IEA/HIA TASK 25: HIGH TEMPERATURE HYDROGEN

PRODUCTION PROCESS

High Temperature Electrolysis (HTE)

Process principle

Overall reaction
H2O
H2 + O2
(endothermic reaction)
Cathode reaction:
H2O + 2eH2 + O2Anode reaction:
2O
O2 + 2eCathode
steam electrode

Anode
air electrode

High Temperature Electrolysis

Current status :
High temperature solid oxide electrolyser cells (SOEC)
have a great potential for hydrogen production, as SOECs
can split H2O into H2 and O2 in a very efficient and economical way. When coupled to an external heat source
like solar, geothermal or nuclear, a very high efficiency
can be achieved without any greenhouse gas emissions.
Advantages :
Low overall energy demand
High efficiency, increasing with temperature
Use of several high temperature steam sources
Splitting of CO2 into CO and O2 for syngas production
Broad know-how from SOFC technology available
Challenges :
Due to the high operation temperature of 700 or 800 C
to 1000 C, the SOEC components have to meet specific
requirements for a cost effective hydrogen production :
Electrolyte : chemically stable and gastight with high
ionic and low electronic conductivity
Electrodes : porous, chemically stable in highly
reducing/oxidizing environments with good electronic
conduction and CTE (coefficient of thermal expansion)
close to the electrolyte
Interconnects : chemically stable in reducing/
oxidizing environments

Process description :
Steam is dissociated at the cathode. Simultaneously, oxygen ions migrate through the electrolyte material. Oxygen molecules form on the anode surface by releasing electrons.
Heat source :
Solar, Nuclear, Geothermal, Industrial waste : to
provide low temperature heat needs
(vaporization) only solar or nuclear for the high
temperature heat supplies to the electrolyser.
Conditions : 700 C to 1000 C
Materials :
Gastight electrolyte: Zirconia, doped with Y2O3,
Sc2O3, Gd2O3, LaGO3
Porous cathode : Ni-YSZ remains the state of the
art cathode material, new developments like
(LaSr)TiO3
Porous anode : LSM-YSZ as standard material,
LSF-YSZ and others in development
Total efficiency (thermal to hydrogen) :
40-50 % vs. ~30 % for conventional electrolysis4
Cost evaluation : 2.0 to 3.5 /kg H21, 9 for nuclear heat source
Version 1

Version 1

IEA/HIA TASK 25: HIGH TEMPERATURE HYDROGEN

PRODUCTION PROCESS

Principle of the SOEC process

4

H (total energy demand)

Liquid water

Spec. Energy (kWh/m3 H2)

The key components of a SOEC are a dense ionic

conducting electrolyte and the porous anode and
cathode. Steam is fed to the cathode (steam electrode)
and an electrical potential is applied to the SOEC.
Water molecules dissociate to form H2 gas and oxygen ions at the triple-phase boundary. The hydrogen
gas diffuses to the surface and gets collected, the
oxygen ions are transported through the dense electrolyte to the porous anode (air electrode), where they
are oxidized to oxygen gas and thus release electrons.
The total energy demand (H) for SOEC hydrogen
production is expressed by :
H = G + TS
where G is the electrical energy demand and TS is
the thermal energy demand. An increase in operating
temperature decreases the electrical energy demand
but increases the thermal energy demand. The total
energy demand changes only little with temperature.
Thus, the SOEC provides the opportunity to use several heat sources for an economical hydrogen production.7, 10

G (electric energy demand)

Steam
Q=TS (Heat demand)

0
0

100 200 300 400 500 600 700 800 900 1000
Temperature (C)

Thermodynamics of steam electrolysis : The

electrolysis becomes increasingly endothermic with
11
temperature

Autothermal :

Allothermal :

The SOEC should be operated at the thermoneutral

voltage (1.29V) or slightly above. The energy for the
water splitting is completely supplied by the electric
power, providing the electric potential (G) and the
heat (TS).11

The SOEC is operated below the thermoneutral

voltage. The heat requirement (TS) for the water
splitting is partly supplied by an external high temperature heat source.11

Flow-sheet
For the extrapolation to the industrial scale, INL performed a conceptual high temperature electrolysis
plant design. This calculation is based on coupling
an electrolyser with a high temperature gas-cooled
600 MWth nuclear reactor. At an overall process efficiency of 50 %, hydrogen production could achieve
2.4 kg H2 per second at 850 C. Due to the fact that
the hydrogen product will have to be compressed for
storage and distribution, a high temperature heat exchanger will supply superheated steam to the cells at
750-950 C and a pressure of about 5 MPa. The water consumption is calculated as 21.7 kg/s.5
Flow-sheet for nuclear cycle

Version 1

Version 1

IEA/HIA TASK 25: HIGH TEMPERATURE HYDROGEN

PRODUCTION PROCESS

Experimental, existing prototypes

Description of heat sources

Cylindrical design was chosen for the prototypes of the

HOT ELLY project in the 1980s.4, 8 Current investigations focus on planar designs.2,7,9,10,11 Single and multiple cell experiment studies have been performed.
Within the Hi2H2 project for single cells with an active
cell area of 16 cm, maximum current density of -3.6
A/cm2 at a cell voltage of 1.48 V and hydrogen production of 1.34 kg/m2h was reached.9 Idaho National
Laboratory (INL) have demonstrated a 15 kW integrated laboratory scale (ILS) facility with a hydrogen
production rate of 0.9 Nm3/h.2

Gas cooled nuclear reactors such as the VHTR

and solar central receiver systems are considered for high temperature heat supply (9001000C) for allothermal operation. Such high
temperatures are not required for autothermal
operation mode. Low temperature heat (150200 C) for steam generation can be supplied
from various sources like geothermal or waste
heat.1,3,5,12

Materials

Cost evaluation

Up to now for the SOEC technology materials from

the SOFC has been used with quite promising results.
For future projects the materials have to be adapted
and optimised with respect to long term stability, efficiency, cost reduction as well as the presence of
highly reducing and oxidizing environments. The material selection also depends on the working temperature and compatibility with other components.6,10 The
electrode materials have to be favourable to gas transport and electrochemical activity. Noble metals are
excluded due to the costs.

In allothermal mode, the investment cost for a

process will be relatively high, due to the necessary increase in the total active area (lower current
density) and the necessity of more sophisticated
high temperature heat exchanger devices. The
lower overall efficiency of the autothermal process may be compensated by reducing capital investment, due to smaller electrolysis units (higher
current density) and omission of external high
temperature devices. For this reason mainly autothermal operation of the SOEC has been analyzed
resulting in production costs of 1.1-1.8 /kg H2
depending on the electricity price.9 Considering
variations in the electricity cost for different nuclear reactors, hydrogen could be produced between 2.0 and 2.4 /kg for Sodium cooled fast
reactor (SFR) and 2.4 to 3.0 /kg for European
pressurised reactor (EPR) respectively.1 The influence of the electricity cost has been found to be
the key factor1,9. Hydrogen production costs are
tightly related to techno-economic models.

New materials under development :10, 13, 14, 15

Electrolyte : LSGM, GDC, SDC, LaGO3 proton con
ducting parasites
Cathode : only limited studies on alternative
materials are available, like SDC-Ni,
(LaSr)TiO3
Anode :
electronically conducting mixed oxides
with perovskite structure (LSF, LSC)

Expected efficiency

Characteristics of the two operation modes for HT electrolysis

compared to conventional water electrolysis (HOT ELLY)11
Version 1

Version 1

IEA/HIA task 25 : High Temperature Hydrogen Production Process

High Temperature Electrolysis (HTE)

Contacts :

Ulrich VOGT, EMPA, ulrich.vogt@empa.ch

Franois LE NAOUR, francois.le-naour@cea.fr
Pierre BAURENS, pierre.baurens@cea.fr
Sune D Ebbesen, Sune.Ebessen@risoe.dk

Main initiatives
European development : Hi2H2 consortium,
www.hi2h2.com,
EU Project Relhy : www.relhy.net
Denmark : Risoe DTU : www.risoe.dk
France : CEA : www.cea.fr
Germany : DORNIER - Doenitz (D) in
1979 and 1986, DLR Stuttgart, www.dlr.de
Eifer : www.eifer.uni-karlsruhe.de
Switzerland : EMPA : www.empa.ch/h2e

https:// www-prodh2-task25.cea.fr

USA : INL (Idaho National Laboratory,

www.inl.gov

References
[1]

R. Rivera-Tinco, C. Mansilla, C. Bouallou, F. Werkhoff, Hydrogen production by high temperature electrolysis coupled with EPR, SFR, or HTR: techno-economic study and coupling possibilites, Int. J. Nuclear Hydrogen Production
and Applications, Vol. 1, No. 3, 2008,

[2]

M.G. McKellar, J.E. OBrien, C.M. Stoots, J.S. Herring, Demonstration and System Analysis of High Temperature
Steam Electrolysis for Large-Scale Hydrogen Production Using SOFCs, 8th EUROPEAN SOFC Forum, 2008, Lucerne,

[3]

Sigurvinsson J, Mansilla C, Lovera P, Werkoff F., Can high temperature steam electrolysis function with geothermal
heat ?, Int J Hydrogen Energy 2007;32(9):117482,

[4]

W. Doenitz, R. Schmidberger, E. Steinheil, R. Streicher, Hydrogen production by high temperature electrolysis of

water vapour, International Journal of Hydrogen Energy, Vol. 5, pp. 55-63, 1980,

[5]

J.S. Herring, P. Lessing, J.E. OBrien, C. Stoots, J. Hartvigsen, S. Elangovan, Hydrogen production through High
Temperature Electrolysis in a Solid Oxide Cell Second Information Excahnge Meeting on Nuclear Production of
Hydrogen, 2-3. October 2003,

[6]

U.F. Vogt, J. Sfeir, J. Richter, C. Soltmann, P. Holtappels, B-site substituted lanthanum strontium ferrites as electrode
materials for electrochemical applications, Pure Appl. Chem., Vol. 80, No. 11, pp. 25432552, 2008,

[7]

S.H. Jensen, P.H. Larsen, M. Mogensen, Hydrogen and synthetic fuel production from renewable energy sources, Int.
J. Hydrogen Energy 32 (2007), 3253-3257,

[8]

W. Doenitz, E. Erdle, High temperature electrolysis of water vapour Status of development and perspectives for
application, International Journal of Hydrogen Energy, Vol. 10, pp. 291-295, 1985,

[9]

A. Hauch, S.D. Ebbesen, S.H. Jensen, M. Mogensen, Highly efficient high temperature electrolysis, J. Mater. Chem.,
2008, 18, 2331-2340,

[10]

Meng Ni, Michael K.H. Leung_, Dennis Y.C. Leung, Technological development of hydrogen production by solid
oxide electrolyzer cell (SOEC), Int. J. of Hydrogen Energy 33 (2008) 2337-2354,

[11]

W. Dnitz, E. Erdle, R. Streicher, High temperature electrochemical technology for hydrogen production, chapter 3,
Electrochemical Hydrogen Technologies, edited by Hartmut Wendt, Elsevier 1990,

[12]

E. Erdle, J. Gross, V. Meyringer, Possibilities for Hydrogen production by combination of a solar thermal central receiver system and high temperature electrolysis of steam, Solar thermal central receiver systems, Proceedings of third
int. workshop, June 23-27, Konstanz, Springer-Verlag, Vol. 2, pp. 727-736, 1986,

[13]

G. Tsekouras, J. T.S. Irvine, (La,Sr)TiO3 perovskites as cathode for solid oxide electrolysis cell, International
Workshop on High Temperature Electrolysis Limiting Factors, 2009 Karlsruhe,

[14]

T. Ishihara, T. Kannou, S. Hiura, N. Yamamoto, T. Yamada, Steam Electrolysis Cell Stack using LaGaO3-based
Electrolyte, International Workshop on High Temperature Electrolysis Limiting Factors, 2009 Karlsruhe,

[15] H. Matsumoto, T. Sakaia, S. Matsushitab, T. Ishihara, Intermediate-temperature steam electrolysis using protonconducting perovskite, International Workshop on High Temperature Electrolysis Limiting Factors, 2009 Karlsruhe

Version 1

Version 1