WO2014208730A1 - セル、セルスタック装置、モジュールおよびモジュール収納装置 - Google Patents
セル、セルスタック装置、モジュールおよびモジュール収納装置 Download PDFInfo
- Publication number
- WO2014208730A1 WO2014208730A1 PCT/JP2014/067191 JP2014067191W WO2014208730A1 WO 2014208730 A1 WO2014208730 A1 WO 2014208730A1 JP 2014067191 W JP2014067191 W JP 2014067191W WO 2014208730 A1 WO2014208730 A1 WO 2014208730A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- solid electrolyte
- support
- electrode layer
- cell
- Prior art date
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
- H01M8/10—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
- H01M8/1246—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 the electrolyte consisting of oxides
- H01M8/1253—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 the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
-
- 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/002—Shape, form of a fuel cell
- H01M8/004—Cylindrical, tubular or wound
-
- 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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- 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
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
-
- 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
- H01M8/1246—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 the electrolyte consisting of oxides
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- the present invention relates to a cell, a cell stack device, a module, and a module storage device.
- next-generation energy various fuel cell devices in which a cell stack device in which a plurality of solid oxide fuel cells are electrically connected in series are accommodated in a storage container have been proposed as next-generation energy.
- a solid oxide fuel cell of such a fuel cell device for example, it has a support body having a pair of flat surfaces parallel to each other and a fuel gas passage for circulating fuel gas inside,
- a solid oxide fuel cell in which a fuel electrode layer, a solid electrolyte layer, and an oxygen electrode layer are laminated in this order on a flat surface on one side of the support, and an interconnector layer is laminated on the flat surface on the other side.
- a cell has been proposed (see, for example, Patent Document 1).
- fuel cells called a cylindrical type or a horizontal stripe type have also been proposed.
- the ionic conductivity improves as the thickness of the solid electrolyte layer decreases, and the power generation performance of the fuel cells improves.
- the thickness of the solid electrolyte layer is reduced.
- the strength improvement effect by the solid electrolyte layer is lowered, and there is a possibility that cracks may occur in the fuel cell.
- An object of the present invention is to provide a cell, a cell stack device, a module, and a module storage device that can suppress the occurrence of cracks.
- the cell of the present invention has an element portion in which a first electrode layer that also serves as a cylindrical support, a solid electrolyte layer, and a second electrode layer are laminated in this order, and the solid electrolyte layer is mainly composed of an oxide.
- the oxide contains a rare earth element, has a thickness of 30 ⁇ m or less, has a portion where the second electrode layer is not provided, and a portion where the second electrode layer is not provided.
- the cell of the present invention has a plurality of element parts in which a first electrode layer, a solid electrolyte layer, and a second electrode layer are laminated in this order on an insulating and cylindrical support, and the solid electrolyte layer is
- the main electrode is an oxide, the oxide contains a rare earth element, the thickness is 30 ⁇ m or less, and the second electrode layer is not provided, and the second electrode In a portion where no layer is provided, a first layer having the same oxide as the main component of the solid electrolyte layer and a main component having a different rare earth element content and higher strength than the solid electrolyte layer is provided. It is characterized by that.
- the cell of the present invention has an element portion in which a first electrode layer, a solid electrolyte layer, and a second electrode layer are laminated in this order on one main surface of a cylindrical support having a pair of main surfaces.
- the solid electrolyte layer has an oxide as a main component, the oxide contains a rare earth element, has a thickness of 30 ⁇ m or less, and has a portion where the second electrode layer is not provided.
- the portion where the second electrode layer is not provided includes a main component that is the same oxide as the main component of the solid electrolyte layer and has a different rare earth element content, and is stronger than the solid electrolyte layer.
- a high first layer is provided.
- the cell stack device of the present invention comprises a plurality of the above-described cells and is electrically connected to the plurality of cells.
- the module of the present invention is characterized in that the cell stack device is stored in a storage container.
- the module storage device of the present invention is characterized in that the above module and an auxiliary machine for operating the module are stored in an outer case.
- the thickness of the solid electrolyte layer is as thin as 30 ⁇ m or less, the performance of the cell can be improved, and the thin solid electrolyte layer can be reinforced by the first layer, and the generation of cracks in the cell can be prevented.
- the cell stack device, a module, and a module storage device with high performance and high long-term reliability.
- FIG. 1 shows an example of a solid oxide fuel cell of a cylindrical type and a horizontal stripe type, where (a) is a partially broken perspective view, (b) is a longitudinal sectional view, (c) is a perspective view, and (d) is a perspective view. It is a longitudinal cross-sectional view of one end side.
- 1 shows a hollow plate type solid oxide fuel cell, where (a) is a cross-sectional view, (b) is a cross-sectional view on one end side, and (c) is a side view seen from the oxygen electrode layer side. is there.
- FIG. 2 is a side view showing an example of a first layer in a solid electrolyte layer, showing a hollow plate type solid oxide fuel cell.
- FIG. 1 shows a hollow plate type solid oxide fuel cell having a first layer on one main surface of a support and a second layer on the other main surface
- (a) is a cross-sectional view
- (b) ) Is a side view of (a) as viewed from the interconnector layer side.
- FIG. 2 is a side view showing an example of a second layer, showing a hollow flat plate type solid oxide fuel cell.
- An example of a cell stack apparatus is shown, (a) is a side view schematically showing the cell stack apparatus, (b) is an enlarged cross-sectional view showing a part of the cell stack apparatus surrounded by a broken line in (a). It is.
- 3A is a side view showing a state where the cell of FIG.
- FIG. 3A is fixed to a gas tank using a bonding material
- FIG. 3B is a state where the cell of FIG. 3D is fixed to the gas tank
- FIG. 3C is a side view showing a state in which the cell of FIG. 3E is fixed to the gas tank
- FIG. 3D is a side view showing a state in which the cell of FIG. 3F is fixed to the gas tank
- FIG. 5A is a side view showing a state where the cell of FIG. 5A is fixed to a gas tank using a bonding material
- FIG. 5B is a state where the cell of FIG. 5B is fixed to the gas tank
- a side view and (c) are side views showing the state where the cell of (c) of Drawing 5 was fixed to the gas tank.
- It is an external appearance perspective view which shows an example of a fuel cell module. It is a perspective view which abbreviate
- FIG. 1 shows an example of a solid oxide fuel cell of a cylindrical type and a horizontal stripe type (hereinafter sometimes abbreviated as a fuel cell), (a) is a partially broken perspective view, ) Is a longitudinal sectional view, (c) is a perspective view, (d) is a longitudinal sectional view on one end side, and FIG. 2 shows a hollow plate type solid oxide fuel cell, (a) Is a transverse sectional view, (b) is a transverse sectional view on one end side, and (c) is a side view as seen from the oxygen electrode layer side.
- a part of each configuration of the fuel cells 100, 200, 300 is shown in an enlarged manner.
- the same components will be described using the same reference numerals. First, the configuration of each fuel cell will be described below.
- a fuel cell 100 shown in FIGS. 1A and 1B is an example of a so-called cylindrical fuel cell, and is a porous fuel electrode layer (first electrode layer) that also serves as a cylindrical support. 3, a dense solid electrolyte layer 4 and a porous oxygen electrode layer (second electrode layer) 6 are laminated in this order to form a cylindrical shape.
- the inside of the fuel electrode layer 3 is a fuel gas passage 2 through which the fuel gas flows, and is provided along the longitudinal direction L.
- the solid electrolyte layer 4 is preferably 30 ⁇ m or less in thickness made of ceramics having gas barrier properties, and particularly preferably 20 ⁇ m or less, and more preferably 15 ⁇ m or less from the viewpoint of improving power generation performance.
- the portion where the fuel electrode layer 3, the solid electrolyte layer 4 and the oxygen electrode layer 6 overlap functions as an element part a that generates power. That is, electricity is generated by flowing an oxygen-containing gas such as air outside the oxygen electrode layer 6 and flowing a fuel gas (hydrogen-containing gas) through the fuel gas passage 2 and heating it to a predetermined operating temperature.
- an oxygen-containing gas such as air outside the oxygen electrode layer 6
- a fuel gas hydrogen-containing gas
- the oxygen electrode layer 6 is not provided at one end (lower end) and the other end (upper end) of the fuel cell 100. That is, the portion of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided is at one end and the other end of the fuel electrode layer 3 that also serves as a support. And the 1st layer 7 mentioned later is provided in this one end part in which the oxygen electrode layer 6 is not provided.
- a fuel cell 200 shown in FIGS. 1C and 1D shows an example of a so-called horizontal stripe type fuel cell, which has a flat cross section and an elliptical cylindrical body as a whole (in other words, an ellipse).
