US20070237998A1 - Solid Oxide Fuel Cell Having Internal Active Layers - Google Patents
Solid Oxide Fuel Cell Having Internal Active Layers Download PDFInfo
- Publication number
- US20070237998A1 US20070237998A1 US11/755,945 US75594507A US2007237998A1 US 20070237998 A1 US20070237998 A1 US 20070237998A1 US 75594507 A US75594507 A US 75594507A US 2007237998 A1 US2007237998 A1 US 2007237998A1
- Authority
- US
- United States
- Prior art keywords
- solid oxide
- accordance
- electrochemical device
- oxide electrochemical
- electrode layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
- H01M8/243—Grouping of unit cells of tubular or cylindrical configuration
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/2475—Enclosures, casings or containers of fuel cell stacks
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
- H01M8/2485—Arrangements for sealing external manifolds; Arrangements for mounting external manifolds around a stack
-
- 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
- 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
-
- 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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
-
- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- TSOFC tubular solid oxide fuel cell
- the internal support structure comprises a tubular, porous, ceramic cathode. Since the cathode is the support member of the device, it must be of a sufficiently thick cross-section to provide requisite strength. A layer of dense, gas-tight electrolyte—yttria-stabilized zirconia (YSZ) for example—is deposited on the external surface of the cathode, and a layer of anode—Ni—YSZ for example—is deposited on the surface of the electrolyte layer. Fabrication of currently available TSOFC is expensive in terms of resources and time.
- YSZ yttria-stabilized zirconia
- a solid oxide electrochemical device that includes: a porous support structure having a porous outer surface and a tubular porous inner surface; a first electrode layer disposed radially inside the tubular porous inner surface and supported by the porous support structure; a dense electrolyte layer disposed radially inside and supported by the first electrode composition; and a second electrode layer disposed radially inside and supported by the dense electrolyte.
- a solid oxide electrochemical device includes: a composite electrode including 1) a porous support structure having pores, a porous outer surface, and a tubular porous inner surface and 2) a first electrode layer disposed throughout the pores, the porous outer surface, and the tubular porous inner surface and supported by the porous support structure; a dense electrolyte layer disposed radially inside and supported by the composite electrode; and a second electrode layer disposed radially inside and supported by the dense electrolyte.
- Solid oxide electrochemical devices include fuel cells and electrolyzers.
- FIG. 1 is an oblique, not-to-scale view of a portion of a TSOFC support tube in accordance with an embodiment of the present invention.
- FIG. 2 is an oblique, not-to-scale view of a portion of a TSOFC in accordance with an embodiment of the present invention.
- FIG. 3 is an oblique, not-to-scale view of a portion of a TSOFC in accordance with an embodiment of the present invention.
- FIG. 4 is an oblique, not-to-scale view of a portion of a TSOFC support tube sheet in accordance with an embodiment of the present invention.
- FIG. 5 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet in accordance with an embodiment of the present invention.
- FIG. 6 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet in accordance with an embodiment of the present invention.
- FIG. 7 is a magnified, two-dimensional, schematic, sectional view of a portion of a TSOFC porous support in accordance with an embodiment of the present invention.
- FIG. 8 is a magnified, two-dimensional, schematic, sectional view of a portion of a TSOFC composite porous support-anode in accordance with an embodiment of the present invention.
- FIG. 9 is a magnified, two-dimensional, schematic, sectional view of a portion of a TSOFC having a composite porous support-anode in accordance with an embodiment of the present invention.
- FIG. 10 is an oblique, not-to-scale view of a portion of a TSOFC having a composite porous support-anode in accordance with an embodiment of the present invention.
- FIG. 11 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet having a composite porous support-anode in accordance with an embodiment of the present invention.
- FIG. 12 is an oblique, not-to-scale view of a portion of a TSOFC tube having interlayers in accordance with an embodiment of the present invention.
- FIG. 13 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet having interlayers in accordance with an embodiment of the present invention.
- the invention begins with a porous support tube 11 that may, for example, comprise any porous, sinterable material selected from the group consisting of a non-noble transition metal, metal alloy, and a cermet incorporating one or more of a non-noble transition metal and a non-noble transition metal alloy, preferably a stainless steel, and more preferably a ferritic and/or austenitic stainless steel.
- the support tube 11 can be of any diameter or length with a wall thickness no greater than about 4 mm, preferably no greater than 1 mm.
- the support should have an average pore size in the range of 1 to 30 ⁇ m, preferably 1.5 to 20 ⁇ m, and more preferably 2 to 15 ⁇ m. Moreover, the support should have an average pore volume in the range of 20 to 50 volume percent and it should be electrically conductive at all operating temperatures.
- the support tube 11 can be formed in any suitable cross-sectional shape, including circular, elliptical, triangular, rectangular, irregular, or any other desired shape. A round shape, especially an essentially circular shape as shown in FIG. 1 , accommodates uniform deposition of layers on the inner surface 16 .
- the porous support tube 11 may be prepared by conventional powder metallurgy techniques, such as molding, extrusion, casting, forging, isostatic compression, etc.
- the support tube 11 should be open on both ends.
- active fuel cell membrane layers are deposited as layers 12 , 13 , 14 on the inside (inner) surface 16 of the porous support tube 11 to form an annular TSOFC 10 . It can be seen that each successive layer supports the layers that are subsequently deposited thereon.
- the first active fuel cell membrane layer 12 is an anode material, which can be any anode material, but is preferably comprised of a cermet composition.
- suitable cermet compositions include, but are not limited to Ni—YSZ, Ni—GdCeO 2 , Ni—SmCeO 2 , and Ag—SmCeO 2 .
- the anode thickness should be in a range of 5-70 ⁇ m, preferably 5-60 ⁇ m, more preferably 5-50 ⁇ m, most preferably 5-40 ⁇ m.
- the anode should have an average pore size of 1-20 ⁇ m and pore volume of 25-40 volume percent.
- the anode 12 is applied to the support tube 11 by a conventional method such as sol-gel, slurry, or wash coating, for example.
- the anode 12 can be sintered before or after the application of subsequent layers.
- the next active fuel cell membrane layer 13 is a non-porous and/or essentially fully dense O 2 -permeable or H 2 -permeable electrolyte composition.
- suitable electrolyte compositions include but are not limited to YSZ, GdCeO 2 , SmCeO 2 , LaSrGaMg0 3 , BaCeYO 3 , and La 2 Mo 2 O 9 .
- the electrolyte should have a thickness in a range of 2-80 ⁇ m, preferably 2-70 ⁇ m, more preferably 2-60 ⁇ m, most preferably 2-50 ⁇ m.
