Research Proposal for the ‫תכנית מחקר לעבודת גמר‬

Master of Science Degree ‫לקראת תואר מוסמך למדעים‬

Investigation of the Co-electrolysis and Hybrid Conduction Properties of Solid

Electrolytes for High Temperature Dissociation of CO2 and H2O

‫אלקטרוליזה והולכה היברידית של אלקטרוליטים מוצקים‬-‫חקירת תכונות קו‬

‫בתהליכי פירוק בטמפרטורות גבוהות של‬
.CO2 -‫ ו‬H2O

Advisor: :‫מנחה‬
Professor Jacob Karni ‫פרופ' יעקב קרני‬

October 2010 ‫ תש"ע‬,‫חשוון‬

Jeremy M. Seltzer
‫ שלצר‬.‫ג'רמי מ‬
Abstract
The production of syngas (a mixture of CO and H2) from carbon dioxide, water,
and renewable energy represents a feasible mechanism for battling the two-front war
against climate change and the diminishing world oil supply. Concentrated solar power
(CSP) can be converted to heat and electricity and utilized for high temperature
electrolytic reduction of H2O to H2 and CO2 to CO using a solid-oxide electrolyzer
(SOE). Performing electrolysis at high-temperature increases the efficiency, because a
fraction of the necessary energy, as indicated by the gap between the enthalpy and the
Gibbs free energy, is provided directly in the form of heat. CSP is extending the upper
operational temperature limits, where the new challenge is the search for suitable material
performance and design for SOE. Co-electrolysis of CO2 and H2O has been performed,
but in limited configurations. A highly efficient performance breakthrough depends on
the identification and characterization of an electrolytic membrane material capable of
conducting both O2- anions from the cathode side, and H+ cations from the anode side –
termed ‘hybrid conduction’. Recent PhD work by Yury Alioshin detected hybrid
conduction by 8%-Yttria Stabilized Zirconia (8%-YSZ) at temperatures ranging from
600°C to 1400°C. The advantages of hybrid conduction can be many, including higher
overall efficiency, decreased material costs, and better control of the final mole ratio of
H2:CO in the syngas product. The key, however, is to find suitable electrolytic materials.
In the proposed MSc project I will study the parameters governing the ‘hybrid
conduction’, such as resistivity, efficiency and stability of the membrane and electrode
materials at high temperatures and high PH2O and PCO2 environments. The study will
incorporate both a theoretical model study and experimental data collection and analysis.

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I. Introduction
i. Background
Energy sustainability requires affordability, safety, abundance, and compatibility
with society, infrastructure, and the environment 1. Solar energy’s abundance yet abysmal
utilization to date makes it the prime candidate for research leading to large scale clean
power generation and fuel production. The conversion of solar energy to useful energy
encompasses work in the subfields of photovoltaics2-5, solar desalination6-10, solar
thermal11-14 and solar thermochemical cycles15-21, high temperature electrolysis22-27 and
many others. Concentrating solar power (CSP) systems such as dish- concentrators, or
solar towers, like ours at the Weizmann Institute of Science (WIS), can provide the high
temperatures (500<T<1500) necessary to maximize process efficiencies (see Figure 1).
Many papers have discussed the viability of solving both diminishing oil and the
climate change problem by producing a ‘clean’ fuel, like hydrogen, from solar energy15-
18, 20-23
. However, hydrogen’s energy density, even as a liquid, consistently falls short of
the energy density requirements per unit mass and unit volume28-35 when compared to the
benchmark performance of gasoline (35 MJ/L, 44 MJ/kg). Furthermore, difficulties of
storage, transportation and handling have yielded the biggest questions about hydrogen’s
viability as the fuel of the future28-35. Other means of on-board storage of hydrogen such
as in ammonia28-32, ammonia-borane33-35, metal–oxides for on-board production36-42, have
already been extensively categorized and/or are currently being investigated, without
extraordinary breakthrough. A transitional stage is imminent, via the renewable
production of syngas (CO and H2) and subsequent Fischer-Tropsch synthesis of
methanol, gasoline or possibly other synthetic fuels, which conform to society’s current
distribution and storage infrastructure, provides a viable interim solution.
(i) H2O + CO2  H2 + CO + O2
(ii) 2H2 + CO  CH3OH and / or other synthetic fuels
Syngas is traditionally produced by either steam reformation of methane43, or the
reaction of methane with carbon dioxide (dry reforming), which has been proposed for
solar applications44-45. Thermochemical cycles provide another method to produce syngas
from H2O and CO2, but strong uncertainties remain, as these cycles generally require the
handling of rare, expensive and/or corrosive materials15-21. S, the ratio of H2:CO produced

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in syngas production, is 3 and 1 for the reactions of CH4 with H2O and CO2, respectively.
The products’ final composition is determined by the fast kinetics and equilibrium of the
water gas shift reaction at the operating temperature. Methanol production requires S=2,
and gasoline production requires larger S, exemplifying the importance of S-control.
ii. Project
Syngas may also be produced by converting CSP heat to electricity for the
electrolysis of H2O to H2 and CO2 to CO using high temperature SOE. Performing
electrolysis at high-temperature increases the efficiency, because a fraction of the
necessary energy, as indicated by the gap between the enthalpy and the Gibbs free
energy, is provided directly in the form of heat (See Figure 2). Previous studies have
examined the feasibility of high-temperature electrolysis up to 850°C, an upper
operational limit for nuclear energy18,22. With state-of-the-art CSP technology, solar
energy can extend the upper operational limit 1200oC, where the new challenge is the
search for suitable material performance and design. Work in the field of high-
temperature co-electrolysis of H2O and CO2 has been performed since 2008 using
schematic configurations similar to that seen in Figure 3, Configuration A23-24,27. In these
works, Yttrium Stabilized Zirconia (8%-YSZ) is the most commonly used electrolyte for
conducting O2- ions, with nickel-cermet constituting the electrodes. Co-electrolysis has
many potential advantages including, increased process efficiency, decreased material
costs, and better control of the H2:CO ratio in the syngas product, but it remains
efficiency-limited by a competition for electrons at the cathode.
A major efficiency and functionality in high temperature electrolysis of CO2 and
H2O is possible, if one can isolate an electrolytic membrane material capable of
conducting both O2- anions from the cathode side, and H+ cations from the anode side –
henceforth termed ‘hybrid conduction’. Figure 3, Configuration A, shows the commonly
used approach of co-electrolysis, where both CO2 and H2O are introduced from the
cathode side. Figure 3, Configuration B, shows the newly-proposed configuration for
‘hybrid conduction’, which could allow both higher efficiencies (partial pressures of CO2
and H2O up to 100%), and better control of S. Hybrid conduction at high T, to date, has
received little scientific attention because of a lack of perceived utility. There have been
many detailed studies on proton conducting membranes (PCM) since the 1960’s for

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applications to fuel cells (primarily using Nafion®), but their traditional design was at
relatively low temperatures (up to 120°C), and hence they were efficiency-limited,
because their mechanism required water present in the liquid phase46-48. Work on
perovskite-type materials has been performed to try to achieve higher temperature PCMs,
but not in excess of 600°C49. Perovskite-type materials are characterized by the formula
ABO3 where A is a large +2 cation, and B is a +4 cation, whose size is comparable to
oxygen. More recent research on perovskite-type materials, like samarium doped ceria-
carbonate (SDC-carbonate) composite, shows the feasibility of hybrid conduction (Figure
4)49-54. Additional candidates will come from the family of altervalently-doped ceria- and
zirconia-perovskites. Any membrane’s stability in the presence of high partial pressures
of CO2 and H2O, or at temperatures above 1000 oC remains largely uncertain. Recent
work by Y. Alioshin25 detects the occurrence of hybrid conduction by YSZ, at
temperatures in excess of 600°C, though a thorough characterization and experimentation
process is required to fully understand the hybrid conduction properties of 8%YSZ, and
pinpoint other candidates for the membrane.

II. Goals:
The main goals of the proposed MSc study are to develop a predictive model and test
experimentally the performance of candidate hybrid conducting membranes. The
parameters to be evaluated are: hybrid conductivity, material stability at 500<T<1400, 0<
PCO2 <100 and 0< PH2O<100, where Pi is the partial pressure of molecule i. The work will
be divided into the following tasks:
 Build a predictive model to determine the expected dissociation percentage and
composition for a specified, PCO2, PH2O, V, orientation and membrane electrode
assembly
 Determine and prepare candidate Membrane Electrode Assemblies capable of
hybrid conduction
 Determine performance of candidates via evaluation of V-I and impedance (Z)
over temperature ranging from 500-1400oC and different pressures of H2O and
CO2.
 Determine material stability w.r.t high T, high PCO2 and high PH2O by sintering
tests and checking with composition changes with a SEM.
 Determine to what extent we can control the ‘S’ mole ratio in each configuration

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  Compare between the co-electrolysis and the hybrid conduction approaches.
 Investigating alternate applications of the technology, for example systems that
conduct different ions at different times of the diurnal cycle of the sun.

III. Workplan:
 Build a predictive model based upon similar work in the field27
 Design and build a new experimental apparatus to be incorporated with existing
equipment for performing the necessary experiments.
 A 8%-YSZ electrolyte will be tested thoroughly for the occurrence of hybrid
conduction via Figure 4, Configuration B. The impedence values, overpotentials,
H+ conduction, O2- conduction will all be measured and analyzed.
 Comparisons between configurations A and B will be made for 8%-YSZ.
 Prepare/test other membrane candidates with potential for hybrid conduction.
 Comparisons between configurations A and B will be made for all materials.

IV. Literature:
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Change”. Applied Thermal Engineering 23(3), 251-283. 2003.

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13. M. Thirugnanasambandam, S. Iniyan. “A Review of Solar Thermal Technologies”. Renewable
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of Minnesota. 2001.
15. T. Kodama, N. Gokon. “Thermochemical Cycles for High-Temperature Solar Hydrogen
Production”. Chem. Rev., 107(10), 4048–4077 Niigata Universita, Japan. 2007.
16. W. A. Summers, C. Corgnale. “Hydrogen Production via Solar Water-splitting Using the Hybrid
Sulfur Process”. Savannah River National Laboratory. 2009.
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Cycles Potentially Attractive for Hydrogen Production by Concentrated Solar Energy”. Energy
31(14), 2805-2822. Materials and Solar Energy Laboratory, France. 2005.
18. L.C. Brown, G.E. Besenbruch, P.S. Pickard, J.F. Funk. “Nuclear Production of Hydrogen Using
Thermochemical Water-splitting Cycles”. United States Department of Energy General Atomics
Project. 2002.
19. M.E. Galvez, I. Hischier, and A. Steinfeld. “CO2 Splitting via Two-step Solar Thermochemical
Cycles with Zn/ZnO and FeO/Fe3O4 Redox Reactions: Thermodynamic Analysis”. Energy &
Fuels 22, 3544–3550 ETH Zurch and Paul Scherrer Institute, Switzerland. 2008.
20. M. A. Rosen. “Advances in Hydrogen Production by Thermochemical Water Decomposition: A
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26(3), 185-190. University of Kentucky. 2001.
22. S. Fukiwara, S. Kasai. “Hydrogen Production by High-Temperature Electrolysis with Nuclear
Reactor”. Progress in Nuclear Energy 50 (2-6), 422-426. Toshiba Corporation. 2007.
23. J.E. O’Brien, M.G. McKellar, C.M. Stoots, J.S. Herring, G.L. Hawkes. “Parametric Study of
Large-scale Production of Syngas via High-Temperature Co-electrolysis”. Int. J. Hydrogen
Energy 34(9), 4216-4226. Idaho National Laboratory. 2009.
24. Z. Zhan, W. Kobsirphat, J. Wilson, M. Pillai, I. Kim, S. Barnett. “Syngas Production by Co-
electrolysis of CO2/H2O: The Basis for a Renewable Energy Cycle”. Energy Fuels 6(23), 3089-
3096. Northwestern University. 2009.
25. Y. Alioshin. “Study of a Method for Utilization of Solar Energy by Means of High Temperature
Electrolysis of CO2”. PhD Thesis. Weizmann Institute of Science. 2010. (Supervised by J. Karni)
26. H. Iwahara. “Proton Conduction in Sintered Oxides and Its Application to Steam Electrolysis for
Hydrogen Production”. Solid State Ionics 3, 359-363. 1981.
27. G. Hawkes, J. O’Brien, C. Stoots, R. Jones. “3D CFC Model of High Temperature H2O/CO2 Co-
Electrolysis.” Idaho National Laboratory. 2007.
28. C. Zamifirescu, I. Dincer. “Ammonia as a Green Fuel and Hydrogen Source for Vehicular
Applications”. University of Ontario Institute of Technology. Fuel Processing Technology 90(5),
727-737. 2009.
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Cogeneration Application”. Int. J. Applied Thermodynamics 2, 125-131. Royal Institute of
Technology, Sweden. 1999.
30. K.M. Lovegrove. “High Pressure Ammonia Dissociation Experiments for Solar Energy Transport
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(ANU). 1995.
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(ANU). 2003.
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Australian National University (ANU). 2006.
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Dalton Trans. Los Alamos National Laboratory, New Mexico, USA. 2007.
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Regeneration”. European J. of Inorg. Chem. Is. 4. Los Alamos National Laboratory, New Mexico,
USA. 2009.
35. T. Marder. “Will We Soon be Fueling our Automobiles with Ammonia-borane?” Angewandte
Chemie Int. Ed. 46(43), 8116–8118, Durham University, UK. 2006.

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36. I. Vishnevetsky, M. Epstein, T. Abu-Hamed, J. Karni. “Boron Hydrolysis at Moderate
Temperatures: First Step to Solar Fuel Cycle for Transportation”. J. Solar Engineering. Weizmann
Institute of Science. 2008.
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Nano-materials, and Metals Production Technologies”. Weizmann Institute of Science, Texas
A&M University at Qatar. 2009.
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2005.
40. T. Abu-Hamed, J. Karni, M. Epstein. “The Use of Boron for Thermochemical Storage and
Distribution of Solar Energy”. Solar Energy 81(1), 93-101. Weizmann Institute of Science. 2006.
41. P. Grad. “Storing Solar Energy: Solar Technologies for a Future Hydrogen Economy?” Refocus
7(2), 32-36. 2008.
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Vehicles”. Solar Energy 78(5), 687-694. University of Massachusetts. 2004.
43. D. J. Wilhelm, D. R. Simbeck, A. D. Karp and R. L. Dickenson. “Syngas Production for Gas-to-
Liquids Application: Technologies, Issues and Outlook”. Fuel Processing Technology. 71(1-3),
139-148. 2002.
44. Z. Jiang, T. Xiao, V. L. Kuznetsov and P. P. Edwards. “Turning Carbon Dioxide into Fuel”. Phil.
Trans. R. Soc. 368. 2010.
45. H. Klein, J. Karni. “Dry Methane Reforming without a Metal Catalyst in a Directly Irradiated
Solar Particle Reactor.” J. Solar Energy. 131(2). 2009
46. K. Kreuer. “On the Complexity of Proton Conduction Phenomena”. Solid State Ionics 136, 149-
160. 2000.
47. S. Haile, P. Pintauro. “Proton Transport for Fuel Cells”. J. Materials Chem. 2009.
48. M.L. Fontaine, T. Norby. “Novel High Temperature Proton Conducting Fuel Cells: Production of
La0.995Sr0.005NbO4- Electrolyte Thin Films and Compatible Cathode Architectures”. J. of Power
Sources 188(1), 106-113. 2008.
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V. Figures:

Figure 1. WIS Solar Tower

Figure 2. Plot of G and T with Temperature for CO2 and H2O

9
Figure 3. Configuration A: Co-electrolysis in a typical orientation
Configuration B: Co-electrolysis in a hybrid conduction orientation

Figure 4. See Literature Reference51

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IV. Tables:

Table 1. Relevant Reactions and Thermodynamic Data

G298 H298
H2O H2 + ½O2 228 kJ/mol 241 kJ/mol
CO2 CO + ½O2 319 kJ/mol 282.5 kJ/mol
H2O + CO H2 + CO2 -91 kJ/mol -41.03 kJ/mol

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