- An insulating support 1 having a columnar shape is provided.
- a plurality of fuel gas passages 2 are formed in the support 1 so as to penetrate in the longitudinal direction L of the fuel cell 300 at appropriate intervals.
- the support 1 is composed of a pair of parallel flat surfaces n and arcuate surfaces (side surfaces) m respectively connecting the pair of flat surfaces n. It is configured. Both surfaces of the flat surface n are formed substantially parallel to each other, and on each flat surface n, a porous fuel electrode layer 3, a dense solid electrolyte layer 4 and a porous oxygen electrode layer 6 are formed as one set. A plurality of sets are provided adjacent to each other, and these are electrically connected by a dense interconnector layer 8. The portion where the fuel electrode layer 3, the solid electrolyte layer 4 and the oxygen electrode layer 6 overlap functions as the element portion a that generates power.
- the solid electrolyte layer 4 preferably has a thickness of 30 ⁇ m or less, particularly 20 ⁇ m or less, and more preferably 15 ⁇ m or less from the viewpoint of improving power generation performance.
- a solid electrolyte layer 4 made of ceramics having gas barrier properties is provided in order to prevent the gas flowing through the fuel gas passage 2 from leaking to the outside. That is, the fuel gas flowing through the solid electrolyte layer 4 and the interconnector layer 8 is configured not to leak to the outside.
- 1D shows an example in which the fuel electrode layer 3 and the oxygen electrode layer 6 are each one layer on the insulating support 1, but each may be composed of two or more layers. Further, the fuel electrode layer 3 may be in a form in which at least a part thereof is embedded in the support 1.
- the oxygen electrode layer 6 is not provided at one end (lower end) of the fuel cell 200. That is, a portion of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided is at one end of the support 1. And the 1st layer 7 mentioned later is provided in this one end part in which the oxygen electrode layer 6 is not provided.
- FIG. 2 shows an example of a hollow plate type fuel cell 300, where (a) is a cross-sectional view thereof, (b) is a cross-sectional view of one end side, and (c) is from the oxygen electrode layer side.
- FIG. 2 shows an example of a hollow plate type fuel cell 300, where (a) is a cross-sectional view thereof, (b) is a cross-sectional view of one end side, and (c) is from the oxygen electrode layer side.
- a fuel battery cell 300 shown in FIG. 2 has a hollow flat plate type, a flat cross section, and an electrically conductive support 1 having an elliptic cylinder (in other words, an elliptic cylinder) as a whole. Inside the support 1, a plurality of fuel gas passages 2 are formed at appropriate intervals so as to penetrate in the longitudinal direction L of the fuel cell 300, and the fuel cell 300 is formed on the support 1 in various ways. It has a structure in which members are provided.
- the support 1 includes a pair of flat surfaces n and a pair of flat surfaces n. It is comprised with the arcuate surface (side surface) m connected, respectively. Both surfaces of the flat surface n are formed substantially parallel to each other, and are porous fuel electrode layers (first electrode layers) so as to cover one flat surface n (one main surface: lower surface) and both arc-shaped surfaces m. Further, a solid electrolyte layer 4 made of ceramics having a gas barrier property and having a thickness of 30 ⁇ m or less is arranged so as to cover the fuel electrode layer 3. The thickness of the solid electrolyte layer 4 is particularly preferably 20 ⁇ m or less, and more preferably 15 ⁇ m or less from the viewpoint of improving power generation performance.
- a porous oxygen electrode layer (second electrode layer) 6 is disposed on the surface of the solid electrolyte layer 4 so as to face the fuel electrode layer 3 through the intermediate layer 9.
- the intermediate layer 9 is formed on the solid electrolyte layer 4 on which the oxygen electrode layer 6 is formed.
- the intermediate layer 9 may also be provided in the cylindrical fuel cell 100 and the horizontal stripe fuel cell 200 shown in FIG.
- an interconnector layer 8 made of conductive ceramics having gas barrier properties is formed on the other flat surface n (the other main surface: the upper surface) where the oxygen electrode layer 6 is not laminated.
- the fuel electrode layer 3 and the solid electrolyte layer 4 are connected to the other flat surface n (the other side) from one flat surface (one main surface: the lower surface) via the arcuate surfaces m at both ends.
- both end portions of the interconnector layer 8 are laminated and bonded to both end portions of the solid electrolyte layer 4.
- the solid electrolyte layer 4 is formed on the entire surface on one side.
- the solid electrolyte layer 4 having gas barrier properties and the interconnector layer 8 surround the support 1 so that fuel gas flowing through the inside does not leak to the outside.
- the solid electrolyte layer 4 and the interconnector layer 8 form an elliptic cylindrical body having gas barrier properties.
- the inside of the elliptic cylindrical body serves as a fuel gas flow path and is supplied to the fuel electrode layer 3.
- the fuel gas and the oxygen-containing gas supplied to the oxygen electrode layer 6 are blocked by an elliptic cylinder.
- the oxygen electrode layer 6 having a rectangular planar shape is formed except for the upper and lower ends of the support 1, while the interconnector layer 8 is Although not shown, it is formed from the upper end to the lower end of the support 1, and its left and right ends are joined to the surfaces of the left and right ends of the solid electrolyte layer 4.
- the interconnector layer 8 may be configured not to have a lower end portion as will be described later.
- a portion where the fuel electrode layer 3 and the oxygen electrode layer 6 face each other through the solid electrolyte layer 4 functions as a power generation element portion a. That is, an oxygen-containing gas such as air is allowed to flow outside the oxygen electrode layer 6 and a fuel gas (hydrogen-containing gas) is allowed to flow in the fuel gas passage 2 in the support 1 to generate power by heating to a predetermined operating temperature. . And the electric current produced
- the oxygen electrode layer 6 is provided at one end (lower end) of the fuel cell 300. Not. That is, a portion of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided is at one end of the support 1. And the 1st layer 7 mentioned later is provided in this one end part in which the oxygen electrode layer 6 is not provided.
- each member constituting the fuel battery cell of the present embodiment will be described using the fuel battery cell 300.
- the same materials as described below can be used unless otherwise specified.
- the support 1 is required to be gas permeable in order to permeate the fuel gas to the fuel electrode layer 3 and to be conductive in order to collect current through the interconnector layer 8, for example, Ni and / or NiO and an inorganic oxide such as a specific rare earth element oxide are preferable.
- the specific rare earth element oxide is used to bring the thermal expansion coefficient of the support 1 close to the thermal expansion coefficient of the solid electrolyte layer 4, and includes Y, Lu, Yb, Tm, Er, Ho, Dy, Rare earth element oxides containing at least one element selected from the group consisting of Gd, Sm, and Pr can be used in combination with Ni and / or NiO.
- Specific examples of such rare earth element oxides include Y 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Er 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Gd 2.
- the support 1 is the conductive support 1, Ni and / or Ni and / or in that the good conductivity is maintained and the thermal expansion coefficient is approximated to that of the solid electrolyte layer 4.
- NiO: rare earth element oxide is preferably present in a volume ratio of 35:65 to 65:35.
- the support 1 when used as the insulating support 1, it is preferably formed of, for example, Mg oxide (MgO), Ni and / or NiO, and a specific rare earth oxide.
- MgO Mg oxide
- Ni and / or NiO a specific rare earth oxide.
- the rare earth element oxide the same ones as described above can be used.
- MgO is preferably 70 to 80% by volume
- rare earth element oxide is 10 to 20% by volume
- Ni and / or NiO is 10 to 25% by volume
- the whole preferably has a resistivity of 10 ⁇ ⁇ cm or more.
- the support 1 may contain other metal components and oxide components as long as required characteristics are not impaired.
- the support 1 is required to have fuel gas permeability, the support 1 is porous and usually has an open porosity of 30% or more, particularly 35 to 50%. . Further, the conductivity of the support 1 is preferably 300 S / cm or more, and particularly preferably 440 S / cm or more.
- the length of the flat surface n of the support 1 (the length of the support 1 in the width direction W) is, for example, 15 to 35 mm, and the length of the arcuate surface m (the length of the arc) is 2 to 8 mm.
- the thickness of the support 1 (thickness between the flat surfaces n) is 1.5 to 5 mm.
- the length of the support 1 is, for example, 100 to 300 mm.
- the fuel electrode layer 3 causes an electrode reaction, and can be formed of a well-known porous conductive ceramic.
- it can be formed of ZrO 2 in which a rare earth element is dissolved or CeO 2 in which a rare earth element is dissolved, and Ni and / or NiO.
- the rare earth element the rare earth elements exemplified in the support 1 can be used.
- the rare earth element can be formed from ZrO 2 (YSZ) in which Y is dissolved and Ni and / or NiO.
- the content of ZrO 2 in which the rare earth element is dissolved in the fuel electrode layer 3 or CeO 2 in which the rare earth element is dissolved is preferably in the range of 35 to 65% by volume, and the content of Ni or NiO Is preferably 65 to 35% by volume. Further, the open porosity of the fuel electrode layer 3 is preferably 15% or more, particularly preferably in the range of 20 to 40%, and the thickness thereof is preferably 1 to 30 ⁇ m.
- the fuel electrode layer 3 only needs to be formed at a position facing the oxygen electrode layer 6, for example, the fuel electrode layer only on the flat surface n on the lower side of the support 1 on which the oxygen electrode layer 6 is provided. 3 may be formed. That is, the fuel electrode layer 3 is provided only on the lower flat surface n of the support 1, the solid electrolyte layer 4 is formed on the surface of the fuel electrode layer 3, the both arcuate surfaces m of the support 1 and the fuel electrode layer 3 are formed. It may have a structure formed on the flat surface n on the upper side of the support 1 that is not.
- the solid electrolyte layer 4 preferably contains, as a main component, partially stabilized or stabilized ZrO 2 in which 3 to 15 mol% of a rare earth element such as Y, Sc, Yb or the like is dissolved.
- a rare earth element such as Y, Sc, Yb or the like
- Y is preferable because it is inexpensive.
- the solid electrolyte layer 4 is not limited to ceramics made of partially stabilized or stabilized ZrO 2 , and is conventionally known, for example, a ceria-based material in which a rare earth element such as Gd or Sm is dissolved, or a lanthanum garade. Of course, a solid electrolyte layer may be used.
- the solid electrolyte layer 4 and the oxygen electrode layer 6 are strongly bonded to each other between the solid electrolyte layer 4 and the oxygen electrode layer 6 described later, and the components of the solid electrolyte layer 4 react with the components of the oxygen electrode layer 6.
- the intermediate layer 9 is formed for the purpose of suppressing the formation of a reaction layer having a high electrical resistance.
- the intermediate layer 9 is made of a CeO 2 based sintered body containing a rare earth element other than Ce.
- a CeO 2 based sintered body containing a rare earth element other than Ce For example, (CeO 2 ) 1-x (REO 1.5 ) x (where RE is Sm , Y, Yb, and Gd, and x preferably has a composition represented by the following formula: 0 ⁇ x ⁇ 0.3.
- Sm or Gd as RE, and for example, it is preferably made of CeO 2 in which 10 to 20 mol% of SmO 1.5 or GdO 1.5 is dissolved.
- the intermediate layer 9 can also have a two-layer structure.
- the oxygen electrode layer 6 is preferably formed of a conductive ceramic made of a so-called ABO 3 type perovskite oxide.
- perovskite oxides include La-containing transition metal perovskite oxides, particularly at least one of LaMnO 3 oxides, LaFeO 3 oxides, and LaCoO 3 oxides in which Sr and La coexist at the A site.
- LaCoO 3 -based oxides are particularly preferable from the viewpoint of high electrical conductivity at an operating temperature of about 600 to 1000 ° C.
- Fe and Mn may exist together with Co at the B site.
- the oxygen electrode layer 6 needs to have gas permeability. Therefore, the conductive ceramic (perovskite oxide) forming the oxygen electrode layer 6 has an open porosity of 20% or more, particularly 30 to 50%. It is preferable that it exists in the range. Further, the thickness of the oxygen electrode layer 6 is preferably 30 to 100 ⁇ m from the viewpoint of current collection.
- the interconnector layer 8 is made of conductive ceramics.
- fuel gas hydrogen-containing gas
- oxygen-containing gas oxygen-containing gas
- lanthanum chromite-based perovskite oxides LaCrO 3 -based oxides
- a LaCrMgO 3 -based oxide in which Mg is present at the B site is used.
- the interconnector layer 8 material may be conductive ceramics and is not particularly limited.
- the thickness of the interconnector layer 8 is preferably 10 to 60 ⁇ m from the viewpoint of preventing gas leakage and electric resistance. Within this range, gas leakage can be prevented and electrical resistance can be reduced.
- an adhesion layer (not shown) is formed between the support 1 and the interconnector layer 8 in order to reduce the difference in thermal expansion coefficient between the interconnector layer 8 and the support 1. Can do.
- Such an adhesion layer may have a composition similar to that of the fuel electrode layer 3.
- it can be formed from at least one of rare earth oxide, ZrO 2 in which a rare earth element is dissolved, and CeO 2 in which a rare earth element is dissolved, and Ni and / or NiO.
- a composition composed of Y 2 O 3 and Ni and / or NiO, a composition composed of ZrO 2 (YSZ) in which Y is solid-solved and Ni and / or NiO, Y, Sm, Gd and the like are solid.
- It can be formed from a composition comprising dissolved CeO 2 and Ni and / or NiO.
- the volume ratio of ZrO 2 (CeO 2 ) in which rare earth oxide or rare earth element is dissolved and Ni and / or NiO is preferably in the range of 40:60 to 60:40.
- the oxygen electrode layer 6 of the solid electrolyte layer 4 in which the main component is an oxide and the oxide contains a rare earth element Is provided with a first layer 7 that includes a main component that is the same oxide as the main component of the solid electrolyte layer 4 and has a different rare earth element content and that is stronger than the solid electrolyte layer 4. ing.
- the first layer 7 may contain less rare earth element than the solid electrolyte layer 4. preferable.
- the first layer 7 may have a higher rare earth element content than the solid electrolyte layer 4. preferable.
- the strength of the first layer 7 can be made higher than that of the solid electrolyte layer 4, and the components are similar to those of the solid electrolyte layer 4.
- the bonding strength with the first layer 7 can be increased.
- the main component refers to a component occupying 90% by volume or more among elements constituting the solid electrolyte layer 4 and the first layer 7.
- which of the solid electrolyte layer 4 and the first layer 7 has higher strength is determined by, for example, the solid electrolyte layer 4 in the fuel cell 300 that is broken and mirror-exposed using an ultra-micro hardness meter. And it can discriminate
- the solid electrolyte layer 4 is mainly composed of partially stabilized zirconia, for example, ZrO 2 in which 7 to 9 mol% of Y 2 O 3 is dissolved, in order to improve power generation performance.
- the first layer 7 is preferably composed mainly of ZrO 2 having a rare earth element content of, for example, 3 to 5 mol% of Y 2 O 3 as a solid solution.
- the first surface of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided at one end of each fuel cell is the first.
- the place which provides the 1st layer 7 is not restricted to this. That is, the first layer 7 only needs to be provided on the solid electrolyte layer 4 on which the oxygen electrode layer 6 is not provided. Therefore, for example, between the support 1 and the solid electrolyte layer 4 or between the fuel electrode layer 3 and the solid electrode layer 6. It may be provided between the electrolyte layer 4.
- the first layer 7 will be described with reference to the hollow flat plate fuel cell 300 shown in FIG. In the following description, the first layer 7 will be described as being provided on the exposed solid electrolyte layer 4 unless otherwise specified.
- a portion of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided is at one end (lower end) of the fuel cell 300, and the first layer is located at this portion.
- An example in which 7c is provided is shown.
- One end of the first layer 7 c is provided up to the lower end of the fuel cell 300.
- the lower end portion of the fuel battery cell 300 becomes a root portion joined to the gas tank, and the upper end portion releases fuel gas from the open fuel gas passage 2. Thereby, the base part of the fuel cell 300 can be strengthened, and generation
- FIG. 3A shows an example in which the first layer 7 c is provided so as not to overlap the oxygen electrode layer 6.
- the first layer 7c and the oxygen electrode layer 6 can be provided to overlap each other. That is, in the present embodiment, the first layer 7 may be in a portion where the oxygen electrode layer 6 of the solid electrolyte layer 4 is not provided, and a part thereof is provided in a portion where the oxygen electrode layer 6 is provided. You can also. However, since the first layer 7 c is lower in terms of power generation performance than the solid electrolyte layer 4, it is preferable to provide the first layer 7 c so as not to overlap the oxygen electrode layer 6 when performing more efficient power generation.
- first layer 7c and the oxygen electrode layer 6 are provided so as to overlap with each other, an intermediate layer 9 is also provided between them in order to prevent mutual reaction between the first layer 7c and the oxygen electrode layer 6. It is desirable to form.
- the width of the first layer 7 (the length of the fuel cell 300 in the width direction W) can be set as appropriate, but can be the same as the width of the flat surface n of the support 1, for example.