- the electrolyte should be dense and gas tight to prevent the air and fuel from mixing.
- the electrolyte layer 13 may be deposited using a conventional method such as sol-gel, slurry, or wash coating, for example, and subsequently sintered.
- the first two layers 12 , 13 are preferably sintered simultaneously under either neutral (neutral as used herein means neither oxidizing nor reducing) or reducing conditions so that the anode maintains or attains the characteristics described hereinabove while achieving full densification of the electrolyte layer.
- the sintered electrolyte is preferably at least 95% dense and essentially defect-free. Sintering parameters are not critical to the invention; suggested parameters include a temperature range of 1200-1500° C., preferably about 1300° C., and a duration of 0.5 to 3 hours, preferably about 1 to 2 hours.
- the final layer is the cathode 14 , which is generally comprised of alkaline earth substituted lanthanum manganite, alkaline earth substituted lanthanum ferrite, lanthanum strontium iron cobaltite, or a mixed ionic-electronic conductor, but the composition of the cathode 14 is not critical to the invention.
- the cathode 14 thickness should be in a range of 5-70 ⁇ m, preferably 5-60 ⁇ m, more preferably 5-50 ⁇ m, most preferably 5-40 ⁇ m.
- the cathode 14 should have an average pore size of 1-15 ⁇ m and pore volume of 25-40 volume percent.
- the cathode 14 can also be deposited using a conventional method such as sol-gel, slurry, or wash coating, for example.
- the final step is a sintering process that is composed of heating the entire TSOFC 10 in a neutral environment to 1000-1300° C. for 1-2 hours depending on the cathode material used.
- the cathode can be metallic comprising Pt, Pd, Ag—Pd, or other metallic material, or cermet comprising Ni—BaCeYO 3 or Ni—SrCeO 3 .
- neutral as used herein means neither oxidizing nor reducing.
- a TSOFC 20 can have the internal active layers deposited on the inside surface 16 of the support tube 11 in reverse order ( 14 , 13 , 12 ).
- the skilled artisan will recognize that the fuel and oxygen supplies will also need to be reversed in operation.
- a TSOFC is supported by a tube sheet.
- a simplified example of a tube sheet 21 defines an array of any number of integral openings having inner surfaces 28 .
- the tube sheet 21 and inner surfaces 28 can be formed in any suitable cross-sectional shapes, including circular, elliptical, triangular, rectangular, irregular, or any other desired shapes.
- a round shape, especially an essentially circular shape as shown in FIG. 4 accommodates uniform deposition of layers on the inner surfaces 28 .
- the tube sheet 21 can be comprised of any of the materials described hereinabove for the support tube 11 .
- the tube sheet 21 may be prepared by conventional powder metallurgy techniques, such as molding, extrusion, casting, forging, isostatic compression, etc.
- the tube sheet should be open on both ends.
- active fuel cell membrane layers can be deposited and sintered as described hereinabove to form a SOFC tube sheet 30 .
- Each inner surface 28 defined by the tube sheet 21 is coated on the inside thereof with a porous anode 22 such as Ni—YSZ, for example.
- the anode 22 is coated on the inside with a dense electrolyte 23 such as Y 2 O 3 —ZrO 2 , for example.
- the dense electrolyte 23 is coated on the inside with a porous cathode 24 such as LaMnO 3 , for example. It can be seen that each successive layer supports the layers that are subsequently deposited thereon.
- the cross-sectional shape of the tube sheet 21 and the openings 28 defined thereby are not critical to the invention, although some shapes will be found to be more beneficial, especially those shapes which promote contact of reactive gases with respective surfaces of the tube sheet 21 .
- a TSOFC tube sheet 35 can have the internal active layers deposited on the inside of the tube sheet 21 in reverse order ( 24 , 23 , 22 ).
- the skilled artisan will recognize that the fuel and oxygen supplies will also need to be reversed in operation.
- Some embodiments of the present invention comprise a TSOFC having a composite porous support-anode. See U.S. Patent Application Publication No. US 2006/0234112 A1 to Visco, et al. published on Oct. 19, 2006.
- fabrication of a TSOFC in accordance with the present invention begins with a porous support 40 .
- a network of metal 42 and pores 44 is shown schematically; open porosity of the porous support 40 is 20 to 60 vol. %, preferably 30 to 50 vol. %, more preferably 35 to 50 vol. %.
- the porous support 40 can be comprised of any metal, alloy, or cermet composition suitable for fuel cell construction, as described hereinabove.
- the porous support 40 is wash coated with an anode-forming composition comprised of NiO/YSZ, NiO/CeO 2 , NiO/Gd or Sm doped CeO 2 with a conventional binder such as polyethylene glycol (PEG), for example.
- the wash coat can be done in air or under vacuum (for a few minutes to assist coating).
- the coated porous support 40 is dried and sintered in Ar at 1000-1350° C. for 0.5 to 2 hrs.
- a conventional pore former comprised of a starch, for example, is included in the anode-forming composition in order to impart or enhance porosity thereof.
- the resulting structure shown in FIG. 8 is a composite porous support-anode 48 wherein the metal 42 is coated throughout, including within the pores 44 and on the external surface 50 and interior surface 52 a continuous anode layer 46 forming a three dimensional composite structure that serves as both support and anode.
- FIG. 9 is a schematic magnification showing a TSOFC 60 that includes a composite porous support-anode 48 as described above and shown in FIG. 8 , a dense electrolyte layer 54 , and a porous cathode layer 56 .
- FIG. 10 is an unmagnified view of the TSOFC 60 showing the composite porous support-anode 48 , dense electrolyte layer 54 , and porous cathode layer 56 .
- FIG. 11 shows an example of a SOFC tube sheet 70 that includes a composite porous support-anode 72 , a dense electrolyte layer 74 , and a porous cathode layer 76 .
- TSOFC's made in accordance with the present invention can vary widely, and are not critical to the present invention.
- compositions used to make the SOFC dense electrolyte and porous cathode coatings described herein, and thicknesses thereof, are not critical to the present invention.
- metal acts a structural backbone imparting increased strength to entire fuel cell package, increases potential for rapid start-up.
- composite porous support-anodes of the present invention include the elimination of physical interconnect material and respective constituent layer.
- Arrays of the elements described herein can be used in electric power generators to power automobiles and other equipment.
- one or more buffer layers (interlayers) 101 , 103 , 105 can be deposited between any of the active layers in any of the above described embodiments of the present invention, according to preference for a particular application.
- an interlayer of Sm doped CeO 2 can be deposited thereover to reduce interfacial polarization.
