases could be used for electricity
metric pressure electrolysis’ [153] or ‘unbalanced high pres- production (using FCs or gas turbines) in order to make up for
sure’ conditions. In such systems [26], compressed hydrogen shortfall of electric power.
of electrolytic grade is produced at the cathode while on the Another perspective is that high-temperature electrolysis
anode side, oxygen (and the feed water) is under atmospheric systems could advantageously comply with HTGRs. HTGRs
conditions. In such cases the additional energy cost required Gen IV have an outlet temperature of ca. 850 C and are suit-
for gas pressurization is used for hydrogen compression only. able as heat sources for SOECs. In the high operating tem-
Currently, this approach can only be realized by using a perature range (800e1000 C), approximately two thirds of the
reinforced solid polymer electrolyte membrane, which allows energy required for the electrolysis reaction must be supplied
the operation with a pressure gradient up to several hundred as electricity and one third may be supplied as heat (Fig. 11).
bars [79,80]; however, the efficiency is penalized because of Hence, the high-temperature heat produced by such a nuclear
the larger membrane resistance. Another prospective feature plant could be employed in a high-temperature water elec-
is intermediate temperature (120e130 C) electrolysis based trolyzer to produce hydrogen, and increase the energy effi-
on PEM technology (using polybenzimidazole-based mem- ciency of the HTGRs (which is close to 30%), hence maximizing
branes, in particular) [154]. a formal electrical efficiency of SOECs. Similarly, concentrated
Water electrolyzers can also be used for grid balancing solar energy could be utilized as a high-temperature thermal
services [12,31] and energy storage systems [10,16,34]. Market energy source [164].
applications are foreseen in the short-term period. Artificial In order to meet challenges of the future, a new generation
intelligence methods and neural network technologies could of water electrolyzers should be developed. The main re-
be efficiently used for designing, planning, and controlling the quirements for innovative electrolysis systems are compact-
operation of these types of systems [155e160]. Moreover, ness, improved gas management, liquid and thermal
water electrolyzers require direct current (DC) for operation. management, high load flexibility, durability and maintain-
They could therefore find applications in DC microgrids which ability, reduced cost, advanced stack design using compo-
are the right candidates for future energy systems (energy nents suitable for mass production, highly efficient power
losses in DC microgrids are up to 20% less than in AC micro- electronics, and improved diagnostics and control. A highly
grids) [161]. Thus, it is expected that water electrolyzers, efficient electrolyzer coupled to power plants that are oper-
especially those operating in NAT conditions, will be attrac- ated with renewable energy sources should be constructed
tive for the digitalization of energy and economy. For instance, and demonstrated.
water electrolyzers could be easily integrated within Smart Finally, codes and standards that are used to define the
Home and Internet of Energy concepts, as well with so-called legal framework of hydrogen technologies should become
Power-to-X technologies (X ¼ gas, heat, mobility, etc.). more flexible, and safety-related issues should be carefully
Hydrogen would then play its role of energy carrier combined addressed in order to avoid technical incidents and skepticism
to electricity and heat. For example, Toyota has very recently of public opinions.
Fig. 16 e Network architecture of power grid with hydrogen-based energy storage system.
that should lead to the emergence of an alternative alkaline

Limitations and challenges technology in the near future [165].
The concept of a PEM water electrolysis cell was designed
In the future, it can be expected that water electrolysis and developed to take advantage of proton conduction, which
plants will contribute to the large-scale storage of transient is higher than hydroxyl conduction (due to proton jumping or
renewable energy sources. Hydrogen of electrolytic grade the Grotthuss mechanism). The development and commercial
obtained by water electrolysis is therefore potentially a availability of PFSA materials in the late 1960s was game
game-changing energy vector. A SWOT analysis of PEM, changing it opened the way to the commercial exploitation
alkaline, and SOWE technologies has recently been reported of PEM technology, first for military and space applications
res et al. [31]. The current level of advancement
by Allidie (oxygen production in anaerobic environments), more
and maturity of each technology is quite different. Alkaline recently for civil applications. PEM cells can be operated quite
water electrolysis is the more advanced one because it has easily between zero and very large current densities (10 A/cm2
been used in the industry for over a century now. This is and above [28]). It is still more expensive in terms of Capex
currently the cheapest way to produce hydrogen of electro- (~1000e1500 V/kW) than alkaline technology, but significant
lytic grade (~700e800 V/kW). progress has been made over the past few years to reduce the
The use of porous diaphragms makes it difficult or even cost down, closer to alkaline technology. In particular, non-
dangerous to operate under pressure because poor manage- platinum catalysts are appearing for the HER [164] and
ment of the pressure difference between anode and cathode reduced IrO2 contents are being used at the anode for the
can lead to the formation of explosive atmospheres. That oxygen evolution reaction (OER) [67]. Furthermore, new
being said, porosity control provides flexibility [21]. The proton-conducting polymers able to sustain higher operating
introduction of zero gap design has increased the operating temperatures (up to 150 C for short-side-chain PFSA [166] and
current density. However, the management of a concentrated even higher [167]), at which higher efficiencies can be ob-
hot caustic electrolyte under pressure still poses problems, for tained, are appearing and are being used in commercial
example of stray currents, corrosion, safety, and mainte- electrolyzers. It should also be noted that despite issues
nance. The recent appearance of ionomer-type polymer ma- related to the cross-permeation of hydrogen during operation
terials with hydroxyl ion conduction, sufficiently chemically [168], a PEM can be used for operation at elevated pressure
stable under operating conditions, opens up new perspectives and/or under a strong pressure difference, which is another
advantage for the direct storage of hydrogen in pressurized
75 000e100 000
Notes: LHV ¼ lower heating value; m2/kWe ¼ square metre per kilowatt electrical. No projections made for future operating pressure and temperature or load range characteristics. For SOEC, electrical
Long term
vessels and mobility applications.
500e1000
SOWE is less advanced than the two other technologies
77e90
77e90
and considered mainly as a challenger. Significant progress
CAPEX represents system costs, including power electronics, gas conditioning and balance of plant; CAPEX ranges reflect different system sizes and uncertainties in future estimates.
has been made over the last decade [100] but still, there are
SOEC electrolyzer
significant challenges: (i) cells do not support thermal
40 000e60 000
cycling well and thermal equilibrium cannot be reached
2030
800e2800
rapidly; (ii) operation under pressure is a problem because
77e84
77e84
the cell gaskets made of vitreous materials cannot sustain
elevated pressures; (iii) the hot and pure oxygen produced at
the anode is very corrosive and must be diluted to protect
10 000e30 000
metallic components; this adds complexity and heat ex-

2 800e5600
Today
650e1000
change problems.
20e100
74e81
74e81
However, the main challenge faced by water electrolysis to

promote clean hydrogen as an energy vector is to produce that
1
hydrogen in a cost-competitive way, with a specific cost (in

100 000e150 000
V/kgH2) compatible with market and tax requirements. The

Long term
production cost of electrolytic hydrogen is set by Capex and

200e900
Opex contributions that dictate an optimum operating current

67e74
67e74
density [28]. Currently, molecular hydrogen is mainly pro-

PEM electrolyzer
duced in the chemical industry by the steam reforming of

60 000e90 000
natural gas:
2030
650e1500
CH4(g) þ 2 H2O(g) / CO2(g) þ 4 H2(g) DDH ¼ þ41 kJ/molH2

63e68
63e68
Compared to water electrolysis (DH ¼ þ286 kJ/molH2), the

30 000e90 000
energy required to extract one mole of hydrogen from water is

1 100e1800
Today
therefore seven times larger than the energy required to

extract one mole of hydrogen from methane. Assuming that,
56e60
30e80
50e80
56e60
0e160
Table 3 e Techno-economic characteristics of different electrolyzer technologies [169].
0.048
in the long term, the Capex of both processes becomes similar

(in both cases this is a chemical reactor operating in some-
100 000e150 000
what similar T,P conditions), then the Opex will make the cost
Long term
difference. The interest of producing hydrogen by water

electrolysis will come by the carbon tax (or the cost of CO2
200e700
70e80
70e80
sequestration) and by the use of cheap kW*h (solar or

Alkaline electrolyzer
nuclear).
90 000e100 000
Various international targets for water

2030
400e850
electrolysis
65e71
65e71
efficiency does not include the energy for steam generation.
Table 3 provides key techno-economical characteristics of

60 000e90 000
different electrolysis technologies suggested by the Interna-

Today
tional Energy Agency (IEA).

500e1400
10e110
In addition, the International Renewable Energy Agency

63e70
60e80
63e70
0.095
1e30
(IRENA) provided the following techno-economic character-

istics of alkaline and PEM electrolyzers (Table 4).
Load range (%, relative to nominal load)
Key Performance Indicators for PEM water electrolysis

as suggested by EU are captured and listed in the Table 5.
Technical targets for water electrolysis published by US
Stack lifetime (operating hours)
DOE are similar, however, most of the related companies in US

Electrical efficiency (%, LHV)
Electrical efficiency (%, LHV)

Operating temperature ( C)
have their own targets. In many cases, proprietary informa-

Plant footprint (m2/kWe)
Operating pressure (bar)
tion such as anode catalyst loading etc is not publicly avail-

able. One of the most recent US DOE Hydrogen and Fuel Cells
CAPEX (USD/kWe)
Program Record, available in the public domain as of Feb 3,

2020, provides additional cost targets as well as some of the
key performance targets [172]. For example, for distributed
and central production scale, the assumed targets for current
density and cell voltage for plants operating in 2020 are 1.6 A/
cm2 and 1.7 V/cell.
Table 4 e Techno-economic characteristics of alkaline and PEM water electrolyzers (2017, 2025) [170].
Technology Alkaline PEM
Unit 2017 2025 2017 2025
Efficiency kWh of electricity/kg of H2 51 49 58 52
Efficiency (LHV) % 65 68 57 64
Lifetime Stack Operating hours 80 000 h 90 000 h 40 000 h 50 000 h
CAPEX e total system cost (incl. power supply and installation costs) EUR/kW 750 480 1200 700
OPEX % of initial CAPEX/year 2% 2% 2% 2%
CAPEX e stack replacement EUR/kW 340 215 420 210
Typical output pressurea Bar Atmospheric 15 30 60
System lifetime Years 20 20
Notes: H2 ¼ hydrogen; h ¼ hour; kg ¼ kilogram; kW ¼ kilowatt; kWh ¼ kilowatt hour; LHV ¼ lower heating value; OPEX ¼ operating expenditure;
CAPEX and OPEX are based on a 20 MW system.
a
Higher output pressure leads to lower downstream cost to pressurize the hydrogen for end use.
Table 5 e State-of-the-art and future targets for hydrogen production from renewable electricity for energy storage and grid
balancing [171].
State-of-the-art 2017 2020 2023
H2 production electrolysis, energy 57-60 @100 kg/d 55 @500 kg/d 52 @1000 þ kg/d 50 @1000 þ kg/d
consumption (kW*h/kg) @ rated
power
H2 production electrolysis, CAPEX 8,0 MV/(t/d) 3,7 MV/(t/d) 2,0 MV/(t/d) 1,5 MV/(t/d)
@ rated power including
ancillary equipment and
commissioning
H2 production electrolysis, 2%e4%/year 2%/year 1,5%/year <1%/year
efficiency degradation @ rated
power and considering 8000 H
operations/year
H2 production electrolysis, 5%e100% of 5%e150% of 0%e200% of 0%e300% of
flexibility with a nominal power nominal power nominal power nominal power
degradation < 2% year (refer to
KPI 3)
H2 production electrolysis, hot 1 min 10 s 2s <1 s
start from min to max power
(refer to KPI 4)
H2 production electrolysis, cold 5 min 2 min 30 s 10 s
start
particular proton exchange membrane water electrolyzers,

Conclusions could comply with Smart Home and Internet of Energy con-
cepts. High-temperature electrolysis systems could advanta-
In this paper, a brief review of the state-of-the-art of water geously dovetail with high-temperature helium-cooled
electrolysis is presented. A description of the three main types reactors of Generation IV. Large-scale implementation of
of water electrolyzers alkaline, proton exchange membrane, electrolysis technologies still requires cost reductions; none-
and solid oxide is provided. Their electrochemical perfor- theless, investments made towards the development of
mances and limitations are presented and analyzed. Research macroscale Power-to-Gas systems and breakthroughs in sis-
trends in the field are summarized and discussed. Possible ter fuel cell technologies facilitate cost reduction down to the
solutions for performance improvements are provided. target of 500 V/kW.
Several perspectives, in terms of future applications are also
discussed. There is today a growing interest for water elec-
trolysis technologies. The coupling of water electrolysis sys-
tems to renewable or nuclear power sources, including the so- Acknowledgment
called Power-to-X technologies (X ¼ gas, heat, mobility, etc.), is
currently under intensive consideration. Commercially avail- This work was carried out with the financial support from the
able systems are capable of producing wind- and solar-driven Ministry of Science and Higher Education of the Russian
hydrogen on the scale of tens of MWs 100-MW-scale systems Federation within the framework of the agreement on the
are under development. Hydrogen-based energy systems, in provision of grants from the federal budget in the form of
subsidies in accordance with paragraph 4 of Article 78.1 of the [19] Kuleshov VN, Kuleshov NV, Grigoriev SA, Udris EY, Millet P,
Budgetary Code of the Russian Federation No. 075-15-2019- Grigoriev AS. Development and characterization of new
1847 dated 04.12.2019 (unique project identifier nickel coatings for application in alkaline water electrolysis.
Int J Hydrogen Energy 2016;41(1):36e45.
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international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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

Current status, research trends, and challenges in

S.A. Grigoriev a,*, V.N. Fateev a, D.G. Bessarabov b, P. Millet c

article info abstract

Troostwijk in 1789 [1]. The electricity used in these experi-

Table 1 e Comparison of main water electrolysis technologies.

Fig. 1 e PEM water electrolysis process flowsheet [12].

Alkaline water electrolysis

Hydrogen production by AWEs is now a well-established

Furthermore, due to their high maneuverability, rapid start/

in efficiency (e.g., they could decrease the energy of water

Solid oxide electrolysis

Thermodynamic analysis of the water splitting reaction

Fig. 12 e Schematic of a SOEC cell showing the internal components.

that should lead to the emergence of an alternative alkaline

advantage for the direct storage of hydrogen in pressurized

significant challenges: (i) cells do not support thermal

metallic components; this adds complexity and heat ex-

However, the main challenge faced by water electrolysis to

hydrogen in a cost-competitive way, with a specific cost (in

V/kgH2) compatible with market and tax requirements. The

production cost of electrolytic hydrogen is set by Capex and

Opex contributions that dictate an optimum operating current

density [28]. Currently, molecular hydrogen is mainly pro-

duced in the chemical industry by the steam reforming of

CH4(g) þ 2 H2O(g) / CO2(g) þ 4 H2(g) DDH ¼ þ41 kJ/molH2

Compared to water electrolysis (DH ¼ þ286 kJ/molH2), the

energy required to extract one mole of hydrogen from water is

therefore seven times larger than the energy required to

in the long term, the Capex of both processes becomes similar

difference. The interest of producing hydrogen by water

sequestration) and by the use of cheap kW*h (solar or

Various international targets for water

efficiency does not include the energy for steam generation.

Table 3 provides key techno-economical characteristics of

different electrolysis technologies suggested by the Interna-

tional Energy Agency (IEA).

In addition, the International Renewable Energy Agency

(IRENA) provided the following techno-economic character-

Key Performance Indicators for PEM water electrolysis

DOE are similar, however, most of the related companies in US

Electrical efficiency (%, LHV)

have their own targets. In many cases, proprietary informa-

tion such as anode catalyst loading etc is not publicly avail-

Program Record, available in the public domain as of Feb 3,

particular proton exchange membrane water electrolyzers,

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