- the length of the first layer 7 depends on the length of the fuel battery cell 300. From the viewpoint of improving the strength of the fuel battery cell 300 while securing the power generation region, for example, the length of the first layer 7 is About 3 to 10%.
- the thickness of the first layer 7 is preferably larger than the thickness of the solid electrolyte layer 4 from the viewpoint of further improving the strength. Therefore, for example, the thickness of the first layer 7 can be set to 30 to 100 ⁇ m, whereas the thickness of the solid electrolyte layer 4 is 30 ⁇ m or less.
- the thickness of the solid electrolyte layer is as thin as 30 ⁇ m or less, the power generation performance can be improved, and even if the fuel cell 300 is to be deformed, the first layer 7 can deform the fuel cell 300. And the occurrence of cracks in the fuel cell 300 can be prevented. Thereby, the fuel cell 300 having high power generation performance and high long-term reliability can be provided.
- the conductive support 1 containing a large amount of Ni has a large degree of expansion and contraction when exposed to a reducing atmosphere. Therefore, when the fuel cell 300 is exposed to a reducing atmosphere, the solid electrolyte A large stress acts on the layer 4. Further, when the lower end portion is fixed to a gas tank, which will be described later, with a heat-resistant sealing material or the like, a large stress acts on the solid electrolyte layer 4 as the sealing material expands or contracts. Thereby, in the thin solid electrolyte 4, cracks and the like may occur due to these stresses. However, since the fuel cell 300 according to the present embodiment includes the first layer 7, the solid electrolyte layer 4 can be reinforced. The occurrence of cracks in the fuel cell 300 can be suppressed.
- FIG. 3B a portion of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided is provided along the longitudinal direction L of the support 1, and the first layer 7 is attached to this portion of the support 1.
- FIG. 3B shows an example in which the first layer 7 is provided in the form of two rods along the longitudinal direction L of the fuel cell 300 on both sides in the width direction W of the support 1. ing.
- the upper end of the first layer 7 in the longitudinal direction L is located at a predetermined distance from the upper end of the support 1, the lower end is located at the lower end of the support 1, and the first layer 7 is located in the entire longitudinal direction L. Not formed.
- a coating layer is formed between the upper end of the first layer 7 in the longitudinal direction L and the upper end of the support 1 and on the upper end surface of the support 1 although not shown.
- This coating layer alleviates adverse effects caused by the combustion of the fuel gas released from the fuel gas passage 2.
- the coating layer is made of cordierite, steatite, forsterite, mullite, alumina, zirconia, or the like.
- a coating layer between the upper end of the first layer 7 in the longitudinal direction L and the upper end of the support 1 is formed on the solid electrolyte layer 4.
- the oxygen electrode layer 6 is located between the two first layers 7 provided on both sides of the support 1 in the width direction W. Thereby, a sufficient area of the oxygen electrode layer 6 can be secured.
- the oxygen electrode layer 6 may cover a part of the upper surface of the first layer 7. When a part of the upper surface of the first layer 7 is covered with the oxygen electrode layer 6, in order to prevent a mutual reaction between a part of the first layer 7 and the oxygen electrode layer 6, as described above, It is desirable to form the intermediate layer 9 between them.
- the width of the first layer 7 depends on the width of the fuel cell 300, for example, 1.0 to 3 0.0 mm, which is set so as not to narrow the power generation region as much as possible.
- the thickness of the first layer 7 can make the central portion in the longitudinal direction L of the fuel cell 300 thicker than both end portions. Although high stress tends to be generated in the central portion in the longitudinal direction L of the fuel cell 300, the central portion can be reinforced by making the thickness of the first layer 7 in the central portion in the longitudinal direction L thicker than both ends.
- the lower end portion of the fuel cell 300 becomes a root portion joined to the gas tank 16, and a large stress may be generated at the lower end portion.
- the lower end side of the fuel cell 300 can be reinforced by increasing the thickness of the first layer 7 on the lower end side as compared with other regions.
- two first layers 7a are arranged on both sides in the width direction W on the one main surface side of the support 1, and between them, Further, one first layer 7b is disposed. That is, in addition to the portion of the solid electrolyte layer 4 where the oxygen electrode layer 6 is not provided, the first layer is also provided at the portion where the oxygen electrode layer 6 is provided. That is, the oxygen electrode layer 6 is disposed between the two first layers 7a and covers the first layer 7b. The oxygen electrode layer 6 is also provided on the upper surface of the first layer 7b via the intermediate layer 9, and power is also generated in this portion. In such a fuel cell 300, the power generation performance can be sufficiently exhibited, and the crack generation suppressing effect in the fuel cell 300 can be sufficiently exhibited by the first layers 7a and 7b.
- the first layer 7b contains a rare earth element more than the first layer 7a. It is desirable that the content of rare earth elements is smaller than that of the solid electrolyte layer 4. In this case, it can be said that the portion where the first layer 7 b is formed has a thick solid electrolyte layer 4.
- the solid electrolyte 4 can be further reinforced by the first layer 7b, and the occurrence of cracks in the fuel cell 300 can be suppressed.
- FIG. 3D shows that the temperature is low at the lower end portion (upstream fuel portion) of the fuel cell 300 in the longitudinal direction L, and the fuel concentration is low at the upper end portion (downstream fuel portion). Since the amount tends to decrease, the width is gradually increased toward both ends in the longitudinal direction L of the first layer 7a. In such a fuel cell 300, the power generation performance can be sufficiently exhibited, and the crack generation suppressing effect in the fuel cell 300 can be sufficiently exhibited by the first layer 7a.
- the first layer 7c is a first layer in the case where, for example, the solid electrolyte layer 4 is mainly composed of ZrO 2 in which a rare earth element is dissolved, in order to reinforce the lower end portion of the fuel cell 300. It is desirable that the rare earth element content is higher than that of 7a and the rare earth element content is lower than that of the solid electrolyte layer 4.
- the lower end portions in the longitudinal direction L of the two first layers 7a are connected to each other.
- the first layer 7c is provided.
- the power generation performance can be sufficiently exhibited, and the crack generation suppressing effect in the fuel cell 300 can be sufficiently exhibited by the first layers 7a and 7c.
- the width of the first layer 7c (the length in the width direction W of the fuel cell 300) is, for example, the same as the width of the flat surface n of the support 1. be able to.
- FIG. 3G shows that the temperature is low at the lower end portion (upstream fuel portion) of the fuel cell 300 in the longitudinal direction L, and the fuel concentration is low at the upper end portion (downstream fuel portion). Since the amount tends to decrease, the first layer 7c is provided so as to connect both ends in the longitudinal direction L of the two first layers 7a. Note that the oxygen electrode layer 6 is not provided in the solid electrolyte layer 4 at the upper end portion of the fuel cell 300, and the first layer 7c is provided at this portion. In such a fuel cell 300, the power generation performance can be sufficiently exhibited, and the crack generation suppressing effect in the fuel cell 300 can be sufficiently exhibited by the first layers 7a and 7c.
- the lower end portion of the fuel cell 300 in the case where the lower end portion of the fuel cell 300 is joined and fixed to the gas tank, the lower end portion of the fuel cell 300 can be reinforced, the occurrence of cracks can be suppressed, When the fuel gas discharged from the upper end of the fuel cell 300 burns, the upper end of the fuel cell 300 can be reinforced.
- the width of the first layer 7c (the length in the width direction W of the fuel cell 300) is, for example, the same as the width of the flat surface n of the support 1. be able to.
- the first layer 7 is provided on one main surface of the support 1, and the same main oxide of the solid electrolyte layer 4 is formed on the other main surface of the support 1.
- the fuel cell 300 is shown in which a second layer 11 containing a main component having a different rare earth element content and having a higher strength than the solid electrolyte layer 4 is provided. Note that the second layer 11 may be made of the same material as the first layer 7.
- 4 shows a fuel cell 300 in which the second layer 11 is provided in the form shown in FIG. 2, and FIG. 4 (a) is a cross-sectional view taken along the line AA in FIG. 4 (b). .
- the second layer 11 is provided at the lower end (base portion) of the other main surface of the support 1, the lower end of the second layer 11 is located at the lower end of the support 1, and the second layer 11 is covered with an interconnector layer 8.
- the lower end portion of the interconnector layer 8 covers both ends of the solid electrolyte layer 4 and the upper end portion of the second layer 11, and the other portions cover the support 1.
- a second layer 11 is provided between the support 1 and the support 1.
- the width of the second layer 11 is substantially the same as the width of the interconnector layer 8, and both end portions in the width direction W of the second layer 11 are formed on both end portions of the solid electrolyte layer 4.
- the width of the second layer 11 may be the same as the width of the flat surface n of the support 1, for example.
- the interconnector layer 8 may be provided so as to cover the entire second layer 11 or may be provided so as not to cover the lower end of the second layer 11.
- the thickness of the second layer 11 is preferably larger than the thickness of the solid electrolyte layer 4 from the viewpoint of improving the strength. Therefore, for example, as with the first layer 7, the thickness of the second layer 11 can be set to 30 to 100 ⁇ m, whereas the thickness of the solid electrolyte layer 4 is 30 ⁇ m or less.
- the lower end portion of the fuel battery cell 300 can be further reinforced than the embodiment of FIG. 2, and the occurrence of cracks can be suppressed.
- the length of the first layer 7 c in the longitudinal direction L of the support 1 can be made shorter than the length of the second layer 11 in the longitudinal direction L of the support 1.
- the lower end portion of the support 1 can be made strong by the second layer 11 having a long length in the longitudinal direction L of the support 1. In this case, it is preferable that the first layer 7 and the second layer 11 have the same width and thickness in the width direction W of the support 1.
- FIG. 5 shows an example of the interconnector layer 8 and the second layer 11.
- FIG. 5A shows an interconnector layer 8 formed at the upper and lower ends of the support 1. All of the second layer 11 formed on the lower end of the support 1 is covered.
- (B) is a form in which the interconnector layer 8 is not formed on the upper end portion of the support 1, and a part of the second layer 11 at the lower end portion of the support 1 is not covered with the interconnector layer 8. The form is shown. In this case, the upper end portion of the support 1 can be covered with the above-described covering layer.
- FIG. 4 shows a form in which the interconnector layer 8 is formed up to the upper end portion of the support 1 and a part of the second layer 11 at the lower end portion of the support 1 is not covered with the interconnector layer 8. Is. Even with such a fuel battery cell, the same effect as in FIG. 4 can be obtained.
- each of the second layers 11 may be provided in the form having the first layers 7a, 7b, and 7c of FIGS.
- Ni and / or NiO powder a rare earth oxide powder such as Y 2 O 3 , an organic binder, and a solvent are mixed to prepare a clay, and this clay is used for extrusion molding.
- a support molded body is prepared and dried.
- a calcined body obtained by calcining the support molded body at 900 to 1000 ° C. for 2 to 6 hours may be used.
- raw materials of NiO and ZrO 2 (YSZ) in which Y 2 O 3 is dissolved are weighed and mixed. Thereafter, an organic binder and a solvent are mixed with the mixed powder to prepare a slurry for the fuel electrode layer.
- ZrO 2 powder in which the rare earth element was solid-dissolved was slurried by adding toluene, binder powder (below, polymer higher than binder powder attached to ZrO 2 powder, for example, acrylic resin), commercially available dispersant, and the like.
- binder powder lower, polymer higher than binder powder attached to ZrO 2 powder, for example, acrylic resin
- dispersant commercially available dispersant, and the like.
- the sheet is molded by a method such as a doctor blade to produce a sheet-shaped solid electrolyte layer molded body.
- the fuel electrode layer slurry is applied onto the obtained sheet-shaped solid electrolyte layer molded body and dried to form a fuel electrode layer molded body, thereby forming a sheet-shaped laminated molded body.
- the surface on the fuel electrode layer molded body side of the sheet-shaped laminated molded body in which the fuel electrode layer molded body and the solid electrolyte layer molded body are laminated is laminated on the conductive support molded body to form a molded body.
- the laminated molded body is calcined at 800 to 1200 ° C. for 2 to 6 hours. Thereafter, a slurry for the first layer using a ZrO 2 powder and a binder powder, etc., in which the solid solution of the rare earth element is smaller than the slurry for the solid electrolyte layer molded body described above, is used for the solid electrolyte molded body (calcined body).
- the slurry is applied in the shape shown in FIGS. 3A to 3G and dried.
- the shape as shown in FIGS. 5A to 5C is used. Then, it is applied to a portion of the support molded body where the solid electrolyte molded body is not formed and dried to produce a second layer molded body.
- an interconnector layer material for example, LaCrMgO 3 -based oxide powder
- an organic binder for example, LiCrMgO 3 -based oxide powder
- a solvent for example, a solvent
- a method for producing a fuel cell having an adhesion layer will be described.
- an adhesion layer molded body is formed between the support 1 and the interconnector layer 8, it is produced as follows.
- ZrO 2 in which Y is dissolved and NiO are mixed and dried so that the volume ratio is in the range of 40:60 to 60:40, an organic binder or the like is added to adjust the slurry for the adhesion layer, and the solid electrolyte
- An adhesion layer molded body is formed by coating on a support molded body between both ends of the layer molded body.
- the interconnector layer slurry is applied onto the adhesion layer molded body.
- an intermediate layer disposed between the solid electrolyte layer 4 and the oxygen electrode layer 6 is formed.
- CeO 2 powder in which GdO 1.5 is dissolved is heat-treated at 800 to 900 ° C. for 2 to 6 hours to prepare a raw material powder for the intermediate layer molded body.
- Toluene is added to the raw material powder as a solvent to prepare an intermediate layer slurry, and this slurry is applied onto the solid electrolyte layer formed body and the first layer formed body to prepare an intermediate layer formed body.
- the interconnector layer slurry is applied on both ends of the solid electrolyte molded body (calcined body) so that both ends of the interconnector layer molded body are laminated, thereby producing a laminated molded body.
- An interconnector layer sheet was prepared by preparing an interconnector layer sheet and laminating both ends of the interconnector layer sheet on both ends of the solid electrolyte molded body. Can be laminated to produce a laminated molded body.
- seat for interconnector layers is laminated
- the above-mentioned laminated molded body is debindered and simultaneously sintered (simultaneously fired) in an oxygen-containing atmosphere at 1400 to 1450 ° C. for 2 to 6 hours.
- a slurry containing an oxygen electrode layer material for example, LaCoO 3 oxide powder
- a solvent and a pore increasing agent is applied onto the intermediate layer by dipping or the like, and baked at 1000 to 1300 ° C. for 2 to 6 hours.
- an oxygen electrode layer material for example, LaCoO 3 oxide powder
- a solvent and a pore increasing agent is applied onto the intermediate layer by dipping or the like, and baked at 1000 to 1300 ° C. for 2 to 6 hours.
- FIG. 6 shows an example of a cell stack device configured by electrically connecting a plurality of the above-described fuel cells 300 in series via the conductive member 13, and (a) shows a cell stack.
- the side view which shows an apparatus roughly (b) is a partial expanded sectional view of the cell stack apparatus of (a), and has shown and extracted the part enclosed with the broken line shown by (a).
- the part corresponding to the part enclosed by the broken line shown in (a) is shown by an arrow, and in the fuel cell 300 shown in (b), the intermediate layer described above is shown.
- each fuel cell 300 is arranged via the conductive member 13 to constitute the cell stack 12, and the lower end of each fuel cell 300 is connected to the fuel cell 300 as a fuel.
- a gas tank 16 for supplying gas is fixed by an insulating bonding material 17 such as a glass sealing material.
- the cell stack 12 is sandwiched from both ends of the fuel cell 300 in the arrangement direction by the elastically deformable end conductive member 14 whose lower end is fixed to the gas tank 16.
- FIG. 7 shows a structure for fixing the fuel cell 300 to the gas tank 16.
- the lower end portion of the fuel battery cell 300 is inserted into an opening formed on the upper surface of the gas tank 10 and is fixed by a bonding material 17 such as a glass sealing material.
- FIG. 7A shows an example in which the fuel cell 300 of the type shown in FIG. 3A is fixed to the gas tank 16.
- the lower end portion of the first layer 7 c is embedded in the bonding material 17 such as a glass sealing material, whereby the portion bonded by the bonding material 17 of the fuel cell 300 can be reinforced, and the fuel cell 300 The lower end of can be reinforced.
- the bonding material 17 such as a glass sealing material
- stress is applied to the lower end portion of the fuel cell 300 due to the difference in materials constituting the gas tank 16, the fuel cell 300, and the first bonding material 17 made of a heat resistant alloy.
- the lower end portion of the first layer 7 is embedded in the bonding material 17, the occurrence of cracks at the lower end portion of the fuel cell 300 can be suppressed.
- the boundary portion in the fuel cell 300 can be reinforced.
- the length of the first layer 7c exposed from the bonding material 17 can be set as appropriate, but is preferably 2 to 10 mm, for example. The same applies to other embodiments below.
- FIG. 7B shows an example in which the fuel cell 300 of the type shown in FIG. 3B is fixed to the gas tank 16. Also in FIG. 7B, the lower end portion of the first layer 7c is embedded in the bonding material 17 such as a glass sealing material, whereby the portion bonded by the bonding material 17 of the fuel cell 300 can be reinforced, and the fuel cell The lower end of the cell 300 can be reinforced.
- the bonding material 17 such as a glass sealing material
- Fig. 7 (c) shows an example in which the fuel cell 300 of the type shown in Fig. 3 (e) is fixed to the gas tank 16.
- the first layer 7c portion is a bonding material 17 such as a glass sealing material.
- the upper end portion of the first layer 7 c is exposed from the bonding material 17.
- the three first layers 7c may not be continuous on the boundary line between the portion where the bonding material 17 exists and the portion where the bonding material 17 does not exist, and the first layer 7c is 30% or more in the width direction. Desirably, layer 7c is exposed.
- FIG. 7 (d) shows an example in which the fuel cell 300 of the type shown in FIG. 3 (f) is fixed to the gas tank 16. Specifically, the lower ends of the two first layers 7a are connected to each other by the first layer 7c, and the first layer 7c is joined by the joining material 17 such as a glass sealing material, so that the first layer The upper end portion of 7 c is exposed from the bonding material 17. In such a cell stack device, the occurrence of cracks at the lower end of the fuel cell 300 can be further suppressed.
- FIG. 7 (e) shows an example in which the fuel cell 300 of the type shown in FIG. 3 (g) is fixed to the gas tank 16. Specifically, the upper and lower end portions of the two first layers 7a are connected to each other by the first layer 7c, and the lower first layer 7c portion is joined by a joining material 17 such as a glass sealing material. ing. In such a cell stack device, the occurrence of cracks at the lower end of the fuel cell can be further suppressed. In addition, when burning above the fuel cell 300, the fuel cell 300 can be reinforced by the first layer 7c at the upper end.
- FIG. 8 shows a structure for fixing the fuel battery cell 300 to the gas tank 16 on the interconnector layer side.
- FIGS. 8A to 8C show the fuel battery cell shown in FIGS. 5A to 5C as a gas tank. 16 shows the case of joining.
- the cell stack 12 is configured by using the fuel cell 300 described above, thereby providing a cell stack device with high power generation performance and improved long-term reliability. it can.
- FIG. 9 is an external perspective view showing an example of a fuel cell module 18 that is a module in which a cell stack device is housed in a storage container.
- the cell stack shown in FIG. It is configured to house the device.
- a reformer 20 for reforming raw fuel such as natural gas or kerosene to generate fuel gas is disposed above the cell stack 12. ing.
- the fuel gas generated by the reformer 20 is supplied to the gas tank 16 via the gas flow pipe 21 and supplied to the fuel gas passage 2 provided inside the fuel cell 300 via the gas tank 16. .
- FIG. 9 shows a state in which a part (front and rear surfaces) of the storage container 19 is removed, and the cell stack device and the reformer 20 housed inside are taken out rearward.
- the cell stack device can be slid and stored in the storage container 19.
- the cell stack device may include the reformer 20.
- the oxygen-containing gas introduction member 22 provided inside the storage container 19 is disposed between a pair of cell stacks 12 juxtaposed to the gas tank 16, and the oxygen-containing gas flows into the fuel gas flow.
- an oxygen-containing gas is supplied to the lower end portion of the fuel cell 300 so that the side of the fuel cell 300 flows from the lower end portion toward the upper end portion.
- the temperature of the fuel cell 300 can be increased by reacting the fuel gas discharged from the fuel gas passage 2 of the fuel cell 300 with the oxygen-containing gas and burning it on the upper end side of the fuel cell 300. This can accelerate the activation of the cell stack device.
- the fuel cell 300 is placed above the fuel cell 300 (cell stack 12).
- the arranged reformer 20 can be warmed. Thereby, the reforming reaction can be efficiently performed in the reformer 20.
- the cell stack device using the above-described fuel cell 300 is housed in the housing container 19, so that the fuel cell has high power generation performance and improved long-term reliability. Module 18 may be used.
- FIG. 10 is a perspective view showing an example of a fuel cell device which is a module housing device in which the fuel cell module 18 shown in FIG. 9 and an auxiliary machine for operating the cell stack device are housed in an outer case. is there. In FIG. 10, a part of the configuration is omitted.
- the fuel cell device 23 shown in FIG. 10 has a module housing chamber in which an outer case made up of support columns 24 and an outer plate 25 is divided into upper and lower portions by a partition plate 26 and the upper side thereof houses the above-described fuel cell module 18. 27, the lower side is configured as an auxiliary equipment storage chamber 28 for storing auxiliary equipment for operating the fuel cell module 18. In addition, auxiliary machines stored in the auxiliary machine storage chamber 28 are not shown.
- the partition plate 26 is provided with an air circulation port 29 for flowing the air in the auxiliary machine storage chamber 28 to the module storage chamber 27 side, and a part of the exterior plate 25 constituting the module storage chamber 27 An exhaust port 30 for exhausting the air in the module storage chamber 27 is provided.
- the power generation performance is high by having the fuel cell module 18 housed in the module storage chamber 27 with high power generation performance and improved reliability.
- the fuel cell device 23 is high and has high reliability.
- a fuel battery cell in which the oxygen electrode layer 6, the solid electrolyte layer 4, and the fuel electrode layer 3 are disposed on a support may be used.
- water vapor water
- SOEC electrolytic cell
- a NiO powder having an average particle size of 0.5 ⁇ m and a Y 2 O 3 powder having an average particle size of 0.9 ⁇ m are mixed, and a clay prepared with an organic binder and a solvent is molded by an extrusion molding method and dried. Degreasing was performed to produce a conductive support molded body. The volume ratio of the support molded body after reduction was 48% by volume for NiO and 52% by volume for Y 2 O 3 .
- a slurry obtained by mixing a binder powder and a solvent with ZrO 2 powder solid electrolyte layer raw material powder having a particle diameter of 0.8 ⁇ m by a microtrack method in which 8 mol% of Y 2 O 3 is solid-dissolved.
- a solid electrolyte layer sheet was prepared by using a doctor blade method.
- the slurry for forming the intermediate layer molded body was prepared by using a complex oxide containing 90 mol% of CeO 2 and 10 mol% of rare earth element oxide (GdO 1.5 , SmO 1.5 ) as a solvent, isopropyl alcohol (IPA) is pulverized with a vibration mill or ball mill, calcined at 900 ° C. for 4 hours, pulverized again with a ball mill to adjust the degree of agglomeration of the ceramic particles. And a solvent were added and mixed.
- IPA isopropyl alcohol
- a slurry for the fuel electrode layer is prepared by mixing the NiO powder having an average particle size of 0.5 ⁇ m, the ZrO 2 powder in which Y 2 O 3 is dissolved, an organic binder, and a solvent, and screen-printed on the solid electrolyte layer sheet. It was applied by the method and dried to form a fuel electrode layer molded body.
- the sheet-shaped laminated molded body in which the fuel electrode layer molded body was formed on the solid electrolyte layer sheet was laminated at a predetermined position of the support molded body with the surface on the fuel electrode layer molded body side inward.
- stacked the above molded objects was calcined at 1000 degreeC for 3 hours.
- the slurry which comprises a 1st layer was apply
- the slurry forming the first layer is, for example, a slurry 4 mol% of Y 2 O 3 contains ZrO 2 powder having an average particle diameter of 0.8 ⁇ m was dissolved.
- the slurry for forming the intermediate layer formed body was applied to the upper surface of the solid electrolyte calcined body and the upper surface of the first layer formed body by a screen printing method and dried to form an intermediate layer formed body.
- the average particle diameter 0.7 ⁇ m of La (Mg 0.3 Cr 0.7) 0.96 O 3 was prepared to prepare a slurry for interconnector layer of a mixture of organic binder and a solvent.
- the adjusted interconnector layer slurry was applied to a portion of the support where the fuel electrode layer (and the solid electrolyte layer) was not formed (a portion where the support was exposed).
- the above-mentioned laminated molded body was debindered and co-fired at 1450 ° C. for 2 hours in an oxygen-containing atmosphere.
- a mixed liquid composed of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 powder having an average particle diameter of 2 ⁇ m and isopropyl alcohol was prepared, and an intermediate between the solid electrolyte upper surface and the first layer upper surface
- the fuel cell having the first layers 7a and 7c shown in FIG. 3 (f) is formed by spray-coating on the surface of the layer to form an oxygen electrode layer molded body and baking at 1100 ° C. for 4 hours to form an oxygen electrode layer. A cell was produced.
