WO2000064814A1 - Ceramiques a conduction electronique et ionique melangee - Google Patents

Ceramiques a conduction electronique et ionique melangee Download PDF

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Publication number
WO2000064814A1
WO2000064814A1 PCT/CA2000/000426 CA0000426W WO0064814A1 WO 2000064814 A1 WO2000064814 A1 WO 2000064814A1 CA 0000426 W CA0000426 W CA 0000426W WO 0064814 A1 WO0064814 A1 WO 0064814A1
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Prior art keywords
strontium
compound
sublattice
dopant atoms
range
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PCT/CA2000/000426
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English (en)
Inventor
Anthony Petric
Shiquiang Hui
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Mcmaster University
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Application filed by Mcmaster University filed Critical Mcmaster University
Priority to AU40956/00A priority Critical patent/AU4095600A/en
Publication of WO2000064814A1 publication Critical patent/WO2000064814A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to electronically and ionically conducting mixed metal oxide ceramics, and more particularly the present invention relates to strontium titanate doped with yttrium as a fuel cell anode material.
  • High temperature fuel cells with ceramic electrolytes require anodes and cathodes to increase reaction kinetics with gases at their surfaces.
  • the electrodes are both catalysts and current collectors/distributers. Typical operating temperatures are 700 - 1000°C although long term trends are towards temperatures of 500 - 700°C.
  • oxygen ions are transported from air through the cathode/electrolyte/anode laminate to oxidize the fuel on the other side. Since the electrodes must have sufficient thickness to transport a current of electrons along the surface, the electrode itself is a barrier to oxygen flow normal to the surface, unless it is also an oxygen ion conductor.
  • LaCr0 3 This is primarily because both Cr and Ni form p-type oxides which require high oxygen pressure for high conductivity.
  • Perovskites are preferred as anodes because they have the potential for mixed ionic and electronic conduction in contrast to simpler compounds like spinels which are not ionic conductors and in addition exhibit good environmental stability.
  • N-type perovskites are based on transition metals such as Ti, V, Nb, Mo and W. Of these, perovskites such as SrTi0 3 and SrV0 3 (with Ca/Ba or rare earth elements substituted for Sr) are the most likely candidates for anode materials. Nb is too difficult to reduce to the 3+ or 4+ valence state; Mo and W have limited 4+ stability ranges.
  • LaV0 3 or other rare earth vanadates are not good conductors, nor are CaV0 3 or BaV0 3 .
  • SrV0 3 is an excellent electronic conductor with a conductivity at 800°C of 1000 S/cm at low oxygen pressure (Po 2 ). However, at higher oxygen pressures, SrV0 3 oxidizes to Sr 3 V 2 0 8 , an apatite-type phase which is extremely stable and which cannot be reversed to perovskite at oxygen pressures common to fuel cell anode environments.
  • CaTi0 3 with 10 - 50% Fe substitution for Ti has shown conductivities close to 1 S/cm, see L.A. Dunyushkina, A.K. Demin and B.V. Zhuravlev,
  • a compound having a formula I there is provided a compound having a formula I;
  • R- are first dopant atoms replacing some strontium atoms on a strontium sublattice
  • x is a fraction of vacancies and said dopant atoms R on the strontium sublattice and 0.10 ⁇ x ⁇ 0.20
  • said dopant atoms R. being selected from the group consisting of yttrium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and wherein n.,% is a mole percent of R and n. > 5.
  • R ⁇ may be yttrium (Y) and n-% is in a range from about 6% to about 15%.
  • a compound having a formula II wherein R 1 is first dopant atom replacing some strontium atoms on a strontium sublattice, x is a fraction of vacancies and said dopant atoms R ⁇ on the strontium sublattice and 0J0 ⁇ x ⁇ 0.20, said dopant atoms R 1 being selected from the group consisting of yttrium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and wherein n.,% is a mole percent of R 1 and n., > 5; and R 2 is second dopant atoms replacing some titanium atoms on a titanium sublattice, y is a fraction
  • R may be yttrium (Y) and n.,% is in a range from about 6% to about 15%.
  • a solid oxide fuel cell comprising; a laminate of a cathode, an anode and an electrolyte sandwiched between said cathode and anode, said anode comprising an oxide compound having a formula Sr ⁇ - iG ⁇ n ⁇ /oR., wherein R is first effective dopant atoms replacing some strontium atoms on a strontium sublattice, x is a fraction of vacancies and said dopant atoms R ⁇ on the strontium sublattice and 0.10 ⁇ x ⁇ 0.20, said dopant atoms R being selected from the group consisting of yttrium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and wherein n.,% is a mole percent of R and n., > 5.
  • R ⁇ may be yttrium and n.,% may be in a range from about 6% to about 15%.
  • the invention also provides a compound having a formula III; Sr 1 . iO 3 :n 1 %Y [III] wherein x is in the range 0J4 ⁇ x ⁇ 0J5 and _ is between 8% to 10%.
  • the present invention also provides a compound having a formula Sr 86 Y 08 TiO 3 . ⁇ wherein ⁇ is in a range from 0 to about 0.03 when said compound is in the presence of a reducing atmosphere.
  • Figure 1 is a prior art plot of ionic conductivities of various perovskites as a function of temperature in air: 1-LaAI0 3 , 2-CaTi0 3 , 3-SrTi0 3 , 4-La 07 Ca 03 AIO 3 . ⁇ 5-La 09 Ba 0 1 AI0 3 . ⁇ 6-SrTi 09 AI 0 ,0 ⁇ , 7-CaTi 095 Mg 005 O 3 . ⁇ 8-CaTi 05 AI 05 0 3 . ⁇ , 9-CaTi 07 AI 03 O 3 . ⁇ , taken from T. Takahashi and H. Iwahara, "Energy
  • Figure 2 shows the change in electrical conductivity of strontium titanate doped with 10 mol% Y and 5 mol% Co during cycling between oxidizing and reducing environments which are indicated by the corresponding partial oxygen pressures;
  • Figure 3 is a plot of electrical conductivity of strontium titanate containing 8 mol% Yb, Sm and Y; strontium titanate containing 10 and 50 mol% La; and calcium titanate containing 8 mol% Y;
  • Figure 4 is a plot of electrical conductivity of Y-doped SrTi0 3 at 800°C in low Po 2 ;
  • Figure 5 is a plot of conductivity versus Log Po 2 (atm) for 10% at yttrium- doped SrTi0 3 with 5% of different dopants on the B-site at 800°C;
  • Figure 6 is a perspective view of a solid oxide fuel cell constructed using the present anode material
  • Figure 7 is a plot of voltage and power as a function of current for a fuel cell comprising a YSZ electrolyte, a strontium titanate anode containing 10% Y and 5% Ga, and a Pt cathode running on air and pure H 2 fuel.
  • the inventors have produced new materials that exhibit relatively high levels of mixed ionic and electronic conductivity at temperatures in the range from 500 to 1000°C and low oxygen pressures (10 13 - 10 ⁇ 20 atm) suitable as fuel cell anodes.
  • the new materials are oxide compounds based on the perovskite, strontium titanate (SrTi0 3 ), having the formula Sr 1 .
  • x Ti0 3 :n l %R 1 where x is the fraction of vacancies and dopant atoms R on the strontium sublattice and 0J0 ⁇ x ⁇ 0.20, wherein 6-15 mol% of the strontium is replaced by R which is preferably yttrium or a late rare earth element from the group samarium, europium, gadolinium, terbium, disprosium, holmium, erbium, thulium, ytterbium and lutetium.
  • the strontium vacancies compensate for some of the charge.
  • One method of producing this material comprises mixing powders of SrC0 3 , Y 2 0 3 and Ti0 2 , pressing the mixture into pellets and sintering the pellets. More particularly, this material was processed in a reducing atmosphere at temperatures of 1400°C Hydrogen-5% argon was used as the reducing gas. The conductivity of the pellets in a reducing atmosphere of carbon monoxide and carbon dioxide at 800°C was measured to be over 60 S/cm. When the pellets were retested at 800°C in air, the conductivity dropped to a level below 1.0 S/cm. When the atmosphere was replaced by reducing gas, the conductivity returned to its initial value in a period of several days, see Figure 2.
  • Yttrium is the preferred dopant for this material, and although other late rare earths are contemplated by the inventors to produce similarly high conductivities, the highest conductivities have been observed with yttrium, as seen from the data of Figure 3, and yttrium is by far the least expensive. These other rare earths include samarium, europium, gadolinium, terbium, disprosium, holmium, erbium, thulium, ytterbium and lutetium. Doping by La, one of the early rare earths, is not as effective as Y, even at levels of 50%, as shown in Figure 3.
  • perovskite is far less conductive when doped with Y in a similar manner, as can also be seen from the data in Figure 3.
  • the maximum conductivity occurs at a dopant level of about 8 mol% yttrium.
  • n is between 8% to 10% in x is in the range 0J4 ⁇ x ⁇ 0J5 which give the highest conductivities.This is the concentration of Y at the limit of solubility.
  • the conductivity can be further increased by adding excess vacancies to the strontium site.
  • the present new mixed oxide exhibits a maximum in electronic conductivity of more than 60 S/cm at the composition Sr 88 Y 08 TiO 3 .
  • the dopant atoms R 2 may be from the transition metals or lower valency metal ions, wherein n 2 % is the mole percent of R 2 and is in the range from about 1 % to about 15%. Examples of dopant atoms R 2 include aluminum, gallium and the transition metal ions. When R 2 is 5%, the value of R ⁇ corresponding to the maximum conductivity is between 10 and 11% which is also at the limit of solubility. With 10 mol% Y on the A-site, doping the B-site with 5 mol% Co, Ga,
  • the B-site dopants may add beneficial catalytic properties or increase oxygen ion conductivity when the material is used as an anode or in other applications.
  • the surprisingly high level of conductivity for these new compositions is unprecedented for an oxide under the normal reducing conditions of common hydrocarbon fuels, and the high conductivity is recoverable from oxidizing to reducing conditions which makes this material useful for numerous practical applications.
  • a fuel cell was constructed to demonstrate the feasibility of the new mixed metal oxide anode materials.
  • a solid oxide fuel cell shown generally at 10 comprises a laminate structure including a first interconnect layer 12 in electrical contact with a cathode 14 and a second interconnect layer 20 in electrical contact with an anode 18. Sandwiched between anode 18 and cathode 14 is a solid electrolyte 16.
  • the electrolyte 16 was a yttria-stabilized zirconia (YSZ) ceramic and approximately 0.5 mm thick which provided support for the other layers.
  • the anode layer 18 and cathode layer 14 are formed on the opposed surfaces of the electrolyte layer 16.
  • the anode 18 comprises the novel doped strontium titanate disclosed herein and more particularly the anode was strontium titanate doped with 10 mol% Y and 5 mol% Ga.
  • the cathode 14 was porous Pt with air as the oxidant.
  • the fuel was a mixture of H 2 gas.
  • SrTi0 3 is thermodynamically very stable and does not form a reaction product with typical electrolytes such as YSZ and lanthanum gallate (LSGM), nor causes a phase change, which means the mixed oxide disclosed herein is very compatible with solid oxide fuel cell components.
  • the SrTi0 3 with some of the Sr substituted by Y has a relatively high electronic conductivity of more than 60 S/cm, compared to Ni-YSZ which, depending on the mixture, is around 500 S/cm.
  • the new metal oxides disclosed herein may be used in a mixture including a metallic second phase to increase total conductivity and/or catalytic activity.
  • Non-limiting exemplary examples of such metals includes such as Fe, Ni, Co and Cu.
  • the oxide exhibits ionic conductivity of up to 0.01 S/cm ( Figure 1 ) compared to 0.035-0J5 S/cm for typical electrolytes.
  • the new material will support reaction between oxygen ions and fuel over the entire surface of the anode, rather than only at the junction between ionically and electronically conducting phases as in 2-phase anodes like Ni-YSZ.
  • the oxide anode will allow a fuel cell to operate in the range of high current densities not possible with a Ni- YSZ anode where the nickel metal is subject to oxidation. Although it is a single phase material, grain growth is restricted to a size near 5 microns by a phenomenon known as the donor dopant anomaly. A fine grain size has the advantage of higher strength and fracture toughness.
  • the new perovskite materials disclosed herein exhibiting high ionic and electronic conductivity are not as prone to carbon deposition from hydrocarbon fuels on the surface as other materials.
  • the new mixed oxide anode materials will not react with sulfur in the fuel, or sulfur compounds such as H 2 S. (Currently, H 2 S needs to be scrubbed from natural gas to prevent fouling and corrosion.) Further, when used with the LSGM electrolyte, it will be lattice matched, eliminating any interphase boundary, and reducing resistance losses.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne de nouvelle matières présentant des niveaux élevés de conduction électronique et ionique mélangée à haute température (500-1000 °C) et basse pression d'oxygène (10?-13 - 10-20¿ atm) pouvant être utilisées comme anode de cellule électrochimique. Ces matières se composent de titanate de strontium pérovskite, représenté par la formule Sr¿1-x?TiO3:n1%R1, dans laquelle x est la fraction de lacunes et d'atomes dopants R1 sur le sous-réseau de strontium dans lequel 0,10 ≤ x ≤ 0,20, 6-15 mol % du strontium étant remplacé par R1 qui est, de préférence, de l'yttrium ou un élément tardif parmi les élément suivants du groupe des terres rares: samarium, europium, gadolinium, terbium, disprosium, holmium, erbium, thulium, ytterbium et lutetium. L'invention concerne également de nouvelles matières semblables représentées par la formule Sr1-xTi1-yO3:n1%R1,n2%R2, dans laquelle une fraction du titanium est remplacée par R2 qui peut être un ion métallique de transition ou un ion à faible valence tels que l'aluminium et le gallium. Des conductions électroniques supérieures à 60 S/cm à 800 °C et à des pressions d'oxygène de 10?-20¿ atm ont été observées avec la composition Sr¿.88?Y.08TiO3-δ, et supérieures à 80 S/cm avec la composition Sr.86Y.08TiO3-δ.
PCT/CA2000/000426 1999-04-27 2000-04-25 Ceramiques a conduction electronique et ionique melangee WO2000064814A1 (fr)

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AU40956/00A AU4095600A (en) 1999-04-27 2000-04-25 Mixed electronic and ionic conducting ceramics

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US13113699P 1999-04-27 1999-04-27
US60/131,136 1999-04-27

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1263071A2 (fr) * 2001-05-09 2002-12-04 Delphi Technologies, Inc. Procédé pour prévenir l'oxydation des anodes dans une cellule à combustible
WO2003094268A2 (fr) * 2002-05-03 2003-11-13 Battelle Memorial Institute Compositions de titanate de strontium dope au cerium modifie pour des anodes de piles a combustibles oxyde solides et des electrodes pour d'autres dispositifs electrochimiques
FR2862163A1 (fr) * 2003-11-07 2005-05-13 Electricite De France Anode de pile a oxyde solide a base d'un cermet particulier et pile a oxyde solide la comprenant
DE102006030393A1 (de) * 2006-07-01 2008-01-03 Forschungszentrum Jülich GmbH Keramische Werkstoffkombination für eine Anode für eine Hochtemperatur-Brennstoffzelle
US7604892B2 (en) 2003-06-27 2009-10-20 National Research Council Of Canada Y and Nb-doped SrTiO3 as a mixed conducting anode for solid oxide fuel cells

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US5807642A (en) * 1995-11-20 1998-09-15 Xue; Liang An Solid oxide fuel cell stacks with barium and strontium ceramic bodies

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US5807642A (en) * 1995-11-20 1998-09-15 Xue; Liang An Solid oxide fuel cell stacks with barium and strontium ceramic bodies

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CARLOS E. BAMBERGER: "Homogeneity Ranges of phases Sr(4-x)Ln(2x/3)Ti4O12 and Sr(1-y)Eu(y)TiO3", J. AM. CERAM. SOC., vol. 80, no. 4, 1997, pages 1024 - 1026, XP002146550 *
CHEMICAL ABSTRACTS, vol. 128, no. 20, 1997, Columbus, Ohio, US; abstract no. 251547, ZHANG, YULING; LU, KUNQUAN; WEN WEIJIA: "Doped Strontium titanate current liquid and preparation method" XP002146552 *
CHEMICAL ABSTRACTS, vol. 131, no. 15, 11 October 1999, Columbus, Ohio, US; abstract no. 202155, G. PUDMICH, W. JUNGEN, F. TIETZ: "characterization of new ceramic anode materials for direct methane oxidation in SOFC" XP002146551 *
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1263071A2 (fr) * 2001-05-09 2002-12-04 Delphi Technologies, Inc. Procédé pour prévenir l'oxydation des anodes dans une cellule à combustible
EP1263071A3 (fr) * 2001-05-09 2005-04-27 Delphi Technologies, Inc. Procédé pour prévenir l'oxydation des anodes dans une cellule à combustible
WO2003094268A2 (fr) * 2002-05-03 2003-11-13 Battelle Memorial Institute Compositions de titanate de strontium dope au cerium modifie pour des anodes de piles a combustibles oxyde solides et des electrodes pour d'autres dispositifs electrochimiques
WO2003094268A3 (fr) * 2002-05-03 2004-06-03 Battelle Memorial Institute Compositions de titanate de strontium dope au cerium modifie pour des anodes de piles a combustibles oxyde solides et des electrodes pour d'autres dispositifs electrochimiques
US7670711B2 (en) 2002-05-03 2010-03-02 Battelle Memorial Institute Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices
US7838141B2 (en) 2002-05-03 2010-11-23 Battelle Memorial Institute Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices
US7604892B2 (en) 2003-06-27 2009-10-20 National Research Council Of Canada Y and Nb-doped SrTiO3 as a mixed conducting anode for solid oxide fuel cells
FR2862163A1 (fr) * 2003-11-07 2005-05-13 Electricite De France Anode de pile a oxyde solide a base d'un cermet particulier et pile a oxyde solide la comprenant
WO2005045961A2 (fr) * 2003-11-07 2005-05-19 Electricite De France Sa Anode de pile a oxyde solide a base d'un cermet particulier et pile a oxyde solide la comprenant
WO2005045961A3 (fr) * 2003-11-07 2006-07-13 Electricite De France Anode de pile a oxyde solide a base d'un cermet particulier et pile a oxyde solide la comprenant
DE102006030393A1 (de) * 2006-07-01 2008-01-03 Forschungszentrum Jülich GmbH Keramische Werkstoffkombination für eine Anode für eine Hochtemperatur-Brennstoffzelle
US8518605B2 (en) 2006-07-01 2013-08-27 Forschungszentrum Juelich Gmbh Ceramic material combination for an anode of a high-temperature fuel cell

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