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Publication numberUS20080261099 A1
Publication typeApplication
Application numberUS 12/081,124
Publication dateOct 23, 2008
Filing dateApr 10, 2008
Priority dateApr 13, 2007
Also published asUS20170200964, WO2008127601A1
Publication number081124, 12081124, US 2008/0261099 A1, US 2008/261099 A1, US 20080261099 A1, US 20080261099A1, US 2008261099 A1, US 2008261099A1, US-A1-20080261099, US-A1-2008261099, US2008/0261099A1, US2008/261099A1, US20080261099 A1, US20080261099A1, US2008261099 A1, US2008261099A1
InventorsDien Nguyen, Ravi Oswal, Tad Armstrong, Emad El Batawi
Original AssigneeBloom Energy Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Heterogeneous ceramic composite SOFC electrolyte
US 20080261099 A1
Abstract
A solid oxide fuel cell (SOFC) includes a cathode electrode, a solid oxide electrolyte, and an anode electrode. The electrolyte includes yttria stabilized zirconia and scandia stabilized zirconia, such as scandia ceria stabilized zirconia.
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Claims(12)
1. A solid oxide fuel cell (SOFC), comprising:
a cathode electrode;
a solid oxide electrolyte; and
an anode electrode;
wherein the electrolyte comprises a yttria stabilized zirconia and a scandia stabilized zirconia.
2. The electrolyte of claim 1, wherein the electrolyte comprises a mixture of the yttria stabilized zirconia and the scandia stabilized zirconia.
3. The SOFC of claim 2, wherein the scandia stabilized zirconia comprises up to 1 molar percent ceria, alumina or yttria, about 6 to about 11 molar percent scandia and a balance comprising zirconia.
4. The SOFC of claim 3, wherein the electrolyte comprises a mixture of the yttria stabilized zirconia and scandia ceria stabilized zirconia.
5. The SOFC of claim 1, wherein the electrolyte comprises a mixture of yttria stabilized zirconia and [(ZrO2)1-y(CeO2)y]1-x(Sc2O3)x, where 0.06≦x≦0.11 and 0≦y≦0.01.
6. The SOFC of claim 5, wherein the yttria stabilized zirconia comprises 3 to 10 molar percent yttria.
7. The SOFC of claim 1, wherein a weight ratio of the yttria stabilized zirconia to the scandia stabilized zirconia in the electrolyte ranges from 1:4 to 1:1.
8. The SOFC of claim 7, wherein the weight ratio of the yttria stabilized zirconia to the scandia stabilized zirconia in the electrolyte ranges from 1:2 to 1:3.
9. The SOFC of claim 1, wherein the electrolyte is about 150 to about 300 microns thick.
10. A solid oxide fuel cell (SOFC), comprising:
a cathode electrode;
a solid oxide electrolyte comprising a mixture of about 25 weight percent yttria stabilized zirconia which comprises 3 molar percent yttria, and about 75 weight percent scandia ceria stabilized zirconia which comprises 1 molar percent ceria and 10 molar percent scandia; and
an anode electrode.
11. The SOFC of claim 10, wherein the anode electrode comprises:
a first sublayer comprising samaria doped ceria; and
a second sublayer comprising a scandia ceria stabilized zirconia and gadolinia doped ceria ceramic phase and a nickel containing phase.
12. A method of making a solid oxide fuel cell, comprising:
mixing yttria stabilized zirconia powder with scandia stabilized zirconia powder to form a powder mixture;
shaping the powder mixture;
sintering the shaped powder mixture to form an electrolyte;
forming an anode electrode on a first side of the electrolyte; and
forming a cathode electrode on a second side of the electrolyte.
Description
    CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
  • [0001]
    The present application claims benefit of U.S. provisional application 60/907,706, filed Apr. 13, 2007, which is incorporated herein by reference in its entirety.
  • BACKGROUND
  • [0002]
    The present invention is generally directed to fuel cell components, and to solid oxide fuel cell electrolyte materials in particular.
  • [0003]
    Fuel cells are electrochemical devices which can convert energy stored in fuels to electrical energy with high efficiencies. Electrolyzer cells are electrochemical devices which can use electrical energy to reduce a given material, such as water, to generate a fuel, such as hydrogen. The fuel and electrolyzer cells may comprise reversible cells which operate in both fuel cell and electrolysis mode.
  • [0004]
    In a high temperature fuel cell system, such as a solid oxide fuel cell (SOFC) system, an oxidizing flow is passed through the cathode side of the fuel cell while a fuel flow is passed through the anode side of the fuel cell. The oxidizing flow is typically air, while the fuel flow can be a hydrocarbon fuel, such as methane, natural gas, propane, ethanol, or methanol. The fuel cell, operating at a typical temperature between 750 C. and 950 C., enables the transport of negatively charged oxygen ions from the cathode flow stream to the anode flow stream, where the ion combines with either free hydrogen or hydrogen in a hydrocarbon molecule to form water vapor and/or with carbon monoxide to form carbon dioxide. The excess electrons from the negatively charged ion are routed back to the cathode side of the fuel cell through an electrical circuit completed between anode and cathode, resulting in an electrical current flow through the circuit. A solid oxide reversible fuel cell (SORFC) system generates electrical energy and reactant product (i.e., oxidized fuel) from fuel and oxidizer in a fuel cell or discharge mode and generates the fuel and oxidant using electrical energy in an electrolysis or charge mode.
  • SUMMARY
  • [0005]
    A solid oxide fuel cell (SOFC) includes a cathode electrode, a solid oxide electrolyte, and an anode electrode. The electrolyte includes yttria stabilized zirconia and a scandia stabilized zirconia, such as a scandia ceria stabilized zirconia.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0006]
    FIG. 1 illustrates a side cross-sectional view of a SOFC of the embodiments of the invention.
  • [0007]
    FIG. 2 illustrates a side cross sectional view of a SOFC stack of an embodiment of the invention.
  • [0008]
    FIG. 3 illustrates a plot of conductivity versus temperature for the electrolyte of the embodiment of the invention and for electrolytes of the comparative examples.
  • [0009]
    FIG. 4 illustrates a bar graph comparing the CTE of the electrolyte of the embodiment of the invention and of electrolytes of the comparative examples
  • [0010]
    FIG. 5 illustrates a plot of cell voltage versus time for a SOFC cell containing the electrolyte of the embodiment of the invention.
  • DETAILED DESCRIPTION OF THE EMBODIMENTS
  • [0011]
    The embodiments of the invention provide a higher strength electrolyte material to enable a thinner electrolyte and/or larger footprint electrolyte, while lowering the cost for electrolyte production. The composite electrolyte material comprises a composite yttria and scandia stabilized zirconias. The mixture of yttria and scandia stabilized zirconia exhibits a good flexural strength increase, and reasonable conductivity decrease compared to scandia stabilized zirconia. The electrolyte composition provides a coefficient of thermal expansion (CTE) which is closely matched to that of a chromium-iron alloy interconnect component of a SOFC stack. SOFC cells comprising the composite electrolyte can operate for a long time with a low degradation rate. By mixing a lower cost yttria stabilized zirconia powder with a higher cost, higher performance scandia stabilized zirconia powder, the overall cost of the electrolyte is reduced without significantly impacting the electrolyte performance compared to a scandia stabilized zirconia electrolyte.
  • [0012]
    FIG. 1 illustrates a solid oxide fuel cell (SOFC) 1 according to an embodiment of the invention. The cell 1 includes an anode electrode 3, a solid oxide electrolyte 5 and a cathode electrode 7. The electrolyte 5 may comprise a sintered mixture of scandia stabilized zirconia (“SSZ”) (including scandia ceria stabilized zirconia (“SCSZ”), which can also be referred to as scandium and cerium doped zirconia), and yttria stabilized zirconia (“YSZ”). The electrolyte may also contain unavoidable impurities. For example, the electrolyte 5 may comprise a mixture of YSZ and one of SSZ with no ceria or SCSZ, such as a YSZ/SCSZ mixture in an about 1:1 to about 1:4 weight ratio, such as an about 1:2 to 1:3 weight ratio. Thus, YSZ may comprise up to 50% by weight of the electrolyte 5. In alternative embodiments, the SCSZ may be substituted by SSZ.
  • [0013]
    Preferably, 3 molar percent yttria YSZ is used. However, YSZ compositions having more than 3 molar percent yttria, such as 3 to 10 molar percent yttria, for example 5 to 10 molar percent yttria (i.e., (ZrO2)1-z(Y2O3)x, where 0.03≦z≦0.1) may be used.
  • [0014]
    Preferably, the scandia stabilized zirconia has the following formula: [(ZrO2)1-y(CeO2)y]1-x(Sc2O3)x, where 0.06≦x≦0.11 and 0≦y≦0.01. While a stoichiometric stabilized zirconia is described by the formula, a non-stoichiometric stabilized zirconia having more or less than two oxygen atoms for each metal atom may be used. For example, the electrolyte may comprise SCSZ having 1 molar percent ceria and 10 molar percent scandia (i.e., [(ZrO2)1-y(CeO2)y]1-x(Sc2O3)x where x=0.1 and y=0.01). The ceria in SCSZ may be substituted with other ceramic oxides. Thus, alternative scandia stabilized zirconias can be used, such as scandia yttria stabilized zirconia (“SYSZ”), which can also be referred to as scandium and yttrium doped zirconia, and scandia alumina stabilized zirconia (“SAlSZ”), which can also be referred to as scandium and aluminum doped zirconia. The yttria or alumina may comprise 1 molar percent or less in the scandia stabilized zirconia.
  • [0015]
    The cathode electrode 7 may comprise an electrically conductive material, such as an electrically conductive perovskite material, such as lanthanum strontium manganite (LSM). Other conductive perovskites, such as La1-xSrxCoO3, La1-xSrxFe1-yCOyO3 or La1-xSrxMn1-yCOyO3 where 0.1≦x≦0.4 and 0.02≦y≦0.4, respectively, may also be used. The cathode electrode 7 can also be composed of two sublayers (a SCSZ/LSM functional layer adjacent to the electrolyte and a LSM current collection layer over the functional layer).
  • [0016]
    The anode electrode 3 may comprise one or more sublayers. For example, the anode electrode may comprise a single layer Ni-YSZ and/or a Ni-SSZ cermet. In a preferred embodiment, the anode electrode comprises two sublayers, where the first sublayer closest to the electrolyte is composed of samaria doped ceria (“SDC”) and the second sublayer distal from the electrolyte comprises nickel, gadolinia doped ceria (“GDC”) and a scandia stabilized zirconia (“SSZ”), such as a scandia ceria stabilized zirconia (“SCSZ”).
  • [0017]
    The samaria doped ceria preferably comprises 15 to 25 molar percent, such as for example 20 molar percent samaria and a balance comprising ceria. The SDC may have the following formula: SmzCe1-zO2-δ, where 0.15≦z≦0.25. While a non-stoichiometric SDC is described by the formula where there is slightly less than two oxygen atoms for each metal atom, an SDC having two or more oxygen atoms for each metal atom may also be used. Preferably, the first sublayer contains no other materials, such as nickel, besides the SDC and unavoidable impurities. However, if desired, other materials may be added to the first sublayer, such as a small amount of nickel in an amount less than the amount of nickel in the second sublayer.
  • [0018]
    The second sublayer comprises a cermet including a nickel containing phase and a ceramic phase. The nickel containing phase of the second sublayer preferably consists entirely of nickel in a reduced state. This phase forms nickel oxide when it is in an oxidized state. Thus, when the anode is fabricated, the nickel containing phase comprises nickel oxide. The anode electrode is preferably annealed in a reducing atmosphere prior to operation to reduce the nickel oxide to nickel. The nickel containing phase may include other metals and/or nickel alloys in addition to pure nickel, such as nickel-copper or nickel-cobalt alloys (in a reduced state) and their oxides (in an oxidized state), for example Ni1-xCuxO or Ni1-xCoxO where 0.05≦x≦0.3. However, the nickel containing phase preferably contains only nickel or nickel oxide and no other metals. The nickel is preferably finely distributed in the ceramic phase, with an average grain size less than 500 nanometers, such as 200 to 400 nanometers, to reduce the stresses induced when nickel converts to nickel oxide.
  • [0019]
    The ceramic phase of the second sublayer preferably comprises gadolinia doped ceria and scandia stabilized zirconia. The ceramic phase may comprise a sintered mixture of GDC and SSZ (containing some or no cerium) ceramic particles. The scandia stabilized zirconia may have the same composition as the scandia stabilized zirconia of the electrolyte 5. Preferably, the scandia stabilized zirconia of sublayer 23 has the following formula: [(ZrO2)1-y(CeO2)y]1-x(Sc2O3)x, where 0.06≦x≦0.11 and 0≦y≦0.01. While a stoichiometric stabilized zirconia is described by the formula, a non-stoichiometric stabilized zirconia having more or less than two oxygen atoms for each metal atom may be used. For example, the electrolyte may comprise SCSZ having up to 1 molar percent ceria, about 6 to about 11 molar percent scandia and a balance comprising zirconia, such as SCSZ having 1 molar percent ceria and 10 molar percent scandia (i.e., ScxCeyZr1-x-yO2 where x=0.1 and y=0.01).
  • [0020]
    Any suitable GDC may be used in the second sublayer. For example, 10 to 40 molar percent gadolinia containing GDC may be used. GDC is preferably slightly non-stoichiometric with less than two oxygen atoms for each metal atom: Ce1-mGdmO2-δ where 0.1≦m≦0.4. However, GDC containing two or more oxygen atoms for each metal atom may also be used. The weight ratio of GDC to SSZ or SCSZ in the sublayer ranges from about 2:1 to about 5:1. For example, the weight ratio may be 5:1. If the ceramic phase contains no other components besides GDC and the stabilized zirconia, then the ceramic phase in the second sublayer may range from about 70 (such as for example 66.66) weight percent GDC and about 30 (such as for example 33.33) weight percent stabilized zirconia to about 85 (such as for example 83.33) weight percent GDC and about 15 (such as for example 16.66) weight percent stabilized zirconia. The ceramic phase preferably contains no other ceramic materials besides GDC, one of SSZ or SCSZ and unavoidable impurities.
  • [0021]
    The second sublayer preferably comprises 60 to 80 weight percent of the nickel containing phase and 40 to 20 weight percent of the ceramic phase, such as for example 75 weight percent of the nickel containing phase and 25 weight percent of the ceramic phase.
  • [0022]
    Any suitable layer thicknesses may be used. For example, the anode electrode 3 may be 20 to 40 microns thick, where the first sublayer is about 5 to about 10 microns thick and the second sublayer is about 15 to about 30 microns thick. The fuel cell is preferably a planar electrolyte supported cell in which the electrolyte is at least one order of magnitude thicker than the anode electrode. For example, the electrolyte 5 may be about 150 to about 300 microns thick. The cathode 7 may also be between 10 and 50 microns thick.
  • [0023]
    Fuel cell stacks are frequently built from a multiplicity of SOFC's 1 in the form of planar elements, tubes, or other geometries. Fuel and air has to be provided to the electrochemically active surface, which can be large. As shown in FIG. 2, one component of a fuel cell stack is the so called gas flow separator (referred to as a gas flow separator plate in a planar stack) 9 that separates the individual cells in the stack. The gas flow separator plate separates fuel flowing to the fuel electrode (i.e. anode 3) of one cell in the stack from oxidant, such as air, flowing to the air electrode (i.e. cathode 7) of an adjacent cell in the stack. The fuel may be a hydrocarbon fuel, such as natural gas for internally reforming cells, or a reformed hydrocarbon fuel comprising hydrogen, water vapor, carbon monoxide and unreformed hydrocarbon fuel for externally reforming cells. The separator 9 contains gas flow passages or channels 8 between the ribs 10. Frequently, the gas flow separator plate 9 is also used as an interconnect which electrically connects the fuel electrode 3 of one cell to the air electrode 7 of the adjacent cell. In this case, the gas flow separator plate which functions as an interconnect is made of or contains electrically conductive material, such as a Cr—Fe alloy. An electrically conductive contact layer, such as a nickel contact layer, may be provided between the anode electrode and the interconnect. FIG. 2 shows that the lower SOFC 1 is located between two gas separator plates 9.
  • [0024]
    Furthermore, while FIG. 2 shows that the stack comprises a plurality of planar or plate shaped fuel cells, the fuel cells may have other configurations, such as tubular. Still further, while vertically oriented stacks are shown in FIG. 2, the fuel cells may be stacked horizontally or in any other suitable direction between vertical and horizontal.
  • [0025]
    The term “fuel cell stack,” as used herein, means a plurality of stacked fuel cells which share a common fuel inlet and exhaust passages or risers. The “fuel cell stack,” as used herein, includes a distinct electrical entity which contains two end plates which are connected to power conditioning equipment and the power (i.e., electricity) output of the stack. Thus, in some configurations, the electrical power output from such a distinct electrical entity may be separately controlled from other stacks. The term “fuel cell stack” as used herein, also includes a part of the distinct electrical entity. For example, the stacks may share the same end plates. In this case, the stacks jointly comprise a distinct electrical entity. In this case, the electrical power output from both stacks cannot be separately controlled.
  • [0026]
    A method of forming a planar, electrolyte supported SOFC 1 shown in FIG. 1 includes forming the planar solid oxide electrolyte 5 followed by forming the cathode electrode 7 on a first side of a planar solid oxide electrolyte 5 and forming the anode electrode 3 on a second side of electrolyte 5. The anode and the cathode may be formed in any order on the opposite sides of the electrolyte.
  • [0027]
    For example, the electrolyte may be formed by mixing the YSZ powder with SSZ or SCSZ powder followed by shaping (such as tape casting, roll pressing or other suitable ceramic shaping techniques) and sintering the powders at any suitable temperature to form the electrolyte. The anode electrode containing a plurality of sublayers shown in FIG. 1 may be formed by a screen printing method or by other suitable methods. The first anode 3 sublayer can be screen printed on the electrolyte 5, followed by screen printing the second anode sublayer on the first sublayer using any suitable ceramic powder screen printing techniques. The screen printed cell is then sintered or fired at any suitable temperature, such as a temperature between 1150 and 1400 C. in air. The cell may be separately fired or sintered after the anode deposition and after the cathode deposition at the same or different temperature. The completed cell is preferably further annealed in a reducing atmosphere, such as a hydrogen or forming gas atmosphere, to covert nickel oxide to nickel in the anode prior to using fuel cell to generate electricity as part of a fuel cell system.
  • [0028]
    A performance of various electrolytes were tested. Specifically, the performance of the YSZ and SCSZ composite electrolyte of the embodiments of the invention having the following composition (25% by weight of 3 molar percent yttria YSZ and 75% by weight of [(ZrO2)1-y(CeO2)y]1-x(Sc2O3)x where x=0.1 and y=0.01) (“YSZ+SCSZ”) was compared to the following comparative example electrolyte compositions: (a) 3 molar percent yttria YSZ (“3YSZ”); (b) 8 molar percent yttria YSZ (“8YSZ”); and (c) ScxCeyZr1-x-yO2 where x=0.1 and y=0.01 (“SCSZ”).
  • [0029]
    FIG. 3 illustrates a plot of conductivity versus temperature for the four electrolytes. The conductivity of the YSZ+SCSZ electrolyte is higher than that of the 8YSZ and 3YSZ electrolytes, but slightly lower than that of the SCSZ electrolyte.
  • [0030]
    FIG. 4 illustrates a bar graph comparing the CTE of the four electrolytes. The CTE of the YSZ+SCSZ electrolyte is about the same as that of the electrolytes of the comparative examples.
  • [0031]
    FIG. 5 illustrates a plot of cell voltage versus time for a SOFC cell containing the YSZ+SCSZ electrolyte. This endurance test indicates that the cell voltage degrades about 3-4% for the first 1000 hours and about 1-2% for the second thousand hours of operation.
  • [0032]
    The foregoing description of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The description was chosen in order to explain the principles of the invention and its practical application. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4272353 *Feb 29, 1980Jun 9, 1981General Electric CompanyMethod of making solid polymer electrolyte catalytic electrodes and electrodes made thereby
US4426269 *Mar 5, 1979Jan 17, 1984The British Petroleum Company LimitedMethod of stabilizing electrodes coated with mixed oxide electrocatalysts during use in electrochemical cells
US4459340 *Apr 30, 1982Jul 10, 1984Board Of Trustees, Stanford UniversityMethod for producing electricity from a fuel cell having solid-oxide ionic electrolyte
US4575407 *Oct 24, 1984Mar 11, 1986Diller Isaac MProduct and process for the activation of an electrolytic cell
US4686158 *Oct 23, 1985Aug 11, 1987Mitsubishi Jukogyo Kabushiki KaishaSolid electrolyte fuel cell and method for preparing it
US4804592 *Oct 16, 1987Feb 14, 1989The United States Of America As Represented By The United States Department Of EnergyComposite electrode for use in electrochemical cells
US4847173 *Dec 30, 1987Jul 11, 1989Mitsubishi Denki Kabushiki KaishaElectrode for fuel cell
US4898792 *Dec 7, 1988Feb 6, 1990Westinghouse Electric Corp.Electrochemical generator apparatus containing modified high temperature insulation and coated surfaces for use with hydrocarbon fuels
US4913982 *Oct 19, 1988Apr 3, 1990Allied-Signal Inc.Fabrication of a monolithic solid oxide fuel cell
US4917971 *Mar 3, 1989Apr 17, 1990Energy Research CorporationInternal reforming fuel cell system requiring no recirculated cooling and providing a high fuel process gas utilization
US4925745 *Mar 29, 1985May 15, 1990Institute Of Gas TechnoloySulfur tolerant molten carbonate fuel cell anode and process
US4983471 *Dec 28, 1989Jan 8, 1991Westinghouse Electric Corp.Electrochemical cell apparatus having axially distributed entry of a fuel-spent fuel mixture transverse to the cell lengths
US5034287 *Apr 23, 1990Jul 23, 1991International Fuel Cells CorporationFuel cell cooling using heat of reaction
US5047299 *Jul 25, 1990Sep 10, 1991Westinghouse Electric Corp.Electrochemical cell apparatus having an integrated reformer-mixer nozzle-mixer diffuser
US5143800 *Jul 25, 1990Sep 1, 1992Westinghouse Electric Corp.Electrochemical cell apparatus having combusted exhaust gas heat exchange and valving to control the reformable feed fuel composition
US5192334 *May 4, 1992Mar 9, 1993Abb Patent GmbhMethod for mechanically connecting high-temperature fuel cells to a fuel cell support
US5213910 *Mar 17, 1992May 25, 1993Ngk Insulators, Ltd.Solid electrolyte type fuel cell having gas from gas supply ducts impinging perpendicularly on electrodes
US5215946 *Aug 5, 1991Jun 1, 1993Allied-Signal, Inc.Preparation of powder articles having improved green strength
US5290323 *Dec 9, 1991Mar 1, 1994Yuasa CorporationManufacturing method for solid-electrolyte fuel cell
US5290642 *Sep 11, 1990Mar 1, 1994Alliedsignal AerospaceMethod of fabricating a monolithic solid oxide fuel cell
US5302470 *Jul 31, 1992Apr 12, 1994Osaka Gas Co., Ltd.Fuel cell power generation system
US5342705 *Jun 4, 1993Aug 30, 1994Allied-Signal, Inc.Monolithic fuel cell having a multilayer interconnect
US5441821 *Dec 23, 1994Aug 15, 1995Ballard Power Systems Inc.Electrochemical fuel cell system with a regulated vacuum ejector for recirculation of the fluid fuel stream
US5498487 *Aug 11, 1994Mar 12, 1996Westinghouse Electric CorporationOxygen sensor for monitoring gas mixtures containing hydrocarbons
US5501914 *Aug 26, 1994Mar 26, 1996Mitsubishi Jukogyo Kabushiki KaishaSolid oxide electrolyte fuel cell
US5505824 *Jan 6, 1995Apr 9, 1996United Technologies CorporationPropellant generator and method of generating propellants
US5518829 *Feb 17, 1995May 21, 1996Mitsubishi Jukogyo Kabushiki KaishaSolid oxide electrolyte fuel cell having dimpled surfaces of a power generation film
US5527631 *Oct 4, 1995Jun 18, 1996Westinghouse Electric CorporationHydrocarbon reforming catalyst material and configuration of the same
US5601937 *Jan 25, 1995Feb 11, 1997Westinghouse Electric CorporationHydrocarbon reformer for electrochemical cells
US5733675 *Aug 23, 1995Mar 31, 1998Westinghouse Electric CorporationElectrochemical fuel cell generator having an internal and leak tight hydrocarbon fuel reformer
US5741406 *Apr 2, 1996Apr 21, 1998Northerwestern UniversitySolid oxide fuel cells having dense yttria-stabilized zirconia electrolyte films and method of depositing electrolyte films
US5741605 *Mar 8, 1996Apr 21, 1998Westinghouse Electric CorporationSolid oxide fuel cell generator with removable modular fuel cell stack configurations
US5922488 *Aug 15, 1997Jul 13, 1999Exxon Research And Engineering Co.,Co-tolerant fuel cell electrode
US5955039 *Dec 19, 1996Sep 21, 1999Siemens Westinghouse Power CorporationCoal gasification and hydrogen production system and method
US6013385 *Jul 25, 1997Jan 11, 2000Emprise CorporationFuel cell gas management system
US6051125 *Sep 21, 1998Apr 18, 2000The Regents Of The University Of CaliforniaNatural gas-assisted steam electrolyzer
US6106964 *Jun 30, 1998Aug 22, 2000Ballard Power Systems Inc.Solid polymer fuel cell system and method for humidifying and adjusting the temperature of a reactant stream
US6228521 *Dec 8, 1998May 8, 2001The University Of Utah Research FoundationHigh power density solid oxide fuel cell having a graded anode
US6238816 *Jan 13, 1999May 29, 2001Technology Management, Inc.Method for steam reforming hydrocarbons using a sulfur-tolerant catalyst
US6280865 *Sep 24, 1999Aug 28, 2001Plug Power Inc.Fuel cell system with hydrogen purification subsystem
US6287716 *Oct 14, 1999Sep 11, 2001Mitsubishi Materials CorporationSolid oxide fuel cell having composition gradient between electrode and electrolyte
US6361892 *Dec 6, 1999Mar 26, 2002Technology Management, Inc.Electrochemical apparatus with reactant micro-channels
US6403245 *May 21, 1999Jun 11, 2002Microcoating Technologies, Inc.Materials and processes for providing fuel cells and active membranes
US6436562 *Nov 23, 1999Aug 20, 2002Emprise Technology Associates Corp.Fuel-cell engine stream conditioning system
US6451466 *Apr 6, 2000Sep 17, 2002Utc Fuel Cells, LlcFunctional integration of multiple components for a fuel cell power plant
US6558831 *Aug 18, 2000May 6, 2003Hybrid Power Generation Systems, LlcIntegrated SOFC
US6582845 *Dec 15, 2000Jun 24, 2003Corning IncorporatedSolid oxide electrolyte, fuel cell module, and method
US6592965 *Jul 7, 1997Jul 15, 2003Igr Enterprises, Inc.Ductile ceramic composite electrolyte
US6605316 *Jul 27, 2000Aug 12, 2003The Regents Of The University Of CaliforniaStructures and fabrication techniques for solid state electrochemical devices
US6623880 *May 29, 2001Sep 23, 2003The United States Of America As Represented By The Department Of EnergyFuel cell-fuel cell hybrid system
US6677070 *Apr 19, 2001Jan 13, 2004Hewlett-Packard Development Company, L.P.Hybrid thin film/thick film solid oxide fuel cell and method of manufacturing the same
US6682842 *Jul 27, 2000Jan 27, 2004The Regents Of The University Of CaliforniaComposite electrode/electrolyte structure
US6767662 *Oct 10, 2001Jul 27, 2004The Regents Of The University Of CaliforniaElectrochemical device and process of making
US6787261 *Oct 22, 2001Sep 7, 2004Toho Gas Co., Ltd.Solid oxide fuel cell
US6854688 *Nov 20, 2002Feb 15, 2005Ion America CorporationSolid oxide regenerative fuel cell for airplane power generation and storage
US6924053 *Mar 24, 2003Aug 2, 2005Ion America CorporationSolid oxide regenerative fuel cell with selective anode tail gas circulation
US6972161 *Oct 10, 2002Dec 6, 2005Hewlett-Packard Development Company, L.P.Fuel cell assembly and method of making the same
US7157173 *Oct 3, 2005Jan 2, 2007Saint-Gobain Ceramics & Plastics, Inc.Fused zirconia-based solid oxide fuel cell
US7255956 *Feb 20, 2003Aug 14, 2007Bloom Energy CorporationEnvironmentally tolerant anode catalyst for a solid oxide fuel cell
US7422822 *Feb 28, 2007Sep 9, 2008Toho Gas Co., Ltd.Single cell for a solid oxide fuel cell
US7494732 *Mar 29, 2005Feb 24, 2009Corning IncorporatedFuel cell device with varied active area sizes
US7550217 *Jun 9, 2004Jun 23, 2009Saint-Gobain Ceramics & Plastics, Inc.Stack supported solid oxide fuel cell
US7563503 *Jan 12, 2004Jul 21, 2009The University Of ConnecticutCoatings, materials, articles, and methods of making thereof
US20020012825 *May 8, 2001Jan 31, 2002Jun SasaharaFuel cell with patterned electrolyte/electrode interface
US20020014417 *May 30, 2001Feb 7, 2002Adolf KuehnleElectrochemical cell for the oxidation of organic compounds, and electrocatalytic oxidation process
US20020028362 *Aug 31, 2001Mar 7, 2002Dennis PredigerAnode oxidation protection in a high-temperature fuel cell
US20020028367 *May 22, 2001Mar 7, 2002Nigel SammesElectrode-supported solid state electrochemical cell
US20020048701 *Oct 23, 2001Apr 25, 2002Toho Gas Co. Ltd.Solid oxide fuel cell having a supported electrolyte film
US20020058175 *Nov 14, 2001May 16, 2002Technology Management, Inc.Multipurpose reversible electrochemical system
US20020098406 *Jan 14, 2002Jul 25, 2002Peng HuangRedox solid oxide fuel cell
US20020106544 *Feb 7, 2001Aug 8, 2002Noetzel John G.Solid oxide auxiliary power unit reformate control
US20020127455 *Dec 17, 2001Sep 12, 2002The Regents Of The University Of CaliforniaCeria-based solid oxide fuel cells
US20020132156 *Mar 25, 2002Sep 19, 2002Technology Management, Inc.Electrochemical apparatus with reactant micro-channels
US20030162067 *Feb 20, 2003Aug 28, 2003Ion America CorporationFuel water vapor replenishment system for a fuel cell
US20030165732 *Feb 20, 2003Sep 4, 2003Ion America CorporationEnvironmentally tolerant anode catalyst for a solid oxide fuel cell
US20040081859 *Aug 7, 2003Apr 29, 2004Ion AmericaSolid oxide regenerative fuel cell
US20040191595 *Jun 20, 2003Sep 30, 2004Ion America CorporationSORFC system and method with an exothermic net electrolysis reaction
US20040191597 *Mar 24, 2003Sep 30, 2004Ion America CorporationSolid oxide regenerative fuel cell with selective anode tail gas circulation
US20040191598 *Mar 24, 2003Sep 30, 2004Ion America CorporationSORFC power and oxygen generation method and system
US20050048334 *Sep 3, 2003Mar 3, 2005Ion America CorporationCombined energy storage and fuel generation with reversible fuel cells
US20050074650 *Feb 20, 2003Apr 7, 2005Ion America CorporatonTextured electrolyte for a solid oxide fuel cell
US20050164051 *Dec 3, 2004Jul 28, 2005Ion America CorporationHigh temperature fuel cell system and method of operating same
US20050271919 *Oct 9, 2003Dec 8, 2005Kazuo HataElectolyte sheets for solid oxide fuel cell and method for manufacturing same
US20060008682 *Jul 8, 2004Jan 12, 2006Mclean Gerard FThin-layer fuel cell structure
US20060040168 *Aug 19, 2005Feb 23, 2006Ion America CorporationNanostructured fuel cell electrode
US20060166070 *Mar 27, 2006Jul 27, 2006Ion America CorporationSolid oxide reversible fuel cell with improved electrode composition
US20060216575 *Mar 21, 2006Sep 28, 2006Ion America CorporationPerovskite materials with combined Pr, La, Sr, "A" site doping for improved cathode durability
US20070045125 *Aug 25, 2006Mar 1, 2007Hartvigsen Joseph JElectrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water
US20070082254 *Aug 6, 2004Apr 12, 2007Kenichi HiwatashiSolid oxide fuel cell
US20070141423 *Dec 13, 2006Jun 21, 2007National Inst Of Adv Industrial Science And Tech.Tubular electrochemical reactor cell and electrochemical reactor system which is composed of the cell
US20070141443 *Dec 15, 2005Jun 21, 2007Saint-Gobain Ceramics & Plastics, Inc.Solid oxide fuel cell having a buffer layer
US20070141444 *Dec 16, 2005Jun 21, 2007Saint-Gobain Ceramics & Plastics, Inc.Fuel cell component having an electrolyte dopant
US20080029388 *Jul 23, 2007Feb 7, 2008Elangovan SEfficient Reversible Electrodes For Solid Oxide Electrolyzer Cells
US20080075984 *Sep 27, 2006Mar 27, 2008Michael Edward BaddingElectrolyte sheet with regions of different compositions and fuel cell device including such
US20080076006 *Sep 25, 2006Mar 27, 2008Ion America CorporationHigh utilization stack
US20080096080 *Oct 10, 2007Apr 24, 2008Bloom Energy CorporationAnode with remarkable stability under conditions of extreme fuel starvation
US20080102337 *Jan 13, 2006May 1, 2008The Tokyo Electric Power Company, IncorporatedSolid Oxide Type Fuel Battery Cell and Process for Producing the Same
US20090029195 *Oct 16, 2006Jan 29, 2009Eidgenossische Technische Hochschule ZurichThin film and composite element produced from the same
US20090068533 *Sep 5, 2008Mar 12, 2009Kabushiki Kaisha ToshibaFuel electrodes for solid oxide electrochemical cell, processes for producing the same, and solid oxide electrochemical cells
US20090186250 *Dec 27, 2007Jul 23, 2009Saint-Gobain Ceramics & Plastics, Inc.Bilayer interconnects for solid oxide fuel cells
US20090214919 *Feb 27, 2009Aug 27, 2009National Institute Of Adv Industrial Sci And TechElectrochemical reactor bundles, stacks, and electrochemical reactor systems consisting of these components
US20110039183 *Aug 5, 2010Feb 17, 2011Bloom Energy CorporationInternal reforming anode for solid oxide fuel cells
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US8449702 *Aug 17, 2011May 28, 2013Bloom Energy CorporationMethod for solid oxide fuel cell fabrication
US8580456Jan 19, 2011Nov 12, 2013Bloom Energy CorporationPhase stable doped zirconia electrolyte compositions with low degradation
US8617763Aug 5, 2010Dec 31, 2013Bloom Energy CorporationInternal reforming anode for solid oxide fuel cells
US8748056Oct 10, 2007Jun 10, 2014Bloom Energy CorporationAnode with remarkable stability under conditions of extreme fuel starvation
US8822101Mar 18, 2013Sep 2, 2014Bloom Energy CorporationFuel cell mechanical components
US8940112 *Apr 24, 2013Jan 27, 2015Bloom Energy CorporationMethod for solid oxide fuel cell fabrication
US9065104 *Jun 10, 2011Jun 23, 2015Commissariat A L'energie Atomique Et Aux Energies AlternativesProcess for manufacturing elementary electrochemical cells for energy- or hydrogen-producing electrochemical systems, in particular of SOFC and HTE type
US9356298Mar 7, 2014May 31, 2016Bloom Energy CorporationAbrasion resistant solid oxide fuel cell electrode ink
US9413024Oct 16, 2013Aug 9, 2016Bloom Energy CorporationPhase stable doped zirconia electrolyte compositions with low degradation
US9515344Nov 19, 2013Dec 6, 2016Bloom Energy CorporationDoped scandia stabilized zirconia electrolyte compositions
US9755263Mar 13, 2014Sep 5, 2017Bloom Energy CorporationFuel cell mechanical components
US9799909Jul 8, 2016Oct 24, 2017Bloom Energy CorporationPhase stable doped zirconia electrolyte compositions with low degradation
US9812714May 6, 2014Nov 7, 2017Bloom Energy CorporationAnode with remarkable stability under conditions of extreme fuel starvation
US20100297527 *Jan 28, 2010Nov 25, 2010Ut-Battelle, LlcFast Ion Conducting Composite Electrolyte for Solid State Electrochemical Devices
US20120043010 *Aug 17, 2011Feb 23, 2012Bloom Energy CorporationMethod for Solid Oxide Fuel Cell Fabrication
US20130309597 *Apr 24, 2013Nov 21, 2013Bloom Energy CorporationMethod for solid oxide fuel cell fabrication
US20140367249 *Feb 1, 2013Dec 18, 2014Carleton Life Support Systems, Inc.Composite electrolyte consisting of fully stabilized zirconia and partially stabilized zirconia
US20140377478 *Sep 4, 2014Dec 25, 2014Bloom Energy CorporationMethod for solid oxide fuel cell fabrication
CN103155255A *Aug 16, 2011Jun 12, 2013博隆能源股份有限公司Method for solid oxide fuel cell fabrication
CN103636042A *Jan 31, 2012Mar 12, 2014Toto 株式会社Solid oxide fuel cell
EP2529442A4 *Jan 19, 2011May 27, 2015Bloom Energy CorpPhase stable doped zirconia electrolyte compositions with low degradation
EP2672554A1 *Jan 31, 2012Dec 11, 2013Toto Ltd.Solid oxide fuel cell
EP2672554A4 *Jan 31, 2012Oct 15, 2014Toto LtdSolid oxide fuel cell
EP2810330A4 *Feb 1, 2013Jul 15, 2015Carleton Life Support Sys IncComposite electrolyte consisting of fully stabilized zirconia and partially stabilized zirconia
WO2013116712A1 *Feb 1, 2013Aug 8, 2013Carelton Life Support Systems, Inc.Composite electrolyte consisting of fully stabilized zirconia and partially stabilized zirconia
Classifications
U.S. Classification429/418, 75/343, 429/465
International ClassificationH01M8/10, B22F1/00
Cooperative ClassificationH01M8/126, H01M4/9066, C04B2235/3224, H01M8/1253, C04B2235/96, C04B2235/3246, C04B2235/602, C04B2235/3225, H01M4/8657, C04B35/64, H01M4/9033, H01M2008/1293, C04B35/48, H01M2300/0091, Y02E60/525, H01M4/8621, H01M2300/0077, Y02P70/56
European ClassificationH01M4/90D2D, H01M8/12E2B, H01M4/86K2, H01M4/86B6
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Jul 2, 2008ASAssignment
Owner name: BLOOM ENERGY CORPORATION, CALIFORNIA
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Dec 15, 2015ASAssignment
Owner name: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGEN
Free format text: SECURITY INTEREST;ASSIGNOR:BLOOM ENERGY CORPORATION;REEL/FRAME:037301/0093
Effective date: 20151215