- the size of the produced fuel cell is 25 mm ⁇ 200 mm, the thickness of the support (thickness between the flat surfaces n) is 2 mm, the open porosity is 35%, the thickness of the fuel electrode layer is 10 ⁇ m, and the open porosity is 24%.
- the thickness of the solid electrolyte layer was 20 ⁇ m, the thickness of the oxygen electrode layer was 50 ⁇ m, the open porosity was 40%, and the thickness of the interconnector layer was 40 ⁇ m.
- the thickness of the first layers 7a and 7c was 80 ⁇ m. Furthermore, a fuel battery cell having a solid electrolyte layer thickness of 30 ⁇ m was also produced.
- the prepared fuel cells 300 are inserted into the opening of the gas tank at the lower end of a cell stack electrically connected via a current collecting member, and made of crystallized glass.
- the cell stack device was manufactured by bonding and fixing with the bonding material 17.
- the upper end portion of the first layer 7c connecting the lower end portions of the two parallel first layers 7a was exposed 5 mm upward from the end of the bonding material 17.
- a cell stack was formed using seven fuel cells that do not form the first layer 7, and a cell stack device was manufactured in the same manner as described above.
- Hydrogen gas was supplied into the gas tanks of these cell stack devices, hydrogen gas was allowed to flow inside the fuel cell, and the support and the fuel electrode layer were subjected to reduction treatment at 850 ° C. for 10 hours and cooled.
- the presence or absence of cracks at the center and lower end of the fuel cell was confirmed by visual inspection.
- the occurrence of cracks was observed even when the thickness of the solid electrolyte layer was 30 ⁇ m and 20 ⁇ m.
- the thickness of the solid electrolyte layer is 20 ⁇ m, 5 out of 7 cracks are observed at the lower end (exposed portion from the bonding material), and 30 ⁇ m In the case of the above, one out of seven cracks was observed at the lower end (exposed from the bonding material).
- For the second layer after applying the slurry for the first layer, apply the same slurry as that constituting the first layer to the positions shown on FIG. 5B (on the support molded body and the solid electrolyte layer molded body).
- an intermediate layer formed body was formed, an interconnector layer slurry was applied and co-fired, and then an oxygen electrode layer was formed.
- Example 2 Thereafter, evaluation was made in the same manner as in Example 1. As a result, in the fuel cell having the first layer and the second layer, no crack was generated even when the thickness of the solid electrolyte layer was 30 ⁇ m or 20 ⁇ m.
- Support body 2 Fuel gas passage 3: First electrode layer (fuel electrode layer) 4: Solid electrolyte layer 6: Second electrode layer (oxygen electrode layer) 7, 7a, 7b, 7c: first layer 8: interconnector layer 11: second layer 18: fuel cell module 23: fuel cell device a: element portion
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
Description
2:燃料ガス通路
3:第1電極層(燃料極層)
4:固体電解質層
6:第2電極層(酸素極層)
7、7a、7b、7c:第1層
8:インターコネクタ層
11:第2層
18:燃料電池モジュール
23:燃料電池装置
a:素子部
Claims (14)
- 筒状の支持体を兼ねる第1電極層、固体電解質層および第2電極層がこの順に積層された素子部を有し、前記固体電解質層は、主成分が酸化物であって、当該酸化物が希土類元素を含有しており、かつ厚みが30μm以下であるとともに、前記第2電極層が設けられていない部位を有し、当該第2電極層が設けられていない部位に、前記固体電解質層の主成分と同じ酸化物であって希土類元素の含有量が異なる主成分を含み、かつ前記固体電解質層よりも強度の高い第1層を備えることを特徴とするセル。
- 絶縁性でかつ筒状の支持体に、第1電極層、固体電解質層および第2電極層がこの順に積層された素子部を複数有し、前記固体電解質層は、主成分が酸化物であって、当該酸化物が希土類元素を含有しており、かつ厚みが30μm以下であるとともに、前記第2電極層が設けられていない部位を有し、当該第2電極層が設けられていない部位に、前記固体電解質層の主成分と同じ酸化物であって希土類元素の含有量が異なる主成分を含み、かつ前記固体電解質層よりも強度の高い第1層を備えることを特徴とするセル。
- 一対の主面を有する筒状の支持体の一方側主面に、第1電極層、固体電解質層および第2電極層がこの順に積層された素子部を有し、前記固体電解質層は、主成分が酸化物であって、当該酸化物が希土類元素を含有しており、かつ厚みが30μm以下であるとともに、前記第2電極層が設けられていない部位を有し、当該第2電極層が設けられていない部位に、前記固体電解質層の主成分と同じ酸化物であって希土類元素の含有量が異なる主成分を含み、かつ前記固体電解質層よりも強度の高い第1層を備えることを特徴とするセル。
- 前記固体電解質層の前記第2電極層が設けられていない部位が、前記支持体の一端部にあり、当該部位に前記第1層が設けられていることを特徴とする請求項1乃至請求項3のうちいずれかに記載のセル。
- 前記固体電解質層の前記第2電極層が設けられていない部位が、前記支持体の長手方向に沿って設けられており、当該部位に前記第1層が前記支持体の長手方向に延びて設けられていることを特徴とする請求項2または請求項3に記載のセル。
- 前記固体電解質層の前記第2電極層が設けられていない部位が、前記支持体の他端部にあり、当該部位に前記第1層が設けられていることを特徴とする請求項1乃至請求項5のうちいずれかに記載のセル。
- 前記第1層の厚みが、前記固体電解質層の厚みよりも厚いことを特徴とする請求項1乃至請求項6のうちいずれかに記載のセル。
- 前記支持体の他方側主面にインターコネクタ層を備えるとともに、前記支持体と前記インターコネクタ層との間に、前記固体電解質層の主成分と同じ酸化物であって希土類元素の含有量が異なる主成分を含み、かつ前記固体電解質層よりも強度の高い第2層を備えることを特徴とする請求項3に記載のセル。
- 前記第2層の厚みが、前記固体電解質層の厚みよりも厚いことを特徴とする請求項8に記載のセル。
- 前記固体電解質層の前記第2電極層が設けられていない部位が、前記支持体の一方側主面における一端部にあり、当該部位に前記第1層が設けられているとともに、前記第2層が前記支持体の他方側主面における一端部に設けられており、前記第1層の前記支持体の長手方向おける長さが、前記第2層の前記支持体の長手方向おける長さよりも短いことを特徴とする請求項8または請求項9に記載のセル。
- 請求項1乃至請求項10のうちのいずれかに記載のセルを複数具備してなるとともに、該複数のセルを電気的に接続してなることを特徴とするセルスタック装置。
- 前記支持体の一端部が、絶縁性の接合剤でガスタンクに接合されていることを特徴とする請求項11に記載のセルスタック装置。
- 請求項11または請求項12に記載のセルスタック装置を収納容器内に収納してなることを特徴とするモジュール。
- 請求項13に記載のモジュールと、該モジュールを作動させるための補機とを、外装ケース内に収納してなることを特徴とするモジュール収納装置。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015524136A JP6122497B2 (ja) | 2013-06-27 | 2014-06-27 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
US14/898,910 US9666892B2 (en) | 2013-06-27 | 2014-06-27 | Cell, cell stack device, module, and module housing device |
KR1020157036590A KR101869305B1 (ko) | 2013-06-27 | 2014-06-27 | 셀, 셀 스택 장치, 모듈 및 모듈 수납 장치 |
EP14817280.2A EP3016190B1 (en) | 2013-06-27 | 2014-06-27 | Cell, cell stack, and module |
CN201480033446.2A CN105283994B (zh) | 2013-06-27 | 2014-06-27 | 电池单元、电池堆装置、模块以及模块收纳装置 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-135186 | 2013-06-27 | ||
JP2013135186 | 2013-06-27 | ||
JP2013219382 | 2013-10-22 | ||
JP2013-219382 | 2013-10-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014208730A1 true WO2014208730A1 (ja) | 2014-12-31 |
Family
ID=52142055
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/067191 WO2014208730A1 (ja) | 2013-06-27 | 2014-06-27 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9666892B2 (ja) |
EP (1) | EP3016190B1 (ja) |
JP (1) | JP6122497B2 (ja) |
KR (1) | KR101869305B1 (ja) |
CN (1) | CN105283994B (ja) |
WO (1) | WO2014208730A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017027841A (ja) * | 2015-07-24 | 2017-02-02 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
JP2017069134A (ja) * | 2015-10-01 | 2017-04-06 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
WO2017145902A1 (ja) | 2016-02-25 | 2017-08-31 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
CN107925097A (zh) * | 2015-08-22 | 2018-04-17 | 京瓷株式会社 | 单体、单体堆装置、模块及模块收纳装置 |
JP2020074263A (ja) * | 2019-09-04 | 2020-05-14 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019225235A1 (ja) | 2018-05-25 | 2019-11-28 | 京セラ株式会社 | セルスタック装置、モジュール及びモジュール収容装置 |
JP7250910B2 (ja) * | 2019-04-24 | 2023-04-03 | 京セラ株式会社 | セル、セルスタック装置、モジュール及びモジュール収容装置 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0850913A (ja) * | 1994-08-08 | 1996-02-20 | Fujikura Ltd | 固体電解質型燃料電池とその製造方法 |
JPH0963603A (ja) * | 1995-08-25 | 1997-03-07 | Nippon Telegr & Teleph Corp <Ntt> | 固体燃料電池用多層型固体電解質 |
JPH11111309A (ja) * | 1997-10-06 | 1999-04-23 | Mitsubishi Heavy Ind Ltd | 固体電解質燃料電池の製造方法 |
JP2004146334A (ja) * | 2002-05-29 | 2004-05-20 | Kyocera Corp | 燃料電池セル及び燃料電池 |
JP2008084716A (ja) | 2006-09-28 | 2008-04-10 | Kyocera Corp | 燃料電池セルおよび燃料電池セルスタック、ならびに燃料電池 |
WO2013077445A1 (ja) * | 2011-11-25 | 2013-05-30 | 京セラ株式会社 | 複合体、集電部材および燃料電池セル装置ならびに燃料電池装置 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6139985A (en) * | 1998-07-24 | 2000-10-31 | Siemens Westinghouse Power Corporation | Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells |
US7820332B2 (en) * | 2006-09-27 | 2010-10-26 | Corning Incorporated | Electrolyte sheet with regions of different compositions and fuel cell device including such |
US8722281B2 (en) * | 2008-10-29 | 2014-05-13 | Kyocera Corporation | Fuel cell, fuel cell module, and fuel cell device |
JP5351688B2 (ja) * | 2009-09-30 | 2013-11-27 | 東京瓦斯株式会社 | 固体酸化物形燃料電池セルスタック及びその作製方法 |
-
2014
- 2014-06-27 CN CN201480033446.2A patent/CN105283994B/zh active Active
- 2014-06-27 WO PCT/JP2014/067191 patent/WO2014208730A1/ja active Application Filing
- 2014-06-27 KR KR1020157036590A patent/KR101869305B1/ko active IP Right Grant
- 2014-06-27 US US14/898,910 patent/US9666892B2/en active Active
- 2014-06-27 JP JP2015524136A patent/JP6122497B2/ja active Active
- 2014-06-27 EP EP14817280.2A patent/EP3016190B1/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0850913A (ja) * | 1994-08-08 | 1996-02-20 | Fujikura Ltd | 固体電解質型燃料電池とその製造方法 |
JPH0963603A (ja) * | 1995-08-25 | 1997-03-07 | Nippon Telegr & Teleph Corp <Ntt> | 固体燃料電池用多層型固体電解質 |
JPH11111309A (ja) * | 1997-10-06 | 1999-04-23 | Mitsubishi Heavy Ind Ltd | 固体電解質燃料電池の製造方法 |
JP2004146334A (ja) * | 2002-05-29 | 2004-05-20 | Kyocera Corp | 燃料電池セル及び燃料電池 |
JP2008084716A (ja) | 2006-09-28 | 2008-04-10 | Kyocera Corp | 燃料電池セルおよび燃料電池セルスタック、ならびに燃料電池 |
WO2013077445A1 (ja) * | 2011-11-25 | 2013-05-30 | 京セラ株式会社 | 複合体、集電部材および燃料電池セル装置ならびに燃料電池装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3016190A4 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017027841A (ja) * | 2015-07-24 | 2017-02-02 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
CN107925097A (zh) * | 2015-08-22 | 2018-04-17 | 京瓷株式会社 | 单体、单体堆装置、模块及模块收纳装置 |
US10998569B2 (en) | 2015-08-22 | 2021-05-04 | Kyocera Corporation | Cell, cell stack device, module and module housing device |
CN107925097B (zh) * | 2015-08-22 | 2021-06-01 | 京瓷株式会社 | 单体、单体堆装置、模块及模块收纳装置 |
JP2017069134A (ja) * | 2015-10-01 | 2017-04-06 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
WO2017145902A1 (ja) | 2016-02-25 | 2017-08-31 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
KR20180116264A (ko) | 2016-02-25 | 2018-10-24 | 쿄세라 코포레이션 | 셀, 셀 스택 장치, 모듈 및 모듈 수납 장치 |
US10700365B2 (en) | 2016-02-25 | 2020-06-30 | Kyocera Corporation | Cell, cell stack device, module and module containing device |
US11296332B2 (en) | 2016-02-25 | 2022-04-05 | Kyocera Corporation | Cell, cell stack device, module and module containing device |
JP2020074263A (ja) * | 2019-09-04 | 2020-05-14 | 京セラ株式会社 | セル、セルスタック装置、モジュールおよびモジュール収納装置 |
Also Published As
Publication number | Publication date |
---|---|
US9666892B2 (en) | 2017-05-30 |
JPWO2014208730A1 (ja) | 2017-02-23 |
KR20160012217A (ko) | 2016-02-02 |
CN105283994A (zh) | 2016-01-27 |
EP3016190A1 (en) | 2016-05-04 |
EP3016190A4 (en) | 2016-12-21 |
EP3016190B1 (en) | 2018-08-01 |
JP6122497B2 (ja) | 2017-04-26 |
KR101869305B1 (ko) | 2018-06-20 |
US20160372774A1 (en) | 2016-12-22 |
CN105283994B (zh) | 2018-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6208499B2 (ja) | 燃料電池セル又は電解セル、セルスタック装置、モジュールおよびモジュール収納装置 | |
JP6122497B2 (ja) | セル、セルスタック装置、モジュールおよびモジュール収納装置 | |
JP5744348B1 (ja) | セル、セルスタック装置、モジュールおよびモジュール収容装置 | |
KR101820755B1 (ko) | 셀, 셀 스택 장치, 모듈 및 모듈 수용 장치 | |
JP5566405B2 (ja) | 燃料電池セル、燃料電池セル装置および燃料電池モジュールならびに燃料電池装置 | |
JP5377599B2 (ja) | 燃料電池セルならびにそれを用いたセルスタック装置、燃料電池モジュールおよび燃料電池装置 | |
JP5574891B2 (ja) | 固体酸化物形燃料電池セル | |
JP5489673B2 (ja) | 燃料電池セルならびにそれを備えるセルスタック装置、燃料電池モジュールおよび燃料電池装置 | |
JP5404973B1 (ja) | 固体酸化物形燃料電池セルおよび燃料電池モジュールならびに燃料電池装置 | |
JP6585407B2 (ja) | セル、セルスタック装置、モジュールおよびモジュール収納装置 | |
JP6803437B2 (ja) | セル、セルスタック装置、モジュールおよびモジュール収納装置 | |
JP5289010B2 (ja) | 固体酸化物形燃料電池セル、燃料電池セルスタック装置、燃料電池モジュールおよび燃料電池装置 | |
JP5363888B2 (ja) | 固体酸化物形燃料電池セルおよびその製法、ならびに燃料電池セルスタック装置、燃料電池モジュール、燃料電池装置 | |
JP6166151B2 (ja) | セル、セルスタック装置、モジュールおよびモジュール収納装置 | |
JP6174503B2 (ja) | セル、セルスタック装置、モジュールおよびモジュール収容装置 | |
JP2015159027A5 (ja) | ||
JP6215727B2 (ja) | セル、セルスタック装置、モジュールおよびモジュール収容装置 | |
JP2012114033A (ja) | 燃料電池用支持体、燃料電池セル、燃料電池セル装置、燃料電池モジュールおよび燃料電池装置 | |
JP5818656B2 (ja) | 固体酸化物形燃料電池セル、セルスタック装置、燃料電池モジュールおよび燃料電池装置 | |
JP2012156107A (ja) | 固体酸化物形燃料電池セル | |
JP5448880B2 (ja) | 燃料電池セル、セルスタック装置および燃料電池モジュールならびに燃料電池装置 | |
JP2013097977A (ja) | 固体酸化物形燃料電池セルおよび燃料電池モジュールならびに燃料電池装置 | |
JP2011175968A (ja) | 燃料電池セル、それを用いたセルスタック装置、燃料電池モジュールおよび燃料電池装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480033446.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14817280 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015524136 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014817280 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14898910 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20157036590 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |