energies

Review
Recent Advances in High-Temperature Steam Electrolysis with
Solid Oxide Electrolysers for Green Hydrogen Production
Mohsen Fallah Vostakola 1 , Hasan Ozcan 2,3 , Rami S. El-Emam 4,5 and Bahman Amini Horri 2, *

1 School of Metallurgy and Materials Engineering, Iran University of Science and Technology,
Tehran 16846-13114, Iran
2 School of Chemistry and Chemical Engineering, University of Surrey, Guildford GU2 7XH, UK
3 Department of Mechanical Engineering, Ankara Yildirim Beyazit University, Ankara 06010, Turkey
4 Faculty of Engineering and Applied Science, Ontario Tech University, Oshawa, ON LG1 0C5, Canada
5 Faculty of Engineering, Mansoura University, Mansoura 35516, Egypt
* Correspondence: [email protected]; Tel.: +44-(0)-1483-689846

Abstract: Hydrogen is known to be the carbon-neutral alternative energy carrier with the highest
energy density. Currently, more than 95% of hydrogen production technologies rely on fossil fuels,
resulting in greenhouse gas emissions. Water electrolysis is one of the most widely used technologies
for hydrogen generation. Nuclear power, a renewable energy source, can provide the heat needed
for the process of steam electrolysis for clean hydrogen production. This review paper analyses the
recent progress in hydrogen generation via high-temperature steam electrolysis through solid oxide
electrolysis cells using nuclear thermal energy. Protons and oxygen-ions conducting solid oxide
electrolysis processes are discussed in this paper. The scope of this review report covers a broad
range, including the recent advances in material development for each component (i.e., hydrogen
electrode, oxygen electrode, electrolyte, interconnect, and sealant), degradation mechanisms, and
countermeasures to mitigate them.

Keywords: hydrogen production; steam electrolysis; solid oxide electrolysers; nuclear thermal energy;
Citation: Fallah Vostakola, M.; Ozcan,
water electrolysis; solid oxide electrolytes
H.; El-Emam, R.S.; Amini Horri, B.
Recent Advances in
High-Temperature Steam Electrolysis
with Solid Oxide Electrolysers for 1. Introduction
Green Hydrogen Production. Energies Future environmental security and economic growth greatly rely on answering the
2023, 16, 3327. https://doi.org/ continually increasing energy demand in different sectors, such as buildings (commercial
10.3390/en16083327 and residential), transportation, and industrial sectors. Although the energy consumption
Academic Editors: Eugenio Meloni, rate declined during the context of the global pandemic until 2020, it rebounded with a
Marco Martino and Concetta Ruocco 5% growth afterwards in 2021. As energy resources dwindle and need rise, several ap-
proaches have been proposed to address this demand [1–3]. The availability, environmental
Received: 19 February 2023 friendliness, sustainability, and costs of energy have determined the course of human life
Revised: 1 April 2023 during the past century. Many energy sources have been unlocked so far, from fossil fuels
Accepted: 4 April 2023
to nuclear, hydropower, wind energy, biomass, solar energy, etc. Currently, the accelerating
Published: 8 April 2023
energy demand is mainly addressed using the combustion of fossil fuels, such as natural
gas, petroleum, etc., which is considered one of the main sources of greenhouse gas (GHG)
emissions [2,4,5]. To mitigate the adverse effects of using fossil fuels, a more robust and
Copyright: © 2023 by the authors.
efficient source of energy must be developed to tackle both the energy and environmental
Licensee MDPI, Basel, Switzerland.
challenges. Solar cells [6], geothermal systems [7], thermoelectric materials [8], biomass [9],
This article is an open access article fuel cells [2,10], batteries [11], hydrogen energy [12], etc., are among the inexhaustible,
distributed under the terms and cheap, and clean energy systems that can offer economic, environmental, and reliable
conditions of the Creative Commons advantages over fossil fuels [13]. Amongst all of the novel clean energy systems, there is
Attribution (CC BY) license (https:// a growing interest in hydrogen as a carbon-neutral alternative that can address both the
creativecommons.org/licenses/by/ ever-increasing energy demand and environmental considerations. The strong interest in
4.0/). developing hydrogen production technologies is mainly due to its favourable attributes,

Energies 2023, 16, 3327. https://doi.org/10.3390/en16083327 https://www.mdpi.com/journal/energies

Energies 2023, 16, 3327 2 of 51

systems, there is a growing interest in hydrogen as a carbon-neutral alternative that can

address both the ever-increasing energy demand and environmental considerations. The
Energies 2023, 16, 3327 2 of 50
strong interest in developing hydrogen production technologies is mainly due to its fa-
vourable attributes, such as being the lightest chemical element with the highest energy
density, high efficiency, renewability, high conversion, quick recovery, versatility, clean-
such ashigh
liness, being the lightest
overall chemical
storage element
capacity, with the highest
zero emissions, energy
etc. (Table density, high efficiency,
1) [13–16].
renewability, high conversion, quick recovery, versatility, cleanliness, high overall storage
capacity, zero emissions,
Table 1. Energy etc. (Table
content of several fuels 1) [13–16].
[14].

Fuel
Table 1. Energy content of several fuels [14]. Energy Content (MJ.kg−1)
Hydrogen 120
Fuel Energy Content (MJ.kg−1 )
Liquefied Natural Gas (LNG) 54.4
Hydrogen
Propane 120
49.6
Liquefied Natural Gas (LNG) 54.4
Gasoline 45.6–46.8
Propane 49.6
Ethanol
Gasoline 29.6
45.6–46.8
Methanol
Ethanol 19.7
29.6
Methanol
Coke 19.7
27
Coke
Dry wood 27
16.2
Dry wood 16.2
Bagasse
Bagasse 9.6
9.6

Hydrogen plays a crucial role in several chemical industries, such as petroleum, am-
monia,Hydrogen
oil sands,plays
etc., aascrucial
well asrole in several
being a cleanchemical industries,
transportation fuel, such as petroleum,
making am-
nitrogen ferti-
monia, oil sands, etc., as well as being a clean transportation fuel, making
lizers, semiconductor manufacturing, pharmaceuticals, aerospace applications, etc. nitrogen fertilizers,
semiconductor
[13,14,17,18]. Amanufacturing, pharmaceuticals,
scheme of the current and futureaerospace applications,
application of hydrogenetc. is
[13,14,17,18].
illustrated inA
scheme of the current and future application of hydrogen is illustrated in Figure
Figure 1. As can be seen from the historical transition from fossil fuels to novel fuel con- 1. As can
be seen from the historical transition from fossil fuels to novel fuel consumptions, hydrogen
sumptions, hydrogen shows great potential for addressing current and future clean en-
shows great potential for addressing current and future clean energy demand by virtue of
ergy demand by virtue of its high greenisation factor (GF = 0–1, a factor indicating the
its high greenisation factor (GF = 0–1, a factor indicating the amount of GHG emissions,
amount of GHG emissions, higher values correlates with lower GHG emissions) and other
higher values correlates with lower GHG emissions) and other exciting properties [14,19].
exciting properties [14,19].

Figure 1. Wide application of hydrogen in the industry [14].

Hydrogen is very reactive and does not exist as a molecule; thus, it must be produced
by extracting it from other hydrogen-containing sources, such as water, hydrocarbons,
Energies 2023, 16, 3327 3 of 50

carbohydrates, etc. [13,14]. Hydrogen can be generated through diverse resources, in-
cluding biomass, fossil fuels, water electrolysis, etc. [13,20]. As of today, more than 95%
of hydrogen production technologies rely on fossil fuel burning, including natural gas,
naphtha reforming, and coal gasification, which requires high energy utilisation and re-
leases significant greenhouse gases [13,21]. There have been remarkable advances in
hydrogen production source inputs, including water (e.g., electrolysis, photolysis, and
thermolysis) [22–25], biogas (such as biomethane reforming) [26,27], biomass (e.g., biomass
gasification, pyrolysis, and bio-chemical) [28–30], coal gasification [31], partial oxidation
of liquid hydrocarbons [32], and natural gas (such as steam methane reforming (SMR),
autothermal reforming (ATR), chemical looping, partial oxidation (POX), and pyrolysis
(methane splitting)) [33–37].
Nuclear energy is considered to be a sustainable and clean energy source and has
a strong potential for large-scale hydrogen production. It has been reported that the US
Department of Energy (DoE), in cooperation with various laboratories and companies in the
USA, has been working on three projects since 2020 [38–40]. Although large-scale hydrogen
generation based on nuclear power was in its infancy up to around 2003 [39], it attracted
great interest during the past decade, and several researchers have focused on addressing
the technical obstacles of using nuclear power to improve hydrogen generation and reduce
pollution. Hydrogen production via a thermochemical cycle or high-temperature water
electrolysis can benefit from the heat generated by the nuclear process. It has been reported
that the efficiency of a nuclear power-supported high-temperature electrolysis system
has the potential to be near to that of thermochemical cycles without using fossil fuels,
GHG emissions, and severe materials corrosion [41]. In this context, steam electrolysis
coupled with a solid acid electrolysis cell is an effective approach for hydrogen production
at intermediate temperatures (<300 ◦ C) and high efficiency, but water vapour and hydrogen
separation needs a separate process [42]. The integration of steam electrolysis with a solid
oxide electrolysis cell (SOEC) is another approach for hydrogen production, but it also
suffers from unstable electrodes and safety issues [43].
Despite the significant engineering advances obtained in the last couple of decades
in developing water-splitting technologies, the commercialised methods currently avail-
able for producing green hydrogen (such as alkaline electrolysis and proton-exchange
membrane—PEM electrolysis) are still incapable of meeting all the market requirements,
which necessitates the development of more robust and cost-effective systems. Other
challenges include handling, storage complications, safety issues, transportation difficul-
ties, dependence on fossil fuels, etc. In order to minimise the utilisation of fossil fuels for
producing (grey) hydrogen and to meet the Paris Agreement’s priorities, electrolysis of
steam is widely considered a viable technique for large-scale applications in the mid-term.
Hence, this review aims to critically discuss the application of high-temperature steam elec-
trolysis as a potential clean energy technology and pinpoint the main challenges associated
with its commercialisation, such as production costs, electrochemical performance, energy
conversion efficiency, etc.

2. Hydrogen Generation Technologies

As mentioned earlier, fossil fuel-based technologies are the most industrial processes
for hydrogen generation, among which steam methane reforming (SMR) is the most widely
used route, with a high conversion efficiency of about 75–85%, which decreases by 5–14%
when integrated with a carbon capture system [44]. The primary feedstock of the SMR
process is natural gas, but it should be de-sulphurised and reformed at about 700–825 ◦ C
using active carbon. The process of converting methane to hydrogen in this process
is based on using heat and pressure in which methane reacts with steam to produce a
mixture of hydrogen and carbon monoxide (syngas). Then hydrogen can be separated from
carbon monoxide by passing the mixture through a water-gas shift reactor, and the final
step is the removal of other impurities such as water, methane, carbon dioxide, and the
 a mixture of hydrogen and carbon monoxide (syngas). Then hydrogen can be separated
from carbon monoxide by passing the mixture through a water-gas shift reactor, and the
final step is the removal of other impurities such as water, methane, carbon dioxide,
Energies 2023, 16, 3327 4 of and
50
the remaining carbon monoxide (Figure 2) [14,45–48]. The following reactions take place
during this process:
remaining carbon monoxide (Figure 2) [14,45–48]. The following reactions take place during
Methane and steam reaction: CH + H O ⇆ CO + 3H
this process: ∆H = +206.3 kJ. mol (1)

CO and steam reaction:

Methane CO + H OCH
and steam reaction: ⇆4 +
COH2 O
+H CO + 3H
∆H
2 =∆H
◦
−41.16 kJ.mol−1
kJ. mol
= +206.3 (1)(2)
CO and steam reaction: CO + H2 O  CO2 + H2 ∆H◦ = −41.16 kJ · mol−1 (2)
Overall reaction: CH + 2H O ⇆ CO + 4H ∆H = +165.2 kJ. mol (3)
Overall reaction: CH4 + 2H2 O  CO2 + 4H2 ∆Ho = +165.2 kJ · mol−1 (3)

Figure 2. A
Figure 2. A schematic ofschematic
hydrogen of hydrogen production
production using using the SMR
the SMR process
process [48].
[48].
In order to facilitate the reforming process, some catalysts, such as Ni-based catalysts,
In ordertransition
to facilitate the(such
metals reforming process,
as Cu, Fe, Co, Ni, some catalysts,
etc.), noble metalssuch(suchas as Ni-based catalysts,
Ru, Pt, Ir, etc.), and
transition metals
oxide (such
supports as(such
Cu, asFe,Ru/Mg(Al)O,
Co, Ni, etc.), noble Ni.Al
Ni/MgO, metals2 O3(such as Ru,
, etc.), have been Pt, Ir, amongst
used etc.), and
which
oxide supports Ni-based
(such catalysts are the Ni/MgO,
as Ru/Mg(Al)O, most widelyNi.Al
used materials
2O3, etc.), due to their
have beencost-efficiency
used amongstand
high performance [49]. The existing infrastructure and relatively
which Ni-based catalysts are the most widely used materials due to their cost-efficiency high efficiency (74–85%) of
this technology are the most important advantages of this process, but unstable supply and
and high performance [49]. The existing infrastructure and relatively high efficiency (74–
the production of carbon monoxide and carbon dioxide are the most significant drawbacks
85%) of this of
technology
it [50]. are the most important advantages of this process, but unstable
supply and the production
Chemical looping of carbon monoxide
is an innovative and carbon
approach dioxide
for hydrogen are the most
production signifi-
and carbon
capture method
cant drawbacks of it [50]. that involves the reaction and regeneration of solid chemical materials
(fuel). Due to the in situ creation of oxygen, there is no need for an external supply of oxygen,
Chemical looping is an innovative approach for hydrogen production and carbon
resulting in reducing the operating costs and energy needed for the process [51]. Based
capture method
on thisthat involves
concept, thetechniques
several reactionhave
andbeenregeneration
driven, as seenof solid chemical
in Figure materials
3. Besides these
(fuel). Due to
traditional technologies, there are also some relatively new processes, including chemical of
the in situ creation of oxygen, there is no need for an external supply
looping
oxygen, resulting insteam methane
reducing thereforming
operating (CL-SMR or CLRM),
costs and energy steam reforming
needed for theintegrated
process with
[51].
chemical looping combustion (SR-CLC or CLR(s)), auto thermal chemical looping reforming
Based on this concept, several techniques have been driven, as seen in Figure 3. Besides
(CLR(a)), chemical looping gasification (CLG), oxygen-carrier aided combustion (OCAC),
these traditional technologies, there are also some relatively new processes, including
chemical looping steam methane reforming (CL-SMR or CLRM), steam reforming inte-
grated with chemical looping combustion (SR-CLC or CLR(s)), auto thermal chemical
looping reforming (CLR(a)), chemical looping gasification (CLG), oxygen-carrier aided
 Energies 2023, 16, 3327 5 of 50

etc. [52–55]. Among all of the chemical looping systems, chemical looping combustion
(CLC) is the most industrial and widely used technology. CLC is highly energy efficient
with intrinsic CO2 capture, which can produce hydrogen production with relatively high
efficiency. In order to keep the products away from the air (used for the combustion step),
oxygen carriers (OCs) continuously circulate between air and fuel reactors and partially
or completely oxidise the fuel (Figure 4) [35,52]. Oxygen carriers should have some key
Energies 2023, 16, 3327 properties, including chemical lifetime, suitable mechanical properties, the least possible 5 of 51
environmental effect, no toxicity, high oxygen transport capacity, low cost, high tendency to
carbon deposition on the surface of OCs, high reactivity with oxygen and other combustible
materials, etc. [54]. Generally, OC materials with the highest performance can be divided
looping combustion (CLC) is the most industrial and widely used technology. CLC is
into five classes, including Fe-, Cu-, Mn-, Co-, and Ni-based compounds, amongst which
highly energy
Ni-based materialsefficient
exhibitwith intrinsic
the highest CO2 capture,
performance. Otherwhich can produce
OCs candidates hydrogen
are natural OCs produc
tion with
(such relatively
as FeTiO high efficiency. In order to keep the products away from the air (used
3 ), synthetic OCs (Cu0.95 Fe0.05 AlO4 ), or other active materials such as NiO,
for the combustion step),
(Mn, Fe)2 O3 , Al2 O3 , TiO oxygen
2 , SiO 2 , MgAlcarriers
2 O4 , ZrO(OCs) continuously
2 , bentonite, circulate
etc. [13,56]. between
The first step of air and
the
fuelprocess
reactorsinvolves an exothermic
and partially oxidationoxidise
or completely reaction offuel
the the metal oxide
(Figure (reaction
4) [35,52]. 4) and carriers
Oxygen
supplies the heat
should have someneeded
keyfor the secondincluding
properties, step (reaction 5). Reactions
chemical 6 and
lifetime, 7 take place
suitable in air prop
mechanical
and fuel reactors, respectively [13].
erties, the least possible environmental effect, no toxicity, high oxygen transport capacity
low cost, high tendency to carbon deposition 1 on the surface of OCs, high reactivity with
M x O
oxygen and other combustible materials, y − a + O 2  Mx Oy (4)
2 etc. [54]. Generally, OC materials with the high
est performance can
(2n + m )Mxbe divided into five classes, including Fe-, Cu-, Mn-, Co-,
Oy + Cn M2 m  (2n + m)Mx Oy−1 + mH2 O + nCO2 (5)
and Ni
based compounds, amongst which Ni-based  materials exhibit the highest performance
 C + O2  CO2
Other OCs candidates are natural OCs (such as FeTiO3), synthetic OCs (Cu0.95Fe0.05AlO4)
Reactions in air reactor: 2C + O2  2CO (6)
or other active materials such as NiO, (Mn,  Fe)2O3, Al 2O3, TiO2, SiO2, MgAl2O4, ZrO2, ben
2Ni + O2  2NiO
tonite, etc. [13,56]. The first stepof the process involvesNian exothermic oxidation reaction
of the metal oxide (reaction 4) and  supplies C2 H5 OHthe+heat ()2COfor
H2 Oneeded + 4Hthe2 second step (reaction

Reactions in fuel reactor: C H OH + 6NiO → 6Ni + 2CO + 3H (7)
5). Reactions 6 and 7 take place in air and fuel reactors, respectively
2 5 2 2O
[13].
CO + H2 O  CO2 + H2


Figure3.3.Different
Figure Different chemical looping
chemical systems
looping [54]. [54].
systems
Energies 2023, 16, 3327 6 of 50

Figure 3. Different chemical looping systems [54].

Figure 4. A schematicFigure
of the CLC
4. A process
schematic of the[54].
CLC process [54].

Another developed cycle is the integrated gasification combined cycle (IGCC), in

which a gas-turbine-steam power plant is coupled with a coal gasification unit. IGCC uses
liquid or solid hydrocarbon fuels to generate electricity in a cleaner process than fossil
fuel burning. The removal of undesirable compounds such as mercury, sulphur, and other
substances and the production of syngas is performed after converting the solid/liquid
fuel to the gas phase [57]. The most developed IGCC system is coupled with a carbon
capture system that results in higher plant energy efficiency and lower operational and
capital costs. The future of IGCC depends on solving its major technological barriers, such
as high operating and capital costs, indicating that it needs additional development prior
to commercialisation [58,59].
Coal gasification converts carbonaceous compounds (petroleum, coke, biomass, etc.)
into carbon, hydrogen, carbon monoxide (syngas), and a small amount of carbon dioxide
and methane [60]. In coal gasification, dry coal reacts with steam and oxygen under high
pressure in the gasifier and produces hydrogen and carbon dioxide. Then, air passes
through the gasifier and partially oxidises the coal (C + O2 → CO2 ) and generates heat.
Next, steam replaces air in the system (water gas shift reaction) and reacts with a part of
the coal to separate hydrogen from the coal gas (C + H2 O → CO2 + H2 ). After reaching
a specific heat level, the air is fed to the gasifier once more [31,44,61]. Underground coal
gasification (UCG) is a new type of coal gasification in which the gasification process takes
place without mining. In this in situ process, the product gases are mainly carbon monoxide,
hydrogen, carbon dioxide, and methane, which are brought up to the surface. The ratio of
each gas depends on the depth of the coal mine, pressure, and oxidant balance [59,62]. It
should be noted that coal gasification needs high operating temperatures (>900 ◦ C), and
different types of coal have been used as feedstock in this process, including anthracites
(high rank), bituminous (medium rank), sub-bituminous (low rank), and lignite (low
rank) [31,44,63].
Regarding biomass-based hydrogen production technologies, dark fermentation is a
simple and facile process that can generate hydrogen at ambient conditions with a simple
reactor design and without any need to light, as well as contribute to waste recycling.
However, limited hydrogen yield, low efficiency, low conversion efficiency, fatty acid
removal, large reactor volume, and high by-product production are the main drawbacks of
this process [50,64,65]. Photofermentation is another biomass-based process that can use
different wastewater and organic wastes with carbon dioxide neutrality and waste recycling
Energies 2023, 16, 3327 7 of 50

contribution. However, it requires sunlight for the process and low conversion efficiency;
the requirement of large reactor volume, low hydrogen production yields and rates, and
oxygen sensitivity limited its further development [64,65]. Biomass gasification is the third
class of biomass-based hydrogen production technologies. Biomass gasification is a carbon-
neutral emission process with copious and cheap feedstock. On the other hand, varying
hydrogen production yield (depending on feedstock impurities and seasonal availability)
and tar formation are their major disadvantages [14,50,64,66]. Biomass pyrolysis is a
developed process with similar pros and cons to biomass gasification but with relatively
lower hydrogen production efficiency [65,66]. Steam reforming of biomass is another
developed process with higher efficiency and costs of hydrogen production and carbon
co-product formation [64,66]. Hydrothermal liquefaction of biomass seems to have the
highest hydrogen production efficiency (~85–90%) with moderate production costs, but
nitrogenated compounds may exist in the process, and hydrogen production still depends
on the quality of the feedstock [67,68]. Compared to water-based technologies, it seems
that biomass-based technologies have almost similar hydrogen yields with higher energy
efficiency and lower costs than those of water-based ones [66].
Table 2 provides a summary of different hydrogen production technologies and some
of their characteristics. Each of these technologies has some advantages and disadvantages.
For example, water splitting using electrolysis is a simple technology with low operating
temperature and zero carbon emission, which can be easily coupled with fuel cells. Electric
power converts to chemical energy in this process in the form of H2 and O2 as follows [66]:

1
Anode half reaction :H2 O → O2 + 2H+ + 2e− (8)
2
Cathode half reaction : 2H+ + 2e− → H2 (9)
1
Overall reaction : H2 O → H2 + O2 (10)
2

Table 2. General properties of some of the most important hydrogen production technologies [66,69]
(Reproduced with permission form [69], Elsevier: 2020).

Process Feedstock Operating Condition Level of Development Efficiency (%)

Steam reforming Light hydrocarbons 700–1000 ◦C Commercial 74–85
Hydrocarbons, coal,
Partial oxidation 800–1000 ◦ C Commercial 60–75
and heavy fuel oil
Autothermal refining Light hydrocarbons 700–1000 ◦ C Early commercial 60–75
Pyrolysis Hydrocarbons 1000–1400 ◦ C Commercial 35–50
Coal gasification Coal 700–1200 ◦ C Commercial -
Ammonia reforming Ammonia 800–900 ◦C Early commercial 28
Biomass gasification Biomass 800–1000 ◦C Commercial 30–60
>2500 ◦C
(1000 ◦C
< for
Thermolysis - R&D 20–50
thermochemical cycles)
Photoelectrolysis Water and sunlight Ambient conditions R&D 0.06–14
Biophotolysis of
- Ambient conditions R&D 10–15
microorganisms
Carbohydrate-rich
Dark fermentation of Anoxic conditions R&D 60–80
substrates
Small organic Anaerobic conditions at
Photofermentative R&D 0.1–12
molecules and sunlight ambient temperature
300–1000 ◦ C (under an
Pyrolysis of biomass Biomass Commercial 21.9–75
oxygen-free atmosphere)
Energies 2023, 16, 3327 8 of 50

Table 2. Cont.

Process Feedstock Operating Condition Level of Development Efficiency (%)

Alkaline electrolysis Water and electricity 40–90 ◦C Commercial 62–82
PEM electrolysis Water and electricity 20–100 ◦C Commercial 67–82
Water, electricity,
SOEC 700–1000 ◦ C R&D ~100
and heat
Hydrothermal 4–22 MPa
Wet biomass R&D 85–90
liquefaction 250–370 ◦ C
Thermochemi-
Heat and water 500–1000 ◦ C R&D 20–45
cal water splitting

Despite its simplicity, high hydrogen purity, and other advantages, water splitting tech-
nologies require high operating pressure and have relatively low efficiency (~55–80%) as
well as high capital costs and challenges with energy storage and transportation compared
to those of fossil fuel-based technologies, which limits its large-scale application [50,65,70].
Thermolysis of water offers a clean and sustainable route with no carbon emission and
abundant feedstock, but its capital cost is relatively high and also needs a separation step
to prevent the recombination into an explosive mixture. Furthermore, this technology has
other issues with corrosion problems and element toxicity [50,71,72]. High-temperature
water splitting methods using nuclear reactors with near-zero greenhouse gas emissions is
another technology for hydrogen production in which nuclear energy powers the hydrogen
production process, increases its efficiency, and dramatically reduces pollution [46]. At the
high voltage and power, high-temperature electrolysis can sustain its operating temper-
ature (i.e., 600–900 ◦ C) exothermally, allowing the input streams to be provided at much
lower temperatures. This operation can allow steam at 150 to 200 ◦ C to be the input stream
to the high-temperature steam electrolysis (HTSE) plant, enabling the coupling of HTSE
with currently operating nuclear reactors [73]. This technology will be further discussed
in the next chapters. Photoelectrolysis needs low operating temperature and pressure but
has very low efficiency (~0.06–14%), and the need for a significant surface for this process
is still a challenge to photoelectrolysis [65,66,72]. Biophotolysis is another water-splitting
technology that consumes carbon dioxide as an input and generates hydrogen at ambient
conditions along with oxygen as a by-product, but with low hydrogen yield and efficiency
(~10%), the requirement of a large surface area for collecting sunlight, high costs of raw ma-
terials, oxygen sensitivity, large reactor, and challenges with controlling different bacteria
are the technical challenges that restrict its implementation [50,65,66,72].
As hydrogen is recently receiving great attention among all stakeholders, including
decision-makers, politicians, economists, and the general public, colour-based taxonomy
has been adopted to indicate the different energy sources used to produce hydrogen (e.g.,
nuclear, renewable, methane, etc.) [44,74]. Different schemes have been proposed and
adopted by different organisations. Such schemes are helpful in highlighting the pathways
of hydrogen production to some of the involved stakeholders. However, this approach
is not adopted in the current study as this classification and colour-coded indexing of
hydrogen is helpful within the scope of research and scientific articles. Other measures
of carbon intensity and contribution to climate change mitigation can be utilised in this
regard. In addition, the scope of the current review paper does not cover this part as it
depends heavily on the energy source used along with the hydrogen technology itself.
Currently, most of the hydrogen produced around the world is blue, grey, and
black/brown hydrogen due to their relatively low costs and including more controllable
reactions. The hydrogen produced during these processes is mainly used in ammonia
production and petrochemical plants. The ever-increasing need for grey and black/brown
hydrogen accounts for 6% and 2% of worldwide natural gas and coal, respectively [31,44].
Due to its large coal reserve, most of the black/brown hydrogen (hydrogen generated from
Energies 2023, 16, 3327 9 of 50

coal gasification) is currently produced in China [31]. Hydrogen purity of SMR, ATR, and
coal gasification processes are 94%, 93%, and 87%, respectively [75]. Hydrogen generation
using fossil fuels coupled with carbon capture and storage facilities has the potential to
halve the GHG emissions of coal gasification. However, the problem remains as these
hydrogen production technologies generate about 830 Mt CO2 annually. Another impor-
tant challenge facing fossil fuel-based methods is carbon capturing and storage facilities,
which increase capital costs. This heavy dependence on hydrogen production on fossil
fuel-based routes means that the current hydrogen production technologies have similar
GHG emission challenges [75,76].
Despite all of the advances, the most important challenges that hinder the widespread
application of hydrogen production technologies are high costs and low production ef-
ficiency, storage, slower availability compared to fossil fuel-based routes, etc. [14,16,77].
Decreasing the GHG footprint is one of the primary goals of promoting hydrogen produc-
tion technologies, which implies the necessity of switching to low GHG emission methods
with a threshold CO2 emission value of about 36.4 gCO2 e.MJ−1 [75,78]. Although some
hydrogen production technologies, such as SMR, methane pyrolysis, etc., are matured and
well-developed, most of the non-fossil fuel-based technologies, such as photofermentation,
photoelectrolysis, biophotolysis, etc., still need fundamental research. Thus, the large-scale
production of non-fossil fuel-based hydrogen production routes is tied to the technological
developments of these methods or the invention of the novel, highly efficient ones.
Hydrogen production using nuclear power (pink/purple hydrogen) has been pro-
posed as a potential candidate for hydrogen production. Nuclear energy can increase
efficiency and decrease pollution in comparison with fossil fuel-based technologies [79].
Generally, nuclear power can improve hydrogen generation processes such as electrolysis,
steam reforming of methane, and thermochemical water splitting cycles such as sulphur-
iodine. Nuclear power is of great interest in the sulphur-iodine water-splitting process
mainly because it results in higher hydrogen production efficiency without carbon dioxide
emissions [38,39,80,81]. As mentioned earlier, reforming and shift reactions occur in the
SMR process, followed by a separation process. These reactions take place in a reactor
at about 800–900 ◦ C. The heat needed for this process is usually supplied by burning
the excess methane, which reduces the methane needed for the reaction and hydrogen
production. The process can also happen in a helium-cooled reactor. A more effective
route is to use a nuclear reactor to provide the heat needed for this process. Since the
traditional reactor cannot be used for transferring the generated heat, the heat transfers
from the nuclear reactor to the main reactor using a heat exchanger-type reactor. However,
there are still challenges regarding the linking, diffusing hydrogen through the wall and
mixing with the coolant (helium), producing tritium caused by hydrogen diffusion and
reducing the hydrogen purity, material considerations, etc., which should be addressed [39].
In the sulphur-iodine cycle (S-I cycle), there are three reactions in which the dissociation
of sulphuric acid to water vapour, sulphur dioxide, and oxygen at about 850–900 ◦ C is
a high-temperature endothermic reaction. The conjunction of the S-I cycle with nuclear
power can improve hydrogen generation. Other thermochemical cycles, such as the Cu-Cl
cycle, have also been investigated, but generally, the S-I cycle has higher efficiency and is
of greater interest compared to the other cycles [13,38,40,82–85]. Water electrolysis is the
simplest method for hydrogen production with zero GHG emissions and a great potential
for electrical peak shaving. While the thermal efficiency of electrolysis is about 25%, elec-
trolysis and electrical power generation efficiencies are about 75% and 30%, respectively.
As mentioned earlier, hydrogen production costs and storage/transportation issues are the
main challenges [20,84]. Among the three nuclear-powered methods, water electrolysis
has the lowest efficiency (~25–45%) compared to SMR (~70%) and S-I cycle (~50%) and
the highest capital costs (USD 30.97, USD 11.44, and USD 19.96 per GJ of yearly hydrogen
production for water electrolysis, SMR, and SI-cycle, respectively). Integrating electrolysis
with nuclear power can provide cheaper electricity for the process and increase its efficiency
because of the higher thermal efficiencies of nuclear power plants [39].
Energies 2023, 16, 3327 10 of 50

At the moment, hydrogen production technology at the commercial scale is dominated

by fossil fuel-based methods. In addition to the type of technology, other factors, such
as cost of labour, land, raw materials, construction, utility, and product, as well as life
cycle, construction time, etc., should also be considered in choosing the proper technology
for hydrogen production assessment. According to the thermodynamic analyses, the
SMR of natural gas is the most efficient and productive technology due to the larger
amount of hydrogen produced than that of the other ones. Techno-economic evaluation
of the hydrogen production methods shows that coal gasification and SMR of natural
gas are the most developed and cost-effective methods. On the other hand, fossil fuels
are exhaustible and scarce and cannot satisfy the ever-growing hydrogen demand in the
future. Furthermore, assessing each technology in terms of human and environmental
impact, fossil fuel-based hydrogen production technologies, such as SMR of natural gas,
show the highest impact on human health and global warming, while non-fossil fuel-
based technologies, such as water electrolysis, exhibit the lowest impacts. As thermal or
electrical energy is needed for most hydrogen production routes, it results in increased
capital costs. Generally, hydrogen production costs of electrolysis are about 10.30 USD.kg−1,
which is almost four times higher than that of SMR (~2.27 USD.kg−1 ) or coal gasification
(1.8–2.1 USD.kg−1 ) [86]. A useful method to reduce the capital costs of hydrogen production
is to integrate the hydrogen production technologies (such as electrolysis methods) with
a power source, such as photovoltaics, nuclear plants, etc., to supply the heat/electricity
needed for the operation and reduce hydrogen production costs.

3. Water Electrolysis
3.1. Low-Temperature Water Electrolysis
There are several water electrolysis routes, including solid oxide electrolysis (SOE) [87],
alkaline water electrolysis, and proton-exchange membrane (PEM) electrolysis [50]. The
fundamentals of the electrolysis process are briefly discussed in the previous chapter. Gen-
erally, water electrolysis can be divided into three categories according to the operating
temperature: low-temperature, intermediate-temperature, and high-temperature electroly-
sis. Low-temperature, intermediate-temperature, and high-temperature electrolysis usually
operate at temperatures lower than 300 ◦ C, in the range of 300–700 ◦ C, and higher than
700 ◦ C (below 1000 ◦ C), respectively [69,88,89]. In addition to the conventional water
electrolysis process, other low-temperature water electrolysis technologies include alkaline
water electrolysis, PEM water electrolysis, and anion exchange membrane (AEM) water
electrolysis (AEMWT) (Figure 5) [89–92].
Alkaline water electrolysis (Figure 5a) is a well-established, low-cost, the most devel-
oped electrolysis method, long lifetime, and commercialised process that uses non-noble
catalysts. In this process, water splits at the cathode side and produces hydrogen and OH-
ions, followed by the OH- ions travelling to the anode side to produce oxygen and water.
The electrodes are submerged in the electrolyte, and a diaphragm, which is permeable to
water and OH- ions, separates the product gases [69,89,93–97]. The liquid electrolyte in this
process is usually KOH or NaOH. The electrode can be either nickel, iron, cobalt, Ni-S-Co,
La0.5 Sr0.5 CoO3 , Ni50%Al, Ni73%W25%, Ni-Fe-Mo-Zn, porous Co, RuO2 , Raney-Ni-Mo,
etc. However, the most widely used electrode is nickel due to its low cost, availability,
and high activity. The diaphragm can be porous oxides (such as Ni, NiO, BaTiO3 , SrTiO3 ,
etc.) or polymer composites (such as radiation-grafted PTFE, PTFE-ZrO2 , polyantimonic
acid-PTFE, etc.) [92,94,98]. Addressing some challenges, such as carbonate formation, low
current density, low dynamic operation, and low purity of gases, can help further the
development of this process. Nickel is a common electrode, and the most commonly used
electrolytes in this process are potassium hydroxide and sodium hydroxide [93,99–101]. Al-
kaline water electrolysis operates in the temperature range of 20–90 ◦ C [69,102]. Although
this technology has already been commercialised, it still suffers from corrosive electrolyte
materials, gas crossover, low efficiency, low current density, etc. [89].
ies 2023, Energies
16, 33272023, 16, 3327 11 of 50 11 of 5

Figure 5. A schematic of (a) alkaline water electrolysis [63], (b) anion exchange [96], and (c) PEM
Figure 5. A schematic of (a) alkaline water electrolysis [63], (b) anion exchange [96], and (c) PEM
process [97].
process [97].
AEM water electrolysis (Figure 5b) is structurally similar to PEM cells except for the
AEM waterwhich
membrane, electrolysis
transports OH− anions
(Figure 5b) isinstead of H+ protons.
structurally similar to PEM
Similar to thecells except
alkaline wa- for th
ter splitting process, OH − anions serve as the charge carrier in anion exchange membrane
membrane, which transports OH anions instead of H protons. Similar to the alkalin
− +
water electrolysis. AEM water electrolysis shows some advantages over the alkaline and
water PEM
splitting process, OH− anions serve as the charge carrier in anion exchange mem
cells, such as no carbonates precipitation, lower ohmic loss, less expensive raw mate-
brane water electrolysis.
rials (compared to PEM AEM
cells),water
and theelectrolysis showswith
use of electrolytes some lowadvantages
concentrations over the alkalin
[94,103].
and PEM cells, this
Generally, such as no carbonates
technology precipitation,
operates in low concentrations lower ohmic loss,
of electrolytes and a less expensive raw
temperature
range of 20–60 ◦ C. Ni, NiMo, Pt/X, IrOx/IrO , and NiP are the most common cathode
materials (compared to PEM cells), and the use of electrolytes with low concentration
2
materials, and NiFe oxyhydrates, Ni/CeO2 -La2 O3 , CuCoOx , NiFe, and NiFe2 O4 are the
[94,103]. Generally, this technology operates in low concentrations of electrolytes and
most widely used materials for the anode [89,96,104]. Despite all of its advantages, much
temperature
researchrange
has to of 20–60 out
be carried °C.toNi, NiMo,
improve itsPt/X, IrOx/IrO
efficiency 2, and NiP are the most commo
and durability [89].
cathode materials, and NiFe
In PEM electrolysis oxyhydrates,
(Figure Ni/CeO
5c), water splits -La
into 2H+, O2O
2 , 3 ,
andCuCoO
e x, NiFe,
− at the anode.and
ThenNiFe
H+ 2O4 ar
the most widely
(protons) used
travels materials
to the for thethe
cathode through anode
membrane,[89,96,104]. Despite
while electrons exit all
fromofthe
itsanode
advantage
much research has to be carried out to improve its efficiency and durability [89].
In PEM electrolysis (Figure 5c), water splits into H+, O2, and e− at the anode. Then H
(protons) travels to the cathode through the membrane, while electrons exit from the an
ode using an external power source and recombine with protons to produce hydroge
Energies 2023, 16, 3327 12 of 50

using an external power source and recombine with protons to produce hydrogen [50,69,89].
PEM electrolysis offers a fast response, high energy efficiency (~90%), ultrahigh hydrogen
purity, higher hydrogen production rate, high proton conductivity, compact system design,
low gas permeability, low thickness, high current density, etc., but it also suffers from high
costs of materials, acidic environment, etc. The state-of-the-art electrocatalysts for this
process are Pt/Pd and IrO2 /RuO2 as cathode and anode catalysts, respectively. It should
be noted that different categories of Nafion, such as Nafion-115, Nafion-112, Nafion-117,
Nafion-1035, and Nafion-212, are used as membranes in this process [50,95,100,101]. PEM
water electrolysis technology operates in temperatures ranging from 40 to 80 ◦ C [102] and
has lower hydrogen yield efficiency and lower production costs compared to alkaline water
electrolysis. Besides the low hydrogen production efficiency, high costs of raw materials,
acidic corrosion environment, limited durability, etc., are the main drawbacks of PEM water
electrolysis [69,94]. Comparing these three water-splitting technologies, it seems that anion
exchange is still in the lab-scale stage, but alkaline and PEM water-splitting methods have
been commercialised but still need further progress to solve their current challenges.
Compared to high-temperature technologies, low-temperature processes offer facile
operation, compact and easy design, and higher technology readiness levels (TRLs) (TRL
is a means to describe the maturity of a technology for its commercialisation and ranges
from 1 to 9. TRL = 1 means the technology is still under research, and TRL = 9 means
the technology is fully matured) [69]. However, due to the decreased internal resistance
losses as well as improved hydrogen evolution reaction (HER) and oxygen evolution
reaction (OER) kinetics, high-temperature water electrolysis is more efficient compared to
low-temperature ones [89].

3.2. High-Temperature Steam Electrolysis (HTSE)

Compared to low-temperature water electrolysis, high-temperature electrolysis op-
erates in higher temperatures, from 500–900 ◦ C. Although high-temperature electrolysis
or steam electrolysis has not been commercialised so far, it is a promising technology
that can electrochemically split steam into H2 and O2 using electricity and heat at high
temperatures (usually in the range of 700–900 ◦ C) [84,93]. Steam electrolysis at lower
temperatures (500–800 ◦ C) has also been reported in the literature [105]. TRL for HTSE is 7
to 8, and for high-temperature co-electrolysis is 4 to 5 [106]. For HTSE operating at around
700 ◦ C, heat resembles around 25% of the total energy input [73]. The electricity needed
for HTSE is about 35% lower than that of conventional electrolysis at low temperatures
(<80 ◦ C) because the required electricity decreases with increasing temperature. Generally,
the efficiency of electricity-to-hydrogen conversion is about 90%, but the highest overall
hydrogen production efficiency of this technology is about 50% at 900 ◦ C. It has also been
reported that [79] electricity can be used to provide the needed thermal energy when the
high-temperature electrolysis unit is on standby to keep the stack at its high operating
temperature. This will reduce the star-tup time for large-scale operations [107]. Nuclear
power plants can provide heat and electricity for low-cost hydrogen production [108].
Solid oxide electrolysis (SOE) of steam is a well-known high-temperature electrochem-
ical process. SOEs can electrochemically produce hydrogen and are usually comprised
of an anode for oxygen generation by an electric potential of around 1.3 V, a cathode for
hydrogen generation (or in some cases, CO2 electro-reduction), and an oxygen-conducting
electrolyte [79,109]. Similar to the other electrolysis technologies, steam splits into H2 and
O2 at the interface between the hydrogen electrode and electrolyte. Then, oxygen ions
transfer to the anode side through the electrolyte and recombine at the interface between
the oxygen electrode and electrolyte to produce oxygen gas. The operation of SOEC is
the reverse operation of SOFC (Figure 6) [79,110]. Solid oxide electrolysis is a developing
technology that benefits from its high efficiency, and the most commonly used catalysts
are non-noble materials. The electrolyte is usually a ceramic material, and a composite of
yttria-stabilised zirconia (YSZ) or Ni-based cermets are the most widely used electrode
materials. Half-cell reactions in a solid oxide water electrolyser at the cathode side (hy-
 Energies 2023, 16, 3327 13 of 50

drogen evolution reaction (HER) or cathode half-cell reaction) and the anode side (oxygen
evolution reaction (OER) or anode half-cell reaction) are as follows: [43,69,87,101].

Anode side : 2O2− → O2 (g) + 4e− (11)

nergies 2023, 16, 3327 13 o
Cathode side : 2H2 O(g) + 4e− → 2H2 (g) + 2O2− (12)
Overall reaction : 2H2 O(g) → O2 (g) + 2H2 (g) (13)

Figure 6. Comparison
Figure 6. Comparisonof
of SOFC andSOEC
SOFC and SOEC operation
operation [105].[105].

High-temperature water electrolysis technologies can be divided into three main

Anode
classes, namelyside:
proton-conducting solid 2O oxide → electrolysis
O (g) + 4e cell (H-SOEC or protonic ceramic
electrolysis cell (PCEC)), oxygen ion-conducting solid oxide electrolysis cell (O-SOEC),
and co-electrocatalysis of carbon dioxide and steam [84,89,93]. As mentioned earlier, due
to theCathode
enhanced side:
HER and OER kinetics 2H O(g) + as
as well 4elower
→ 2H (g) +
internal 2O
resistance losses, high-
temperature water electrolysis technologies operate at higher efficiency compared to PEM
Overall
or Alkaline reaction:[89]. However,
electrolysis 2HasO(g) →discussed
will be O (g) +further
2H (g) in the upcoming section,
high-temperature electrolysis has some technical issues, including rapid cell degradation,
which is the main reason for the limited number of projects considering this technology
High-temperature
today. water electrolysis
Furthermore, regulatory issues regarding technologies
the coupling canwithbea divided into three m
nuclear thermal
energy source—as nuclear heat is one of the primary candidates to
classes, namely proton-conducting solid oxide electrolysis cell (H-SOEC or protonicdrive high-temperature
electrolysers for large-scale clean hydrogen production—are still to be addressed. It is
ramic electrolysis cell (PCEC)), oxygen ion-conducting solid oxide electrolysis cell
worth mentioning that ongoing demonstration projects considering the coupling of high-
SOEC), and co-electrocatalysis
temperature of carbon
electrolysis with nuclear reactorsdioxide and steam
work through [84,89,93].
the regulatory As mentioned
process and
lier,investigate
due to thethe enhanced
regulatoryHER and OER
and licensing kinetics
needs as wellplants.
of large-scale as lower internal resistance los
The architecture
high-temperature of aelectrolysis
water SOEC is comprised of four constituents,
technologies operate atincluding the hydrogen
higher efficiency compare
(steam) cathode, the oxygen (air) electrode, the electrolyte, and the intermediate layer
PEM or Alkaline electrolysis [89]. However, as will be discussed further in the upcom
(barrier layer) between the oxygen electrode and electrolyte. The interconnect layer is
section, high-temperature
another electrolysis
component that is used in a stackhas some
of cells technical
[69,111]. issues,
Hydrogen including
generation occursrapid
in cell d
radation, whichelectrode
the hydrogen is the main
and atreason for the
the interface limited
between numberand
the electrode of electrolyte.
projects considering
Thus,
technology today. Furthermore, regulatory issues regarding the coupling with a nuc
thermal energy source—as nuclear heat is one of the primary candidates to drive h
temperature electrolysers for large-scale clean hydrogen production—are still to be
dressed. It is worth mentioning that ongoing demonstration projects considering the c
Energies 2023, 16, 3327 14 of 50

the cathode should be a porous material with electronic and ionic conductivity [111].
Similar to SOFCs, this reaction takes place at the triple phase boundaries (TPBs) where
the ionic phase (oxygen ion conductive), the electrical phase (e-conductive), and the gas
(hydrogen release or steam supply) meet [112,113]. Oxygen ions are oxidised at the oxygen
electrode to produce oxygen gas. This reaction occurs at the interface between the oxygen
electrode and electrolyte. Similar to the hydrogen electrode, the oxygen electrode should
be comprised of a porous compound. Suitable thermal and chemical compatibility over
time, as well as high electrocatalytic activity, high electronic and ionic conductivity, etc., are
the most important features of the oxygen electrode [114]. The most common materials for
the oxygen layer are Sr-based and Co-based perovskites, such as (La, Sr)(Co, Fe)O3 and
La0.8 Sr0.2 MnO3−δ . Mixed ionic electronic conductive (MIEC) materials, such as LSCF (with
electronic and ionic conductivities of about 102 and 10−2 S.cm−1 at 800 ◦ C, respectively),
are a new class of oxygen electrode materials [115]. An intermediate layer is usually used
between the oxygen electrode and the electrolyte to achieve suitable thermal and chemical
compatibility between the two layers. One of the most important issues regarding the cell
assembly is the thermal expansion coefficient (TEC) mismatch between the layers, which
can increase ohmic resistance due to the weakened mass transfer and charge exchange [2].
In the case of using Co- and Sr-based materials, the volatility of Co during sintering [116]
and segregation of Sr during operation [117] can increase cell degradation and reduce
cell performance. The main function of this barrier layer is to prevent unwanted element
migration and mitigate the mentioned challenges. The common intermediate materials
are yttrium-doped ceria (YDC) and gadolinium-doped ceria (GDC or CGO) [113,115].
Another approach is to use composite materials such as LSM-YSZ as oxygen electrodes
and avoid using the intermediate layer [111]. The composition of the electrodes (and
the intermediate layer) depends on the composition of the electrolyte. The electrolyte
layer must be sufficiently dense to prevent gas transport between the electrodes. High
oxygen ion conductivity, no electronic conductivity, matching TEC, as well as suitable
mechanical, thermal, and chemical stability, are other important characteristics of the
electrolyte [2]. The most commonly used electrolyte materials are 8YSZ with high ionic
conductivity of about 10−2 –10−1 S.cm−1 (700–850 ◦ C). GDC is another candidate with
high ionic conductivity but suffers from high sintering temperature (1500 ◦ C), which
prevents co-sintering of the layers and reduction in Ce4+ at higher temperatures (>700 ◦ C)
in reducing atmosphere [2,118]. In SOEC stacks, the interconnect layer plays an important
role as a current collector and a physical barrier that separates the electrodes between
the two adjacent cells. The interconnect should meet some technical requirements such
as matching TEC to other layers, high thermal and electrical conductivities, formation of
a dense low-resistive oxide layer in redox atmospheres, and high thermomechanical at
elevated temperatures (600–900 ◦ C) [2,119]. The noteworthy interconnect materials are
Cr-alloys and high Cr-containing stainless steel. Crofer 22 APU is the leading interconnect
material, a Fe-Cr stainless steel alloy with low cost, high thermal conductivity, and ease
of fabrication. Cr-alloys, such as CFY, Ducralloy, CrFe5, etc., are the other promising
candidates [41,120–122]. Interconnect performance and durability challenges of the SOECs,
such as coking, delamination, cracks, etc., are similar to SOFCs.
As discussed earlier, SOECs can be divided into three different classes: (a) O-SOEC,
(b) H-SOEC, and (c) hybrid SOEC. A schematic diagram of different types of SOECs is
shown in Figure 7. In O-SOEC (Figure 7a), hydrogen is generated from the electrolysis
of water at the hydrogen electrode, while protons are produced by water electrolysis
in the air electrode and then transferred through the proton-conducting electrolyte to
produce hydrogen at the hydrogen electrode in H-SOEC [105,110,112,123]. Compared to
the H-SOECs with proton-conducting electrolytes, O-SEOCs exploit oxygen ion-conducting
materials and different principles. In O-SOECs, O2− ions are transported from the hydrogen
electrode to the air electrode, while steam is fed to the hydrogen electrode. Thus, an
additional drying process is needed for the hydrogen produced in O-SOECs [119].
Energies
Energies2023,
2023,16,
16,3327
3327 1515ofof51
50

Figure 7. An illustration of different types of SOEC, including (a) O-SOEC, (b) H-SOEC, and
Figure 7. An illustration of different types of SOEC, including (a) O-SOEC, (b) H-SOEC, and (c)
(c) hybrid-SOEC [110] (Reproduced with permission from [110], Elsevier: 2018).
hybrid-SOEC [110] (Reproduced with permission from [110], Elsevier: 2018).
Due to interlayer diffusion, inferior long-term stability, and problems with materi-
Due to interlayer diffusion,
als selection/fabrication, inferior long-termofstability,
the commercialisation O-SOECand hasproblems
faced criticalwithchallenges.
materials
selection/fabrication, the commercialisation of O-SOEC has
Thus, due to the lower costs of materials, intermediate to low operating temperatures, faced critical challenges. Thus,
due to the lower costs of materials, intermediate to low operating
higher purity of hydrogen, fewer auxiliary components (such as sealant and interconnect), temperatures, higher
purity
lower of hydrogen,
activation fewer auxiliary
energy, easier gascomponents
separation, (such as sealant and
etc., H-SOECs haveinterconnect),
received particularlower
activation energy,
interest [124]. easier gaswater
In H-SOECs, separation,
or steam etc.,undergoes
H-SOECsan have received
oxidation particular
reaction at theinterest
anode
[124]. In H-SOECs, − water or
+ steam undergoes an oxidation
side to produce e and H . Hydrogen is produced at the cathode side by proton migration reaction at the anode side to
produce
across the e− proton-conducting
and H+. Hydrogenelectrolyte is produced and atthe
therecombination
cathode side by withproton migration
electrons [105]. across
Unlike
the proton-conducting electrolyte and the recombination
O-SEOCs, hydrogen produced in H-SOECs (Figure 7b) does not need any additional with electrons [105]. Unlike O-
drying
SEOCs, hydrogen produced in H-SOECs (Figure 7b) does not
process, and pure hydrogen can be achieved at the end of the process, which can reduce need any additional drying
process,
operationalandcosts
pure[125].hydrogen canO-
In both beandachieved
H-SOEC, at the
the end
oxygenof the process,
electrode whichbecan
should reduce
composed
operational
of a porouscostsmaterial [125]. toIn both O-
enable gasand H-SOEC,
diffusion andthe oxygen
provide electrode
enough should
active sites.beIncomposed
H-SOECs,
of a porous
the oxidation material
rate oftowater/steam
enable gas diffusion
should be and provide
higher thanenough
the rate active sites. In H-SOECs,
of hydrogen evolution.
the oxidation rate of +
water/steam should be higher than the
Otherwise, the high rate of H recombination and hydrogen generation results in the disso- rate of hydrogen evolution.
Otherwise,
lution of Hthe + inhigh rate of Hconductor
the protonic + recombination and hydrogen generation results in the dis-
and the formation of holes in the system [126]. Due
solution of Hactivation
to the lower + in the protonic
energyconductor
and higherand ion the formation the
conductivity, of holes
operatingin the system [126].
temperatures of
Due to theare
H-SOECs lower lower activation
than their energy and higher
counterpart (~400–700 ◦ C). The lower
ion conductivity, the operating
operating tempera-
temperature
tures
reducesof H-SOECs
capital costs areandlower than their
facilitates counterpart
searching (~400–700
for suitable sealing °C).and The lower operating
interconnect materi-
temperature reduces
als [127]. Another capital costs
advantage and facilitates
of H-SOECs over thesearching
O-SOECs for is
suitable sealing and
their superior inter-
durability
connect materials
due to their lower[127].materialAnother advantage
degradation (suchof asH-SOECs over the
Cr poisoning, airO-SOECs
electrodeisdelamination
their supe-
rior durability due
at high-current to their lower
densities, materialindegradation
Ni oxidation high humidity (such as Cr poisoning,
environments, etc.)air
byelectrode
contami-
nation or corrosion
delamination owing todensities,
at high-current their lower Ni operating
oxidation in temperature
high humidity [119,128,129].
environments, However,
etc.)
H-SOECs
by suffer from
contamination their largeowing
or corrosion polarisation
to theirresistance. Anothertemperature
lower operating issue regarding the further
[119,128,129].
development
However, H-SOECs of H-SOECs is thetheir
suffer from electrolyte material. Yttrium-doped
large polarisation resistance. Another barium issue zirconates
regard-
(BZY)
ing the are the predominant
further development electrolyte
of H-SOECs materials with relatively
is the electrolyte material.high refractorinessbar-
Yttrium-doped and
poor sinterability, i.e., the development of novel materials
ium zirconates (BZY) are the predominant electrolyte materials with relatively high re- with high proton conductivity
and better sinterability
fractoriness is of paramount
and poor sinterability, importance.
i.e., the development Although
of novel Cematerials
addition withinto thehighcrystal
pro-
structure of BZYand facilitates the processability of BZY, itimportance.
may also result in CeCe 4+ to C3+
ton conductivity better sinterability is of paramount Although addi-
reduction
tion into theand parasitic
crystal electronic
structure of BZY conduction
facilitates [105,119,130].
the processability of BZY, it may also result
in Ce4+Water
to C3+electrolysis
reduction and happens
parasiticin one electrode
electronic of O-SOECs
conduction or H-SOECs because only
[105,119,130].
one Water
ionic species
electrolysis happens in one electrode of O-SOECs orHybrid
can permeate across the electrolyte [105,119]. H-SOECs SOEC (Figure
because 7c)
only
exploits the counter diffusion of both ion species across the MIEC
one ionic species can permeate across the electrolyte [105,119]. Hybrid SOEC (Figure 7c) electrolyte in the opposite
direction,the
exploits i.e.,counter
simultaneousdiffusionmigration
of bothof ionbothspecies
species across
across thethe mixed
MIECionic electrolyte
electrolyte can
in the
 Energies 2023, 16, 3327 16 of 51

Energies 2023, 16, 3327 16 of 50

opposite direction, i.e., simultaneous migration of both species across the mixed ionic elec-
trolyte can take place on both electrodes in hybrid SOECs, leading to higher hydrogen and
oxygen
take production
place than the other
on both electrodes two types.
in hybrid SOECs, In hybrid
leading SOEC, a mixed
to higher ionic electrolyte
hydrogen and oxygen is
used, whichthan
production enablesthewater
otherelectrolysis
two types. atInboth hybridelectrodes
SOEC,as both O2−ionic
a mixed and electrolyte
H+ ions can iscoun-
used,
ter-diffuse
which in the
enables system,
water thereby at
electrolysis morebothhydrogen
electrodes can
asbe O2− and
produced
both thanH+O-SOEC
ions canand H-
counter-
SEOC [110].
diffuse in theIn system,
this context, Kim more
thereby et al. [110]
hydrogenfabricatedcan an
be electrode-supported
produced than O-SOEC SOECand com-H-
posed [110].
SEOC of a BaZrIn 0.1 Ce0.7
this Y0.1Yb0.1O
context, 3−δ (BZCYYb)
Kim et al. [110]electrolyte
fabricatedwith mixed protonic (H+) SOEC
an electrode-supported and
ionic (O2−) of
composed conductivity,
a BaZr0.1 Ce0.7 NdBa 0.5Sr
Y0.1 Yb O
0.5 Co
0.1 3−δ 1.5 Fe O
(BZCYYb)
0.5 5+δ(NBSCF)-BZCYYb
electrolyte with composite
mixed air
protonic (H+ )
elec-
trode,
and and(O
ionic 2− ) conductivity,
Ni-BZCYYb composite
NdBahydrogen electrode.
Fe0.5 O5+δIt(NBSCF)-BZCYYb
should be noted that NBSCF-air
0.5 Sr0.5 Co1.5 composite
layered perovskite
electrode, and Ni-BZCYYbhas electronic,
compositeionic, and protonic
hydrogen conductivity,
electrode. It shouldresulting
be notedin boosting
that NBSCF-
electrochemical
layered perovskite activity by increasing
has electronic, ionic, theand electrochemically active sites
protonic conductivity, [131].in
resulting Nickel is
boosting
also known as an
electrochemical excellent
activity electrocatalytic
by increasing material for water
the electrochemically activesplitting and Nickel
sites [131]. can further
is also
improveashydrogen
known an excellent evolution in hybridmaterial
electrocatalytic SOECs [113]. The splitting
for water SOEC showedand can negligible degra-
further improve
dation after
hydrogen 60 h of testing
evolution in hybridwith much[113].
SOECs lowerThe overpotential
SOEC showed as well as higher
negligible electrochem-
degradation after
icalh performance
60 of testing withand much hydrogen evolution (1.9
lower overpotential as L.h at higher
well−1 as a cell voltage at 700 °C)
of 1.5 Vperformance
electrochemical
thanhydrogen
and PEM electrolysis
evolution and(1.9 L.h−1 at
acidified water
a cellelectrolysis.
voltage of 1.5 A 50 at 700 ◦−2
V mA.cm C)current waselectrolysis
than PEM achieved
by only
and 9 mV overpotential,
acidified water electrolysis.which wasA 50much mA.cm − 2
lower current
than those wasreported
achieved for by
acidified
only 9wa- mV
ter electrolysiswhich
overpotential, systems waswith Pt, lower
much CoP, MoP|S,
than those etc. reported
catalysts for
[132,133].
acidified They claimed
water that
electrolysis
this hybrid
systems withSOEC
Pt, CoP,is a MoP|S,
highly efficient and cost-effective
etc. catalysts [132,133]. They hydrogen
claimedproduction system.
that this hybrid A
SOEC
comparison
is between
a highly efficient andlow- and high-temperature
cost-effective hydrogen production water electrolysis
system. A is comparison
provided in between
Figure
8 [126].
low- and high-temperature water electrolysis is provided in Figure 8 [126].

Figure 8. Typical features of the leading electrolysis processes [126].

Figure 8. Typical features of the leading electrolysis processes [126].

Water is the most abundant feedstock for hydrogen production as a sustainable re-
source. As the most common water-splitting technology, water electrolysis is currently
under development to further progress in order to compete with fossil fuel-based platforms
Energies 2023, 16, 3327 17 of 50

for hydrogen production. PEM electrolysis offers excellent potential for green hydro-
gen production for local use, particularly when highly purified water and renewable
power are abundantly supplied at a low cost. Polyimides, polyethene, and polyether
ketone are the most promising candidates for PEM electrolysis. The purity of the product
gas and current densities in alkaline electrolysis is relatively low. SOEC needs a large
system design and suffers from low durability. However, SOEC showed significant po-
tential for hydrogen production, especially if the costs of electrolyser and durability are
addressed carefully. Compared to low-temperature water electrolysis, high-temperature
water electrolysis requires 35% lower energy due to harnessing the vaporisation heat. As
reported in the literature, a small portion of the energy is used as heat. For example, it has
been reported that a total energy of about 90 kJ.mol−1 is needed for an HTE working at
950 ◦ C, from which 60 kJ.mol−1 is required for decomposing steam at around 200 ◦ C and
30–40 kJ.mol−1 for the electrolyser itself [134]. O-SOECs are far more developed than
H-SOECs due to the instability of the electrode and electrolyte in the water-containing
environment and the fabrication challenges of H-SOEC layers. On the other hand, the
degradation of the electrodes’ performance, poor sealing, and high thermal stress of O-
SOEC have inhibited its commercialisation. Therefore, H-SOEC has attracted more interest
than O-SOEC because of easier gas transportation, lower activation energy, and relatively
lower operating temperature. The lower temperature of H-SOEC, which is mainly due to
the lower activation energy for H+ transport, reduces the capital hydrogen production costs,
mitigates thermal stresses, nickel coarsening/agglomeration, creep of metallic components
of the stack, and Cr poisoning. Compared to O-SOEC, in which hydrogen is needed to
be extracted from the steam cycle, H-SOEC produces hydrogen directly from the steam
cycle. Although hydrogen purity and operating temperature are the main advantages of
H-SOECs over O-SOECs, low Faradaic efficiency owing to the electronic leakage over the
electrolyte is the main barrier that should be addressed.
Like SOFCs, SOECs have four geometries, including anode-supported, cathode-
supported, electrolyte-supported, and metal-supported geometries. The support layer
is the thickest component of the SOEC/SOFC and mechanically supports the structure.
For example, in the case of cathode-supported oxide cells, the thickness of the electrolyte
and anode is lower than the cathode. In order to compare the impedance of each layer,
area-specific resistance (ASR) is defined as ASR = Rp × A = ρ × l , where Rp , A, l, and ρ
are polarisation resistance (Ω), effective area (m2 ), thickness (m), and specific resistance
of the material (Ω.m), respectively. This relationship implies that ASR greatly depends
on the thickness and ohmic losses [135,136]. Thus, reducing ASR depends on lowering
the ohmic losses and thickness. A typical illustration of a metal-supported cell with some
candidate materials for each layer and reported TEC is shown in Figure 9. In this figure,
LSM, LNF, LSCF, SSC, LSC, GDC, YSZ, SCSZ, and LSGM stand for lanthanum strontium
manganite, lanthanum nickel ferrite, lanthanum strontium cobalt ferrite, strontium samar-
ium cobaltite, lanthanum strontium cobaltite, gadolinium-doped ceria, yttria-stabilised
zirconia, scandia-ceria-stabilised zirconia, and lanthanum strontium gallium magnesium
oxide, respectively.
 18 of 51
Energies 2023, 16, 3327 18 of 50

Figure 9. Schematic Figure

of a metal-supported cell [137]. cell [137].
9. Schematic of a metal-supported

Electrolyte-supported cells are classified as the first generation of solid oxide cells.
Electrolyte-supported cells are classified as the first generation of solid oxide cells. In
In the case of electrolyte-supported SOECs for steam electrolysis, Schefold et al. [138]
the case of electrolyte-supported
carried out a 23,000SOECs h test of for steam electrolysis, Schefold
an LSCF//6Sc1CeSZ//Ni-GDC cell and etreported
al. [138] carried
that the
− 1 at − −
A.cm 2 and
out a 23,000 h test voltage
of an LSCF//6Sc1CeSZ//Ni-GDC
degradation and increased ASR were cellabout
and7.4reported
mV.1000 hthat the0.9 voltage deg-
8 mΩ.cm2 .1000 h−1 , respectively. The final voltage of the cell was about 1.33 V at 851 ◦C
radation and increased ASR were about 7.4 mV.1000 h−1 at −0.9 A.cm−2 and 8 mΩ.cm2.1000
with a steam conversion of 51%. However, delamination of the oxygen electrode (~10%)
h−1, respectively. The finaldegradation
and ohmic voltage of werethe cell
also was after
observed about 1.33 V the
dismantling at cell. °C with
851Bernadet a [118]
et al. steam
conversion of 51%. However, delamination of the oxygen electrode (~10%) 2and
reported a high-performance symmetric cell of a SOEC comprised of Sr Fe 1.5 ohmic
Mo O
0.5 6− deg-
δ
(SFM) electrodes, a YbScSZ electrolyte, and two GDC barrier layers between the electrodes
radation were also observed after dismantling the cell. Bernadet et al. [118] reported a
and electrolyte. The current density in SOEC and co-SOEC (H2 O and CO2 ) modes was
high-performanceabout symmetric
1.4 and 1.1cell
A.cm of−2aatSOEC
1.3 V andcomprised of Sr2Fe
900 ◦ C, respectively. The1.5Mo 0.5O6−δ (SFM)
reversibility elec-
of this cell,
trodes, a YbScSZ electrolyte, and twoby
which was corroborated GDC barrier
exchanging gaslayers
between between
the cathodetheand electrodes and elec-
anode, represented
a new self-healing strategy for the continuous operation of the cell with minor degra-
trolyte. The current density in SOEC and co-SOEC (H2O and CO2) modes was about 1.4
dation. Yang et al. [139] developed a nanosized Co-Fe alloy (CFA) that incorporated a
and 1.1 A.cm−2 at 1.3Pr0.4V and
Sr0.6 Co0.2900 °C,0.1respectively.
Fe0.7 Nb O3−δ (P-PSCFN)The reversibility
hydrogen electrode, aof thiselectrolyte,
LSGM cell, which and was
a
corroborated by exchanging
Ba 0.9 Co 0.7 0.2gas
Fe Nb 0.1between
O 3−δ (BCFN)the cathode and anode, represented a new self-
oxygen electrode. The hydrogen production rate of this
electrolyte-supported SOEC was about 707 mL.cm−2 .h−1 at 900 ◦ C and 1.3 V, implying that
healing strategy for the continuous operation of the cell with minor degradation. Yang et
K-PSCFN-CFA may be a promising hydrogen electrode for high-temperature SOEC.
al. [139] developed a nanosized
Although Co-Fe
the thick electrolyte layer alloy (CFA) thatcellsincorporated
in electrolyte-supported can pose higher a
Pr0.4Sr0.6Co0.2Fe0.7Nb 0.1O3−δ (P-PSCFN)
robustness and better sealing,hydrogen
the lower electrode, a LSGM
thickness of electrolyte electrolyte,
in electrode- and a
and metal-
supported geometries resulted in lowered ohmic polarisation, reduced operating tem-
Ba0.9Co0.7Fe0.2Nb0.1O3−δ (BCFN) oxygen electrode. The hydrogen production rate of this
perature, improved cell performance, and boosted cell durability [140,141]. Among the
electrolyte-supported SOEC was about
electrode-supported cells, the707 mL.cm−2.h−1geometry
anode-supported at 900 has°Cattracted
and 1.3much V, implying
more interest. that
K-PSCFN-CFA may be a promising
Different anode materials, hydrogen
including electrode for high-temperature
oxide perovskites, double perovskites, spinels, SOEC.and
Ruddlesden-Popper materials, can be used as anodes in
Although the thick electrolyte layer in electrolyte-supported cells can pose higher SOEC/SOFC applications. The
infiltration of OER active species, combining the anode material with an ionic conductor,
robustness and better sealing, the
and microstructure lower thickness
optimisation can improve ofanode
electrolyte
performancein electrode-
[142]. As the ohmicand metal-
over-
supported geometries resulted
potential in lowered
dominates the overall ohmic polarisation,
performance reduced operating
of the anode-supported cells, increasingtemper-
the
ature, improved cell performance, and boosted cell durability [140,141]. Among the elec-
trode-supported cells, the anode-supported geometry has attracted much more interest.
Different anode materials, including oxide perovskites, double perovskites, spinels, and
Ruddlesden-Popper materials, can be used as anodes in SOEC/SOFC applications. The
Energies 2023, 16, 3327 19 of 50

anode thickness increases ionic transport resistance; however, reducing the thickness of the
anode layer may improve the overall performance [143]. Gondolini et al. [144] fabricated
a planar anode-supported SOEC comprised of a porous LSM/GDC anode, a dense GDC
electrolyte, and a porous NiO-GDC cathode using a single-step thermal treatment route.
This method enabled the use of lower sintering temperatures and the production of an
electrodic substrate with finer microstructure and more than 40% porosity. It should also
be noted that no pore former was used during the preparation of the layers using this
single-step method.
Several researchers have investigated the performance of cathode-supported SOECs,
such as Nechache et al. [145], who investigated the degradation behaviour of a commercial
LSCF//YSZ//Ni-YSZ cathode-supported SOEC for high-temperature water electrolysis
using electrochemical impedance spectroscopy (EIS) analysis combined with chronopoten-
tiometry. They also conducted another study investigating the premature degradation of an
LSCF//YSZ//Ni-YSZ cathode-supported SOEC with yttria doped ceria (YDC) as an inter-
mediate layer and concluded that impurity has a strong effect on hydrogen electrode and
cell functioning [146]. Hjalmarsson et al. [147] worked on an LSC-CGO//YSZ//Ni-YSZ
cathode-supported SOEC with CGO as the intermediate layer. The long-term durability of
the cell was examined at −1 A.cm−2 for 2700 h in a co-electrolysis (H2 O and CO2 mixture)
condition. The results showed that the initial ASR of the cell was about 0.2 Ω.cm2 at 800 ◦ C.
The first 350 h of the test was accompanied by a rapid degradation rate but slowed down to
about 5–10 mΩ.cm2 .khs−1 . They also reported partial reactivation of cell performance after
turning off the electrolysis current. The Ni-YSZ electrode was also partially reactivated after
the first rapid degradation during the first 350 h. Although cathode-supported cells have a
higher lifetime, it suffers from higher activation potential loss; however, their intercalat-
ing with electrolyte during sintering results in lower electrochemical performance [2,140].
Leonard et al. [148] reported a cathode-supported SOEC for hydrogen generation at inter-
mediate temperatures (550–600 ◦ C) comprised of Ba(Zr0.5 Ce0.4 )8/9 Y0.2 O2.9 (BZCY(54)8/9 2)
and SrZr0.5 Ce0.4 Y0.1 O2.95 (SZCY541) proton-conducting perovskites as electrolytes, NiO-
SrZr0.5 Ce0.4 Y0.1 O3−δ composite cathode, and Ba0.5 La0.5 CoO3 as anode material. The results
showed that SZCY541 offered a higher performance due to its higher driving force for the
cathode, showing the effect of the cathode material on the densification of the electrolyte
and overall cell performance. Chelmehsara and Mahmoudimehr [149] conducted a techno-
economic evaluation of cathode-, anode-, and electrolyte-supported cells and reported that
the performance of each cell is inversely proportional to the supporting thickness. The
results showed that cathode-supported and electrolyte-supported cells have the highest
power density and most uniform current density distribution among all geometries, respec-
tively. The best trade-off between the material cost of the PEN layer and maximum power
density was attributed to the anode-supported cell. However, their analysis did not en-
compass all of the economic considerations, such as the costs of operation, manufacturing,
maintenance, fuel, and the system’s lifespan and interest rate.
It has been reported that electrolyte-supported, anode-supported, and metal-supported
oxide cells are considered the first, second, and third generations of oxide cells, respec-
tively [137]. Decreasing the thickness of the electrolyte led to the development of other
geometries, especially the metal-supported oxide cells, which enabled the lowering of the
operating temperature of the oxide cells [2]. The thermal expansion coefficient mismatch
between the layers is the main source of cell degradation. The low thermal conductivity
of ceramics can lead to an uneven distribution in temperature to the extent that the ther-
mal gradient can even reach 200 ◦ C in a plane-type stack. Therefore, metal supports can
help increase thermal conductivity and mitigate thermal stress induced in the cell [2,137].
Metal-supported cells (MSC) offer higher mechanical robustness, higher thermomechanical
stability in rapid thermal and redox cycling, fast start-up capability, reduced costs, high
power densities, high thermal conductivity, etc., compared to the other geometries. How-
ever, chromium poisoning, the support of metal oxidation at elevated temperatures, thermal
expansion mismatch, etc., are major challenges yet to be solved [2,137,150]. Tucker [151]
Energies 2023, 16, 3327 20 of 50

comprehensively studied different aspects of metal-supported SOECs and pinpointed the

critical challenges regarding their large-scale manufacturing. According to the literature,
metal-supported cells are far behind the anode-supported ones and other geometries. These
challenges include performance, costs, durability, etc. One of the most important degra-
dation mechanisms in MS-SOECs is the oxidation of the metal supports in high-steam
atmospheres or oxygen atmospheres. In the case of stainless steel, which is the most com-
monly used support metal, the oxidation product is a Cr-based compound with electronic
conductivity. However, when this conductive scale grows, it may increase electronic resis-
tance and total ASR. Spallation is another challenge that may take place if the thickness
of this scale exceeds a few microns, resulting in increased oxidation rates, breaking the
electronic pathway, and, eventually, mechanical failure of the stainless steel. Other support
metals, such as NiMo, NiFe, etc., do not form a protective layer, but they can be in a
stable condition if a proper system design is chosen. A brief comparison of the different
geometries of solid oxide cells is provided in Table 3.

Table 3. Main benefits and drawbacks of common solid oxide cell geometries [2].

Cell Geometry Strength Weakness

Anode-supported • Highly conductive anode • Re-oxidation

• Low operating temperature • Gas transportation

• Higher resistance
Electrolyte-supported • Strong backbone
• Requires higher operating temperature
• Uniform current density
for diminishing ohmic losses

Cathode-supported • Low operating temperature • Low conductivity

• No oxidation • Gas transportation issues

• Oxidation at high temperatures

• Excellent structural robustness
• Moderate the cell
• High tolerance toward rapid
Metal-supported electrochemical performance
thermal cycling
• Thermal expansion mismatch between
• Excellent electrical and
individual cell parts
thermal conductivity
• High cost of fabrication

Lifetime (measured in hours), stack efficiency (%), ASR (measured in Ω.cm2 ), degrada-
tion rate (measured in %V.1000 h−1 ), and stack costs (measured in USD.kW−1 or USD per
stack) are the main parameters for evaluating the SOEC stacks [152]. Another important
factor is the current efficiency of electrolysis, which is closely related to the electron trans-
port number (te ) and ion transport number (ti ) of the electrolyte. These transport numbers
can be calculated according to the following equations (assuming steam-partial pressure is
on both electrode sides) [153]:  0 
RT P o2
E = ti ln 00 (14)
4F P o2

E
ti = (15)
E0
ti + te = 1 (16)
where E, E0 , R, T, F, P 0 O2 , and P 00 O 2 are the actual open circuit voltage (OCV) of the
oxygen concentration cell, theoretical OCV of the oxygen concentration cell, universal gas
constant, absolute temperature (K), Faraday constant, oxygen partial pressure of the air
electrode, and oxygen partial pressure of the fuel electrode, respectively. Higher current
efficiency results in higher SOEC performance. It has been reported that the current
efficiency of hydrogen evolution in proton conductors is in the range of 50–95% [153].
Energies 2023, 16, 3327 21 of 50

In order to improve hydrogen yields, the surface area (the interface between the cell
and the interconnector) should be increased. As it is not easy to increase the area of a single
cell, a number of SOECs should be connected to each other in parallel or series and build a
stack of SOECs [154,155]. SOEC stacks can be either in planar or tubular configurations. The
mechanical strength of the tubular configuration is higher than that of its planar counterpart.
Despite the facilitated sealing and higher mechanical strength of tubular SOECs, planar
SOECs have attracted considerable interest, mainly because of better manufacturability
and easier mass production [155,156]. Conventional SOEC stacks are cylindrical in which
steam passes through the inside of the tube and produces hydrogen gas and O2− ions.
Oxygen gas is extracted from the outer layer of the tube [157]. It has been reported that
the performance of planar SOECs is remarkably higher than that of tubular ones due to
the uniform distribution of gas species. In other words, while the tubular design offers
easier sealing and higher thermal cycling stability, the planar design offers higher power
densities, higher volumetric power density, lower manufacturing costs, etc. [156,158]. As
SOEC operates in the opposite direction of SOFCs, the same configurations of SOFCs, such
as integrated planar (IP) [159], cone-shaped, flat-tube, honeycomb, etc., may be used for
SOECs, as well [2].
Different criteria should be considered for evaluating the performance of SOECs. The
first and foremost parameter is Faraday efficiency which can be defined as follows:
νmeas νmeas
η= × 100 = × 100(%) (17)
νtheo I × (Z × F ) −1

where νmeas , νtheo , I, z, and F are the calculated hydrogen evolution rate, theoretical
hydrogen evolution rate, applied current, electron transport number of steam electrolysis,
and Faraday’s constant (96,485 C.mol−1 ) [160]. An important factor that has a strong
effect on the overall performance and stack lifetime capacity (SLC) is stack electrical power
consumption (EPC). EPC, which is usually expressed as kWh electricity power Nm3 of
product, is defined as follows:
EPC = U i ncells/V (18)
where U, i, ncells , and V are average cell voltage, stack current, number of cells in a stack,
and volumetric production rate (Nm3 .h−1 ), respectively. It should be noted that external
power sources such as a furnace or heater are excluded from EPC. Higher EPC values mean
a higher SOEC stack performance [152]. In addition to the Faradaic efficiency, another
important parameter in evaluating stack performance is called energetic efficiency, which
is defined as:
E0 ε k, faradaic
εenergetic = ∑ k 0 (19)
k Ek + η

where E0k , ε k , faradaic , and η are the equilibrium cell potential for product k, Faradaic effi-
ciency of the product, and cell overpotential, respectively [161]. E0 is directly proportionate
to the standard Gibbs free energy of the reaction; for example, in the case of CO2 electrolysis,
its value is about 1.33 and 1.00 V at 25 and 750 ◦ C, respectively. Generally, a higher value of
energetic efficiency close to 1 corresponds to better performance. Increasing the production
rate (higher current densities) can improve stack lifetime capacity (SLC) but also increases
its degradation rate. Thus, an optimised value should be chosen in order to obtain the
highest SLC without negatively affecting the robustness of the stack. Another possible
solution is to improve the performance of each individual layer and optimise system
design/configuration [152]. Lang et al. [159] carried out an assessment of the long-term
behaviour of a SOEC stack comprised of 30 cells operating for 3370 h under SOEC mode
followed by 2500 h in reversible electrolysis/fuel cell mode at about 820 ◦ C. The overall
efficiency of the stack was calculated according to the following equation:
Energies 2023, 16, 3327 22 of 50

fi,out
∑ni=1 LHVi · Vi,m ×60 s
ηel,LHV = (20)
Pel

Energies 2023, 16, 3327 where LHVi , fi,out , Vi,m , and Pel are lower heating values, volume flow of produced 22 fuel
of 51
gas component i, the molar volume of reactant component i, and consumed electrolysis
power. According to the results (Figure 10), a low degradation of 5% per 1000 h was
recorded during the first 3370 h of operation, indicating high efficiency, high gas tightness,
and desirable performance. During the 2500-h operation, higher degradation rates were
and desirable performance. During the 2500-h operation, higher degradation rates were
observed because
observed because of
of increasing
increasing stack
stack temperature
temperature owing
owing to
to aa slight
slight decrease
decrease in
in stack
stack gas
gas
tightness. According to the results, they concluded that purifying the input
tightness. According to the results, they concluded that purifying the input water and water and op-
timising the
optimising operating
the operating conditions
conditionsofofthe
thereversible
reversiblemode
modecancanmitigate
mitigatestack
stackdegradation.
degradation.

(a)Long-term
Long-termbehaviour
behaviourof of ◦ C and
Figure
Figure 10.
10. (a) thethe stack
stack after
after operating
operating for for
35703570
h ath820at 820
°C and −520
− −2; (b) −
520 mA.cm
mA.cm
2 ; (b) Long-term behaviour of the stack after operating for 2500 h at 750 ◦ C and
Long-term behaviour of the stack after operating for 2500 h at 750 °C and 810 °C in
810 ◦ C and
SOFC in SOFC
SOEC and SOECrespectively;
modes, modes, respectively; (c) EIS in
(c) EIS results results
SOEC inmode
SOECat mode at 820
820 °C ◦ COCV
near near of
OCV of
about
−15.6 mA.cm
about −2
−15.6 mA.cm − 2
; (d) EIS; results
(d) EIS in SOFC
results inmode
SOFCatmode750 °C
at 750 ◦
near COCVnearofOCV
aboutof −15.6
aboutmA.cm
−15.6 −2 −2;
; (e) Deg-
mA.cm
radation
(e) of the stacks
Degradation of theafter
stacks3750 h in3750
after SOEC and
h in 2500and
SOEC h in 2500
SOFC/SOEC mode (fuelmode
h in SOFC/SOEC gas in(fuel
SOEC: gas80%
in
H2O + 80%
SOEC: 9% HH2 +11%O + N2 H
9% and+11%
air fuel
N gas
andinair
SOFC:
fuel 40%inHSOFC:
gas 2 + 60% N2) [159].
40% H + 60% N ) [159].
2 2 2 2 2

Skafte et al. [162] employed an AC voltage on top of the DC voltage to keep the tem-
perature profile flat across the cell, reducing thermal stress and cell overpotential. Another
advantage of using AC/DC voltage is to improve cell tolerance against impurities owing
to the inhibition of the nucleation of the impurities such as silica or carbon at the TPBs.
They also observed no nickel agglomeration or migration, probably due to the low elec-
trode overpotential and its degradation rates. A novel opposite trapezoidal flow channel
Energies 2023, 16, 3327 23 of 50

Skafte et al. [162] employed an AC voltage on top of the DC voltage to keep the
temperature profile flat across the cell, reducing thermal stress and cell overpotential.
Another advantage of using AC/DC voltage is to improve cell tolerance against impurities
owing to the inhibition of the nucleation of the impurities such as silica or carbon at the TPBs.
They also observed no nickel agglomeration or migration, probably due to the low electrode
overpotential and its degradation rates. A novel opposite trapezoidal flow channel has
been proposed by Zhang et al. [163], considering the importance of channel shape for gas
transportation in SOEC stacks. The results derived from COMSOL Multiphysics analysis
showed that the electrolysis performance of the proposed channel design was much higher
than the conventional ones, including higher current density (2.5 times), higher water
vapour concentration (2 times), and higher product hydrogen concentration (2.5 times).
The proposed channel design offers higher water vapour diffusivity, significantly higher
electrolysis efficiency, higher current densities, enhanced mass transfer between the adjacent
channels, more uniform distribution of the reactants, and economical and tractable in the
fabrication process.
An important aspect of using SOECs for hydrogen generation is the fabrication tech-
niques used in preparing each cell or co-sintering the components. Minary-Jolandan [164]
studied different manufacturing techniques and reported that additive manufacturing (AM)
is a promising technique for SOEC manufacturing with lower costs. The advantages and
disadvantages of two main AM processes, including injecting printing and lithography-
based processes (stereolithography (SL) and digital light processing (DLP)), were discussed.
Reducing delamination, improving durability, facilitating co-sintering, low capital costs,
and high-volume production, as well as enabling lower working temperature, morphology
control, and manufacturing complex geometries, are some of the main opportunities that
can be addressed by AM techniques.
An effective way to improve the electrochemical performance of SOECs is by increas-
ing the operating pressure. The pressurised operation has been studied for oxygen-ion
and proton-conducting SOECs, especially the former. Increasing the operating pressure
may offer lower ASR, lower power consumption, lower overall operational costs, sim-
plified plant design, reduced leakage, etc.; however, increasing pressure is shown to be
more advantageous in CO2 electrolysis than pure steam electrolysis [165]. As shown by
Riedel et al. [166], increasing the operating temperature does not significantly affect the
ASR of the electrolyte-supported cells because the ohmic resistance is independent of
the operating pressure. On the other hand, increasing operating pressure improves the
performance of cathode-supported cells (Figure 11) due to a higher frequency of reactants
at the triple phase boundaries (in the case of steam electrolysis). For example, increasing
the operating pressure from 2.1 to 12.6 bar decreased ohmic and polarisation resistances by
33% and 60%, respectively, along with improving the Faradaic efficiency to 100% (at 5 bar
and 15% steam concentration), improving performance by 60%, etc. [130].
In proton-conducting materials, oxygen and hydrogen compete for absorption into
the oxygen vacancies and the surface during water electrolysis. The following reactions
take place during water electrolysis:

H2 O( g) + OxO + V̈O  2OḢO (Hydration reaction) (21)

1
O2 ( g) + V̈O 2ḣ + OxO (Membrane parasitic oxidation) (22)
2
Thus, the following equation can be derived from the net reaction of the above
two reactions:
1
−1
[ḣ] = Kox · [OHO ] · PH 2O · PO4
2 2
(23)

According to this equation, [ḣ]. depends on the partial pressure of oxygen and steam.
Oxygen partial pressure increases with increasing system pressure, resulting in decreasing
electron-hole concentration in the electrolyte and improving the Faradaic efficiency. Higher
 fied plant design, reduced leakage, etc.; however, increasing pressure is shown to be more
advantageous in CO2 electrolysis than pure steam electrolysis [165]. As shown by Riedel
et al. [166], increasing the operating temperature does not significantly affect the ASR of
the electrolyte-supported cells because the ohmic resistance is independent of the operat-
ing pressure. On the other hand, increasing operating pressure improves the performance
Energies 2023, 16, 3327 of cathode-supported cells (Figure 11) due to a higher frequency of reactants at the24tripleof 50
phase boundaries (in the case of steam electrolysis). For example, increasing the operating
pressure from 2.1 to 12.6 bar decreased ohmic and polarisation resistances by 33% and
60%, respectively,
operating pressurealong withimprove
may also improving the Faradaic
electrode activityefficiency
leading totohigher
100% (at 5 bar and
currents 15%
at lower
steam concentration),
voltages improving
and lower energy demand performance
for hydrogenby production
60%, etc. [130].
[130,165].

Figure 11.
Figure 11. Pressure
Pressuredependence of ASR
dependence for electrolyte-supported
of ASR and cathode-supported
for electrolyte-supported cell stacks
and cathode-supported cell
[166].
stacks [166].

Degradation of SOEC components (electrodes, electrolytes, and even degradation

caused by sealant) can decrease the overall electrochemical performance of the cell. Based
on the degradation origins, physical, chemical, and microstructure degradations are classi-
fied as “intrinsic degradation”, which means that the source of degradation is related to
the electrodes and electrolyte nature or their operating conditions. Intrinsic degradation
is known to be the major factor in decreasing the overall performance of SOECs. On the
contrary, poisoning and deposition of Cr, poisoning and deposition of boron from the glass
sealant on electrodes, carbon deposition and delamination, and deposition and accumula-
tion of contaminants (sulphur, alumina, and silica) on hydrogen electrodes are classified as
“extrinsic degradation”. Overall, electrode delamination and electrolyte deterioration are
the key factors in the performance degradation of SOECs [167–169]. An interesting study
was carried out by Léon et al. [170] on the effect of scaling up from a single to 30-cell stack
and 90-cell integrated stack module on the performance of electrolyte-supported SOEC
composed of a 3YSZ electrolyte, a Ni/GDC hydrogen electrode, a LSXF oxygen electrode,
and a GDC diffusion barrier layer. The electrochemical performance of the samples was
evaluated at 830 ◦ C under an atmosphere containing 90 vol% H2 O and 10 vol% H2 with an
operation time of 8756, 4224, and 2200 h for a single cell, a stack, and a module, respectively.
The degradation rate of the stack was about 10.5 mV.kh−1 (0.8% kh−1 at 1.3 V) in the
electrolysis mode, while the degradation rate of a single cell was about 5.5 mV.kh−1 .
As a consequence of the corrosive environment (which demands further progress in
materials development) and challenges with providing a suitable waste heat source, solid
oxide electrolysis cells have only been in small stack capacities below 10 kW compared to
6 MW and 2 MW for alkaline electrolysis and PEM electrolysis, respectively [88]. The main
issue inhibiting the commercialisation of SOECs is their insufficient long-term durability,
especially at above 0.5 A.cm−2 . Generally, degradation mechanisms can be divided into
five categories:
Energies 2023, 16, 3327 25 of 50

• Delamination
• Poisoning
• Microstructure coarsening during sintering
• Decomposition of electrodes
• Formation of an unwanted secondary phase due to the chemical reaction between the
components [137].
Delamination occurs due to the differences in the TEC of the materials. Decomposition
may take place during the co-sintering of SOEC components. In the case of using metal-
supported SOEC, reducing the atmosphere is beneficial, but the cathode material may be
decomposed in such environments. A high operating temperature may result in chemical
reactions between the electrolyte and the electrode and produce insulating oxide phases
(such as the formation of La2 Zr2 O7 pyrochlores as a product of the reaction between the YSZ
electrolyte and LaMnO3 -based cathodes) at the interface. This type of degradation can be
suppressed using a diffusion barrier layer or lowering the operating temperature [137,171].
Another critical factor that has a significant influence on improving cell durability is
homogeneous current and temperature distribution in the SOEC. The more inhomogeneous
current and temperature distribution throughout the cell, the larger its degradability rate.
Higher steam utilisation may benefit the system efficiency; however, it also increases cell
inhomogeneity and reduces its lifetime. Thus, the highest performance of a SOEC can be
achieved by considering a trade-off between cell efficiency and its inhomogeneity [172].
Thermal stress may have a critical impact on the performance of SOEC stacks, especially at
high operating temperatures. A numerical study on the thermal stresses induced by the
SOECs, caused by the TEC mismatch between the layers, at high operating temperatures
showed that the maximum stress is applied to the electrolyte layer. Increasing the TEC of
the electrolyte layer and water mole fraction can mitigate this thermal stress [173].
It has been reported that the efficiency of a typical SOEC (a 30 µm LSM-YSZ com-
posite oxygen electrode, a 10–15 µm Ni-YSZ hydrogen electrode, and a 10 µm YSZ dense
electrolyte) dropped from 96% to 75% after 420 h with a degradation rate of 0.952 V.kh−1
at 1 A.cm−2 [174]. In another attempt, cell resistance increased from 0.50 to 0.62 Ω after
300 h at 0.7 A.cm−2 (degradation rate = 0.28 V.kh−1 ) [175]. Graves et al. [174] proposed
a 1 h electrolysis mode followed by a 5 h fuel cell mode to eliminate the microstructural
damage and tackle the degradation mechanism, but it was found to not be suitable by Tong
et al. [176]. They suggest using MIEC materials to address this issue. The degradation
rate of the Ni-YSZ electrode showed drastic microstructural degradation at high current
densities, such as YSZ reduction to zirconia nanoparticles and Ni coarsening and migra-
tion [146,177,178]. Monaco et al. [179] analysed the long-term stability of solid oxide cells in
SOEC and SOFC modes using three different scenarios (8YSZ electrolyte, Ni-YSZ hydrogen
electrode, LSCF-GDC oxygen electrode, GDC barrier layer, and LSC current collector).
The results showed that the degradation rate in the electrolysis mode was higher than in
the fuel cell mode. The relation between the formation of insulating phases and material
destabilisation, as well as the possible evolution of the inter-diffusional layer (IDL), was
investigated using synchrotron-based µXRD/µXRF and SEM/EDX analyses. The results
revealed the formation of strontium zirconates and a Gd-rich IDL after sintering. The loss of
Zr4+ in the electrolyte at high temperatures simplified Gd inter-diffusion and reduced local
ionic conductivity. The increase in ohmic resistances in SOEC mode was attributed to this
reduction in ionic conductivity. Kim et al. [180] tailored the microstructure of SOEC oxygen
electrodes to improve their electrochemical performance and stability. They fabricated an
LSCF/GDC oxygen electrode with a graphite pore former (6%) to optimise the amount of
porosity in the system and analyse its long-term stability using a 1000 h chronopotentiome-
try test. The tailored microstructure improved SOEC performance at 800 ◦ C by as much
as 30%. Delamination at the interface of the electrolyte/air electrode was avoided using
the optimised microstructure. Another advantage of this microstructure was reducing the
diffusion of Sr from the oxygen electrode towards the electrolyte and GDC barrier as well as
Energies 2023, 16, 3327 26 of 50

reducing oxygen partial pressure build-up over the air electrode/barrier layer/electrolyte
due to the increase in TPB density, interface porosity, and larger active surface area.
Using an anode functional layer (AFL) may also improve electrolysis performance. In
this context, Toriumi et al. [160] improved the overall efficiency of an H-SOEC (comprised
of a thin film BZCY622 electrolyte, LSCF anode, and a porous cermet cathode) by mitigating
the ohmic resistance, improving anode polarisation resistance (ohmic and polarisation
resistances decreased from 0.81 and 0.95 Ω.cm−2 to 0.30 and 0.29 Ω.cm−2 , respectively),
and enhancing interfacial proton transfer over the electrolyte/anode interface. The Faradaic
efficiency of the La0.5 Sr0.5 CoO3−δ (LSC) anode functional nanolayer with a thickness of
about 40 nm was about 65% under a current density of 400 mA.cm−2 . This AFL generated
an electrolysis current of about 0.87 A.cm−2 at 600 ◦ C and 1.3 V, which is twice that of the cell
without this AFL. It has been reported that LSC shows relatively low proton conductivity
under ambient conditions, but it also improves the proton transfer at the TPBs [181]. It
has also been reported that a surface coating of nano-electrocatalysts can improve cell
durability [182]. Although perovskite materials have also shown promising candidates as
hydrogen electrode materials, their performance and hydrogen evolution reaction have not
reached those of Ni/YSZ electrodes [176]. Tong et al. [176] prepared a planar SOEC with
an LSC-Pr, Gd co-doped ceria (CGPO)-CGO oxygen electrode, a CGO-modified Ni/YSZ
hydrogen electrode, and YSZ electrolyte via chemical infiltration. They reported that the
CGO coating significantly reduced microstructural degradation by disconnecting the Ni
and YSZ and the TPBs and improving cell durability.
Zhou et al. [137] studied the degradation mechanisms of metal-supported SOECs
and provided some solutions to address them. Implementing deposition techniques, such
as pulsed laser deposition (PLD), atomic layer deposition (ALD), spark plasma sintering
(SPS), tape casting, etc., can help fabricate electrolytes with reduced thickness (<1–2 µm).
However, their long-term stability should be further investigated along with balancing the
size and thickness of the electrolyte. They pinpointed that the infiltrated anode can prevent
coarsening during the co-sintering of the layers. Coarsening of the cathode and anode
strongly affects the stability of SOECs. Ceramic metal composites (cermets) such as Ni/GDC
and Ni-SDC can further suppress nano Ni coarsening and improve infiltrated anodes’
stability. Using a diffusion barrier layer enables the use of ferritic stainless steels instead of
nickel supports and improves oxidation resistance. The SOEC working temperature can be
diminished to below 600 ◦ C using a thin-film electrolyte. Proton-conducting compounds
such as yttrium-doped barium zirconates (BaZr0.9 Y0.1 O3−δ or BZY), yttrium-doped barium
zirconate-cerate (BaCe1−y−x Zrx Yy O3−δ or BZCY), and yttrium-, cerium-, and yttrium-
and ytterbium-doped barium-zirconium-cerate (BaZr0.1 Ce0.7 Y0.2−x Ybx O3−δ or BZCYYb)
showed high resistance against Cr and P poisoning. Furthermore, coating the metal support
is an effective way to improve the lifetime and performance of SOECs as well as decrease
their degradation by preventing metal oxidation, but it also increases fabrication costs.
Although using metal supports increases the robustness and thermal conductivity of the
stack, the durability of the MS-SOECs should be further developed in terms of optimising
process design and developing novel materials with promoted properties.
Chen et al. [183] thoroughly investigated material degradation in SOEC components,
including oxygen electrodes (such as LSM- and LSCF-based ones), hydrogen electrodes, and
electrolytes, as well as some strategies to overcome their degradation. The main physical,
chemical, and microstructure degradation of the electrolyte, electrodes, and their interface
is listed in Table 4. As shown in this table, the most important phenomena in LSM and LSCF
are delamination and secondary phase formation. The major degradation phenomenon in
the YSZ electrolyte is void/pore formation at the interface of the electrode/electrolyte. The
Ni/YSZ hydrogen electrode is exposed to nickel agglomeration, and poisoning or undesired
element deposition (such as Cr, B, etc.) may also take place during SOEC operation. It is
interesting to note that degradation in LSM-based oxygen electrodes is more severe than
that of LSCF-based ones [169]. Wang et al. [184] also comprehensively studied the different
degradation mechanisms in SOECs and the relevant strategies to mitigate the problem.
Energies 2023, 16, 3327 27 of 50

They reported that cathode degradation is the dominant mechanism at lower current
densities (0.25 A.cm−2 ), while anode degradation is the primary degradation mechanism at
higher current densities (0.5 A.cm−2 ). The same degradation mechanisms were reported for
the LSM and LSCF oxygen electrodes, electrolytes, and hydrogen electrodes. Moçoteguy
et al. [185] listed a series of degradation mechanisms in SOECs and reported that secondary
phase formation and delamination and formation of intergranular/intragranular pores
are the major degradation mechanisms in electrodes and electrolytes, respectively. An
interesting study conducted by Wolf et al. [186] showed that the long-term stability of the
cell under co-electrolysis was higher than that of steam electrolysis. The degradation rate
of the co-electrolysis system (178 mV.kh−1 ) was much lower than that of steam electrolysis
(370 mV.kh−1 ) at 800 ◦ C.

Table 4. Material degradation in SOEC components [183] (Reproduced with permission from [183],
IOP: 2016).

Region Degradation Test Conditions

Physical, chemical, and microstructure change
LSM-YSZ: formation of small YSZ grains; YSZ:
1–2 A.cm−2 , 850 ◦ C, 50%H2 O/50%H2 ,
LSM-YSZ//YSZ intergranular fracture and hole/pore formation along
80–900 h
the grain boundaries of YSZ close to the air electrode.
LSM: delamination, disintegration of LSM particles at
LSM//YSZ 500 mA.cm−2 , 800 ◦ C, 48 h. 895 ◦ C
the interface; YSZ: grain boundary widening.
YSZ: void formation; no phase change; LSM-YSZ:
LSM-YSZ//YSZ 895 ◦ C up to 2.5 A.cm−2 , 70% H2 O
delamination but no cation diffusion.
LSM: delamination, disintegration of LSM particles at
LSM-YSZ//YSZ 500 mA.cm−2 , 800 ◦ C, 100 h
the interface; YSZ: surface roughening.
LSM-YSZ//YSZ LSM-YSZ: delamination. 0.5 A.cm−2 , 750 ◦ C, 640 h
LSM-YSZ//YSZ LSM-YSZ: La2 Zr2 O7 formation 1.5–1.7 V, 800–950 ◦ C
LSCF//YSZ Delamination 800 mA.cm−2 , 800 ◦ C, 50 h
LSCF: phase change from rhombohedral to cubic; GDC
LSCF/GDC//YSZ 800 mA.cm−2 , 800 ◦ C, 100 h
interlayer: pore formation
LSCF/GDC//YSZ LSCF: SrZrO3 formation within GDC layer As prepared
LSCF: SrZrO3 formation within GDC layer; YSZ: pore
LSCF/GDC//YSZ formation near the interface; GDC: Y and Zr diffusion 0.75–1.0 A.cm−2 , 780 ◦ C, 9000 h.
into GDC interlayer, forming a dense reaction layer.
LSCF/GDC//YSZ LSCF: reduction of Co4+ to Co3+ ; GDC: Sr enrichment. 0.8 A.cm−2 for 1000 h
LSCF-GDC/GDC//YSZ LSCF-GDC: no delamination. 0.5 A.cm−2 , 750 ◦ C, 640 h
LSC-GDC/GDC//YSZ LSC-GDC: delamination at air inlet. 0.5 A.cm−2 , 750 ◦ C, 640 h
Ni-YSZ: agglomeration of Ni particles, no change in
Ni-YSZ//YSZ 0.8 A.cm−2 , 800 ◦ C, 90%H2 O/10%H2 , 1000 h
YSZ phase.
Ni-YSZ//YSZ Ni-YSZ: 2–4 µm dense Ni/YSZ layer 2 A.cm−2 , 950 ◦ C, 90%H2 O
Ni-YSZ: Ni agglomeration and depletion at the
Ni-YSZ//YSZ 0.75–1.0 Acm−2 , 780 ◦ C, 80%H2 O, 9000 h.
interface; YSZ: pore formation at the interface
10Sc1CeSZ: presence of Ce3+ , phase change from cubic
//10Sc1CeSZ over 2 V.
to rhombohedral
Effect of Contaminants/Impurities
Ni-YSZ: formation of carbon nano-fibre in Ni-YSZ 2.25 A.cm−2 , 875 ◦ C,
Ni-YSZ (porosity: 25%)//YSZ
electrode close to YSZ; Delamination 45%H2 O/45%CO2 /10%H2 , 11 h
Ni-YSZ: No carbon deposition in Ni-YSZ electrode at 2.0 A.cm−2 , 875 ◦ C,
Ni-YSZ (porosity: 40%)//YSZ
the interface; No delamination 45%H2 O/45%CO2 /10%H2 , 677 h
Ni-infiltrated GDC//YSZ
Ni-YSZ: carbon deposition 0.1 A.cm−2 , 600 ◦ C, 5%CO/95%CO2 , 5 h
Ni-YSZ//YSZ:
Energies 2023, 16, 3327 28 of 50

Table 4. Cont.

Region Degradation Test Conditions

Ni-YSZ: SiO2 deposition at region close to 0.5 A.cm−2 , 850 ◦ C in 50%H2 O/50%H2 for
Ni-YSZ//YSZ: glass
YSZ electrolyte. 1316 h
LSM: Cr deposition and SrCrO4 formation at the
LSM//YSZ: Fe-Cr alloy 0.2–0.5 A.cm−2 , 800 ◦ C, air
interface and in the electrode bulk.
LSCF: Cr deposition mainly on the outmost surface of
LSCF//GDC: Fe-Cr alloy 0.2 A.cm−2 , 800–900 ◦ C, air
the electrodes in the form of SrCrO4 , CrO2.5 , and Cr2 O3
LSC contact layer: Cr deposition mainly on the LSC
LSC 2000 h.
contact layer.
LSM: accelerated Sr segregation and boron deposition
LSM//YSZ: glass 0.2 A.cm−2 , 800 ◦ C, air
at the interface, forming lanthanum borates

High current densities and low operating temperatures increase electrode overpoten-
tial by more than 0.2 V, resulting in SOEC failure. The main reason seems to be fracture at
the interface of electrode-electrolyte owing to the low fracture toughness of the electrode
and high effective O2 partial pressure. Different polarisation resistance of electrode materi-
als under different operating conditions may also lead to the failure of the electrode [187].
It has been reported that lowering the operating temperature can increase short-term degra-
dation rates, mainly owing to the increased ohmic resistance. This short-term degradation
is not always irreversible and can be mitigated if detected at the early stages of the opera-
tion [188]. However, it is known that decreasing the operating temperature has a negative
and irreversible effect on the SOEC performance owing to the increased ohmic resistance
and activation over-voltages [189]. Impurities can significantly accelerate cell degradation
by transportation to the grain boundaries and blocking the TPBs and, consequently, in-
creasing the polarisation resistance. Impurity segregation is another possible degradation
mechanism in SOECs. Removing impurities from the system can help improve durability
and suppress degradation, at least under low current densities. It has been reported that
cleaning the feeding gas may completely eliminate the degradation of the Ni/YSZ electrode
while eliminating the degradation of LSM/YSZ can be achieved by removing the impuri-
ties within the system [190]. Papaefthimiou et al. [191] proposed a core-shell morphology
for Ni-GDC electrodes of SOECs in which a NiO-CeO2 core is covered with Ni-CeO1.5
skin. This morphology can keep the electronic conductivity of the electrode and also the
microstructure of the electrode. Poisoning and corrosion of the component from chromium,
silica, etc., can significantly decrease the performance. Doping cell components with proper
elements can hinder surface segregation and their microstructural stability [128].
Regarding the effect of chromium on the performance of SOECs, Chen et al. [192]
comprehensively investigate the role of Cr on the surface of the oxide perovskite-based
electrodes, such as LSCF. Generally, segregation of the Cr cation in oxidative conditions
(Cr3+ to Cr6+ oxidation) can take place without the presence of hydrogen in steam electroly-
sis. Despite the deactivation effect of Cr in SOECs, they reported that Cr6+ did not show
any negative impact on the performance of the electrode during the process, probably due
to its positive effect in reacting with SrO on the surface of the electrode and mitigating
the detrimental impact of the presence of SrO on the surface. Since delamination of the
oxygen electrode is mainly due to oxygen released from the electrolyte and electrode,
the ionic conductivity of the oxygen electrode and electrolyte is of greater importance.
Microstructure manipulation and composition optimisation are useful paths to tackle Ni
agglomeration in Ni-YSZ cermets. However, it still needs further development, and in-
tensive study is needed to clarify the effect of materials and the reversible mode of the
electrodes. Further details on material degradation and possible countermeasures can be
found elsewhere [137,182,183,193,194].
Generally, improving the long-term durability of the SOECs under operating condi-
tions is one of the most important factors in developing this technology. Different param-
eters such as layers composition, the microstructure of the cell components, cell design,
Energies 2023, 16, 3327 29 of 50

fabrication technique, and operating conditions, including operating pressure/temperature,

corrosion, agglomeration/coarsening, impurities, surrounding atmosphere, etc., may have
a strong effect on the stability and longevity of the SOECs and their performance. As
the electrodes are permanently exposed to the different atmospheres within the cell, their
degradation seems to be of greater importance. High operating temperatures may even
accelerate interconnect degradation; thus, reducing the operating temperature mitigates
SOEC degradation rates. However, decreasing the operating temperature may also nega-
tively affect the overall efficiency. Therefore, a practical approach to improve cell durability
is to choose the appropriate materials for each layer, protect the cell with suitable coatings,
and optimise the operating pressure, humidity, and temperature. Polarisation resistance
can be tuned by manipulating the microstructure of electrodes and electrolytes. Oxygen
partial pressure, oxygen chemical potential, and operating conditions may also activate
different degradation sources, such as electrode delamination, secondary phase formation,
and cation diffusion. Contaminants in metallic interconnect and sealants, such as Cr, B,
Si, etc., may also increase the degradation rates. Adjusting the thermal expansion coeffi-
cients of the electrodes and electrolytes can mitigate the thermal stress induced on the cell.
Different techniques, such as infiltration of the anode, anode functional layer, diffusion
barrier layer, etc., can mitigate various degradation sources. Another effective approach is
a reversible operation between SOFC and SOEC modes which has been shown to have a
pronounced effect on the long-term durability of the cells.

4. Progress in Materials Development for High-Temperature Steam Electrolysis

Similar materials to SOFC can be used in SOEC components such as YSZ, ScSZ, LSGM,
etc. These materials have been discussed numerous times in the literature [2,154,158,195].
Alternative electrolyte materials should have superior ionic conductivity, match TEC,
have suitable thermomechanical strength, etc. [111]. Oxide perovskite and fluorite-type
materials are considered state-of-the-art oxygen-ion conducting electrolytes. Stabilised
zirconia, lanthanum gallates, doped ceria, etc., are examples of electrolyte materials [158].
Partially or fully stabilised zirconia (such as scandia-doped (ScSZ) and yttria-doped zirconia
(YSZ)) is the predominant electrolyte material for high-temperature SOECs. YSZ shows
high O2− conductivity and thermomechanical properties at 700–900 ◦ C. Compared to the
YSZ electrolyte, ScSZ is of more interest in the temperature range of 600–700 ◦ C, but the
high price, fabrication, and lower chemical stability of ScSZ are still challenging [196]. It
has been reported that the formation of SrZrO3 or La2 Zr2 O7 due to the reaction between
zirconia and strontium or lanthanum is the most important disadvantage of zirconia-based
electrolytes. However, a diffusion barrier layer can prevent this reaction [158].
Due to the high ionic conductivity of doped ceria, such as gadolinium-doped ceria
(GDC) and samarium-doped ceria (SDC), they are considered promising electrolyte can-
didates, but the reduction of Ce4+ to Ce3+ in reducing atmospheres results in an internal
short-circuiting owing to the high electronic conductivity generated as a consequence of
this reduction [2]. Erbium-stabilised bismuth oxide (ESB) with a defective fluorite structure
seems to have higher chemical stability in reducing atmospheres and superior oxygen ion
conductivity, but its tendency to react with air electrodes, phase stability, long-term degrada-
tion, and low efficiency is still challenging [158]. Jun et al. [123] fabricated a PrBaMn2 O5+δ
(PBM)- and PrBa0.5 Sr0.5 Co1.5 Fe0.5 O5+δ (PBSCF50)-layered perovskite material as fuel and
air electrodes with a current density of 1.31 A.cm−2 at 800 ◦ C and 1.3 V. The fabricated
SOEC showed a stable hydrogen production for more than 600 h without any significant
degradation and claimed that this SOEC (PBM/LDC/LSGM/PBSCF50) could be used as a
promising system for hydrogen production with the least possible degradation rate.
There is a growing interest in proton-conducting electrolytes (PCE, i.e., the concept of
H-SOECs. PCEs are usually based on oxide perovskites with a general formula of ABO3 ,
where A and B are alkaline earth materials (such as Ba, Sr, etc.) and tetravalent cations (such
as Zr, Ce, etc.) doped with trivalent cations to generate oxide ion vacancies [2,197]. High
protonic conductivity, high chemical stability, high durability, and negligible electronic
Energies 2023, 16, 3327 30 of 50

conductivity are the main requirements for H-SOEC electrolyte material [119]. Generally,
proton-conducting cells operate with lower efficiency in SOEC mode than SOFC [158].
Examples of these materials are BaCe1−x Mx O3−δ or SrCe1−x Mx O3−δ (M is a trivalent
cation such as yttrium, δ is oxygen deficiency, and x is the upper limit of solid solution
formation range) showing high protonic conductivity of about 10−2 –10−1 at 600–700 ◦ C in
wet atmospheres such as steam electrolysis of water [148].
Although BaCeO3 - and BaZrO3 -based materials possess higher protonic conductivity
among the oxide perovskite materials, they are chemically unstable in water-containing
atmospheres. BaCeO3 -based materials are unstable in water vapour and carbon dioxide
atmospheres. Doping Zr into the crystal structure of BaCeO3 can improve its stability to
some extent [198]. BaZrO3 -based proton conductors have higher mechanical hardness and
chemical stability, but their proton conductivity is lower than BaCeO3 [119,199]. Doping
trivalent cations such as In3+ , Gd3+ , Y3+ , Yb3+ , etc., can improve barium zirconate-based
PCEs [200]. Although yttrium doping resulted in improving chemical stability, it decreased
proton conductivity because of the increased grain-boundary resistance caused by poor
sinterability [201]. Thereby, sintering of zirconate-based PCEs should be performed at
higher temperatures [202]. Generally, due to the very low TEC, low electric loss, and low
thermal conductivity of zirconate materials, they are among the promising materials for
hydrogen generation [203]. In order to fulfil most of the requirements, a solid solution of
BaCe1−x Zrx O3 seems to be an effective approach. SrCe0.95 Yb0.05 O3−δ , SrZr0.9 Yb0.1 O3−δ ,
BaZr0.9 Y0.1 O3−δ , BaCe0.9 Nd0.1 O3−δ , BaCe0.9 Y0.1 O3−δ , etc., are other examples of PCE ma-
terials [148,199,203]. Despite all of the progress in H-SOEC materials, further development
is needed to address the relatively high polarisation losses in this configuration.
It has been reported that BZCYYb significantly improved the performance of zirconate-
based proton conductors. In this context and as mentioned earlier, Kim et al. [110] fab-
ricated a hybrid conducting SOEC with NdBa0.5 Sr0.5 Co1.5 Fe0.5 O5 /BZCYYb oxygen elec-
trode, BZCYYb electrolyte, and Ni/BZCYYb oxygen electrode with a high current density
of 3.16 A.cm−2 at the given operating conditions. Wu et al. [124] fabricated a proton-
conducting cell using the same electrolyte and fuel electrode and a different air electrode
(PrBa0.5 Sr0.5 Co2−x Fex O5 ). The self-architecture ultra-porous (SAUP) 3D steam electrode
showed a high current density of about 2.02 A.cm−2 at 600 ◦ C and at 1.6 V. They reported
an improving performance in the first 75 h at 500 ◦ C and 1.6 V, owing to the bridging
effect. They claimed that this electrode might lead to the next generation of steam electroly-
sers. The same electrolyte and electrodes were used by Choi et al. [204], who fabricated
a steam electrolyser for hydrogen generation. Durability tests of the fabricated cell re-
vealed that the cell underwent a negligible electrochemical loss after 500 h at 550 ◦ C. Leng
et al. [205] studied the effect of sintering aids, including NiO, CuO, and ZnO, on the
BaCe0.7 Zr0.1 Y0.1 Yb0.1 O3−δ proton-conducting electrolytes and found that the sample with
1 wt.% CuO or ZnO addition has the highest conductivity in the hydrogen atmosphere,
while the sample with 1 wt.% NiO or ZnO addition has the highest conductivity in an air
atmosphere. Overall, the results implied that the proton conduction and hydration reaction
of the sample with the CuO sintering aid was higher than that of the NiO sintering aid. The
highest conductivity in air and hydrogen atmospheres for the sample that contained 1 wt%
CuO was about 1.087 × 10−2 S.cm−1 and 9.02 × 10−3 S.cm−1 at 650 ◦ C, respectively.
The electrolyte layer acts as the heart of the solid oxide cells identifying the composition
of the other cell’s individual layers and their electrochemical performance. Among all the
electrolyte materials proposed in the literature, it seems that due to their higher efficiency,
degradation behaviour, and long-term durability, YSZ and ScSZ are still the most suitable
materials for cathode-supported and electrolyte-supported cells, respectively. Ceria-based
electrolytes such as GDC and SDC have also been increasingly used owing to their high ionic
conductivity, but the high sintering temperature of these electrolytes is still challenging,
especially in the co-sintering of the layers.
State-of-the-art hydrogen electrodes should attenuate degradation challenges such
as nickel depletion and agglomeration as well as improve cell durability at high current
Energies 2023, 16, 3327 31 of 50

densities (>1 A.cm−2 ) [111]. Currently, ceramic-metallic composites are among the most
widely used compounds for hydrogen electrode applications. Due to the high electronic
conductivity, activity, and lower costs compared to the other metal candidates, nickel is the
typical metallic component in cermets. YSZ is the ceramic agent in the cermets used for
this application as it provides a suitable adhesion between the electrode and electrolyte
as well as prevents nickel from sintering, provides a pathway for O2− migration into
the porous layer (extending the TPBs), and a close TEC to the other components [126].
In addition to Ni-YSZ as the most widely used hydrogen electrode in SOECs, metal-
exsolution perovskites show promising properties due to their high electrocatalytic activity,
manufacturing flexibility, and high thermal/coking resistance. The exsolution of metal
nanoparticles from the matrix of a cermet under a reducing environment can improve the
electrocatalytic activity of the electrodes [154]. A transition metal exsolution can increase
not only the concentration of oxygen vacancies but also facilitate the contact between water
vapour and the transition metal. Thereby, this strategy can improve the electrochemical
performance of the cell and water (or carbon dioxide) conversion efficiency [206,207].
Titanate oxide perovskites offer high redox stability but suffer from their low elec-
trocatalytic performance. In this context, Qin et al. [208] fabricated a Fe-doped titanate
(La0.2 Sr0.8 )0.9 Ti0.9 Fe0.1 O3−δ (LSTFO) as a potential hydrogen electrode in high-temperature
water electrolysis using O-SOECs. The redox properties of LSTO and the high catalytic
activity of Fe provided a synergic effect and resulted in a high Faraday efficiency of about
100%. The electrochemical performance of a SOEC with a lanthanum strontium chromite
perovskite La0.65 Sr0.3 Cr0.85 Ni0.15 O3−δ fuel electrode at 770–860 ◦ C and in an atmosphere
containing 80% H2 O/20% H2 was studied by Amaya-Dueñas et al. [209]. They observed
a voltage degradation of about 48 mV.kh−1 after 1000 h at 860 ◦ C. Mo-Au-Ni/GDC fuel
electrodes were fabricated by Vibhu et al. [210]. The electrolyte-supported cell comprising
an 8YSZ electrolyte, Mo-Au-Ni/GDC hydrogen electrode, and LSCF oxygen electrode
was tested under electrolysis mode at 1.3 V and 900 ◦ C, and an atmosphere containing
7 vol% H2 , 30 vol% N2 , and 63 vol% H2 O. The results showed a peak current density
of −0.78 A.cm−2 and a relatively low degradation rate of 33 mV.kh−1 after 1700 h and
under a current density of −0.3 A.cm−2 . The degradation mechanism in the hydrogen
electrode was Ni depletion and agglomeration. They reported that a small amount of
Mo (0.3 wt%) and Au (2.3 wt%) could improve the electrocatalytic performance and de-
crease degradation rates, but no evidence was found regarding preventing nickel migration.
Dogdibegovic et al. [211] also fabricated a high-efficiency metal-supported solid oxide cell
with a Pr6 O11 -infiltrated ScSZ oxygen electrode, ScSZ electrolyte, and Ni/SDC-infiltrated
ScSZ hydrogen electrode.
Heterostructure interfaces can offer high-oxygen surface exchange kinetics [212,213].
Xi et al. [214] worked on a heterostructured double perovskite/Ruddlesden-Popper per-
ovskite (DP/RP-P) composite with exsolved Fe-Cu bimetallic nanoparticles with a general
formula of Sr2 Fe1.25 Cu0.25 Mo0.5 O6−δ (SFCuM) as the fuel electrode for high-temperature
LSGM-supported SOEC. Performance tests were performed at 800 ◦ C and 1.4 V with a
carbon monoxide production rate of 12.8 mL.min−1 .cm−2 and Faradaic efficiency of 95.2%.
Although the SOEC was used for carbon dioxide conversion, its concepts may help de-
velop hydrogen generation, too. A critical review of the conventional and alternative
cathode materials for hydrogen production through steam electrolysis in SOEC can be
found elsewhere [215].
Wang et al. [216] developed a symmetrical two-electrode water electrolyser with a
La0.8 Sr0.2 Cr0.69 Ni0.31 O3−δ (LSCN) electrocatalyst. The new strategy was to modify the
surface and interface by exsolution of the discrete Ni2 P nanoparticles from LSCN. The
exsolution process was performed by partial reduction followed by phosphatisation. This
strategy resulted in improving the OER activity and mass activity by 6.2 and 10.2 times,
respectively. Durability and HER activity were also improved using this process with a
current density of 10 mA.cm−2 over 14 h of operation.
Energies 2023, 16, 3327 32 of 50

Overall, ceria-based materials may form secondary isolating phases or pores at the
interface during sintering, which results in lowering cell performance. Despite the nickel
coarsening at high temperatures and nickel depletion (due to nickel migration) [158], Ni-
based cermets such as Ni/YSZ or Ni/GDC are currently the most widely used hydrogen
electrode due to their higher performance and nickel-based cermets.
Similar to hydrogen electrodes, innovative oxygen electrodes should tackle degra-
dation issues at high current densities, crack formation, electrode/electrolyte interface
delamination, element migration, etc. [111]. Impregnating the matrix can extend the TPBs
and improve the overall efficiency by promoting oxygen reduction reaction and preventing
delamination of the oxygen electrode [217–219]. Zhang et al. [220] thoroughly investi-
gated the potential cobalt-based oxide perovskite electrode materials for SOEC operation.
They pinpointed that improving the transport properties in Co-based oxide perovskites
without careful design may result in increasing the TEC mismatch. Some useful tech-
niques, such as La2 NiO4−δ (LNO) impregnating and ceria-based coating, may alleviate
the problem. Interfacial and surface engineering may alter crystal strain and improve
electrocatalytic features of Co-based oxide perovskite electrodes. Lanthanum nickelate
oxide perovskites such as LaNiO3 have also been investigated for their application as air
electrodes in SOECs. However, it needs high partial pressure of oxygen as well as careful
composition tailoring to prevent the conversion of LaNiO3 to La2 NiO4 or NiO [154]. As a
case in point, LaNi0.6 Fe0.4 O3 is an oxide perovskite material with high stability and high
electronic conductivity but with moderate electrochemical performance and ASR values of
about 0.14–0.73 Ω.cm2 [221].
Prasopchokkul et al. [222] synthesised a Ba0.5 Sr0.5 (Co0.8 Fe0.2 )1−x Tax O3−δ (BSCFTax,
x = 0–0.2) oxide perovskite anode for high-temperature SOEC application. Ta’s addition
improved the structural stability and electrochemical performance of BSCF. The best perfor-
mance belonged to the sample with x = 0.1 (10 mol%) despite the lowest oxygen vacancies
in comparison with the other samples. Decreasing the Co3+ to Co4+ ratio induced electronic
conductivity in the samples, and proper Ta5+ doping resulted in a balance between elec-
tronic and ionic conductivities. Compared to Ni-YSZ/YSZ/BSCF, the cathode-supported
Ni-YSZ/YSZ/BSCFTa0.10 showed improved durability at the test conditions. Despite the
significant advances, inadequate stability, relatively high rates of degradation, and low
performance are the most critical barriers to the progress of anode materials. Effective
approaches to fabricate highly efficient anode materials and improve their performance
include (a) in situ microscopic, spectroscopic, and electrochemical characterisation during
long-term operations, (b) light alkanes selective oxidation at the anode side to enhance
electro-reduction reaction at the cathode side and convert the light alkanes to desirable
materials using the oxygen species at the anode side, and (c) predicting the electrochemical
performance of anode materials using machine learning methods [142].
Infiltration of metal nanocatalysts, such as Cu, Ni, NiCu, etc., into the structure of
the La0.75 Sr0.25 Cr0.5 Mn0.5 O3 (LSCM)/SDC cathode, has also been reported to be a highly
efficient way to improve the catalytic activity of SOECs for CO2 conversion into CO by
expanding the active site for carbon dioxide splitting [223]. This technique seems to have the
potential to be used for hydrogen generation with some modifications. Vibhu et al. [224] fo-
cused on the electrochemical performance of HTSE with La0.6 Sr0.4 CoO3−δ (LSC)-infiltrated
La0.58 Sr0.4 Co0.2 Fe0.8 O3−δ (LSCF) oxygen electrode with that of LSCF ones in the tempera-
ture range of 700–900 ◦ C. The results showed that the TEC of both electrodes has a similar
behaviour as increasing temperature. Variation in the lattice parameter against temperature
was also similar with a slight difference. The electrochemical behaviour of the cells with
different cathode materials (Figure 12) shows a polarisation resistance of 22 mΩ.cm2 at
800 ◦ C. The degradation test showed an increase of 25 mV per day with no degradation af-
ter 408 h for LSC-infiltrated LSCF. Both the conventional and infiltrated electrodes showed
similar delamination behaviour. Hydrogen production rates of 627 and 835 mL.cm−2 .h−1 at
800 ◦ C for the SOECs with LSCF and LSC-infiltrated LSCF cathodes, respectively, showing
the positive effect of LSC infiltration.
Energies 2023,
Energies 16,16,3327
2023, 3327 33 of 50

Figure
Figure 12. 12. (a) Nyquist
(a) Nyquist curve atcurve
800 ◦ at 800 °open
C under C under
circuitopen circuit
voltage voltage
conditions and conditions
(b) Arrheniusand
plot(b) Arrh
for different electrodes
for different electrodes [224]. [224].

Zheng et al. [225] studied the effect of La0.8 Sr0.2 Co0.8 Ni0.2 O3−δ impregnation on the
Zheng et al. [225] studied the effect of La0.8Sr0.2Co0.8Ni0.2O3−δ impregnation on
electrochemical performance of GDC/LSM composite oxygen electrode for co-electrolysis
oftrochemical performance
water and carbon dioxide. A peak of current
GDC/LSM composite
density of about 1.6 oxygen
A.cm−2 atelectrode
800 ◦ C and for
1.5 Vco-elect
water and carbon dioxide. A peak current density of about 1.6 A.cm −2 at 800 °C
was recorded for the cell composed of LSCN-infiltrated LSM/GDC cathode, YSZ electrolyte,
and
wasNi/YSZ hydrogen
recorded electrode.
for the Long-termof
cell composed stability 0.4 A.cm−2 current
test results at LSM/GDC
LSCN-infiltrated cathode, YSZ
density and 800 ◦ C for more than 100 h showed that the major degradation mechanism
lyte, and Ni/YSZ hydrogen electrode. Long-term stability test results at 0.4 A.cm
was LSCN nanoparticle coarsening in the oxygen electrode. Ruddlesden-Popper materials
density
with and 800
the general °C of
formula forAmore than 100 h showed that the major degradation m
n+1 Bn O3n+1 or (AO)(ABO3 )m (A = La, Nd, and Pr; B = Cu,
was
Ni, andLSCN
Co; mnanoparticle
= 1) have alsocoarsening in theas
been investigated oxygen electrode.
air electrodes Ruddlesden-Popper
in high-temperature
with the general formula of An+1BnO3n+1 or (AO)(ABO
electrolysis [2]. Lei et al. [226] developed a barium-doped Pr 2 NiO 3)4+δ
m (A = La,
(PNO) Nd, and Pr; B
compound
with
anda general
Co; m formula
= 1) have of Pr 2−x Ba
also x NiOinvestigated
been 4+δ (PBNO-x, x as = 0,air
0.1,electrodes
0.2, 0.3, and in0.4). Ba doping
high-temperature
helped overcome the poor chemical stability of PNO at high temperatures (600–800 ◦ C).
ysis [2]. Lei et al. [226] developed a barium-doped Pr2NiO4+δ (PNO) compound w
eral formula of Pr2−xBaxNiO4+δ (PBNO-x, x = 0, 0.1, 0.2, 0.3, and 0.4). Ba doping help
come the poor chemical stability of PNO at high temperatures (600–800 °C). Th
showed that the sample with x = 0.2 possessed the lowest polarisation of about 0
Energies 2023, 16, 3327 34 of 50

The results showed that the sample with x = 0.2 possessed the lowest polarisation of about
0.06 Ω.cm2 at 800 ◦ C, which is almost 66% of pure PNO. The highest current density
and electrolysis current density was 1 A.cm−2 at 800 ◦ C for 126 h and −723 mA.cm−2 at
1.3 V, respectively.
Pei et al. [227] fabricated a reversible cell with a water-promoted surface restructuring
process. The cell comprised a Ba0.9 Co0.7 Fe0.2 Nb0.1 O3−δ (BCFN) oxide perovskite-based
oxygen electrode with a maximum power density of 1.70 W.cm−2 and current density of
2.8 A.cm−2 at 1.7 V in fuel cell and electrolysis cell mode, respectively. The Nb-rich electrode
was naturally covered with Nb-deficient nanoparticles. In other words, BCFN interacted
with water and produced fine Nb-deficient BCFN nanoparticles on the surface, leading to
higher stability and extended active reaction sites. The A-site deficiency of the perovskite
electrode showed high durability as well as high HER and OER activity.
Zirconate-based materials have also been used as oxygen electrode materials.
Duan et al. [228] fabricated a cell composed of a BaCo0.4 Fe0.4 Zr0.1 Y0.1 O3−δ (BCFZY) oxygen
electrode, BCZYYb electrolyte, and BCZYYb-Ni hydrogen electrode and reported a high
current density and degradation rate of about 1100 mA.cm−2 and <3 mV over 1000 h,
respectively. An exceptional current density of about 2000 mA.cm−2 has been reported
from a steam electrolyser working at 500–650 ◦ C. The cell was composed of a high-activity
PrBa0.5 Sr0.5 Co1.5 Fe0.5 O5+δ (PBSCF) air electrode, BaZr0.4 Ce0.4 Y0.1 Yb0.1 O3 (BZCYYb4411)
electrolyte, and Ni- BZCYYb4411 composite fuel electrode. The concept behind using
PBSCF air electrodes was its high efficiency of oxygen evolution and reduction reaction.
Degradation of the cell was also attributed to the electronic leakage through the electrolyte.
The high stability of the cell was related to the absence of corrosive compounds at the fuel
electrode and the prevention of oxygen bubble formation near the air electrode. Inhibit-
ing the formation of an oxygen bubble has a strong effect on lowering the degradation
rate and decreasing delamination at the interface between the electrolyte and the elec-
trode. The low water vapour gas diffusion resistance enabled operating with low steam
concentrations [119].
Triple-conducting hydrogen electrodes with O2− , H+ , and e− conductivity have also
been investigated. Triple conducting materials were primarily used in fuel cells but ex-
panded to electrolysis cells in recent decades. The conductivity of each carrier can be
optimised by manipulation of structure, composition, and operating conditions [227]. Ba-
based materials doped with high multi-valent transition metals and Zn inclusions such
as (Ba, Sr, La)(Fe, Co, Zn, Y)O3−δ are known to have the highest performance in this
classification [195,229]. Transition metal doping of barium zirconate may result in triple
conductivity [230]. Ding et al. [231] fabricated a PrNi0.5 Co0.5 O3−δ (PNC) oxide perovskite
oxygen electrode with an exceptional electrochemical performance at 400–600 ◦ C. Triple
conduction extended oxygen reduction and water splitting on the entire surface of the
electrode as well as facilitated gas transport and diffusion and, consequently, improved the
electrochemical performance of the cell. Wang et al. [232] studied the electrochemical per-
formance of a protonic ceramic fuel cell and electrolysis cell with La0.8 Sr0.2 Co1−x Nix O3−δ
(LSCN, x = 0–0.3) air electrodes. The electrolysis current and polarisation resistance was
found to be about 1.09 A.cm−2 and 0.09 Ω.cm2 at 600 ◦ C. From the point discussed above,
despite the long-term problems with LSM-based and LSCF-based compounds, they are
the most widely used oxygen electrode materials. In addition to these materials, nickelate-
based compounds, specifically doped LNO and LPNO, showed higher durability.
Overall, the optimisation of the existing materials, followed by the development
of novel materials, is the proposed roadmap for the commercialisation of SOECs. The
main challenge regarding the electrolyte layer is to possess high ionic conductivity at
lower temperatures. Several novel materials, such as GDC, LSGM, and SDC, have been
proposed to increase ionic conductivity. However, YSZ and ScSZ are currently the best
candidates for electrolyte materials. Mitigating the degradation rates and improving the
long-term stability of the electrodes as well as high electrocatalytic performance, are the
main challenges with the electrodes. Besides Ni/YSZ, other anode materials, such as
Energies 2023, 16, 3327 35 of 50

metal-exsolution oxide perovskites, showed enhanced electrocatalytic performance with

higher coking and thermal resistance. Principally, LSCF and LSM are the most widely used
oxygen electrode materials with high mixed ionic-electronic conductivity as well as suitable
thermochemical stability and high electrocatalytic activity. Other materials require much
further development to replace these common materials. Triple-conducting materials, such
as nickelate-based materials, extend the active sites to the entire surface of the electrode.
They can significantly improve the performance of the oxygen electrode by enabling three
different conductive paths, including O2− , H+ , and e− . These triple-conducting materials
show promising properties for future investigations and may open up avenues to replace
the current oxygen electrode materials.
Interconnects are the materials that connect individual cells to each other and provide
mechanical support and conductivity for the stack. They should be able to diminish
chemical interactions between the electrode materials and the redox atmospheres and the
resulting microstructural deteriorations (delamination, cracks, coking) [111]. As mentioned
earlier, interconnect degradation can take place in two different ways: (a) conductivity loss
by oxidation and (b) cathode poisoning by chromium evaporation. In order to improve
durability and maintain their performance, interconnect materials can be coated to prevent
both oxidation and chromium evaporation [2]. Zhou et al. [137] investigated the effect
of coating on the performance of some common interconnect materials, such as SUS430,
Crofer22 APU, AISI 430, and Sanergy HT, and summarised their report in Table 5. Due to
their high cost-effectiveness and performance, perovskite and spinel materials are of great
interest for interconnect coating. Mah et al. [233] carried out a comprehensive study on
metallic interconnect materials, several approaches to protect their properties, and different
deposition techniques. They reported that due to the matching TEC (~9.7 × 10−6 K−1 ) to
interconnect materials for other cell components, high electrical conductivity (60 S.cm−1 at
800 ◦ C), and lower costs compared to the perovskites, Mn-Co spinels received particular
attention as an interconnect coating material. It seems that coating of the interconnect can
be a practical solution to prevent inducing thermal stresses to the stack. On the other hand,
reducing the operating temperature can be a useful way to diminish oxidation [2,233].
Unfortunately, very limited works have been published for SOEC interconnect materials,
and most of the current reported ones are based on SOFC interconnects, as shown in the
following table. However, coating the interconnect materials with a protective layer seems
to improve cell performance.

Table 5. Common interconnect materials and their proposed coatings [137].

Interconnect Material Coating Coating Technique Test Conditions ASR (mΩ)

SUS430 Mn-Co PVD 800 ◦ C/air/1250
h 28.6
AISI 430 Mn-Co DGPA 800 ◦ C/air 29 (480 h)
Crofer22 APU MnCo1.7 Fe0.3 O4 EPD 800 ◦ C/air/1000 h -
Crofer22 APU MnCo1.7 Fe0.3 O4 APS 700 ◦ C/air/1000 h 50
Sanergy HT (Mn, Co)3 O4 Screen printing 800 ◦ C/air/1000 h -

Effective sealing of the cell stacks can greatly improve their efficiency and diminish
their degradation by preventing gas mixing at both electrodes and gas leakage, as well
as providing electrical insulation to the stack. Matching TEC (~10–12 × 10−6 K−1 ), high
toughness under dynamic/static forces, high mechanical strength, high durability, low
fabrication costs, flexibility of design, and high thermal shock resistance are other important
features of the sealants [2]. Conventional sealants include mica, glass ceramics, brazes, etc.
Generally, sealant materials can be divided into two categories; rigid and compressive seals.
Because they have a tight bond with the surface, rigid seals such as glass, glass ceramics,
and alloy-based brazes should have a close TEC to that of other constituents. On the other
hand, as compressive seals, such as metallic- (Pt, Au, Ag, etc.) and mica-based sealants
(phlogopite, muscovite, etc.), make no strong bond with other components, they do not
need close TEC. Rigid sealants are more cost-effective than their counterpart [234–236]. The
Energies 2023, 16, 3327 36 of 50

chemical and mechanical properties of the seals play an important role in their long-term
stability. As a case in point, Li et al. [237] investigated the effect of compressive loads
and thickness of the vermiculite seals and reported that increasing input gas pressure
and thickness resulted in deteriorating the long-term performance of the vermiculite seals.
They concluded that optimising the thickness of the seal towards thinner thicknesses and
increasing the compressive loads can improve the overall performance of the vermiculite
seal. Despite their brittleness and possibility of producing volatile compounds, glass and
glass-ceramics seem to be more advantageous than the other sealants due to their high
rigidity, tolerability of thermal properties, formation of a rigid hermetic compound, high
thermochemical properties, high electrical resistivity, and facilitation of fabrication. Their
properties can be further improved by doping and coating techniques [238,239]. Glass
fibre-reinforced ceramics have been reported to be a new class of sealants with promising
properties [240]. Silicates, borates, aluminosilicates, borosilicates, boro aluminosilicates, etc.,
are the most common sealant with a TEC in the range 10.5–12 × 10−6 K−1 and operating
temperature 614–760 ◦ C [2].
The required properties of sealants are almost the same between SOFCs and SOECs.
However, sealants in SOECs should have high electrical resistivity under operating volt-
ages (>1.2 V), which limits materials selection. Sealant materials should be able to keep
their properties for more than 30,000–40,000 h with negligible degradation [239]. As men-
tioned earlier, silicate- and borate-based glass-ceramics showed more promising behaviour
than the other types. Barium oxide has a strong tendency to react with chromium in
high Cr-containing interconnects such as Crofer22APU and form a high-TEC BaCrO4
phase (20–22 × 10−6 K−1 ) [241]. Da Silva et al. [242] investigated four sealants with dif-
ferent compositions in the B2 O3 -modified BaO-Al2 O3 -SiO2 system and reported that the
sealing temperature and TEC of all of the samples were in the range of 730–830 ◦ C and
8.8–10.5 × 10−6 K−1 , respectively. The excessive presence of BaO in one of the samples pre-
vented complete sintering and incomplete densification of the sample. The shear strength
of this sample was about twice that of the samples with lower BaO content. According
to the results, they concluded that the sample with higher BaO content (BaO: 72 wt%,
B2 O3 : 3 wt%, SiO2 : 20.5 wt%, and Al2 O3 : 4.5%) is a promising candidate for sealing solid
oxide cell working in the temperature range of 700–850 ◦ C. Javed et al. [241] prepared a
Ba-based glass-ceramic sealant with a controlled SiO2 /BaO ratio to obtain a BaSi2 O5 phase.
The interconnect and electrolyte in the SOEC were Crofer22 APU and YSZ, respectively.
The sealant with the composition of SiO2 : 60 mol%, BaO: 22 mol%, CaO 6.5 mol%, B2 O3 :
7.65 mol%, Al2 O3 : 3 mol%, and Y2 O3 : 1 mol% was tested for 2000 h at 850 ◦ C in differ-
ent atmospheres and a voltage of 1.6 V. The results showed desirable thermomechanical
properties with matching TEC (12–14 × 10−6 K−1 ) to Crofer22APU (~12 × 10−6 K−1 )
and YSZ (~10.5 × 10−6 K−1 ) as well as a stable electrical resistivity (106 –107 Ω.cm). On
the contrary, SrO exhibited better performance due to its improved wettability, higher
mechanical properties than BaO-based compounds, and reduced viscosity. However, a
high concentration of SrO resulted in forming a high-TEC SrCrO4 phase [242–244]. In this
context, Javed et al. [239] fabricated a SrO-containing glass-ceramic sealant with TEC in
the range of 9.8–10.3 × 10−6 K−1 in contact with a Crofer22APU interconnect and a 3YSZ
electrolyte as well as having a high electrical resistivity of about 105 Ω.cm. The sealant
was fabricated according to the SiO2 -SrO-Al2 O3 phase diagram to form a SrSiO3 com-
pound with suitable TEC and no unwanted cristobalite or SrCrO4 formation. The results
showed that this glass-ceramic possessed high durability of about 1000 h at 850 ◦ C and at
1.6 V. They also investigated the SrO content on the properties of glass-ceramic sealants
and outlined the different crystallisation and sintering behaviour. The sample indexed as
HJ4 with the composition of SiO2 : 57.6 mol%, B2 O3 : 5.65 mol%, SrO: 28.84 mol%, Al2 O3 :
6.17 mol%, and Y2 O3 : 1.74 mol% was chosen as the reference for their next analysis [245].
They further expanded their results by investigating the electrical resistivity behaviour and
element diffusion across the interfaces between the interconnect and sealant of the samples
during a long-term test for 2800 h at 850 ◦ C and at a high voltage of 1.6 V. The sample
Energies 2023, 16, 3327 37 of 50

used in this study was the sample with the highest performance in their previous test,
labelled as HJ4 ([245]). The highest recorded electrical resistivity of the samples was about
106 –107 Ω.cm with no evidence of element diffusion or the formation of detrimental phases
such as Sr-chromates or any other undesired compounds. In another attempt to accom-
plish their investigation of choosing the appropriate sealant material, they studied the
mechanical properties of two samples labelled HJ3 and HJ4 and compared the results.
Compared to HJ4, HJ3 comprised 10 mol% less silica and SrO, about 2 mol% less B2 O337 of 51
Energies 2023, 16, 3327
and alumina, and the same Y2 O3 content, as well as 11.45 mol% calcia and 12.74 mol%
magnesia. The mechanical properties of both samples were measured at room temperature,
650 ◦ C, and 850 ◦ C.mol%
Both calcia
samples
and showed
12.74 mol% temperature-dependent
magnesia. The mechanicalbehaviour
properties ranging from were
of both samples
14.1 MPa down to 1.8 MPa at
measured roomtemperature,
at room temperature 650and°C, and ◦ C, °C.
850 850 respectively.
Both samples The key factor
showed temperature-
dependent
in controlling mechanical behaviourisranging
properties having from 14.1 MPa
a higher down to
volume 1.8 MPaof
fraction at the
room temperature and
crystalline
850 °C,with
phase, and the samples respectively. The key
the highest factor
glassy in controlling
phase exhibitedmechanical
the lowest properties is having a
mechanical
higher volume fraction of the crystalline phase, and the samples with the highest glassy
properties but improved stress relaxation possibilities to release thermal stresses at elevated
phase exhibited the lowest mechanical properties but improved stress relaxation possibil-
temperatures. Figure ities13
toshows the surface
release thermal microstructure
stresses of HJ3 and
at elevated temperatures. HJ4.13As
Figure depicted
shows in mi-
the surface
this figure, micro pores are present
crostructure of HJ3in
andtheHJ4.
HJ3Assample,
depictedbut HJ4figure,
in this is denser
microthan
poresHJ3 and has
are present in athe HJ3
slight porosity [246].
sample, but HJ4 is denser than HJ3 and has a slight porosity [246].

Figure 13. Surface

Figure 13. Surface microstructure microstructure
of HJ3 at (a) roomof HJ3 at (a) room temperature,
temperature, (b) 650 ◦ C, (b)
(c) 650
850°C, (c)and
◦ C, 850 HJ4
°C, and
at HJ4 at
(d) room temperature,
◦ (e) 650
◦ °C, and (f) 850 °C [246].
(d) room temperature, (e) 650 C, and (f) 850 C [246].
Kiebach et al. [247] fabricated a glass sealant (CaO: 50 mol%, ZnO: 20 mol%, B2O3: 20
mol%, and SiO2: 10 mol%) and investigated the effect of reducing silica content to inhibit
cell contamination caused by Si impurity migration from the sealant material to the
Energies 2023, 16, 3327 38 of 50

Kiebach et al. [247] fabricated a glass sealant (CaO: 50 mol%, ZnO: 20 mol%, B2 O3 :
20 mol%, and SiO2 : 10 mol%) and investigated the effect of reducing silica content to
inhibit cell contamination caused by Si impurity migration from the sealant material to the
electrodes and TPBs. The results implied that the sealant properly performed for about
400 h without any degradation. The TEC and glass transition temperature of this sealant
was about 11.5 × 10−6 K−1 and 594 ◦ C, respectively. Nakane et al. [248] investigated the
applicability of ceramic sealing agents (CSA) as sealants with SUS430 interconnects at
high temperatures. They observed no significant changes in the performance and physical
properties of CSA up to the high operating temperatures of solid oxide cells. By optimising
the TEC of the CSA close to that of SUS430, no leakage was detected after 150 heat cycles
(1 h in the room followed by 1 h at 800 ◦ C). Furthermore, no degradation or Cr or Fe
diffusion happened after 100 h of operating, even at 800 ◦ C. Due to the matching TEC to
Crofer22APU and high chemical stability of diopside (CaMgSi2 O6 )-based glass ceramics,
they have been identified as promising candidates for sealing solid oxide cells [249,250].
Sabato et al. [251] studied the properties of Na-containing diopside-based glass-
ceramic sealants. Heterogeneous nucleation of diopside at the interface formed a barrier
between sodium and chromia. The resistivity measurement of the Crofer22APU/glass-
ceramic/Crofer22APU at 800 ◦ C for 100 h showed a high resistivity value (~106 Ω.cm).
They also investigated the effect of electric loads (0.7 V and 1.3 V) and reported a rapid
decrease in resistivity in the case of applying 1.3 V owing to the formation of chromia at the
interface and bridging the two Crofer22APU plates. The presence of the Na2 CrO4 volatile
phase at 800 ◦ C was accounted as the main source of chromia forming at the cathode side
and the subsequent degradation in sealant performance. However, no such bridging hap-
pened in the case of applying 0.7 V voltage, and the resistivity kept its electrical resistance
steady (~105 –106 Ω.cm) over 100 h test time. This study clarifies the importance of the
applied voltage on Cr vaporisation and lowers the overall performance. It is noteworthy
to mention that surface roughness strongly affects the shear strength of the sealant. For
example, surface modification of crofer22 APU by laser and forming before joining to a
glass sealant of 4.6 µm roughness can improve its torsional shear strength (a mechanical
interlocking mechanism) from about 27 (ac-received Crofer) to 32 MPa [252]. Potential
applications of other types of sealants, such as alumina-glass composite seals [253], Ba-free
glass ceramics (containing Si, Al, Ca, Mb, B, Zr, and Na) [254], SrO–La2 O3 –Al2 O3 –SiO2 glass
sealants [244], SiO2 –B2 O3 -BaO-WO3 with 10 mol% alumina [255], etc., have also showed
interesting long-term durability with improved thermomechanical properties. In the case
of high-temperature SOECs, metal welding can be used, especially in metal-supported
SOECs, as they do not suffer from the brittleness of ceramic materials [137]. Sudireddy
et al. [256] employed the laser welding method and sealed the stack with 0.5–1.2% per
100 h degradation rate.
Si et al. [257] claimed to fabricate a novel Ag-based sealant with a fully tunable
TEC for joining aluminised Crofer 22 H. They combined a negative TEC material called
eucryptite (LiAlSiO4 ) with a conventional Ag-based braze and formed Ag2 CuO-LiAlSiO4 .
The thermomechanical properties of the system were evaluated as a function of eucryptite
content. The results showed that the TEC of the braze material with 8 wt.% of eucryptite
decreased from 19.6 × 10−6 K−1 at RT to 12.2 × 10−6 K−1 at 800 ◦ C. Although they
observed a small amount of voids due to the reduction in CuO precipitates, the sealant kept
its hermeticity and showed no evidence of degradation after operating for 300 h at 800 ◦ C.
Kiebach et al. [258] fabricated an Ag-tialite (Al2 TiO5 ) composite braze as a sealing material.
The TEC of the composite can be tuned by changing the tialite content. The long-term
performance of the composite was tested in a Crofer/Ag-tialite/NiO-YSZ system under
SOFC and SOEC conditions. In the SOEC conditions, no degradation was observed after
900 h at −0.5 A.cm2 and at 850 ◦ C. Referring to these two studies, it seems that Ag-ceramic
composites may have interesting potential to be used as sealant materials. The choice of
sealant depends on several factors, such as operating temperature, fabrication costs, the
interconnect material, etc.
Energies 2023, 16, 3327 39 of 50

In general, sealants can greatly influence the Faradaic efficiency of the SOECs, and
sealing materials should be chosen according to the operating temperature. SOEC sealing is
more challenging at elevated temperatures and pressures. Thus, different types of sealants
should be used in different applications. Most common sealants are made of glass-ceramic
materials, and their main drawback (brittleness) can be tackled using different coatings,
reinforcing with glass fibres, or adding dopants (such as yttria). Other candidates, such as
Ag-Al2 TiO5 , thermiculite 866, etc., have also been developed.

5. Conclusions
This review paper explored the recent advances in hydrogen production through
HTSE. As hydrogen generation technologies completely rely on fossil fuel burning, devel-
oping a new strategy to satisfy both energy demand and environmental issues is mandatory.
Among the non-fossil fuel-based technologies, hydrogen production by water electrolysis
takes up to 4% of the hydrogen economy. This implies that water electrolysis technology
needs to be further improved. Among different types of water electrolysis, solid oxide
electrolysis cells have shown promising potential but are still under development and
are behind the other water-splitting technologies. High-temperature electrolysis of water
needs a heat and electricity supply. In order to supply the heat and electricity needed
for this process, nuclear power plants can be coupled to SOECs to improve their electro-
chemical performance. Generally, HTSE via solid oxide electrolysis cells is a new emerging
technology that needs to be further developed in terms of material development, process
optimisation, microstructure manipulation, etc. Metal exsolution shows promising results
in improving the electrocatalytic activity of the electrodes by increasing oxygen vacancies
and promoting gas-metal contact. Impregnation is another useful strategy to extend triple
phase boundaries and improve the electrochemical performance of the cell by enhancing
oxygen reduction reaction and diminishing delamination. Materials with heterostructure
microstructure showed promoted electrocatalytic performance owing to the improved
oxygen surface exchange kinetics.
One of the most important aspects of improving the electrochemical performance
of SOECs is mitigating their degradation rates. Degradation mechanisms happening
in a SOEC include delamination at the interface of electrolyte-electrode, microstructure
coarsening during co-sintering and/or high-temperature operation (such as Ni coarsening),
formation of detrimental secondary phases such as Sr-chromates, chromium poisoning,
and decomposition of electrodes. Each degradation mechanism was discussed in this paper,
and relevant countermeasures were proposed.
Although hydrogen generation through HTSE is a promising technique, it still needs
further development in terms of materials, efficiency, capital costs of hydrogen production,
etc. Direct conversion of seawater to hydrogen is another potential application of HTSE,
which should be investigated in future studies. Furthermore, co-electrolysis SOECs can
simultaneously produce hydrogen and carbon monoxide (syngas), which is an important
product in the petrochemical industry. Another area of interest is reversible solid oxide
cells, which can operate as SOFC or SOEC, but the material selection range that can retain
their chemical stability under redox atmospheres is very narrow.

Author Contributions: Writing initial draft preparation, M.F.V.; review, editing, H.O.; review, editing,
R.S.E.-E.; conceptualisation, writing, review, editing, supervision, B.A.H. All authors have read and
agreed to the published version of the manuscript.
Funding: The Royal Academy of Engineering has supported part of this work through a Leverhulme
Trust Research Fellowship Award (LTRF2021\17131) and EPSRC IAA grant, which are sincerely
acknowledged here.
Data Availability Statement: Data are available on request.
Acknowledgments: The authors thank the Technology Transfer Department at Surrey, particularly
William Mortimore, William Lovegrove, and Faraz Rizvi, for their support of this project. Also, the
Energies 2023, 16, 3327 40 of 50

opportunity of the EPSRC IAA funding for financially supporting Hasan Ozcan as the postdoc for
this project is acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature

GHG Greenhouse Gas CL-SMR Chemical Looping Steam Methane Reforming

(CLRM)
GF Greenisation Factor SR-CLC Steam Methane integrated with Chemical Loop-
(CLR(s)) ing Combustion
SMR Steam Methane Reforming CLC Chemical Looping Combustion
ATR Auto Thermal Reforming CLR (a) Autothermal Chemical Looping Reforming
POX Partial Oxidation CLG Chemical Looping Gasification
SOE Solid Oxide Electrolysis IGCC Integrated Gasification Combined Cycle
SOEC Solid Oxide Electrolysis Cell UGC Underground Coal Gasification
SOFC Solid Oxide Fuel Cell MIEC Mixed Ionic-Electronic Conductors
HTE High-Temperature Electrolysis ASR Area Specific Resistance
HTSE High-Temperature Steam Electrolysis TEC Thermal Expansion Coefficient
PEM Proton-Exchange Membrane OCAC Oxygen Carrier Aided Combustion
AEM Anion Exchange Membrane OC Oxygen Carrier
AEMWT Anion Exchange Membrane Water EIS Electrochemical Impedance Spectroscopy
Electrolysis
TRL Technology Readiness Level MSC Metal-Supported Cell
HER Hydrogen Evolution Reaction MS-SOEC Metal-Supported Solid Oxide Fuel Cell
OER Oxygen Evolution Reaction OCV Open Circuit Voltage
PCEC(H- Proton-Conducting Solid Oxide Elec- IP Integrated Planar
SOEC) trolysis Cell
O-SOEC Oxygen ion-Conducting Solid Oxide SLC Stack Lifetime Capacity
Electrolysis Cell
TPB Triple Phase Boundary EPC Electrical Power Consumption
AC/DC Alternating Current/Direct Current SL Stereolithography
DLP Digital Light Processing AM Additive Manufacturing
AFL Anode Functional Layer PLD Pulsed Laser Deposition
ALD Atomic Laser Deposition SPS Spark Plasma Sintering
PCE Proton-Conducting Electrolyte SAUP Self-Architecture Ultra Porous
DR/RP-P Double Perovskite/Ruddlesden- CSA Ceramic Sealing Agents
Popper Perovskite
S-I cycle Sulphur-Iodine Cycle Cu-Cl cycle Copper = Chlorine cycle
YSZ Yttria-Stabilised Zirconia LSCF Lanthanum Strontium Cobalt Ferrite
YDC Yttrium-Doped Ceria GDC Gadolinium-Doped Ceria
(CGO)
LSM Lanthanum Strontium Manganite BZY Yttrium-doped Barium Zirconate
BZCYYb Yttrium-and Ytterbium-doped Barium- LNF Lanthanum Nickel Ferrite
Zirconium-Cerate
SSC Strontium Samarium Cobaltite LSC Lanthanum Strontium Cobaltite
LSGM Lanthanum Strontium Gallium Mag- SCSZ Scandia-Ceria-Stabilised Zirconia
nesium oxide
YbScSZ Ytterbium Scandium Stabilized Zirco- CFA Co-Fe alloy
nia
ScSZ Scandia-Stabilised Zirconia ESB Erbium-Stabilised Bismuth oxide
µXRD Synchrotron X-Ray Micro-Diffraction µXRF Synchrotron X-Ray Micro-Fluorescence
IDL Inter-Diffusional Layer CGPO Pr, Gd co-doped Ceria
LSTFO Iron and Lanthanum-doped Strontium LNO Lanthanum Nickelate
Titanate
LSCN Nickel-doped Lanthanum Strontium BSCF Barium Strontium Cobalt Ferrite
Chromite
Energies 2023, 16, 3327 41 of 50

E actual OCV of the oxygen concen- E0 Theoretical OCV of the oxygen concentra-
tration cell tion cell
R Universal gas constant T Temperature (K)
F Faraday constant (96,485 C.mol−1 ) P’O 2 oxygen partial pressure of the air electrode
P”O 2 oxygen partial pressure of the fuel ti ion transport number
electrode
te electron transport number η Faraday efficiency
vmeas calculated hydrogen evolution rate vtheo theoretical hydrogen evolution rate
I applied current Z electron transport number of steam elec-
trolysis
εenergetic Energetic efficiency E0K equilibrium cell potential for product k
εk,faradaic Faradaic efficiency of the product η Cell overpotential
fi,out volume flow of produced fuel gas Vi,m molar volume of reactant component i
component i
Pel consumed electrolysis power

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