- Interlayers can be deposited using conventional methods such as sol-gel, slurry, or wash coating, for example.
- the interlayer(s) can be fully dense, i.e., essentially nonporous, about 1 ⁇ m to 5 ⁇ m thick, and conductive to oxide or hydrogen ions.
- the interlayer(s) can be porous, with pore size of ⁇ 1 ⁇ m to 10 ⁇ m and thickness of 1 ⁇ m to 5 ⁇ m.
- the elements described herein can be used as steam electrolyzers, i.e., high-temperature electrolysis cells.
- an external potential i.e., voltage
- the resultant electrochemical reaction converts water to hydrogen and oxygen respectively by transport of hydrogen or oxygen ions through the electrolyte with recombination to molecular forms on exiting the electrolyte.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
Description
- This application is a continuation-in-part of U.S. patent application Ser. No. 11/103,333 entitled “Stack Configurations for Tubular Solid Oxide Fuel Cells”, filed on Apr. 11, 2005, the entire disclosure of which is incorporated herein by reference.
- Specifically referenced is U.S. patent application Ser. No. 11/314,111 entitled “Solid Oxide Fuel Cell and Stack Configuration”, filed on Dec. 21, 2005, the entire disclosure of which is incorporated herein by reference. Also specifically referenced is U.S. patent application Ser. No. 11/171,655 entitled “Tubular Solid Oxide Fuel Cell Current Collector”, filed on Jun. 30, 2005, the entire disclosure of which is incorporated herein by reference.
- The United States Government has rights in this invention pursuant to contract no. DE-AC05-00OR22725 between the United States Department of Energy and UT-Battelle, LLC.
- This invention arose under Work for Others Agreement No. ERD 03-2338 between UT-Battelle, LLC and Worldwide Energy, Inc.
- Devices commonly known as fuel cells comprise arrays of plates or tubes (elements) that directly convert to electricity (electric power) the energy released by oxidation of hydrogen. Simplistically, the elements comprise layers, including anodes, cathodes, and an oxygen-permeable layer therebetween. Currently available tubular solid oxide fuel cell (TSOFC) elements are limited to those having an internal support structure and external active layers such as anode, electrolyte, and cathode structures, for example. Active layers are disposed on the outer surface of the support. The term TSOFC, for purposes of describing the present invention, also includes electrolyzers.
- In most cases, the internal support structure comprises a tubular, porous, ceramic cathode. Since the cathode is the support member of the device, it must be of a sufficiently thick cross-section to provide requisite strength. A layer of dense, gas-tight electrolyte—yttria-stabilized zirconia (YSZ) for example—is deposited on the external surface of the cathode, and a layer of anode—Ni—YSZ for example—is deposited on the surface of the electrolyte layer. Fabrication of currently available TSOFC is expensive in terms of resources and time.
- In accordance with one aspect of the present invention, the foregoing and other objects are achieved by a solid oxide electrochemical device that includes: a porous support structure having a porous outer surface and a tubular porous inner surface; a first electrode layer disposed radially inside the tubular porous inner surface and supported by the porous support structure; a dense electrolyte layer disposed radially inside and supported by the first electrode composition; and a second electrode layer disposed radially inside and supported by the dense electrolyte.
- In accordance with another aspect of the present invention, a solid oxide electrochemical device includes: a composite electrode including 1) a porous support structure having pores, a porous outer surface, and a tubular porous inner surface and 2) a first electrode layer disposed throughout the pores, the porous outer surface, and the tubular porous inner surface and supported by the porous support structure; a dense electrolyte layer disposed radially inside and supported by the composite electrode; and a second electrode layer disposed radially inside and supported by the dense electrolyte.
- Solid oxide electrochemical devices include fuel cells and electrolyzers.
-
FIG. 1 is an oblique, not-to-scale view of a portion of a TSOFC support tube in accordance with an embodiment of the present invention. -
FIG. 2 is an oblique, not-to-scale view of a portion of a TSOFC in accordance with an embodiment of the present invention. -
FIG. 3 is an oblique, not-to-scale view of a portion of a TSOFC in accordance with an embodiment of the present invention. -
FIG. 4 is an oblique, not-to-scale view of a portion of a TSOFC support tube sheet in accordance with an embodiment of the present invention. -
FIG. 5 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet in accordance with an embodiment of the present invention. -
FIG. 6 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet in accordance with an embodiment of the present invention. -
FIG. 7 is a magnified, two-dimensional, schematic, sectional view of a portion of a TSOFC porous support in accordance with an embodiment of the present invention. -
FIG. 8 is a magnified, two-dimensional, schematic, sectional view of a portion of a TSOFC composite porous support-anode in accordance with an embodiment of the present invention. -
FIG. 9 is a magnified, two-dimensional, schematic, sectional view of a portion of a TSOFC having a composite porous support-anode in accordance with an embodiment of the present invention. -
FIG. 10 is an oblique, not-to-scale view of a portion of a TSOFC having a composite porous support-anode in accordance with an embodiment of the present invention. -
FIG. 11 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet having a composite porous support-anode in accordance with an embodiment of the present invention. -
FIG. 12 is an oblique, not-to-scale view of a portion of a TSOFC tube having interlayers in accordance with an embodiment of the present invention. -
FIG. 13 is an oblique, not-to-scale view of a portion of a TSOFC tube sheet having interlayers in accordance with an embodiment of the present invention. - Several elements that are essentially the same across multiple figs. are assigned like call-out numerals.
- For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims in connection with the above-described drawings.
- Referring to
FIG. 1 in a basic embodiment, the invention begins with aporous support tube 11 that may, for example, comprise any porous, sinterable material selected from the group consisting of a non-noble transition metal, metal alloy, and a cermet incorporating one or more of a non-noble transition metal and a non-noble transition metal alloy, preferably a stainless steel, and more preferably a ferritic and/or austenitic stainless steel. Thesupport tube 11 can be of any diameter or length with a wall thickness no greater than about 4 mm, preferably no greater than 1 mm. In addition, the support should have an average pore size in the range of 1 to 30 μm, preferably 1.5 to 20 μm, and more preferably 2 to 15 μm. Moreover, the support should have an average pore volume in the range of 20 to 50 volume percent and it should be electrically conductive at all operating temperatures. Thesupport tube 11 can be formed in any suitable cross-sectional shape, including circular, elliptical, triangular, rectangular, irregular, or any other desired shape. A round shape, especially an essentially circular shape as shown inFIG. 1 , accommodates uniform deposition of layers on theinner surface 16. - The
porous support tube 11 may be prepared by conventional powder metallurgy techniques, such as molding, extrusion, casting, forging, isostatic compression, etc. Thesupport tube 11 should be open on both ends. - Referring to
FIG. 2 , in some accordance with the present invention, active fuel cell membrane layers are deposited aslayers surface 16 of theporous support tube 11 to form anannular TSOFC 10. It can be seen that each successive layer supports the layers that are subsequently deposited thereon. - The first active fuel
cell membrane layer 12 is an anode material, which can be any anode material, but is preferably comprised of a cermet composition. Examples of suitable cermet compositions include, but are not limited to Ni—YSZ, Ni—GdCeO2, Ni—SmCeO2, and Ag—SmCeO2. The anode thickness should be in a range of 5-70 μm, preferably 5-60 μm, more preferably 5-50 μm, most preferably 5-40 μm. The anode should have an average pore size of 1-20 μm and pore volume of 25-40 volume percent. Theanode 12 is applied to thesupport tube 11 by a conventional method such as sol-gel, slurry, or wash coating, for example. Theanode 12 can be sintered before or after the application of subsequent layers. - The next active fuel
cell membrane layer 13 is a non-porous and/or essentially fully dense O2-permeable or H2-permeable electrolyte composition. Examples of suitable electrolyte compositions include but are not limited to YSZ, GdCeO2, SmCeO2, LaSrGaMg03, BaCeYO3, and La2Mo2O9. The electrolyte should have a thickness in a range of 2-80 μm, preferably 2-70 μm, more preferably 2-60 μm, most preferably 2-50 μm. The electrolyte should be dense and gas tight to prevent the air and fuel from mixing. Theelectrolyte layer 13 may be deposited using a conventional method such as sol-gel, slurry, or wash coating, for example, and subsequently sintered. - The first two
layers - The final layer is the
cathode 14, which is generally comprised of alkaline earth substituted lanthanum manganite, alkaline earth substituted lanthanum ferrite, lanthanum strontium iron cobaltite, or a mixed ionic-electronic conductor, but the composition of thecathode 14 is not critical to the invention. Thecathode 14 thickness should be in a range of 5-70 μm, preferably 5-60 μm, more preferably 5-50 μm, most preferably 5-40 μm. Thecathode 14 should have an average pore size of 1-15 μm and pore volume of 25-40 volume percent. Thecathode 14 can also be deposited using a conventional method such as sol-gel, slurry, or wash coating, for example. - The final step is a sintering process that is composed of heating the
entire TSOFC 10 in a neutral environment to 1000-1300° C. for 1-2 hours depending on the cathode material used. In cases where the electrolyte is H2-permeable, BaCeYO3 or La2Mo2O9, the cathode can be metallic comprising Pt, Pd, Ag—Pd, or other metallic material, or cermet comprising Ni—BaCeYO3 or Ni—SrCeO3. The term neutral as used herein means neither oxidizing nor reducing. - Referring to
FIG. 3 , in accordance with the present invention, a TSOFC 20 can have the internal active layers deposited on theinside surface 16 of thesupport tube 11 in reverse order (14, 13, 12). The skilled artisan will recognize that the fuel and oxygen supplies will also need to be reversed in operation. - In some embodiments of the present invention, a TSOFC is supported by a tube sheet. Referring to
FIG. 4 , a simplified example of atube sheet 21 defines an array of any number of integral openings havinginner surfaces 28. Thetube sheet 21 andinner surfaces 28 can be formed in any suitable cross-sectional shapes, including circular, elliptical, triangular, rectangular, irregular, or any other desired shapes. A round shape, especially an essentially circular shape as shown inFIG. 4 , accommodates uniform deposition of layers on the inner surfaces 28. Thetube sheet 21 can be comprised of any of the materials described hereinabove for thesupport tube 11. Thetube sheet 21 may be prepared by conventional powder metallurgy techniques, such as molding, extrusion, casting, forging, isostatic compression, etc. The tube sheet should be open on both ends. - Referring to
FIG. 5 , in some accordance with the present invention, active fuel cell membrane layers can be deposited and sintered as described hereinabove to form aSOFC tube sheet 30. Eachinner surface 28 defined by thetube sheet 21 is coated on the inside thereof with aporous anode 22 such as Ni—YSZ, for example. Theanode 22 is coated on the inside with adense electrolyte 23 such as Y2O3—ZrO2, for example. Thedense electrolyte 23 is coated on the inside with aporous cathode 24 such as LaMnO3, for example. It can be seen that each successive layer supports the layers that are subsequently deposited thereon. - The cross-sectional shape of the
tube sheet 21 and theopenings 28 defined thereby are not critical to the invention, although some shapes will be found to be more beneficial, especially those shapes which promote contact of reactive gases with respective surfaces of thetube sheet 21. - Referring to
FIG. 6 , in some embodiments of the present invention, aTSOFC tube sheet 35 can have the internal active layers deposited on the inside of thetube sheet 21 in reverse order (24, 23, 22). The skilled artisan will recognize that the fuel and oxygen supplies will also need to be reversed in operation. - Some embodiments of the present invention comprise a TSOFC having a composite porous support-anode. See U.S. Patent Application Publication No. US 2006/0234112 A1 to Visco, et al. published on Oct. 19, 2006.
- Referring to
FIG. 7 , fabrication of a TSOFC in accordance with the present invention begins with aporous support 40. A network ofmetal 42 and pores 44 is shown schematically; open porosity of theporous support 40 is 20 to 60 vol. %, preferably 30 to 50 vol. %, more preferably 35 to 50 vol. %. Theporous support 40 can be comprised of any metal, alloy, or cermet composition suitable for fuel cell construction, as described hereinabove. - The
porous support 40 is wash coated with an anode-forming composition comprised of NiO/YSZ, NiO/CeO2, NiO/Gd or Sm doped CeO2 with a conventional binder such as polyethylene glycol (PEG), for example. The wash coat can be done in air or under vacuum (for a few minutes to assist coating). The coatedporous support 40 is dried and sintered in Ar at 1000-1350° C. for 0.5 to 2 hrs. - Optionally, a conventional pore former comprised of a starch, for example, is included in the anode-forming composition in order to impart or enhance porosity thereof.
- The resulting structure, shown in
FIG. 8 , is a composite porous support-anode 48 wherein themetal 42 is coated throughout, including within thepores 44 and on theexternal surface 50 and interior surface 52 acontinuous anode layer 46 forming a three dimensional composite structure that serves as both support and anode. -
FIG. 9 is a schematic magnification showing a TSOFC 60 that includes a composite porous support-anode 48 as described above and shown inFIG. 8 , adense electrolyte layer 54, and aporous cathode layer 56.FIG. 10 is an unmagnified view of theTSOFC 60 showing the composite porous support-anode 48,dense electrolyte layer 54, andporous cathode layer 56. -
FIG. 11 shows an example of aSOFC tube sheet 70 that includes a composite porous support-anode 72, adense electrolyte layer 74, and aporous cathode layer 76. - The embodiments shown and described herein are set forth as examples, and are not to be construed as limiting the scope of the invention. The physical shape and configuration of TSOFC's made in accordance with the present invention can vary widely, and are not critical to the present invention. The particular compositions used to make the SOFC dense electrolyte and porous cathode coatings described herein, and thicknesses thereof, are not critical to the present invention.
- An advantage of having the metal support on the outside and ceramic materials on the inside is that as the fuel cell reaches operating temperatures, thermal expansion will cause compressive forces on the ceramic materials, which can be more easily withstood than tensile forces produced in devices with the ceramic materials on the outside of the metal tube. Other advantages provided by the present invention include: metal acts a structural backbone imparting increased strength to entire fuel cell package, increases potential for rapid start-up.
- Additional advantages provided by composite porous support-anodes of the present invention include the elimination of physical interconnect material and respective constituent layer.
- Arrays of the elements described herein can be used in electric power generators to power automobiles and other equipment.
- Referring to
FIGS. 12 and 13 , one or more buffer layers (interlayers) 101, 103, 105 can be deposited between any of the active layers in any of the above described embodiments of the present invention, according to preference for a particular application. For example, if a YSZ electrolyte is used, then an interlayer of Sm doped CeO2 can be deposited thereover to reduce interfacial polarization. Interlayers can be deposited using conventional methods such as sol-gel, slurry, or wash coating, for example. The interlayer(s) can be fully dense, i.e., essentially nonporous, about 1 μm to 5 μm thick, and conductive to oxide or hydrogen ions. Alternatively, the interlayer(s) can be porous, with pore size of <1 μm to 10 μm and thickness of 1 μm to 5 μm. - The elements described herein can be used as steam electrolyzers, i.e., high-temperature electrolysis cells. In the electrolysis configuration, an external potential, i.e., voltage, is applied to the unit via a circuit connecting the anode to the cathode. The resultant electrochemical reaction converts water to hydrogen and oxygen respectively by transport of hydrogen or oxygen ions through the electrolyte with recombination to molecular forms on exiting the electrolyte.
- While there has been shown and described what are at present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications can be prepared therein without departing from the scope of the inventions defined by the appended claims.
Claims (30)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/755,945 US20070237998A1 (en) | 2005-04-11 | 2007-05-31 | Solid Oxide Fuel Cell Having Internal Active Layers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/103,333 US7785747B2 (en) | 2005-04-11 | 2005-04-11 | Stack configurations for tubular solid oxide fuel cells |
US11/755,945 US20070237998A1 (en) | 2005-04-11 | 2007-05-31 | Solid Oxide Fuel Cell Having Internal Active Layers |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/103,333 Continuation-In-Part US7785747B2 (en) | 2005-04-11 | 2005-04-11 | Stack configurations for tubular solid oxide fuel cells |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070237998A1 true US20070237998A1 (en) | 2007-10-11 |
Family
ID=37083514
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/103,333 Expired - Fee Related US7785747B2 (en) | 2005-04-11 | 2005-04-11 | Stack configurations for tubular solid oxide fuel cells |
US11/755,945 Abandoned US20070237998A1 (en) | 2005-04-11 | 2007-05-31 | Solid Oxide Fuel Cell Having Internal Active Layers |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/103,333 Expired - Fee Related US7785747B2 (en) | 2005-04-11 | 2005-04-11 | Stack configurations for tubular solid oxide fuel cells |
Country Status (12)
Country | Link |
---|---|
US (2) | US7785747B2 (en) |
EP (1) | EP1878082B1 (en) |
JP (1) | JP2008542977A (en) |
AT (1) | ATE519247T1 (en) |
AU (1) | AU2006235362B2 (en) |
BR (1) | BRPI0609114A2 (en) |
CA (1) | CA2604716A1 (en) |
HK (1) | HK1112113A1 (en) |
NO (1) | NO20075324L (en) |
RU (1) | RU2415498C2 (en) |
WO (1) | WO2006110686A2 (en) |
ZA (1) | ZA200710023B (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009055037A1 (en) * | 2007-10-26 | 2009-04-30 | California Institute Of Technology | Thermochemical synthesis of fuels for storing thermal energy |
US20100112378A1 (en) * | 2006-10-12 | 2010-05-06 | Deininger Mark A | Methods For Providing Prophylactic Surface Treatment For Fluid Processing Systems And Components Thereof |
WO2011041264A1 (en) | 2009-09-29 | 2011-04-07 | Ut-Battelle, Llc | Wire mesh current collector, solid state electrochemical devices including the same, and methods of making the same |
US20110183221A1 (en) * | 2008-06-27 | 2011-07-28 | Serra Alfaro Jose Manuel | Catalytic layer for oxygen activation on ionic solid electrolytes at high temperature |
US20110200910A1 (en) * | 2008-10-14 | 2011-08-18 | University Of Florida Research Foundation Inc. | Advanced materials and design for low temperature sofcs |
US20120102696A1 (en) * | 2007-03-06 | 2012-05-03 | Takamichi Fujii | Piezoelectric device, process for producing the same, and liquid discharge device |
US20130316264A1 (en) * | 2012-05-24 | 2013-11-28 | Phillips 66 Company | Functionally layered electrolyte for solid oxide fuel cells |
US8614023B2 (en) | 2009-02-06 | 2013-12-24 | Protonex Technology Corporation | Solid oxide fuel cell systems with hot zones having improved reactant distribution |
US8623301B1 (en) | 2008-04-09 | 2014-01-07 | C3 International, Llc | Solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same |
KR20160058101A (en) * | 2013-08-13 | 2016-05-24 | 에스오에프씨파워 에스.피.에이. | Method for depositing a layer of material onto a metallic suppport for fuel cells or electrolysis cells |
US9905871B2 (en) | 2013-07-15 | 2018-02-27 | Fcet, Inc. | Low temperature solid oxide cells |
US20180269509A1 (en) * | 2015-02-02 | 2018-09-20 | The University Of Houston System | Porous solid oxide fuel cell anode with nanoporous surface and process for fabrication |
US10109867B2 (en) | 2013-06-26 | 2018-10-23 | Upstart Power, Inc. | Solid oxide fuel cell with flexible fuel rod support structure |
US10344389B2 (en) | 2010-02-10 | 2019-07-09 | Fcet, Inc. | Low temperature electrolytes for solid oxide cells having high ionic conductivity |
US10573911B2 (en) | 2015-10-20 | 2020-02-25 | Upstart Power, Inc. | SOFC system formed with multiple thermally conductive pathways |
US10790523B2 (en) | 2015-10-20 | 2020-09-29 | Upstart Power, Inc. | CPOX reactor control system and method |
US11108072B2 (en) | 2016-08-11 | 2021-08-31 | Upstart Power, Inc. | Planar solid oxide fuel unit cell and stack |
US11784331B2 (en) | 2014-10-07 | 2023-10-10 | Upstart Power, Inc. | SOFC-conduction |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6605316B1 (en) | 1999-07-31 | 2003-08-12 | The Regents Of The University Of California | Structures and fabrication techniques for solid state electrochemical devices |
CN100530766C (en) | 2004-11-30 | 2009-08-19 | 加州大学评议会 | Sealed joint structure for electrochemical device |
US7785747B2 (en) | 2005-04-11 | 2010-08-31 | Worldwide Energy, Inc. Of Delaware | Stack configurations for tubular solid oxide fuel cells |
WO2007005767A1 (en) * | 2005-07-01 | 2007-01-11 | The Regents Of The University Of California | Advanced solid oxide fuel cell stack design for power generation |
US20070141424A1 (en) * | 2005-12-21 | 2007-06-21 | Armstrong Timothy R | Solid oxide fuel cell and stack configuration |
EP2056985A4 (en) | 2006-07-28 | 2012-03-07 | Univ California | Joined concentric tubes |
US20080254335A1 (en) * | 2007-04-16 | 2008-10-16 | Worldwide Energy, Inc. | Porous bi-tubular solid state electrochemical device |
JP5301865B2 (en) * | 2007-12-26 | 2013-09-25 | 東京瓦斯株式会社 | Horizontally striped solid oxide fuel cell |
KR20110005818A (en) * | 2008-04-18 | 2011-01-19 | 더 리전트 오브 더 유니버시티 오브 캘리포니아 | Integrated seal for high-temperature electrochemical device |
ES2362516B1 (en) * | 2008-12-19 | 2012-05-23 | Ikerlan, S.Coop. | SOLID OXIDE FUEL TUBULAR CELL WITH METALLIC SUPPORT. |
ES2364827B1 (en) * | 2010-01-25 | 2012-08-03 | Amurrio Ferrocarril Y Equipos, S.A. | PUNTA MOBILE TRANVIARY CROSSING STRUCTURE |
KR101178675B1 (en) * | 2010-07-16 | 2012-08-30 | 삼성에스디아이 주식회사 | Bundle-type interconnector and the fuel cell having the same |
KR20130036884A (en) * | 2011-10-05 | 2013-04-15 | 삼성에스디아이 주식회사 | Solid oxide fuel cell stack and fuel cell module having the same |
JP5743098B2 (en) * | 2012-02-22 | 2015-07-01 | 三菱日立パワーシステムズ株式会社 | Solid oxide fuel cell |
US20140295303A1 (en) * | 2013-03-28 | 2014-10-02 | Toto Ltd. | Solid oxide fuel cell |
US9728790B2 (en) * | 2013-10-09 | 2017-08-08 | GM Global Technology Operations LLC | Fuel cell stack bus bar assembly systems and methods |
US20180298544A1 (en) * | 2017-04-17 | 2018-10-18 | Greg O'Rourke | High-Efficiency Washer-Dryer System |
RU200605U1 (en) * | 2020-02-07 | 2020-11-02 | Общество с ограниченной ответственностью "Научно-исследовательский центр "ТОПАЗ" (ООО "НИЦ "ТОПАЗ") | DEVICE FOR ELECTROCHEMICAL RESEARCH OF TUBULAR SOLID OXIDE FUEL CELLS |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5629103A (en) * | 1993-04-30 | 1997-05-13 | Siemens Aktiengesellschaft | High-temperature fuel cell with improved solid-electrolyte/electrode interface and method of producing the interface |
US6936367B2 (en) * | 2002-01-16 | 2005-08-30 | Alberta Research Council Inc. | Solid oxide fuel cell system |
US20060234112A1 (en) * | 1999-07-31 | 2006-10-19 | The Regents Of The University Of California | Structures and fabrication techniques for solid state electrochemical devices |
US20070141424A1 (en) * | 2005-12-21 | 2007-06-21 | Armstrong Timothy R | Solid oxide fuel cell and stack configuration |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4490444A (en) | 1980-12-22 | 1984-12-25 | Westinghouse Electric Corp. | High temperature solid electrolyte fuel cell configurations and interconnections |
US4395468A (en) | 1980-12-22 | 1983-07-26 | Westinghouse Electric Corp. | Fuel cell generator |
US4728584A (en) | 1986-10-21 | 1988-03-01 | Westinghouse Electric Corp. | Fuel cell generator containing self-supporting high gas flow solid oxide electrolyte fuel cells |
JPH07211334A (en) * | 1994-01-19 | 1995-08-11 | Fuji Electric Co Ltd | Solid electrolyte fuel cell |
US5985113A (en) | 1995-08-24 | 1999-11-16 | Litton Systems, Inc. | Modular ceramic electrochemical apparatus and method of manufacture therefor |
US5741605A (en) | 1996-03-08 | 1998-04-21 | Westinghouse Electric Corporation | Solid oxide fuel cell generator with removable modular fuel cell stack configurations |
US6423436B1 (en) | 2000-03-30 | 2002-07-23 | The United States Of America As Represented By The United States Department Of Energy | Tubular electrochemical devices with lateral fuel aperatures for increasing active surface area |
US6572996B1 (en) * | 2000-08-10 | 2003-06-03 | Siemens Westinghouse Power Corporation | Electrochemical fuel depletion means for fuel cell generators |
US6416897B1 (en) | 2000-09-01 | 2002-07-09 | Siemens Westinghouse Power Corporation | Tubular screen electrical connection support for solid oxide fuel cells |
AU2002230865A1 (en) | 2000-10-30 | 2002-05-15 | Michael A. Cobb & Company | Solid oxide fuel cells stack |
JP5234554B2 (en) * | 2001-03-22 | 2013-07-10 | 独立行政法人産業技術総合研究所 | Solid oxide fuel cell stack structure |
PT1425814E (en) | 2001-06-04 | 2006-08-31 | Acumentrics Corp | HORIZONTAL TUBE SYSTEM FOR COMBUSTIBLE CELL AND METHODS |
US20020197520A1 (en) | 2001-06-25 | 2002-12-26 | Usf Filtration & Separations Group., Inc | Micro fuel cell array |
US6824907B2 (en) * | 2002-01-16 | 2004-11-30 | Alberta Reasearch Council, Inc. | Tubular solid oxide fuel cell stack |
DE10219096A1 (en) | 2002-04-29 | 2003-11-13 | Siemens Ag | High temperature fuel cell used as a solid oxide fuel cell comprises a ceramic electrolyte and electrodes arranged as functional layers on a metallic support having perforations and/or pores |
CA2509905A1 (en) | 2002-12-17 | 2004-07-01 | Alberta Research Council Inc. | Compact solid oxide fuel cell stack |
JP2004319152A (en) * | 2003-04-14 | 2004-11-11 | Nissan Motor Co Ltd | Cell body for tubular fuel cell and its manufacturing method |
JP4111325B2 (en) * | 2003-05-08 | 2008-07-02 | 東邦瓦斯株式会社 | Solid oxide fuel cell |
US7785747B2 (en) | 2005-04-11 | 2010-08-31 | Worldwide Energy, Inc. Of Delaware | Stack configurations for tubular solid oxide fuel cells |
-
2005
- 2005-04-11 US US11/103,333 patent/US7785747B2/en not_active Expired - Fee Related
-
2006
- 2006-04-11 WO PCT/US2006/013372 patent/WO2006110686A2/en active Application Filing
- 2006-04-11 JP JP2008506583A patent/JP2008542977A/en active Pending
- 2006-04-11 AT AT06749682T patent/ATE519247T1/en not_active IP Right Cessation
- 2006-04-11 EP EP06749682A patent/EP1878082B1/en not_active Not-in-force
- 2006-04-11 RU RU2007141681/07A patent/RU2415498C2/en not_active IP Right Cessation
- 2006-04-11 AU AU2006235362A patent/AU2006235362B2/en not_active Ceased
- 2006-04-11 CA CA002604716A patent/CA2604716A1/en not_active Abandoned
- 2006-04-11 BR BRPI0609114-8A patent/BRPI0609114A2/en not_active IP Right Cessation
-
2007
- 2007-01-01 ZA ZA200710023A patent/ZA200710023B/en unknown
- 2007-05-31 US US11/755,945 patent/US20070237998A1/en not_active Abandoned
- 2007-10-17 NO NO20075324A patent/NO20075324L/en not_active Application Discontinuation
-
2008
- 2008-06-25 HK HK08107033.6A patent/HK1112113A1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5629103A (en) * | 1993-04-30 | 1997-05-13 | Siemens Aktiengesellschaft | High-temperature fuel cell with improved solid-electrolyte/electrode interface and method of producing the interface |
US20060234112A1 (en) * | 1999-07-31 | 2006-10-19 | The Regents Of The University Of California | Structures and fabrication techniques for solid state electrochemical devices |
US6936367B2 (en) * | 2002-01-16 | 2005-08-30 | Alberta Research Council Inc. | Solid oxide fuel cell system |
US20070141424A1 (en) * | 2005-12-21 | 2007-06-21 | Armstrong Timothy R | Solid oxide fuel cell and stack configuration |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9625079B2 (en) | 2006-10-12 | 2017-04-18 | C3 International, Llc | Methods for providing prophylactic surface treatment for fluid processing systems and components thereof |
US20100112378A1 (en) * | 2006-10-12 | 2010-05-06 | Deininger Mark A | Methods For Providing Prophylactic Surface Treatment For Fluid Processing Systems And Components Thereof |
US9879815B2 (en) | 2006-10-12 | 2018-01-30 | C3 International, Llc | Methods for providing prophylactic surface treatment for fluid processing systems and components thereof |
US9353434B2 (en) | 2006-10-12 | 2016-05-31 | C3 International, Llc | Methods for providing prophylactic surface treatment for fluid processing systems and components thereof |
US20120102696A1 (en) * | 2007-03-06 | 2012-05-03 | Takamichi Fujii | Piezoelectric device, process for producing the same, and liquid discharge device |
US8733905B2 (en) * | 2007-03-06 | 2014-05-27 | Fujifilm Corporation | Piezoelectric device, process for producing the same, and liquid discharge device |
WO2009055037A1 (en) * | 2007-10-26 | 2009-04-30 | California Institute Of Technology | Thermochemical synthesis of fuels for storing thermal energy |
US8167961B2 (en) | 2007-10-26 | 2012-05-01 | California Institute Of Technology | Thermochemical synthesis of fuels for storing thermal energy |
US8480923B2 (en) | 2007-10-26 | 2013-07-09 | California Institute Of Technology | Thermochemical synthesis of fuels for storing thermal energy |
US20090107044A1 (en) * | 2007-10-26 | 2009-04-30 | California Institute Of Technology | Thermochemical synthesis of fuels for storing thermal energy |
US8623301B1 (en) | 2008-04-09 | 2014-01-07 | C3 International, Llc | Solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same |
US9670586B1 (en) | 2008-04-09 | 2017-06-06 | Fcet, Inc. | Solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same |
US20110183221A1 (en) * | 2008-06-27 | 2011-07-28 | Serra Alfaro Jose Manuel | Catalytic layer for oxygen activation on ionic solid electrolytes at high temperature |
US20110200910A1 (en) * | 2008-10-14 | 2011-08-18 | University Of Florida Research Foundation Inc. | Advanced materials and design for low temperature sofcs |
US9343746B2 (en) * | 2008-10-14 | 2016-05-17 | University Of Florida Research Foundation, Inc. | Advanced materials and design for low temperature SOFCs |
US8614023B2 (en) | 2009-02-06 | 2013-12-24 | Protonex Technology Corporation | Solid oxide fuel cell systems with hot zones having improved reactant distribution |
US9343758B2 (en) | 2009-02-06 | 2016-05-17 | Protonex Technology Corporation | Solid oxide fuel cell systems with hot zones having improved reactant distribution |
WO2011041264A1 (en) | 2009-09-29 | 2011-04-07 | Ut-Battelle, Llc | Wire mesh current collector, solid state electrochemical devices including the same, and methods of making the same |
US11560636B2 (en) | 2010-02-10 | 2023-01-24 | Fcet, Inc. | Low temperature electrolytes for solid oxide cells having high ionic conductivity |
US10344389B2 (en) | 2010-02-10 | 2019-07-09 | Fcet, Inc. | Low temperature electrolytes for solid oxide cells having high ionic conductivity |
US20130316264A1 (en) * | 2012-05-24 | 2013-11-28 | Phillips 66 Company | Functionally layered electrolyte for solid oxide fuel cells |
US10109867B2 (en) | 2013-06-26 | 2018-10-23 | Upstart Power, Inc. | Solid oxide fuel cell with flexible fuel rod support structure |
US9905871B2 (en) | 2013-07-15 | 2018-02-27 | Fcet, Inc. | Low temperature solid oxide cells |
US10707511B2 (en) | 2013-07-15 | 2020-07-07 | Fcet, Inc. | Low temperature solid oxide cells |
US20160197356A1 (en) * | 2013-08-13 | 2016-07-07 | Sofcpower S.P.A. | Method for depositing a layer of material onto a metallic support for fuel cells or electrolysis cells |
US10707496B2 (en) * | 2013-08-13 | 2020-07-07 | Sofcpower S.P.A. | Method for depositing layer of ceramic material onto a metallic support for solid oxide fuel cells |
KR102328999B1 (en) | 2013-08-13 | 2021-11-19 | 에스오에프씨파워 에스.피.에이. | Method for depositing a layer of material onto a metallic suppport for fuel cells or electrolysis cells |
KR20160058101A (en) * | 2013-08-13 | 2016-05-24 | 에스오에프씨파워 에스.피.에이. | Method for depositing a layer of material onto a metallic suppport for fuel cells or electrolysis cells |
US11784331B2 (en) | 2014-10-07 | 2023-10-10 | Upstart Power, Inc. | SOFC-conduction |
US10547076B2 (en) * | 2015-02-02 | 2020-01-28 | University Of Houston System | Porous solid oxide fuel cell anode with nanoporous surface and process for fabrication |
US20180269509A1 (en) * | 2015-02-02 | 2018-09-20 | The University Of Houston System | Porous solid oxide fuel cell anode with nanoporous surface and process for fabrication |
US10573911B2 (en) | 2015-10-20 | 2020-02-25 | Upstart Power, Inc. | SOFC system formed with multiple thermally conductive pathways |
US10790523B2 (en) | 2015-10-20 | 2020-09-29 | Upstart Power, Inc. | CPOX reactor control system and method |
US11605825B2 (en) | 2015-10-20 | 2023-03-14 | Upstart Power, Inc. | CPOX reactor control system and method |
US11108072B2 (en) | 2016-08-11 | 2021-08-31 | Upstart Power, Inc. | Planar solid oxide fuel unit cell and stack |
US11664517B2 (en) | 2016-08-11 | 2023-05-30 | Upstart Power, Inc. | Planar solid oxide fuel unit cell and stack |
Also Published As
Publication number | Publication date |
---|---|
HK1112113A1 (en) | 2008-08-22 |
ZA200710023B (en) | 2008-10-29 |
US7785747B2 (en) | 2010-08-31 |
JP2008542977A (en) | 2008-11-27 |
EP1878082A2 (en) | 2008-01-16 |
RU2007141681A (en) | 2009-05-20 |
WO2006110686A2 (en) | 2006-10-19 |
CA2604716A1 (en) | 2006-10-19 |
EP1878082B1 (en) | 2011-08-03 |
BRPI0609114A2 (en) | 2010-11-16 |
WO2006110686A3 (en) | 2007-04-05 |
WO2006110686A8 (en) | 2007-08-23 |
AU2006235362A1 (en) | 2006-10-19 |
ATE519247T1 (en) | 2011-08-15 |
NO20075324L (en) | 2008-01-03 |
US20060228615A1 (en) | 2006-10-12 |
AU2006235362B2 (en) | 2010-08-05 |
RU2415498C2 (en) | 2011-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20070237998A1 (en) | Solid Oxide Fuel Cell Having Internal Active Layers | |
EP1228546B1 (en) | Structures and fabrication techniques for solid state electrochemical devices | |
KR101162806B1 (en) | Self-supporting ceramic membranes and electrochemical cells and electrochemical cell stacks including the same | |
JP5179718B2 (en) | Solid oxide fuel cell, solid oxide fuel cell stack, and method for producing solid oxide fuel cell | |
EP1768208A2 (en) | High performance anode-supported solid oxide fuel cell | |
JP5328275B2 (en) | Cell stack, fuel cell module including the same, and fuel cell device | |
US20140099567A1 (en) | Ceramic interconnect for fuel cell stacks | |
US20030148160A1 (en) | Anode-supported tubular solid oxide fuel cell stack and method of fabricating the same | |
JP5171159B2 (en) | Fuel cell and fuel cell stack, and fuel cell | |
US20080254335A1 (en) | Porous bi-tubular solid state electrochemical device | |
JP2004512651A (en) | Fuel cell | |
JP2008226654A (en) | Cell of fuel cell, cell stack of fuel cell, and fuel cell | |
JP5247051B2 (en) | Fuel cell and fuel cell stack, and fuel cell | |
US8697313B2 (en) | Method for making a fuel cell from a solid oxide monolithic framework | |
KR100776299B1 (en) | A method for production of unit cell for solid oxide fuel cell | |
JP4511122B2 (en) | Fuel cell | |
JP2004253376A (en) | Fuel battery cell and method for manufacturing same, and fuel battery | |
JP4350403B2 (en) | Solid oxide fuel cell | |
JP4130135B2 (en) | Surface treatment method for current collecting member | |
JP4173029B2 (en) | Current collector | |
KR102109730B1 (en) | Method for fabricating solid oxide fuel cell | |
JPH06196180A (en) | Manufacture of solid electrolyte type fuel cell | |
US20100297527A1 (en) | Fast Ion Conducting Composite Electrolyte for Solid State Electrochemical Devices | |
JP4544874B2 (en) | Fuel cell and fuel cell | |
JP2009087539A (en) | Fuel battery cell and fuel battery cell stack, as well as fuel battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UT-BATTELLE, LLC, TENNESSEE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ARMSTRONG, TIMOTHY R;JUDKINS, RODDIE R;ARMSTRONG, BETH L;AND OTHERS;REEL/FRAME:019374/0961;SIGNING DATES FROM 20070521 TO 20070524 |
|
AS | Assignment |
Owner name: U.S. DEPARTMENT OF ENERGY, DISTRICT OF COLUMBIA Free format text: EXECUTIVE ORDER 9424, CONFIRMATORY LICENSE;ASSIGNOR:UT-BATTELLE, LLC;REEL/FRAME:019883/0846 Effective date: 20070709 |
|
AS | Assignment |
Owner name: WORLDWIDE ENERGY, INC. OF DELAWARE, TENNESSEE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UT-BATTELLE, L.L.C.;REEL/FRAME:026655/0009 Effective date: 20091006 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |