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High Temperature Electrolysis for Hydrogen or
Syngas Production from Nuclear or Renewable
Energy
Yixiang Shi1 , Yu Luo1 , Wenying Li1 , Meng Ni2 , and Ningsheng Cai1
1 Tsinghua University, Beijing, P. R. China
2 The Hong Kong Polytechnic University, Hong Kong, P. R. China

1 INTRODUCTION Ni/YSZ cermet. At a high operating temperature, about 30%

of energy input for electrolysis is in the form of heat, which
Electrolysis process can convert electrical energy into chem- results in a high electrical-to-hydrogen efficiency. The elec-
ical energy. For instance, water can be split electrochemically trochemical reaction rates are sufficiently fast at a typical
into oxygen and hydrogen, which is a promising fuel for the operating temperature of SOEC, thus low cost catalyst (i.e.,
next-generation transportation applications (de Levie, 1999; Ni) can be used. In addition, the considerable thermal energy
Stoots et al., 2009). There are mainly three types of electrol- demand makes it possible to integrate the SOEC technology
ysis technology, which are alkaline electrolyzers, polymer with nuclear and renewable geothermal energy for clean
membrane electrolyzers operating at relatively lower fuel production (Doenitz et al., 1980; Hauch et al., 2008).
temperature, and solid oxide electrolyzer operating at high In the other aspect, owing to the fossil fuel crisis and
temperature. Actually, solid oxide electrolysis cell (SOEC) global warming, increasing interests lay in carbon dioxide
is the reverse reaction of solid oxide fuel cell (SOFC). capture, storage (CCS), and utilization. The use of oxide-
High temperature electrolysis of CO2 , H2 O, and H2 O/CO2 conducting electrolyte in SOEC enables electrolysis of H2 O,
co-electrolysis using solid oxide cells was first studied in CO2 , and H2 O/CO2 mixture. This offers an alternative way
the 1960s by NASA in order to supply the oxygen for life of utilizing CO2 and H2 O for syngas (CO + H2 ) and pure O2
support and propulsion in submarines and spacecraft (Spacil production via H2 O/CO2 co-electrolysis and reversible water
and Tedmon, 1969a). The concept of hydrogen production gas shift (RWGS) reaction (Graves et al., 2011a; Iacomini,
from high temperature H2 O electrolysis was studied and 2004; Stoots, 2006; O’Brien et al., 2010). The syngas can
demonstrated by German Dornier-system, Lurgi and Bosch be further processed via the Fischer–Tropsch (F–T) process
in the 1980s (Doenitz et al., 1980). SOEC has a solid, to produce methanol and other hydrocarbon fuels, which
nonporous metal oxide electrolyte layer that is typically is one of the most promising and feasible routes to convert
CO2 and H2 O into fuel (Becker et al., 2012). In addition, the
composed of Y2 O3 -stabilized ZrO2 (YSZ), a kind of ionic
SOEC can be powered by electricity from nuclear reactor
conductor material at 600–1000◦ C (Spacil and Tedmon,
with negligible CO2 emission (Stoots et al., 2010). The
1969b; Weissbart and Smart, 1967). The air electrode (posi-
SOEC can also be driven by the renewable power, such as
tive electrode, anode) of SOEC is LaMnO3 /YSZ composite
wind power and solar power (solar thermal power generation
and the fuel electrode (negative electrode, cathode) is usually
and photovoltaic power generation), which are abundant
Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd. but intermittent, site-specific, and thus not reliable (Graves,
This article is © 2015 John Wiley & Sons, Ltd. Ebbesen, and Mogensen, 2011b). The fluctuating nature of
This article was published in the Handbook of Clean Energy Systems
in 2015 by John Wiley & Sons, Ltd. the renewable power can be well solved using the solid oxide
DOI: 10.1002/9781118991978.hces146 cell technology: converting electricity into chemical energy
2 Other Advanced Conversion Technologies

via SOEC when the electricity generation is larger than the particles to increase the length of triple-phase boundary
demand and then converting the chemical energy back into (TPB), where the ionic conductor, electronic conductor, and
electricity via SOFC when the renewable power generation is the gas phase meet with each other. H2 O or CO2 gases
insufficient. The feasibility of operating the solid oxide cell diffuse from the chamber to the TPB sites to obtain the
in both SOEC mode and SOFC mode offers a very promising electrons and to generate hydrogen or syngas (Equations 1
way for future energy storage and power generation (Ebbesen and 2).
et al., 2011; Bierschenk, Wilson, and Barnett, 2011). H2 O + 2𝑒− → H2 + O2− (1)
Owing to their reduced electrical consumption, use of
low cost materials, possible integration with nuclear power CO2 + 2𝑒− → CO + O2− (2)
plant and other renewable sources, SOEC technology has
received increasing interest for large-scale fuel generation, The oxygen ions are conducted through electrolyte to the
carbon dioxide utilization, and energy storage. However, TPB in anode, which lose electrons and produce oxygen
nowadays SOEC is still at its early stage of commercial- (Equation 3).
1
ization, and more efforts are needed to further improve O2− → O2 + 2𝑒− (3)
2
its performance, long-term operation reliability and dura-
bility, scale-up and system integration, and so on. This The total electrochemical reaction of SOEC can be written
article provides an introduction to the key features and as:
1
characteristics of SOEC, working principles, and perfor- H2 O → H2 + O2 (4)
mance, development of electrolyte and electrode materials, 2
cell and stack structures, and the considerations in system 1
CO2 → CO + O2 (5)
integrations. 2
Moreover, heterogeneous chemical reactions play important
roles in the syngas production process. Typically, nickel is
2 WORKING PRINCIPLES AND widely used in fuel electrode as the electronic conductor
PERFORMANCE and catalyst. As nickel is an excellent catalyst for RWGS
reaction (Equation 6) and methanation reaction (Equation 7),
Similar to SOFC, the electrochemical reactions in SOEC these heterogeneous reactions can also take place in the fuel
take place in the PEN (positive electrode-electrolyte- electrode of SOEC.
negative electrode structure) structure, which is also referred
Ni
to as MEA (Membrane Electrode Assembly). As shown H2 + CO2 −−→ H2 O + CO Δ𝐻 ≈ 41 kJ∕mol (6)
in Figure 1, on the fuel electrode (negative electrode) side,
H2 O and CO2 are electrolyzed to generate H2 , CO, and Ni
3H2 + CO −−→ CH4 + H2 O Δ𝐻 ≈ −206 kJ∕mol (7)
oxygen ions (Ni, Leung, and Leung, 2008). The produced
H2 and CO are transported from the reaction sites to the
anode surface where they are collected. The oxygen ions 2.2 Thermodynamics
are transported through the dense electrolyte to the porous
air electrode, where they release electrons and generate Thermodynamics is the basic foundation for the chemical
oxygen molecules. In addition to electrolysis reaction, reactions and the electrochemical cells, which can be used
RWGS reaction and methanation reaction can also occur in to judge whether the reaction can happen spontaneously,
the porous fuel electrode. and can be used to predict the minimum energy needed to
sustain an electrochemical reaction in the ideal operating
conditions (O’Hayre et al., 2008; Huang and Goodenough,
2.1 PEN structures and working principles 2009).
In the open circuit condition, the cell potential Vcell is a
A PEN includes an ionic-conducting electrolyte layer and minimum depending on thermodynamics, which is referred
porous air and fuel electrodes. As Figure 1 shows, the dense as reversible Nernst potential EN . For SOEC mode, free
electrolyte is sandwiched between porous fuel electrode and Gibson energy change ΔG refers to the required minimum
air electrode, which conducts oxygen ions and effectively value of electrical energy input. Therefore, the minimum
separates the air chamber and fuel chamber (Larminie and Vcell , that is reversible Nernst potential EN , can be related
Dicks, 2000). H2 O or H2 O/CO2 mixture is fed into cathode, with ΔG as the equation below:
whereas O2 or air is fed into anode. Generally, porous elec-
trode is composed of mixed ionic and electronic conductor Δ𝐺 = 𝑛𝑒 𝐹𝐸𝑁 (8)

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
 High Temperature Electrolysis for Hydrogen or Syngas Production 3

e−
Ionic conductor
− +
Electronic conductor CO2
O2 TPB
TPB H2O

e− e−
O2−
O2− CO2/H2O
O2 CO/H2

Anode Cathode Current

Electrolyte collector

Figure 1. Working principles of solid oxide electrolysis cells (SOEC).

Considering the effect of gas composition and temperature, decreases, whereas the thermal energy demand increases
the reversible Nernst potential EN can be represented as with increasing temperature. This behavior offers high
(EG&G Technical Services, Inc., 2005): temperature electrolysis advantages over low temperature
∏ 𝜐 electrolysis: considerably lower electrical energy consump-
Δ𝐺 0 Δ𝑆 𝑅𝑇 𝑝products
𝑖
tion for electrolysis and possible integration of SOEC with
𝐸𝑁 = − (𝑇 − 298.15) + ln ∏ 𝜐 other heat supplying technologies, such as nuclear power
𝑛𝑒 𝐹 𝑛𝑒 𝐹 𝑛𝑒 𝐹 𝑝reactants
𝑖
plant and geothermal plant.
(9)

where ΔG0 is the ΔG at standard state (i.e., 298.15 K and 2.3 Thermodynamics of heterogeneous reactions
1 atm), ΔS the entropy change (kJ/K), ne the number of elec-
trons transferred, F = 96,485 (Coulombs per mol electrons) The thermodynamics of heterogeneous catalytic reactions
the Faraday’s constant, R the universal gas constant, T the should also be considered especially when the SOEC is used
temperature (K), p a species partial pressure, and 𝜐i stoi- for H2 O/CO2 co-electrolysis. According to physical chem-
chiometric coefficients in the total reaction. For the water istry, a reaction can spontaneously happen if the Gibbs free
electrolysis reaction, the theoretical Nernst potential can be energy ΔG < 0. Figure 3 shows the ΔG values of RWGS
calculated as: and methanation reaction at different temperatures. The
predictions indicate that H2 production is promoted by
𝑝H2 𝑝O
1∕2
RWGS at T < 820◦ C and methane formation is favorable at
Δ𝐺0 Δ𝑆 𝑅𝑇
𝐸𝑁 = − (𝑇 − 298.15) + ln 2
(10) T < 620◦ C.
𝑛𝑒 𝐹 𝑛𝑒 𝐹 𝑛𝑒 𝐹 𝑝H2 O

For cathode gas H2 O : H2 = 0.5 : 0.5 and with anode gas 2.4 Electrolysis reaction kinetics
air, EN is equal to 1.263 V at 100◦ C, whereas the EN is
equal to 1.016 V at 800◦ C. According to thermodynamics, In the ideal operating conditions, electrolysis in SOEC
the total energy needed for electrolysis can be determined should happen at its reversible potential EN . However,
as, the real operation of SOEC involves complex chemical,
Δ𝐻 = Δ𝐺 + 𝑇 Δ𝑆 (11) electrochemical, and mass transport processes. In operation,
the actual operating potential must be higher than the
It can be seen that electrolysis requires not only electrical reversible potential owing to three irreversible losses: (i)
energy (ΔG) input but also thermal energy (TΔS) input. ohmic overpotential (𝜂 ohm ) due to ionic and electronic
Figure 2 shows the energy demands for H2 O and CO2 charge transport resistances, (ii) activation overpotential
electrolysis at different temperature. It can be seen that for (𝜂 act ) due to irreversibility of electrochemical reactions at
electrolysis of H2 O or CO2 , the electric energy demand the TPB, and (iii) concentration overpotential (𝜂 conc ) due

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
4 Other Advanced Conversion Technologies

300 1.56

250 ΔH (total energy demand) 1.30

Energy input (kJ mol−1)

ΔG (electricity

Voltage demand (V)

200 demand) 1.04

Gaseous H2O
Liquid H2O
150 H2O = H2 + 1/2O2 0.78

CO2 = CO + 1/2O2
100 0.52

50 0.26
TΔS (heat demand)
0 0.00
0 100 200 300 400 500 600 700 800
Temperature (°C)

Figure 2. Energy demands for H2 O and CO2 electrolysis at different temperature.

50 Considering the three overpotential losses, the cell voltage

Vcell can be represented as:
Free Gibson energy ΔG (kJ mol−1)

CO + H2O = H2 + CO2
0 𝑉cell = 𝐸𝑁 + 𝜂act + 𝜂ohm + 𝜂conc (12)

Activation overpotential 𝜂 act includes activation overpo-

−50 tential at cathode (𝜂 act,c ) and anode (𝜂 act,a ), which can be
represented as (Singhal and Kendall, 2003):

−100 𝜂act,c = 𝜙el,c − 𝜙ion,c − 𝑉ref ,c (13)

3H2 + CO = CH4 + H2O
𝜂act,a = 𝜙el,a − 𝜙ion,a − 𝑉ref ,a (14)
−150
100 200 300 400 500 600 700 800 900
where 𝜙el,c , 𝜙el,a are electrical potential in cathode and
Temperature (°C)
anode, respectively, 𝜙ion,c , 𝜙ion,a ionic potential in cathode
and anode, respectively, and Vref,c and Vref,a the cathodic
Figure 3. The free Gibson energy of heterogeneous catalytic reac-
tions with various temperatures. and anodic electrical potential difference at equilibrium
state. When 𝜂 act > 0, the charge transfer reaction is negative;
when 𝜂 act > 0, the charge transfer reaction is negative and
producing electrons; and when 𝜂 act < 0, the charge transfer
to mass transport resistance in the electrode. An SOEC reaction is positive and consuming electrons. Therefore,
with lower overpotential can provide better performance 𝜂 act,a > 0 and 𝜂 act,c < 0.
when operated at a certain voltage. It should be mentioned Generally, electrochemical reaction rate in the electrode
that the overpotential losses increase the required operating can be described by Butler–Volmer equation (O’Hayre et al.,
voltage and are eventually changed into heat. However, 2006):
these losses may not cause energy loss of the SOEC, as [ ( )
the generated heat can be partly or even fully utilized 𝑐𝑃 ,𝑐 𝛼ca 𝑛𝑒 𝐹 𝜂act,c
as electrolysis reactions are endothermic. When the heat 𝑖ca = 𝑖0,𝑐 0 exp
𝑐𝑃 ,𝑐 𝑅𝑇
generation from overpotential losses is equal to the heat ( ( )]
)
demand for electrolysis reactions, the corresponding 𝑐𝑅,𝑐 1 − 𝛼ca 𝑛𝑒 𝐹 𝜂act,c
operating voltage is termed as thermal neutral voltage − 0 exp − (15)
𝑐𝑅,𝑐 𝑅𝑇
(TNV).

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
 High Temperature Electrolysis for Hydrogen or Syngas Production 5

[ ( ) 2.5 SOEC performance

𝑐𝑅,𝑎 𝛼an 𝑛𝑒 𝐹 𝜂act,a
𝑖an = 𝑖0,𝑎 exp
𝑐𝑅,𝑎
0 𝑅𝑇 The performance of SOEC depends on many operating and
( ( ) )] structural parameters, such as temperature, inlet gas compo-
𝑐𝑃 ,𝑎 1 − 𝛼an 𝑛𝑒 𝐹 𝜂act,a
− exp − (16) sition, gas flow rate, electrode and electrolyte materials,
𝑐𝑃0 ,𝑎 𝑅𝑇 the microstructure of the electrodes, and interconnectors.
This article focuses on the effects of important operating
where ica and ian are the local current densities (A/m2 ), parameters, including gas composition, temperature, and
respectively, in cathode and anode, i0,c and i0,a the exchange pressure on the SOEC performance, which will be charac-
current densities (A/m2 ) of cathode and anode, cR and cP terized by polarization curve (i–V curve). Figure 4 shows
the concentrations (mol/m3 ) of reactant and product, 𝑐𝑅0 and the typical button cell experimental testing setup for SOEC
𝑐𝑃0 the reference concentrations of reactant and product, T or SOFC cell. The experimental setup includes five func-
temperature (K), and 𝛼 ca and 𝛼 an the cathodic and anodic tional modules: gas supply module, reaction module, electro-
symmetric parameters. In the B–V equation, the first term chemical performance characteristics, cooling system, and
refers to the backward reaction rate, whereas the second exhaust gas analyzing module. Typically, the cell is located
term is for forward reaction rate. The exchange current between two alumina tubes. Pt wires are used as voltage and
density is a critical parameter and is closely related to current probe. The Pt mesh is used as the cathode current
gas compositions, temperature, electrode materials, effective collector and is fixed to the porous cathode with Pt paste.
TPB area, and so on (Kee et al., 2008; Gorte, Kim, and Vohs, The porous Ni felt is used as the anode current collector
2002). and is fixed to the anode support layer with platinum paste.
Ohmic overpotential 𝜂 ohm drives ions to flow through the Before testing, the anode is fully reduced at 800–850◦ C
electrolyte and can be easily determined with the Ohm’s law in a H2 -containing mixture, and Ar is used as a carrier
(Equation 17). Ohmic resistance R mainly depends on the gas to control the steam-hydrogen ratio fed to the button
thickness and ionic conductivity of the electrolyte. In the cell. The dew-point temperatures for both the inlet stream
real operating condition of SOEC, the ohmic potential is also and the outlet stream are monitored (Liu et al., 2008; Yu
affected by the ohmic resistance of interconnector, contact et al., 2008). The polarization curves and the electrochem-
layer, and so on. ical impedance spectroscopy (EIS) can be measured using
Electrochemical Workstation. After the tests, the cell struc-
𝜂ohm = 𝑖𝑅 (17)
ture can be characterized by Scanning Electronic Microscope
(SEM) and Energy Dispersive Spectrometer (EDS), mercury
As the ohmic resistance is proportional to the thickness of porosimetry, and so on.
the electrolyte, one effective way to decrease the ohmic over- The cell is in SOFC mode if the operating voltage is below
potential is to fabricate thin film electrolyte with a typical OCV and in SOEC mode if the voltage is higher than OCV.
thickness of about 10 𝜇m. In SOFC mode, fuel (H2 or CO) and oxygen are consumed
Concentration overpotential 𝜂 conc is mainly due to the and reversed current density is obtained. With a decrease
mass transport resistance within the porous electrode. For in voltage, the current density increases and more electrical
water electrolysis, the concentration of H2 O at the TPB power can be produced. Conversely, when operating voltage
near the cathode–electrolyte interface is lower than that is over open-circuit voltage (OCV, about 0.9 V depending
on the cathode surface, whereas the concentration of H2 on the operating conditions), the cell is in SOEC mode
at the cathode–electrolyte interface is higher than that and the current density increases with increasing voltage,
on the cathode surface. At the anode side, the concen- resulting in more H2 and CO generation from H2 O/CO2
tration of O2 in the anode–electrolyte interface is higher co-electrolysis. At a given voltage, larger current density is
than that on the anode surface. The above-mentioned gas obtained, indicating better performance of the SOEC.
concentration difference increases the last term in the
Nernst Equation (Equation 10) and EN . This increment
2.5.1 Effects of gas composition
of EN is concentration overpotential. In addition, the gas
transport also affects the activation overpotential as the gas Effects of gas compositions on SOEC performance have been
concentration is included in the B–V equation. Usually, extensively examined experimentally and theoretically (Ni,
the concentration overpotential is significant when the 2012a, b). Results show that the performance of SOEC for
SOEC cell is operated at large current density with thick H2 O electrolysis is better than that for CO2 electrolysis,
electrode or when the electrode microstructure is poorly partly due to faster electrochemical reduction kinetics of H2 O
designed. than that of CO2 . It is also an interesting topic to compare

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
6 Other Advanced Conversion Technologies

Part II:
reactor Part IV:
electrochemical
Globe Reducing Mass Check measurement
Air/Ar valve valve flowmeter valve
Anode inlet Part III:
F1
cooling
Anode outlet

Cathode inlet Electrochemical

workstation

Heat
preservation
Globe Reducing Mass Check
H2 valve valve flowmeter valve
Cooling
F1 water

Mass Check
Globe Reducing
Ar flowmeter valve
valve valve
F1

Cathode
Mass
outlet
Reducing Temperature- Gas
Globe Check
CO2 valve flowmeter
valve controlled waterbath product
valve analysis
F1

Globe Reducing Mass Check

CO valve flowmeter valve
valve
F1
Part V: gas collecting
and analysis
Part I: gas supply

Figure 4. Typical experimental testing system for SOECs.

with the performance of co-electrolysis of H2 O and CO2 with Nernst potential EN , increase the ionic conductivity of
H2 O electrolysis and CO2 electrolysis. In fact, in H2 O/CO2 the electrolyte, and facilitate the reaction rates, which in
co-electrolysis, RWGS reaction occurs in the SOEC cathode turn contributes to faster electrolysis. However, the high
and complicates the reaction mechanism. Both the experi- operating temperature limits the choice of materials for
mental and the theoretical studies show that the support types current collecting and gas sealing and may cause coarsening
or electrode thickness of the SOECs have significant effects of the catalyst particles owing to sintering and may lead to
on the cell performance (Li et al., 2013a). When the cathode much faster cell degradation.
is thick enough, the electrochemical reactions mainly occur
in a zone far away from that of the heterogeneous reac-
2.5.3 Effects of pressure
tions, and the electrochemical performance of the SOEC
is almost independent of the elementary species concentra- Up to now, most of the experimental testing on SOEC is
tion variation owing to the heterogeneous reactions. If the at atmospheric pressure owing to the challenge of sealing.
cathode thickness is small, the electrochemical reaction zone The experimental data for pressurized steam electrolysis is
and the nonequilibrium heterogeneous reactions zone grad- acquired by Risø (Jensen et al., 2010). It suggests that higher
ually overlap each other. Thus, the polarization curve of pressure results in higher OCV, which is favorable to SOFC
CO2 /H2 O electrolysis lies between that of H2 O and CO2 mode but unfavorable to SOEC mode. Moreover, the total
electrolysis with a relatively thick cathode, and gradually number of moles of the gas products is larger than that
approaches to that of H2 O electrolysis as the cathode thick- of the reactants in electrolysis, increasing the gas pressure.
ness reduces. According to Le Chatelier’s principle, high pressure inhibits
electrolysis in SOEC mode and promotes fuel oxidation in
2.5.2 Effects of temperature SOFC mode. While, if the purpose of the SOEC is to produce
CH4 from the H2 O/CO2 co-electrolysis, high pressure will be
Operating temperature is a key factor for electrochemical beneficial as methanation reaction decreases the total number
performance. High temperature can significantly lower of moles of the gas mixture.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
 High Temperature Electrolysis for Hydrogen or Syngas Production 7

2.6 Solid oxide fuel-assisted electrolysis cell Therefore, the fuel can be efficiently utilized in SOFEC
electrolysis (SOFEC) at moderate current density with minimum electrical energy
consumption. In addition, the fuel choice is flexible. If the
Although electricity demand (ΔG) decreases and heat solid carbon fuel, for example, coal, can be directly used
demand (TΔS) increases with increasing temperature, the to drive the operation of SOFEC, the hydrogen produc-
SOEC still consumes a considerable amount of electrical tion cost will further be reduced significantly (Iora et al.,
energy for hydrogen or syngas production at allowable 2010).
operating temperature. And, in fact the price of the hydrogen
from electrolysis is much higher than that from methane
steam reforming (at least 2–3 times) (Zhang et al., 2008). 3 MATERIALS
It is therefore crucial to further reduce the electrical
energy demand. Recently, solid oxide fuel-assisted elec- 3.1 Electrolyte material
trolysis cell (SOFEC) has emerged as a novel approach
for electrolysis with reduced electricity consumption. The The electrolyte of SOEC can be oxygen ion conducting or
difference between SOFEC and SOEC is that fuel is fed proton conducting. The main requirement of the electrolyte
and oxidized in anode for SOFEC mode instead of gener- material of an SOEC include following aspects: thermal,
ating oxygen. Figure 5 compares the working principle of chemical, and mechanical stability; high ionic conductivity;
H2 O electrolysis by SOEC and SOFEC. This method can very low electronic conductivity; no gas leakage; and
effectively reduce the reversible potential (Nerst potential compatibility with electrode materials. The dense electrolyte
EN ) by means of chemical energy from fuel oxidation can be fabricated by several ceramic process methods such
(Wang, Vohs, and Gorte, 2007; Joel, Pham, and Aceves, as the tape casting, dry pressing, plasma spaying, and
2003). chemical vapor deposition.
According to thermodynamics, the Nernst potential is Zirconia-based electrolyte, commonly doped with Y2 O3 ,
greatly reduced in SOFEC. That is, assuming electrolysis by Yb2 O3 , and Sc2 O3 is widely used as the SOEC electrolyte
SOFEC has similar overpotentials to that by SOEC, a large owing to their good ionic conductivity at a high temperature.
The ionic conductivity of the electrolyte greatly depends
amount of electricity can be saved with the addition of some
on the concentration of dopants. The highest oxygen ion
cheaper fuels, including carbon, carbon monoxide, nature
conductivity can be obtained when ZrO2 is doped with
gas, biomass, and other hydrocarbon fuels. Typical polariza-
8 mol% of Y2 O3 (Arachi et al., 1999). ScSZ has relatively
tion curves can be drawn in Figure 6. The power density (P,
higher ionic conductivity than YSZ; however, the higher
W/cm2 ) can be calculated by:
costs limit its wide applications in both SOFC and SOEC
(Singhal and Kendall, 2003). In the other aspect, the high
𝑃 = 𝑖𝑉 (18) operating temperature limits the selection of interconnect
materials and leads to problems for long-term stability,
Current density i is always positive in the above expression. despite of high reaction rate and ion conductivity. To lower
When V < 0, P is negative, which means that SOFEC does the material cost and cell durability, one effective way is
not consume but produce electricity. On the contrary, when to decrease the operating temperature to an intermediate
V > 0 (at large i), P is positive (much smaller than SOEC) temperature (IT) range. Ceria-based electrolyte has high
meaning that a small amount of electrical energy is needed ionic conductivity in the temperature range 500–800◦ C.
to generate a lot of H2 . To better understand this behavior, the The commonly used adopter includes Gd2 O3 (GDC),
polarization curves of both SOEC and SOFEC are shown and (Sm2 O3 ), and (SDC). However, the ceria-based electrolyte
compared in Figure 7. The same current density represents exhibit non-negligible electric conductivity at relatively
the same hydrogen production rate (assuming that current high temperature. In addition, its mixed electrical and ionic
efficiency is equal to 100%), and the working potential of conductivities in a reducing atmosphere due to reduction
SOFEC is considerably lower than that of SOEC (around of Ce4+ to Ce3+ is another concern, which means Ce4+
1 V difference). With the same hydrogen production rate, the could be partially reduced to Ce3+ during the electrol-
electricity consumption of SOFEC is much less than that of ysis process and may further lead to the decrease of the
SOEC, which can be expressed as following: mechanical strength (Jiang and Chan, 2004). Lanthanum
Gallate-based electrolyte (i.e., LSGM) is another promising
𝐸SOEC − 𝐸SOFEC 𝑉 − 𝑉SOFEC 1 electrolyte, which has higher oxygen ion conductivity
= SOEC ≈ (19) than that of YSZ and ScSZ. However, the Lanthanum
𝐸SOEC 𝑉SOEC 𝑉SOEC
Gallate-based electrolyte has relatively low mechanical

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8 Other Advanced Conversion Technologies

Solid oxide electrolysis cell

Humidified CH4 CO/H2 Syngas for chemicals

and fuel production
CH4 electrochemical reforming

−
e
(1+x)CH4 + xH2O+O2−

+ → (1 + x)CO + (2 + 3x)H2 +2e−

New energy and Electrolyte oxide ion

O2−
renewable energy transport
−
Charge transfer

e−
Heterogeneous reactions

H2O H2
Hydrogen

Figure 5. Basic working principle of CH4 -assisted SOFEC for H2 O electrolysis.

0.3
Consume fuel and a little electrical energy 2000
produce H2 and electricity
0.2

Power density (Wm−2)

1000
0.1
Voltage (V)

0.0 0

i-V curve
−0.1 i-P curve
−1000
Consume fuel
−0.2 produce H2 and electrical energy
−2000

−0.3
0 1000 2000 3000 4000 5000 6000
Current density (Am−2)

Figure 6. Typical polarization curve and power density curve of SOFEC.

strength, high cost, and can react with Ni metal in the SOEC. Proton-conducting electrolyte is another choice for
A number of novel ionic conductors have been studied, SOECs, which usually includes cerate-, ziconate-, and
for example, LaGaO3 -based perovskites (Goodenough, titanate-based perovskite materials (Lefebvre-Joud,
2000), La2 Mo2 O9 (LAMOX), Bi4 V2 O11 (BIMEVOX), and Gauthier, and Mougin, 2009). Cerate-based perovskites
several pyrochlores with relatively high ionic transport are the most attractive choice owing to their high proton
such as (Gd,Ca)2 Ti2 O7−𝛿 ,apatite materials derived from conductivity and good stability. The SOEC using proton-
Ln10 − x Si6 O26±𝛿 where Ln is a rare-earth element (Tsipis conducting electrolyte can effectively split the steam to
and Kharton, 2008), as well as the proton-conducting mate- hydrogen and oxygen, which may also be potentially used
rials that allow a significant decrease in operating condition for hydrogen separation, carbon dioxide hydrogenation
with improved performance (Lefebvre-Joud, Gauthier, and reaction, and so on. However, it should be noted that the
Mougin, 2009). proton-conducting electrolyte may be not suitable for CO2

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 High Temperature Electrolysis for Hydrogen or Syngas Production 9

1.4 particles is suppressed to some extent owing to poor sinter-

ability of YSZ. In the operating conditions of SOEC, Ni
1.2
can be easily oxidized to NiO, NiOH, and highly volatile
1.0 Ni(OH)2 when the hydrogen partial pressure is low (Utz
0.8 et al., 2011). To avoid redox issues, the MIEC perovskites
Voltage (V)

CO-assisted H2O electrolysis

can be used as SOEC cathode, which can be operated at
0.6 Directly H2O electrolysis
low hydrogen partial pressure conditions; however, it still
0.4 suffer from the low catalytic activity and electronic conduc-
0.2
tivity (Yang and Irvine, 2008). In H2 O/CO2 co-electrolysis,
carbon deposition in the cathode could occur and decrease
0.0 the SOEC performance. Although the carbon deposition
−0.2 problem can be solved by supplying sufficient steam to
0 1000 2000 3000 4000 5000 6000 7000
remove the deposited carbon faster than it deposits, in order
to effectively increase the anode applicability to nonhy-
Current density (Am−2)
drogen fuels, it is still necessary to look for novel materials.
Figure 7. Polarization curves of H2 O electrolysis by SOEC and The experiences in carbon-resistant material of SOFC anode
CO-SOFEC. fueled with hydrocarbon fuels (Park, Vohs, and Gorte, 2000;
Mocoteguy and Brisse, 2013; Fleig, 2003; Laguna-Bercero,
2012) can be helpful for the development of high perfor-
electrolysis and H2 O/CO2 co-electrolysis owing to the lack mance SOEC cathode for CO2 electrolysis and H2 O/CO2
of protons during CO2 splitting. co-electrolysis.

3.2 Electrode material 3.2.2 Air electrode

Most of the air electrodes of SOEC are composed of porous
The electrode layer should not only have high electronic
mixed conducting perovskite oxide materials (ABO3−𝛿 )
and ionic conductivity and electrochemical reaction (Mocoteguy and Brisse, 2013; Fleig, 2003). Where, the A
activity but also should be porous to enable efficient usually represents a trivalent lanthanide ion, for example,
gas transport between the gas channel and the TPB La3+ , Sm3+ , and Gd3+ . Part of the A sites can be substituted
near the electrode–electrolyte interface. In addition, the by a divalent alkali earth ions, such as Mg2+ , Ca2+ , and
electrode materials must be chemically and physically Ba2+ to increase the material stability and electronic/ionic
stable in high oxidizing/reducing environments and have conductivities. The most commonly used cathode materials
similar coefficient of thermal expansion (CTE) as the in SOFC are strontium doped lanthanum manganite (LSM),
electrolyte. strontium doped lanthanum colbatite (LSC), and relatively
novel strontium doped lanthanum ferrite (LSF). LSM is
3.2.1 Fuel electrode known to have a very high electronic conductivity and a poor
ionic conductivity, which limits the TPB to a small region
The commonly used SOEC fuel electrode materials include between electrolyte and the electrode (Mocoteguy and
the metal, cermet, and mixed ionic and electronic conducting Brisse, 2013). The LSC and LSF are both good electronic
(MIEC) materials. The metal electrode material usually and ionic conductors. LaFeO3 -based material, such as LSF
includes the noble metal (e.g., Pt, Ru, and Pd) and base and LSCF, can be used as the SOEC anode but may not
metal (e.g., Ni, Co, and Cu) (Doenitz et al., 1980). Ni is perform well as SOFC cathode owing to a lower oxygen
the most popular material for SOFC and SOEC fuel elec- vacancy concentration in SOFC mode (Laguna-Bercero,
trode. Ni shows high activity for not only electrochemical 2012).
reactions but also water–gas shift, reforming, and metha- In SOEC mode, high oxygen partial pressures occur at
nations. As Ni only conducts electrons, the Ni particles the air electrode/electrolyte interface, which may lead to
can be mixed with ionic conducting particles (i.e., YSZ) to the delamination of anode from the electrolyte (Sharma
form a cermet electrode (i.e., Ni-YSZ composite). Compared and Yildiz, 2010). Virkar (2010) concluded that the anode
with metal-based electrode, the cermet electrode extends the delamination is mainly due to the high local oxygen partial
electrochemical reaction zone from the electrode–electrolyte pressure at the electrolyte/electrode interface. Chen and
interface to the interior of the electrode. In addition, the long- Jiang (2011) proposed that delamination of the LSM
term stability of electrode is improved as the coarsening of Ni anode from the electrolyte results from LSM disintegration

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10 Other Advanced Conversion Technologies

near the anode–electrolyte interface. In SOEC operation, et al., 2007). The metal-supported configuration of the cell
oxygen would be accumulated around the defect site at the can effectively reduce the material costs and can increase
solid–solid interface. The tensile strains will increase owing the mechanical strength of the PEN structure. And ascribing
to the lattice shrinkage caused by the formation of cation to the excellent heat conductivity of the metal, the metal-
vacancies at high oxygen partial pressures. Keane et al. supported cells have the advantages in the aspect of thermal
(2012) further proposed that the anode delamination may shock characteristics.
result from the development of an uneven anode–electrolyte
interface, as well as the formation of lanthanum zirconate 4.2 Solid oxide electrolysis cell configurations
under electrical testing.
Most of the current SOEC cell configurations are developed
based on the SOFC technologies. The characteristic of the
4 PEN STRUCTURE AND STACK solid-state components enables SOEC to be manufactured in
CONFIGURATIONS many different configurations. Same with SOFC, the SOEC
stacks can be built based on the planar design, tubular design,
4.1 PEN structure of solid oxide electrolysis cell the segmented-cells-in-series design, the monolithic design,
and so on (Minh, 2004). Among these configurations, the
In order to provide sufficient mechanical strength of PEN, tubular cells and planar cells are widely accepted as the
one component layer (electrode or electrolyte) must be thick appropriate design for SOEC commercialization.
enough (a few hundred microns) and the thick layer is called
a support. Accordingly, SOEC can be electrolyte-supported,
4.2.1 Planar cells
air-electrode-supported, or fuel-electrode-supported.
In the electrolyte-supported cell, the thick electrolyte Figure 8 shows the schemes of the unit cell and the stack
(100–1000 𝜇m) has excellent stability but relatively large of the planar SOEC. Each flat single cell is stacked in
ohmic resistance owing to its large thickness. This high series and connected by the metallic or ceramic interconnect
ohmic resistance can be significantly decreased by oper- plates. The planar configuration has the advantages of high
ating the electrolyte-supported SOEC at high temperature, volumetric gas production rate, low complexity in manu-
employing alternative electrolyte with high ionic conduc- facturing and fabrication, and the relatively easier current
tivity at a lower temperature, or adopting an electrode- collecting. However, the sealing and thermal cycling perfor-
supported configuration with a thinner electrolyte (Jiang and mances are big concerns of planar cells. Idaho national lab
Virkar, 2003; Virkar, 2003). has tested planar single electrolysis cell, electrolysis cell
The fuel electrode-supported cell is very popular and is stack, and multiple stacks (O’Brien et al., 2007; Zhang
widely accepted as the most promising structure design et al., 2013a). Ten single cells are connected in series as
for the SOFC (Minh, 2004). The continuous progress in a stack unit, and then an electrolysis module is assem-
the manufacturing techniques allows the production of bled by 24 such stack units. The SOEC module achieved a
fuel electrode-supported cells with extremely thin elec- peak hydrogen production rate of around 5.7 Nm3 /h (O’Brien
trolytes even <5 𝜇m. However, the air electrode-supported et al., 2006). Risø National Lab and Topsøe Fuel Cell
cell would be also a promising choice compared with have assembled the planar SOEC stack that contains 10
electrolyte-supported cells. Especially for SOEC operation, planar single unit cells for H2 O electrolysis and H2 O/CO2
the oxygen production in air electrode is permeated from the co-electrolysis (Graves, Ebbesen, and Mogensen, 2011b;
electrode/electrolyte interface to the electrode/flow channel Ebbesen et al., 2011).
interface and does not suffer from the transport limitation.
This is different from SOFC mode, in which oxygen at 4.2.2 Tubular cells
the TPB can become zero at high current density (limiting
current density). However, the air electrode-supported cell Figure 9 shows the schemes of the unit cell and the stack
is still limited by the common manufacturing process as of the tubular SOEC. Tubular SOEC has the advantages
the performance of the air electrode will be significantly of relatively easier sealing, higher thermal shock resistance
deteriorated during the sintering process of electrolyte layer enabling better thermal cycling performance, high mechan-
(Chen et al., 2007). ical strength, and so on, and it has the disadvantages of manu-
Recently, the metal-supported SOEC cell has emerged facturing difficulties, low gas volumetric production rate, and
as a promising route by employing the metal alloys as the the difficulties in current collecting. Tubular SOEC is consid-
mechanical support for the PEN structures at an intermediate ered to be one of the promising configurations for SOEC
or low operating temperature (Schiller et al., 2009; Franco commercialization applications.

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 High Temperature Electrolysis for Hydrogen or Syngas Production 11

Interconnect
Anode
channel Ι
Air e−

Anode +
Electrolyte O2−

Power
Cathode active
layer

−
Cathode support
layer
e−

H2O/CO2 e−

Cathode
(a) channel

Anode
layer Cathode
Electrolyte active layer
layer

Interconnector Cathode
(current collector) support layer

Single
cell

Cathode Anode
(b) channel channel

Figure 8. Scheme for planar SOEC unit (a) and stack (b).

Typical tubular SOEC cell has been reported by Hino 5 HIGH TEMPERATURE ELECTROLYSIS
et al. (2004). Their tube consists of 12 electrolysis cells, SYSTEMS
each of 19 mm in length and connected in series, and the
maximum hydrogen production rate of 6.9 N L/h at 15.6 V, 5.1 System integration considerations
1.72 A and 950◦ C is achieved with energy efficiency of about
77%. Sandia National Lab has developed Ni-YSZ/YSZ/LSM In the practical application, various system components will
cathode-supported SOEC cell with cell diameter 98 mm and be integrated with the electrolysis system to convert the
length 180 mm (Moyer et al., 2010). Also, novel metal- electrical energy into gaseous or liquid fuels (Fu et al.,
supported tubular cells fabricated at DLR (Schiller et al., 2010; Stempien, Sun, and Chan, 2013). Generally, the system
2009). Recently, the micro tubular configuration of SOEC contains the functional modules for power conditioning,
unit cells has been studied by researchers for steam elec- gas feeding, electrolysis, thermal management, and also the
trolysis (Hashimoto et al., 2009; Laguna-Bercero et al., product processing module (Wang et al., 2014). The design
2011). It suggest that the micro tubular design may greatly of SOEC system involves the component integration and
improve the power density and hydrogen production rate in matching of thermal and power devices and to minimize
per unit volume, and it may be one of the promising routes system cost within the constraints of the certain applications.
for tubular SOEC commercialization (Jin, Yang, and Chen, However, the requirement of low costs and integration of
2011). different types of components usually lead to a trade-off in

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12 Other Advanced Conversion Technologies

Bottom CO
2 /H O
2 Injector tube
Cathode support layer
Cathode active layer
Electrolyte
Air
Anode
(a) Cathode inlet Cathode outlet

CO2/H2O
Cathode
Anode outlet
outlet

Anode
channel Injector tube
(preheat)
Cathode channel
(reaction)

(b) Air

Figure 9. Scheme for tubular SOEC unit (a) and stack (b).

both sides. The design decision should be based on careful Lab developed a 15-kW integrated laboratory scale planar
considerations on technology and economic performances of SOEC facility, built a system model of large-scale syngas
SOEC systems. production powered by nuclear energy and obtained a highest
The thermal management (inlet gas heating, outlet gas theoretical overall syngas production efficiency of 48.3%
cooling, heat recuperation, etc.) is crucial for the SOEC (O’Brien et al., 2005; Steinberger-Wilckens and Lehnert,
system to match the system heat balance. For the SOEC 2010).
stack, the variations in internal heat source and sink will If the SOEC is used for power storage and generation in a
change the temperature distribution within the stack, one of reverse solid oxide fuel, the produced hydrogen or syngas can
the main purposes for the thermal management is to avoid be directly used as the fuel of SOFC. For producing gas or
the thermal crack during operation by carefully control- liquid fuel, product post-processing system is used to convert
ling the temperature profile, especially when the electrolysis the hydrogen and syngas into the desired gas, liquid fuels,
stack is driven by intermittent and fluctuating wind or solar such as methane, gasoline, and diesel through methanation
power. In fact, the heat generation from the various overpo- or F–T synthesis processes, which is suitable for industrial
tential losses in the electrolysis process can be utilized as and domestic applications (Ridjan et al., 2013).
the electrolysis reactions of H2 O and CO2 are endothermic. In the practical application of SOEC, the power condi-
Usually, the thermal management of the electrolysis stack tioning subsystem in the electrolysis system is crucial
is implemented by tuning the air temperature and air flow and challenging when coupling with intermittent energy
rate to cool or heat the stack. The issues in the hydrogen resources, especially for renewable power such as wind
or syngas production recycle, stack electrical configurations, power and solar power. The voltage thresholds are critical
and so on should be carefully considered. Idaho National for tuning operation strategy to reduce the effects of the

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 High Temperature Electrolysis for Hydrogen or Syngas Production 13

intermittent input. One of the main tasks of the power and commercialized for diesel and gasoline production, and
conditioning module is to supply the power at the consistent the main reaction can be written as following (Unruh, Pabst,
operating voltage. In order to study the effects of the and Schaub, 2010):
intermittent operation on the SOEC performance, Petipas
et al. (2013) performed SOEC testing for 600 h both under CO + 2H2 → [–CH2 –] + H2 O −165 kJ∕mol (20)
steady-state and transient conditions. The results give a first
proof that SOEC can be operated under on–off intermittent CO + H2 O → H2 + CO2 −40.6 kJ∕mol (21)
conditions without detrimental impact on the degradation
rate when a reducing atmosphere is maintained at the The methanation process can convert the hydrogen and
hydrogen electrode. However, the operation stability is still carbon monoxide into methane using ruthenium, cobalt,
significant for SOEC operation, and more researches on the nickel, and iron catalysts (Mills and Steffgen, 1974). As
SOEC transient operating should be focused on the practical the produced methane can be fed into existing gas grid,
operating conditions, for example, stack startup, shutdown, the integration of methanation process with SOEC system
current and voltage fluctuations, and even severe thermal can be a promising power storage technology. As an
cycling. interesting application case, the Figure 11 shows a possible
integration of the high temperature H2 O/CO2 electrolysis
with the coal to methane system. In the commercialized
5.2 Typical system layout coal to methane system, both of the byproduct steam
and carbon dioxide can be generated during the metha-
Various system components are required to be incorporated nation and shifting reaction processes, which inherently
into an SOEC system to produce hydrogen, syngas, methane, provide the raw feeding gases for high temperature elec-
or liquid fuels. Moreover, it is also necessary to fully utilize trolysis, especially for some certain places both having the
the available waste heat to achieve higher system efficiency industries for coal chemical engineering and renewable
(Wang, Mori, and Araki, 2010; Perdikaris et al., 2010). The power.
SOEC system usually consists of SOEC stack, power condi-
tioner, hydrogen and syngas post-treatment components, and
the heat exchangers. 6 MATHEMATICAL MODELING OF
Figure 10 shows the typical system layout for steam elec- SOLID OXIDE ELECTROLYSIS CELLS
trolysis and H2 O/CO2 co-electrolysis by nuclear power or
renewable power. As a large amount of thermal energy is Current studies on CO2 /H2 O co-electrolysis in SOECs
needed to generate steam for SOEC, the utilization of various mostly focus on performance testing, materials develop-
heat resources and steam byproduct, such as the low temper- ment, and system analysis and design (Zhang et al., 2013b).
ature steam from the power plant and chemical plant is However, there are complex coupling reacting and transport
significantly important for improving the system technical processes, such as momentum balance, thermochemical and
performance and economic effectiveness. At first, SOEC electrochemical heterogeneous reactions, charge transfer,
integration with nuclear reactor has been paid much atten- and heat and mass transport. AS the existing experimental
tion, as the nuclear power is relatively stable, and the nuclear tool is not capable of exploring all these coupling processes,
reactor can supply enough steam for SOEC. Regarding the a validated mechanistic model can be a complementary
connection between the renewable power and SOEC, the tool to help understand the complex reaction and transport
integration of SOEC with a renewable power system would processes. In addition, more and more researchers recog-
have a positive effect on improving the system stability, espe- nized that the mathematical modeling studies on SOECs is
cially for the intermittent and fluctuating wind or solar power crucial for accelerating the commercialization process of
curtailment. CO2 /H2 O co-electrolysis in SOECs, reducing fabrication
For H2 O/CO2 co-electrolysis system, the layout will be cost, as well as for revealing the reaction mechanism
more complex than the steam electrolysis system. The CO2 governing SOEC performance. Varies SOEC models of
resources and the syngas processing should be considered. H2 O electrolysis (Ni, Leung, and Leung, 2007; Ferrero
Usually, the CO2 can be from the power plant and chemical et al., 2013), CO2 electrolysis (Shi et al., 2013; Ni, 2010),
plant through pre-combustion CO2 capture, post-combustion and CO2 /H2 O co-electrolysis (Xie and Xue, 2012; Ni,
CO2 capture, oxy-fuel combustion processes, and even air- 2012a) at different levels have been developed, including the
capture processes (Smith, 1999). For the utilization of the elementary reaction model (Li et al., 2013b; Janardhanan
syngas product, the main choices include the F–T synthesis and Deutschmann, 2006), PEN model (Njodzefon et al.,
and the methanation. The F–T synthesis has been developed 2013; Grondin et al., 2011), electrolysis unit model (Ni,

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14 Other Advanced Conversion Technologies

Renewable energy
nuclear energy O2

e−

SOEC H2

Separator
H2O

Heat
exchanger
(a)

Renewable energy
nuclear energy O2
e−

SOEC

H2O
CH4
CO/H2
Power plant or Captured Methanation
coal chemical CO2
industry Heat
exchanger
Liquid
fuel

(b) F-T synthesis

Figure 10. Typical system layout for hydrogen production (a) and syngas production (b) from high temperature electrolysis.

Leung, and Leung, 2006), stack model (Laurencin et al., dependence on the anode material design and operating
2011; Iora et al., 2012), and system model (Stempien, Ding, condition optimization. One of the objectives of the anode
and Sun, 2012; Zhang, Yu, and Xu, 2012). It can be predicted mechanism study is to identify the rate limiting steps, which
that novel computational methodology, modeling theory determines the electrode performance. For this purpose,
will be more crucial in the future for the understanding the detail of the anode reaction mechanisms including the
of chemical and physical processes and instructing the reaction rate of the thermochemical and electrochemical
engineering design for SOECs. Moreover, the effective reactions, the surface species and their conversion pathway,
validation of the theoretical model by comprehensive and the combinations of elementary reaction parameters
experiments in different length and time scales is essential are required (Li et al., 2013b). In addition, the rate limiting
(Figure 12). steps depend on the materials and operating conditions,
such as temperature, fuel composition, and polarization
6.1 Elementary reaction models voltage. Therefore, various rate limiting steps have been
identified at different operating conditions, such as adsorp-
The elementary reaction model is used to describe the tion and desorption, surface diffusion, charge transfer,
detailed adsorption/desorption and surface reactions on the sintering, and impurities (Suna and Stimming, 2007). It
catalyst surface. Elementary reaction steps may include is important to develop an elementary reaction model
species adsorption, desorption, dissociation, surface diffu- of CO2 /H2 O co-electrolysis in SOECs to understand the
sion, surface reaction, bulk diffusion, and exchange as reaction and transport mechanisms, which will be beneficial
well as the charge transfer reactions. It is important to for the experimental results interpretation, cell design, and
understand the reaction mechanism and kinetics and their optimizations.

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 High Temperature Electrolysis for Hydrogen or Syngas Production 15

Steam

H2S
Sulfur

Steam

Coal Clean
up CH4

Air seperation O2
Cooling
unit
Shift reactor
Air seperation Methanation
unit
CO2

Tank

Oxygen CO/H2/CH4
CO : H2=1 : 3

AC DC CO2/H2O Steam
Mixer
SOEC
Heat
Renewable exchanger
power

Figure 11. Proposed scheme for renewable power-SOEC/coal to methane integration system.

0.65
CO2 O2 DC power

Power conditioner SOEC

Electrolyte

O(s)
CO CO2(s)
collector
Current

Oxo 0
e− 0
7.18

CO(s)
C(s) YSZ
Vo
Ni
TPB Steam generatior

Cathode outside surface Electrolyte

0.6 Water
H2O/H2/CO2/CO−25/25/25/25 0.05
0.5 0.6
CO2 H2
0.5 H2O
Molar fraction

0.4 H2 CO
0.4 CO2
xi,an

0.3
0.3 Cell voltage = OCV 0.2
Cell voltage = OCV+0.2V 0.1
0.2 Cell voltage = OCV+0.4V 0 5 10 15 20 25 30 35 40 45
H2O 0 0.19
0.1
0.185
CO
0.05
xO2

0.0 0.18
0 100 200 300 400 500 600 700
0.175
Distance from cathode outside surface (μm)
0 0.17
0 5 10 15 20 25 30 35 40 45
/S

Elementary reaction and PEN model Unit cell and stack model System model
Detailed description of transport, electrochemical Coupling momentum transfer, heat transfer, mass Integrating stack model and other BOP model
reaction, and material structure transfer processes based on electrode mechanistic of system, full-load and part-load thermodynamic
model analysis, system design and optimization

Figure 12. Models of SOEC in different levels.

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16 Other Advanced Conversion Technologies

6.2 PEN models and the system techno-economic analysis. Moreover, the
dynamic simulation models are mainly used for under-
Mechanistic PEN models usually considering the mass and standing the system dynamic response and developing
charge transport as well as the detailed chemical and electro- advanced system control strategies. The commercial soft-
chemical reactions. The model in this level usually adopts ware such as Aspen plus and gPROMS can be utilized.
conservation laws to describe the reaction and transport The SOEC stack model for SOEC system modeling usually
processes occurring within the cell and could be used to needs to be simplified to greatly reduce the calculation
identify the effects of each layer in the PEN. The effects complexity. Currently, more and more researchers are trying
of the physical properties, geometries, and microstructures to develop the multiscale system level model by integrating
of the electrolyte and electrode can be studied at this level. the detailed distributed parameter SOEC unit model into
The model usually couples the charge balance and mass the system model. In fact, the distributed parameter model
balance. Charge balance control domains include the anode, along flow channel direction is very beneficial for SOEC
the cathode, and the electrolyte. At the electrodes, elec- system analysis and system control strategy development
trons and oxygen ions are served as conductive particles, (Udagawa, Aguiar, and Brandon, 2008). The multiscale
and at the electrolyte, the conductive particles are only system model can effectively improve the model accuracy
oxygen ions or protons. However, the mass balance mainly and predict the SOEC temperature distribution during the
focuses on the diffusion processes within porous electrode. operation, and so on, which is crucial for system operating
Diffusion inside the porous media is important for electrol- condition choice and control strategy design.
ysis reactions. The free molecular diffusion, Knudsen diffu-
sion, and the surface diffusion processes should be carefully
considered. 7 CONCLUSIONS
The high temperature electrolysis of steam and carbon
6.3 Cell and stack models dioxide based on SOEC is featured with high electricity-
to-fuel efficiency and fast reaction kinetics and it is widely
A comprehensive multidimensional model is necessary for
considered a promising energy conversion and storage
simulating the intricate interdependency among the ionic
technology, especially for efficient utilization and storage of
conduction, electronic conduction, gas transport phenomena,
the nuclear power and renewable power.
and electrochemical processes. Numerous multidimensional
Current researchers have already developed several novel
SOFC models exist in the open literature with varying
applications for high temperature electrolysis based on
sets of assumptions depending on the objectives of the
SOEC; for instance, the high efficiency hydrogen/syngas
simulation. In addition, the multidimensional models of
production, reversible SOEC for renewable power storage,
SOEC could improve understanding of complex physical and
power to methane, power to liquid fuel, biogas upgrading,
chemical phenomena or optimize cell geometries and flow
and integration with coal chemical engineering industry.
patterns.
Especially for the renewable technologies with inherent
At the stack level, the models are mainly used to eval-
intermittent characteristics, such as solar and wind energy,
uate different stacking geometries and to help understand
the high temperature electrolysis of H2 O, CO2 , or co-
the impact of stack operating conditions on the electrol-
electrolysis will be a promising way to accommodate the
ysis performance. Usually, the stack geometry should be
unstable power storage and utilization.
discretized into finite volumes or finite elements. In order
It should be noted that the SOEC is still at its R&D
to reduce the calculation complexity in the stack modeling
stage. Several challenges should be addressed before its
works, the PEN submodel in the stack level is relatively flex-
commercialization: (i) high performance, low cost, long-
ible, which can adopt analytical model, 1-D PEN model or
running life, and material for the electrolyte and electrode;
even the mathematically fitting model of the cell operating
(ii) sealing problems; (iii) stack assembling technology and
curves. In addition, the commercial CFD software, such as stack performance testing, especially in long-time operating
Fluent, CFD-RC, and Comsol multiphysics, can be utilized conditions; (iv) system integration and demonstration, and
to help in stack manifold design and optimization. the control strategy design; (v) BOP components devel-
opment, for example, high efficiency waste heat recovery
6.4 System models for producing steam, novel methanation, and F–T synthesis
reactors. Thus, more deep research and development efforts
The steady-state SOEC system modeling is mainly used for are required for the further development of high temperature
the system design, integration, performance optimization, electrolysis.

Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
 High Temperature Electrolysis for Hydrogen or Syngas Production 17

ACKNOWLEDGMENT Graves, C., Ebbesen, S.D., Mogensen, M., and Lackner, K.S. (2011a)
Sustainable hydrocarbon fuels by recycling CO2 and H2 O with
renewable or nuclear energy. Renewable and Sustainable Energy
The study was supported by Projects 51276098, 51106085 Reviews, 15, 1–23.
(National Natural Science Foundation of China, NSFC),
Graves, C., Ebbesen, S.D., and Mogensen, M. (2011b) Co-
Doctoral Fund of Ministry of Education of China (No. electrolysis of CO2 and H2 O in solid oxide cells: performance and
20110002120017), Project 2014CB249201 (National Basic durability. Solid State Ionics, 192, 398–403.
Research Program of China, 973 Program), and Research Grondin, D., Deseure, J., Ozil, P., et al. (2011) Computing approach
Grant Council (RGC) of Hong Kong (No. PolyU 5326/12E). of cathodic process within solid oxide electrolysis cell: experi-
ments and continuum model validation. Journal of Power Sources,
196, 9561–9567.
Hashimoto, S., Liu, Y., Mori, M., et al. (2009) Study of steam
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This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
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Handbook of Clean Energy Systems, Online © 2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Handbook of Clean Energy Systems in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781118991978.hces146
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