WO2022196053A1 - 固体酸化物型燃料電池およびその製造方法 - Google Patents

固体酸化物型燃料電池およびその製造方法 Download PDF

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Publication number
WO2022196053A1
WO2022196053A1 PCT/JP2022/000685 JP2022000685W WO2022196053A1 WO 2022196053 A1 WO2022196053 A1 WO 2022196053A1 JP 2022000685 W JP2022000685 W JP 2022000685W WO 2022196053 A1 WO2022196053 A1 WO 2022196053A1
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support
mixed layer
cathode
anode
fuel cell
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PCT/JP2022/000685
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English (en)
French (fr)
Japanese (ja)
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李新宇
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太陽誘電株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • 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
    • 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
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • 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
    • 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
    • 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
    • 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 solid oxide fuel cell and its manufacturing method.
  • Patent Documents 1 and 2 In order to develop a solid oxide fuel cell system that can be used in automobiles, etc., it is desired to develop a cell that can withstand vibration and not crack even when the temperature rises rapidly. Therefore, metal support type solid oxide fuel cells have been developed (see, for example, Patent Documents 1 and 2).
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a solid oxide fuel cell that can suppress the occurrence of warping and a method for manufacturing the same.
  • a solid oxide fuel cell according to the present invention comprises: a solid electrolyte layer containing a solid oxide having oxide ion conductivity; and an anode having an anode catalyst in the porous body, and a structure in which the anode is provided on the side opposite to the solid electrolyte layer and a metal material and a ceramic material are mixed.
  • a first mixed layer a first support provided on a surface of the first mixed layer opposite to the solid electrolyte layer and containing a metal as a main component; a cathode having a porous body containing a conductive ceramic and an oxide ion conductive ceramic, and having a cathode catalyst in the porous body; and a second support provided on the surface of the second mixed layer opposite to the solid electrolyte layer and having a metal as a main component.
  • the warp amount of the solid oxide fuel cell may be less than 3%.
  • an insulating member covering the outer peripheries of the first support, the first mixed layer, the anode, the solid electrolyte layer, the cathode, the second mixed layer and the second support may be provided.
  • the solid oxide fuel cell has a substantially rectangular shape in plan view, and the insulating member comprises a surface of the first support opposite to the first mixed layer and a surface of the first support. Extending to the surface of the second support opposite to the second mixed layer, the length of the extension is defined as distance a, and the length of one side of the solid oxide fuel cell is defined as length b. , a/b may be 1/10 or less.
  • the insulating member may be glass.
  • the insulating member penetrates from the outer periphery of the first support, the first mixed layer, the anode, the cathode, the second mixed layer, and the second support to the inside. You may have
  • the anode catalyst may be Ni and GDC, and the cathode catalyst may contain at least one of PrO x , LSM, LSC, and GDC.
  • each of the anode catalyst and the cathode catalyst may have an average particle size of 100 nm or less.
  • first support>first mixed layer> The relationship of the anode is established, and among the porosity of the second support, the porosity of the second mixed layer, and the porosity of the cathode, the second support>the second mixed layer>the A cathodic relationship may also be established.
  • the thickness of the first support > the first mixed layer > the anode is such that the thickness of the first support > the first mixed layer > the anode.
  • a relationship is established between the thickness of the second support, the thickness of the second mixed layer, and the thickness of the cathode: second support>second mixed layer>cathode.
  • the crystal grain size of the metal component of the first support and the second support is larger than the crystal grain size of the metal component of the first mixed layer and the second mixed layer.
  • the porous body may have a porosity of 20% or more in the cross-sectional areas of the anode and the cathode.
  • the thickness of the anode and the cathode may be 2 ⁇ m or more.
  • the cross-sectional area ratio of the ion-conducting ceramics and the electron-conducting ceramics may be 1:9 to 9:1.
  • an electronically conductive ceramics material powder and an oxide ion conductive ceramics material are coated on both sides of an electrolyte green sheet containing a solid oxide material powder having oxide ion conductivity.
  • the support obtained by firing the support green sheet, the mixed layer obtained by firing the mixed layer green sheet, and the A step of covering the outer periphery of the porous body with an insulating member may be included.
  • FIG. 2 is a schematic cross-sectional view illustrating a layered structure of a solid oxide fuel cell
  • FIG. 3 is an enlarged cross-sectional view illustrating details of the first support, first mixed layer, anode, cathode, second mixed layer, and second support
  • FIG. 4 is a diagram for explaining the amount of warpage of a fuel cell
  • (a) and (b) are figures which illustrate an interconnector.
  • 1 is a diagram illustrating a flow of a method for manufacturing a fuel cell
  • FIG. 5 is a schematic cross-sectional view illustrating the laminated structure of a fuel cell according to a second embodiment
  • FIG. 6 is a diagram illustrating the flow of a method for manufacturing a fuel cell according to the second embodiment
  • (a) and (b) are diagrams for explaining the details of the insulating member forming process.
  • FIG. 1 is a schematic cross-sectional view illustrating the layered structure of a solid oxide fuel cell 100 according to the first embodiment.
  • the fuel cell 100 includes an anode 30 on the first surface (lower surface) of a solid electrolyte layer 40 and a first mixed layer 20 on the surface of the anode 30 opposite to the solid electrolyte layer 40.
  • the first support 10 is provided on the surface of the first mixed layer 20 opposite to the solid electrolyte layer 40
  • the cathode 50 is provided on the second surface (upper surface) of the solid electrolyte layer 40
  • the solid electrolyte layer 40 of the cathode 50 and the It has a structure in which the second mixed layer 60 is provided on the opposite side, and the second support 70 is provided on the side of the second mixed layer 60 opposite to the solid electrolyte layer 40 .
  • a plurality of fuel cells 100 may be stacked to form a fuel cell stack.
  • the solid electrolyte layer 40 is a gas-impermeable, gas-impermeable, gas-impermeable, gas-impermeable, gas-impermeable, gas-impermeable dense solid layer.
  • the solid electrolyte layer 40 is preferably made mainly of scandia-yttria-stabilized zirconium oxide (ScYSZ) or the like. When the concentration of Y 2 O 3 +Sc 2 O 3 is between 6 mol % and 15 mol %, the highest oxide ion conductivity is obtained, and it is desirable to use materials with this composition.
  • the thickness of the solid electrolyte layer 40 is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less. The thinner the electrolyte, the better, but a thickness of 1 ⁇ m or more is desirable in order to prevent gas from leaking from both sides.
  • FIG. 2 is an enlarged cross-sectional view illustrating details of the first support 10, the first mixed layer 20, the anode 30, the cathode 50, the second mixed layer 60, and the second support 70.
  • FIG. 2 is an enlarged cross-sectional view illustrating details of the first support 10, the first mixed layer 20, the anode 30, the cathode 50, the second mixed layer 60, and the second support 70.
  • the first support 10 is a member that has gas permeability and can support the first mixed layer 20 , the anode 30 , the solid electrolyte layer 40 , the cathode 50 and the second mixed layer 60 .
  • the first support 10 is a metal porous body, such as an Fe--Cr alloy porous body.
  • the anode 30 is an electrode having electrode activity as an anode, and has a porous ceramic material (electrode skeleton).
  • the porous body does not contain any metal component.
  • the porous body of anode 30 has electronic conductivity and oxide ion conductivity.
  • Anode 30 contains electronically conductive ceramics 31 .
  • the electronically conductive ceramics 31 is, for example, a perovskite-type oxide having a compositional formula of ABO3 , wherein the A site is at least one selected from the group of Ca, Sr, Ba, and La, and the B site is At least one perovskite oxide selected from Ti and Cr can be used.
  • the molar ratio of A sites to B sites may be B ⁇ A.
  • a LaCrO 3 -based material, a SrTiO 3 -based material, or the like can be used as the electron conductive ceramics 31 .
  • the porous body of the anode 30 contains oxide ion conductive ceramics 32 .
  • the oxide ion conductive ceramics 32 is ScYSZ or the like.
  • ScYSZ having a composition range of 5 mol % to 16 mol % of scandia (Sc 2 O 3 ) and 1 mol % to 3 mol % of yttria (Y 2 O 3 ).
  • ScYSZ in which the combined amount of scandia and yttria is 6 mol % to 15 mol % is more preferable. This is because oxide ion conductivity is highest in this composition range.
  • the oxide ion conductive ceramics 32 is, for example, a material having an oxide ion transport number of 99% or higher. GDC or the like may be used as the oxide ion conductive ceramics 32 . In the example of FIG. 2, the same solid oxide as the solid oxide contained in the solid electrolyte layer 40 is used as the oxide ion conductive ceramics 32 .
  • an electron conductive ceramic 31 and an oxide ion conductive ceramic 32 form a porous body.
  • This porous body forms a plurality of voids.
  • An anode catalyst is supported on the surface of the porous body in the void portion. Therefore, a plurality of anode catalysts are spatially dispersed and arranged in the porous body that is spatially continuously formed.
  • a composite catalyst is preferably used as the anode catalyst.
  • oxide ion conductive ceramics 33 and catalyst metal 34 are preferably supported on the surface of a porous body.
  • the oxide ion conductive ceramics 33 may have the same composition as the oxide ion conductive ceramics 32, but may have a different composition.
  • the metal that functions as the catalyst metal 34 may be in the form of a compound when power is not being generated.
  • Ni may be in the form of NiO (nickel oxide). These compounds are reduced by the reducing fuel gas supplied to the anode 30 during power generation, and take the form of metals that function as anode catalysts.
  • the first mixed layer 20 contains a metal material 21 and a ceramic material 22 .
  • the metal material 21 and the ceramic material 22 are randomly mixed. Therefore, a structure in which a layer of the metal material 21 and a layer of the ceramic material 22 are laminated is not formed. A plurality of voids are also formed in the first mixed layer 20 .
  • the metal material 21 is not particularly limited as long as it is metal. In the example of FIG. 2, the same metal material as that of the first support 10 is used as the metal material 21 .
  • the ceramic material 22 electronic conductive ceramics 31, oxide ion conductive ceramics 32, or the like can be used.
  • the ceramic material 22 ScYSZ, GDC, SrTiO3 - based materials, LaCrO3 - based materials, etc. can be used. Since SrTiO 3 -based materials and LaCrO 3 -based materials have high electronic conductivity, the ohmic resistance in the first mixed layer 20 can be reduced.
  • the cathode 50 is an electrode having electrode activity as a cathode, and has a porous ceramic material (electrode skeleton).
  • the porous body does not contain any metal component.
  • the porous body of the cathode 50 has electronic conductivity and oxide ion conductivity.
  • Cathode 50 contains electronically conductive ceramics 51 .
  • the electronically conductive ceramic 51 is, for example, a perovskite-type oxide having a compositional formula of ABO3 , wherein the A site is at least one selected from the group of Ca, Sr, Ba, and La, and the B site is At least one perovskite oxide selected from Ti and Cr can be used.
  • the molar ratio of A sites to B sites may be B ⁇ A.
  • the electronically conductive ceramics 51 preferably contains the same components as the electronically conductive ceramics 31, and preferably has the same composition ratio.
  • the porous body of the cathode 50 contains oxide ion conductive ceramics 52 .
  • the oxide ion conductive ceramics 52 is ScYSZ or the like.
  • ScYSZ having a composition range of 5 mol % to 16 mol % of scandia (Sc 2 O 3 ) and 1 mol % to 3 mol % of yttria (Y 2 O 3 ).
  • ScYSZ in which the combined amount of scandia and yttria is 6 mol % to 15 mol % is more preferable. This is because oxide ion conductivity is highest in this composition range.
  • the oxide ion conductive ceramics 52 is, for example, a material having an oxide ion transport number of 99% or higher. GDC or the like may be used as the oxide ion conductive ceramics 52 .
  • the oxide ion conductive ceramics 52 preferably contains the same components as the oxide ion conductive ceramics 32, and preferably has the same composition ratio. In the example of FIG. 2, the same solid oxide as the solid oxide contained in the solid electrolyte layer 40 is used as the oxide ion conductive ceramics 52 .
  • an electronically conductive ceramics 51 and an oxide ion conductive ceramics 52 form a porous body.
  • This porous body forms a plurality of voids.
  • a cathode catalyst 53 is supported on the surface of the porous body in the void portion. Therefore, the plurality of cathode catalysts 53 are spatially dispersed and arranged in the spatially continuous porous body.
  • Praseodymium oxide (PrO x ), LSM (lanthanum strontium manganite), LSC (lanthanum strontium cobaltite), or the like can be used as the cathode catalyst 53 .
  • LSM is a Sr-doped LaMnO3 - based material.
  • LSM is a Sr-doped LaCoO3 - based material.
  • the second mixed layer 60 contains a metal material 61 and a ceramic material 62 .
  • the metal material 61 and the ceramic material 62 are randomly mixed. Therefore, a structure in which a layer of the metal material 61 and a layer of the ceramic material 62 are laminated is not formed. A plurality of voids are also formed in the second mixed layer 60 .
  • the metal material 61 is not particularly limited as long as it is metal. In the example of FIG. 2, the same metal material as that of the second support 70 is used as the metal material 61 .
  • the ceramics material 62 electronically conductive ceramics 51, oxide ion conductive ceramics 52, or the like can be used.
  • the ceramic material 62 ScYSZ, GDC, SrTiO3 - based materials, LaCrO3 - based materials, etc. can be used. Since SrTiO 3 -based materials and LaCrO 3 -based materials have high electronic conductivity, the ohmic resistance in the second mixed layer 60 can be reduced.
  • the second support 70 is a member that has gas permeability and can support the second mixed layer 60 , the cathode 50 , the solid electrolyte layer 40 , the anode 30 and the first mixed layer 20 .
  • the second support 70 is a metal porous body, such as an Fe--Cr alloy porous body.
  • Fuel cell 100 generates power by the following actions.
  • the second support 70 is supplied with an oxidant gas containing oxygen, such as air.
  • the oxidant gas reaches cathode 50 via second support 70 and second mixed layer 60 .
  • oxygen that reaches the cathode 50 reacts with electrons supplied from an external electric circuit to form oxide ions.
  • the oxide ions conduct through the solid electrolyte layer 40 and move to the anode 30 side.
  • the first support 10 is supplied with a hydrogen-containing fuel gas such as hydrogen gas or reformed gas.
  • the fuel gas reaches anode 30 via first support 10 and first mixed layer 20 .
  • the hydrogen that reaches the anode 30 emits electrons at the anode 30 and reacts with oxide ions that are conducted through the solid electrolyte layer 40 from the cathode 50 side to become water (H 2 O).
  • the emitted electrons are extracted outside by an external electric circuit.
  • the electrons taken out are supplied to the cathode 50 after performing electrical work. Electric power is generated by the above action.
  • the catalyst metal 34 functions as a catalyst in the reaction between hydrogen and oxide ions.
  • the electronically conductive ceramics 31 conducts electrons obtained by the reaction between hydrogen and oxide ions.
  • the oxide ion conductive ceramics 32 conducts oxide ions that reach the anode 30 from the solid electrolyte layer 40 .
  • the cathode catalyst 53 functions as a catalyst in a reaction in which oxide ions are generated from oxygen gas and electrons.
  • Electronically conductive ceramics 51 are responsible for conducting electrons from an external electrical circuit.
  • the oxide ion conductive ceramics 52 is responsible for conduction of oxide ions to the solid electrolyte layer 40 .
  • a fuel cell can be produced by laminating each layer using a powder material and firing them simultaneously. However, if there is a large difference in shrinkage behavior between the layers during the firing process, warping as illustrated in FIG. 3 occurs. If the fuel cells are warped, stress is generated in each fuel cell when stacking a plurality of fuel cells to form a stack, and the fuel cells are likely to crack.
  • distance B the distance between both sides that come into contact with the surface.
  • distance A be the vertical distance from the vertex of the warp to the flat surface.
  • L be the thickness of the cell.
  • the amount of warpage T (%) is defined as (A ⁇ L)/B ⁇ 100 (%).
  • both the anode 30 and the cathode 50 are porous bodies made of electronically conductive ceramics and oxygen ion conductive ceramics. In this configuration, structural differences between anode 30 and cathode 50 are reduced.
  • a first mixed layer 20 is provided on the anode side, and a second mixed layer 60 is provided on the cathode side.
  • a first support 10 is provided on the anode side, and a second support 70 is provided on the cathode side.
  • the fuel cell 100 has a symmetrical structure with the solid electrolyte layer 40 as the center. As a result, the difference in shrinkage behavior of each layer during the firing process is reduced, and warping is suppressed. For example, the warp amount T (%) is within 3%.
  • the first support 10 mainly composed of metal is provided on the anode side and the second support 70 mainly composed of metal is provided on the cathode side, an example is shown in FIG.
  • the contact resistance with the interconnector 80 is lowered, and the ohmic resistance can be reduced.
  • the anode 30 and the cathode 50 are connected to the interconnector via the current collector 82 .
  • FIG. 4(b) by welding the interconnector 80 to the anode 30 and the cathode 50, the ohmic resistance can be further reduced.
  • FIG. 4(b) by welding the interconnector 80 to the anode 30 and the cathode 50, the ohmic resistance can be further reduced.
  • the interconnector 80 is welded to the anode 30 and the cathode 50 via the welding points 81 .
  • the welding technique even if the surface of the metal is covered with an oxide film, the internal metal parts are electrically connected, so the internal resistance becomes almost zero, and the contact resistance becomes almost zero. goes down.
  • the cathode is made of conductive ceramics without providing a support on the cathode side, the contact resistance between the cathode and the interconnector increases. Also, the cathode and the interconnector cannot be welded.
  • both the anode 30 and the cathode 50 are porous bodies made of electron-conducting ceramics and oxygen-ion-conducting ceramics, the difference in structure between the anode 30 and the cathode 50 becomes smaller.
  • Anode 30 and cathode 50 can be fired simultaneously.
  • the adhesion of the anode 30 and the cathode 50 to the solid electrolyte layer 40 is improved, film peeling is suppressed, and the ohmic resistance of the fuel cell 100 as a whole is reduced.
  • firing in a reducing atmosphere is possible.
  • the fuel cell 100 since the fuel cell 100 includes the first support 10 and the second support 70 mainly composed of metal, it has a structure that is resistant to thermal shock, mechanical shock, and the like. Moreover, since the first mixed layer 20 contains the metal material 21 and the ceramic material 22, it has both the material properties of metal and the material properties of ceramics. Therefore, the first mixed layer 20 has high adhesion with the first support 10 and has high adhesion with the anode 30 . As described above, delamination between the first support 10 and the anode 30 can be suppressed. Since the second mixed layer 60 contains the metal material 61 and the ceramic material 62, it has both the material properties of metal and the material properties of ceramics. Therefore, the second mixed layer 60 has high adhesion with the second support 70 and has high adhesion with the cathode 50 . As described above, delamination between the second support 70 and the cathode 50 can be suppressed.
  • the oxide ion conductive ceramics 33 is supported on the porous body of the anode 30.
  • the cathode catalyst 53 is supported on the porous body of the cathode 50.
  • the porosity of the first support 10 the porosity of the first mixed layer 20, and the porosity of the anode 30
  • first support 10>first mixed layer 20>anode 30 It is preferable to be established.
  • a relationship of (second support 70>second mixed layer 60>cathode 50) is established among the porosity of the second support 70, the porosity of the second mixed layer 60, and the porosity of the cathode 50. is preferred.
  • the support can have sufficient gas permeability.
  • having a relatively low porosity provides high electronic conductivity and high oxide ion conductivity while maintaining gas permeability.
  • gas permeability is obtained, and a contact area with the support is obtained, so that adhesion with the support is obtained.
  • the thickness of the first support 10, the thickness of the first mixed layer 20, and the thickness of the anode 30 satisfy the relationship of first support 10>first mixed layer 20>anode 30.
  • the thickness of the second support 70, the thickness of the second mixed layer 60, and the thickness of the cathode 50, the relationship of second support 70>second mixed layer 60>cathode 50 is preferably established.
  • most of the volume (for example, 80% or more) of the entire fuel cell 100 is made of a metal material, so that effects such as rapid heating and cooling and improved mechanical strength such as flexibility can be obtained. .
  • the surface area per unit volume of the catalyst is large from the viewpoint of promoting the chemical reaction.
  • the average crystal grain size of the anode catalyst (the oxide ion conductive ceramics 33 and the catalyst metal 34) and the cathode catalyst 53 is preferably 100 nm or less, more preferably 80 nm or less, and 50 nm or less. is more preferred.
  • the thickness of the anode 30 is within ⁇ 50% of the thickness of the cathode 50
  • the thickness of the first mixed layer 20 is within ⁇ 50% of the thickness of the second mixed layer 60
  • the thickness of the first support 10 is within the second It is preferable that the variation is within ⁇ 50% of the thickness of the support 70 .
  • the crystal grain size of the metal component of the first support 10 and the second support 70 is set to the first mixed layer 20 and second mixed layer 20 It is preferably larger than the crystal grain size of the metal component of layer 60 . If the crystal grain size is large, the gaps between the particles also become large, making it easier for the gas to pass through.
  • the crystal grain size of the metal component of the first support 10 and the second support 70 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more.
  • the crystal grain size of the metal component of the first support 10 and the second support 70 is preferably 100 ⁇ m or less, preferably 80 ⁇ m or less.
  • the porosity of the porous body is preferably 20% or more, and preferably 50% or more, in the cross-sectional area of the anode 30 and the cathode 50. is more preferable.
  • the thickness of the anode 30 and the cathode 50 is preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, more preferably 10 ⁇ m, from the viewpoint of ensuring a sufficient three-phase interface. It is more preferable that it is above.
  • both the lower limit and the upper limit are set for the cross-sectional area ratio of the ion-conducting ceramics and the electron-conducting ceramics in the porous bodies of the anode 30 and the cathode 50.
  • the cross-sectional area ratio of the ion-conducting ceramics and the electron-conducting ceramics is preferably 1:3 to 3:1, preferably 1:9 to 9:1. is more preferable.
  • FIG. 5 is a diagram illustrating the flow of the manufacturing method of the fuel cell 100. As shown in FIG. 5
  • Materials for the support include metal powder (for example, particle size is 10 ⁇ m to 100 ⁇ m), plasticizer (for example, adjusted to 1 wt % to 6 wt % to adjust the adhesion of the sheet), solvent (toluene, 2-propanol (IPA), 1-butanol, terpineol, butyl acetate, ethanol, etc. (20 wt% to 30 wt% depending on viscosity), vanishing material (organic matter), binder (PVB, acrylic resin, ethyl cellulose, etc.) are mixed to form a slurry. .
  • a support material is used as a material for forming a support.
  • the volume ratio of the organic component (vanishing material, binder solid content, plasticizer) to the metal powder is, for example, in the range of 1:1 to 20:1, and the amount of the organic component is adjusted according to the porosity.
  • Ceramic material powder for example, a particle size of 100 nm to 10 ⁇ m
  • small-particle-size metal material powder that is a raw material for the metal materials 21 and 61
  • solvent toluene, 2-propanol (IPA), 1-butanol, terpineol, butyl acetate, ethanol, etc., 20 wt% to 30 wt% depending on viscosity
  • plasticizer for example, sheet adhesion 1 wt % to 6 wt %), a vanishing material (organic matter), and a binder (PVB, acrylic resin, ethyl cellulose, etc.) are mixed to form a slurry.
  • the volume ratio of the organic component (vanishing material, binder solid content, plasticizer) to the ceramic material powder and the metal material powder is, for example, in the range of 1:1 to 5:1, and the amount of the organic component is adjusted according to the porosity. adjust. Also, the pore size of the voids is controlled by adjusting the particle size of the vanishing material.
  • the ceramic material powder may contain electronically conductive material powder and oxide ion conductive material powder. In this case, the volume ratio of the electron conductive material powder and the oxide ion conductive material powder is preferably in the range of 1:9 to 9:1, for example.
  • Ceramic material powder constituting the porous body As materials for the anode, ceramic material powder constituting the porous body, solvent (toluene, 2-propanol (IPA), 1-butanol, terpineol, butyl acetate, ethanol, etc., 20 wt% to 30 wt% depending on viscosity), plasticizer An agent (for example, adjusted to 1 wt % to 6 wt % to adjust the adhesion of the sheet), a vanishing material (organic matter), and a binder (PVB, acrylic resin, ethyl cellulose, etc.) are mixed to form a slurry.
  • solvent toluene, 2-propanol (IPA), 1-butanol, terpineol, butyl acetate, ethanol, etc., 20 wt% to 30 wt% depending on viscosity
  • plasticizer An agent for example, adjusted to 1 wt % to 6 wt % to adjust the adhesion
  • an electronically conductive material powder (for example, a particle size of 100 nm to 10 ⁇ m) that is the raw material of the electronically conductive ceramics 31, and an oxide ion conductive material that is the raw material of the oxide ion conductive ceramics 32.
  • a flexible material powder (for example, a particle size of 100 nm to 10 ⁇ m) may be used.
  • the volume ratio of the organic component (vanishing material, binder solid content, plasticizer) to the electronic conductive material powder is, for example, in the range of 1:1 to 5:1, and the amount of the organic component is adjusted according to the porosity.
  • the pore size of the voids is controlled by adjusting the particle size of the vanishing material.
  • the volume ratio of the electron conductive material powder and the oxide ion conductive material powder is, for example, in the range of 1:9 to 9:1.
  • Ceramic material powder constituting the porous body As materials for the cathode, ceramic material powder constituting the porous body, solvent (toluene, 2-propanol (IPA), 1-butanol, terpineol, butyl acetate, ethanol, etc., 20 wt% to 30 wt% depending on viscosity), plasticizer An agent (for example, adjusted to 1 wt % to 6 wt % to adjust the adhesion of the sheet), a vanishing material (organic matter), and a binder (PVB, acrylic resin, ethyl cellulose, etc.) are mixed to form a slurry.
  • solvent toluene, 2-propanol (IPA), 1-butanol, terpineol, butyl acetate, ethanol, etc., 20 wt% to 30 wt% depending on viscosity
  • plasticizer An agent for example, adjusted to 1 wt % to 6 wt % to adjust the adhe
  • an electronically conductive material powder for example, a particle size of 100 nm to 10 ⁇ m
  • an oxide ion conductive material which is a raw material of the oxide ion conductive ceramics 52.
  • a flexible material powder for example, a particle size of 100 nm to 10 ⁇ m
  • the volume ratio of the organic component (vanishing material, binder solid content, plasticizer) to the electronic conductive material powder is, for example, in the range of 1:1 to 5:1, and the amount of the organic component is adjusted according to the porosity.
  • the pore size of the voids is controlled by adjusting the particle size of the vanishing material.
  • the volume ratio of the electron conductive material powder and the oxide ion conductive material powder is, for example, in the range of 1:9 to 9:1.
  • the anode material may be used as the cathode material.
  • oxide ion conductive material powder for example, ScYSZ, YSZ, GDC, etc., with a particle size of 10 nm to 1000 nm
  • solvents toluene, 2-propanol (IPA), 1-butanol, terpineol , butyl acetate, ethanol, etc., 20 wt% to 30 wt% depending on the viscosity
  • a plasticizer for example, adjusted from 1 wt% to 6 wt% to adjust the adhesion of the sheet
  • a binder PVB, acrylic resin, ethyl cellulose, etc.
  • the volume ratio of the organic component (binder solid content, plasticizer) to the oxide ion conductive material powder is, for example, in the range of 6:4 to 3:4.
  • a first support green sheet is produced by coating a PET (polyethylene terephthalate) film with the material for the first support.
  • a first mixed layer green sheet is produced by coating a first mixed layer material on another PET film.
  • An anode green sheet is produced by coating an anode material on another PET film.
  • An electrolyte layer green sheet is produced by coating the electrolyte layer material on another PET film.
  • a cathode green sheet is produced by coating a cathode material on another PET film.
  • a second mixed layer green sheet is produced by coating a second mixed layer material on another PET film.
  • a second support green sheet is produced by coating a second support material on another PET film.
  • first support green sheets, one first mixed layer green sheet, one anode green sheet, one electrolyte layer green sheet, one cathode green sheet, and one second mixed layer green sheet. , and a plurality of second support green sheets are laminated in this order, and cut into a predetermined size. After that, it is fired at a temperature range of about 1100° C. to 1300° C. in a reducing atmosphere with an oxygen partial pressure of 10 ⁇ 20 atm or less. Thereby, a cell comprising the first support 10, the first mixed layer 20, the anode 30 porous body, the solid electrolyte layer 40, the cathode 50 porous body, the second mixed layer 60, and the second support 70 can be obtained. can.
  • the reducing gas flowing into the furnace may be a gas obtained by diluting H 2 ( hydrogen) with a nonflammable gas (Ar (argon), He (helium), N 2 (nitrogen), etc.). It may be gas. In consideration of safety, it is preferable to set an upper limit up to the explosion limit. For example, in the case of a mixed gas of H 2 and Ar, the concentration of H 2 is preferably 4% by volume or less.
  • the porous body of the anode 30 is impregnated with raw materials of the oxide ion conductive ceramics 33 and the catalyst metal 34 .
  • raw materials of the oxide ion conductive ceramics 33 and the catalyst metal 34 For example, nitrates or chlorides of Zr, Y, Sc, Ce, Gd, and Ni are combined with water or alcohols so that Gd-doped ceria or Sc, Y-doped zirconia and Ni are produced when sintered at a given temperature in a reducing atmosphere. ethanol, 2-propanol, methanol, etc.), impregnated into the porous body of the anode 30, dried, and heat-treated repeatedly.
  • a cathode catalyst 53 such as PrOx is then impregnated into the porous body of the cathode 50 .
  • PrO 2 x is used as the cathode catalyst 53, for example, nitrate or chloride of Pr is dissolved in water or alcohols (ethanol, 2-propanol, methanol, etc.), impregnated into the porous body of the cathode 50, dried, and heat-treated. is repeated the required number of times.
  • LSM low-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-strength-streng/N-propanol, methanol, etc.
  • the half-cell is impregnated, dried, and the heat treatment is repeated a required number of times.
  • both the electron conductive material and the oxide ion conductive material are used. Structural differences between porous materials are reduced.
  • the first mixed layer 20 is fired on the anode side, and the second mixed layer 60 is fired on the cathode side.
  • the first support 10 is fired on the anode side, and the second support 70 is fired on the cathode side.
  • the fuel cell 100 has a symmetrical structure with the solid electrolyte layer 40 as the center. As a result, the difference in shrinkage behavior of each layer during the firing process is reduced, and warping is suppressed. For example, the amount of warp T (%) is 3% or less.
  • the anode 30 and the cathode 50 can be fired at the same time.
  • the adhesion of the anode 30 and the cathode 50 to the solid electrolyte layer 40 is improved, film peeling is suppressed, and the ohmic resistance of the fuel cell 100 as a whole is reduced.
  • the material for the first mixed layer contains the metallic material and the ceramic material
  • the first mixed layer 20 after firing contains the metallic material 21 and the ceramic material 22 .
  • the first mixed layer 20 has both the material properties of metal and the material properties of ceramics. Therefore, delamination between the first support 10 and the anode 30 can be suppressed during the firing process.
  • the second mixed layer material contains the metal material and the ceramic material
  • the second mixed layer 60 after firing contains the metal material 61 and the ceramic material 62 . Thereby, the second mixed layer 60 has both the material properties of metal and the material properties of ceramics. Therefore, delamination between the second support 70 and the cathode 50 can be suppressed during the firing process.
  • a relationship of (first support 10>first mixed layer 20>anode 30) is established among the porosity of the first support 10, the porosity of the first mixed layer 20, and the porosity of the anode 30, and
  • the porosity of the second support 70, the porosity of the second mixed layer 60, and the porosity of the cathode 50 are such that the relationship (second support 70>second mixed layer 60>cathode 50) is established.
  • the support can have sufficient gas permeability. Electrodes are dense and have high oxide ion conductivity. In the mixed layer, gas permeability is obtained, and a contact area with the support is obtained, so that adhesion with the support is obtained.
  • the manufacturing method according to the present embodiment it is possible to first form the porous body by sintering, and then impregnate the porous body with the composite catalyst and sinter it at a low temperature (for example, 850° C. or lower). Therefore, the reaction between the porous material of the anode 30 and the anode catalyst is suppressed. Moreover, the reaction between the porous body of the cathode 50 and the cathode catalyst is suppressed. Therefore, the degree of freedom in selecting the anode catalyst and the cathode catalyst is increased.
  • FIG. 6 is a schematic cross-sectional view illustrating the laminated structure of the fuel cell 100a according to the second embodiment.
  • the fuel cell 100a differs from the fuel cell 100 of FIG. 1 in that an insulating member 90 functioning as a sealing member is provided.
  • the first support 10, the first mixed layer 20, the anode 30, the solid electrolyte layer 40, the cathode 50, the second mixed layer 60, and the second support 70 have substantially the same size (for example, rectangular or square). )have.
  • the positions of the outer peripheries (side surfaces) of the first support 10, the first mixed layer 20, the anode 30, the solid electrolyte layer 40, the cathode 50, the second mixed layer 60, and the second support 70 are substantially aligned.
  • the outer peripheries of the first support 10, the first mixed layer 20, the anode 30, the solid electrolyte layer 40, the cathode 50, the second mixed layer 60 and the second support 70 form an outer peripheral surface.
  • This outer peripheral surface is called a cell outer peripheral surface.
  • the outer peripheral surface of the cell is covered with an insulating member 90 .
  • the insulating member 90 is not particularly limited as long as it is made of a material having insulating properties, and is, for example, glass.
  • the outer peripheral surface of the cell is covered with the insulating member 90, when the catalyst is impregnated, it is suppressed from permeating along the outer peripheral surface of the cell to the electrode on the opposite side due to capillary action.
  • the permeation of the anode catalyst to the cathode 50 is suppressed, and the permeation of the cathode catalyst to the anode 30 is suppressed. Thereby, the short circuit between electrodes can be suppressed.
  • the insulating member 90 preferably extends to the surface (lower surface) of the first support 10 opposite to the first mixed layer 20 . Moreover, the insulating member 90 preferably extends to the surface (upper surface) of the second support 70 opposite to the second mixed layer 60 . By extending the insulating member 90 to at least one of the lower surface of the first support 10 and the upper surface of the second support 70, penetration of the catalyst to the electrode on the opposite side is further suppressed. Become.
  • the length of one side of the rectangular shape of the first support 10, the first mixed layer 20, the anode 30, the solid electrolyte layer 40, the cathode 50, the second mixed layer 60, and the second support 70 is b.
  • the extension distance of the insulating member 90 with respect to the lower surface of the first support 10 and the extension distance of the insulation member 90 with respect to the upper surface of the second support 70 are referred to as distance a.
  • the effective power generation area ratio can be defined as (area of electrode impregnated with catalyst)/(area of entire electrode). Therefore, it is preferable to set an upper limit for the a/b ratio.
  • the a/b ratio is preferably 1/10 or less, more preferably 1/20 or less, and even more preferably 1/50 or less.
  • the insulating member 90 not only cover the outer peripheral surface of the cell, but also partially intrude from the outer peripheral surface of the cell as illustrated in FIG. In this case, the permeation of the catalyst to the electrode on the opposite side is further suppressed.
  • FIG. 7 is a diagram illustrating the flow of the manufacturing method of the fuel cell 100a. A different point from the manufacturing method of FIG. 5 is that an insulating member forming step is performed between the baking step and the impregnating step.
  • FIGS. 8(a) and 8(b) are diagrams for explaining the details of the insulating member forming process.
  • the cell outer peripheral surfaces (four side surfaces) of the cell 200 obtained by the firing step are attached one by one to a container 300 containing, for example, a glass sealing material, and the cell is dipped. Apply sealing material to the outer peripheral surface. The depth of the dip makes it possible to control the coverage of the sealant coating.
  • the insulating member 90 can be formed by drying and firing.
  • the manufacturing method according to the present embodiment eliminates the need for slurry rebuilding, so the cost can be suppressed. Further, in the method of forming an insulating member on the outer peripheral surface of the cell, the above-described distance a can be reduced, so that the effective power generation area ratio can be increased.
  • a fuel cell was manufactured according to the manufacturing method according to the above embodiment.
  • Example 1 SUS (stainless steel) powder was used as the support material. ScYSZ was used as the electrolyte layer. A LaCrO 3 -based material was used for the electron-conducting ceramics of the anode, and ScYSZ was used for the oxide ion-conducting ceramics. A LaCrO 3 -based material was used for the electron-conducting ceramics of the cathode, and ScYSZ was used for the oxide ion-conducting ceramics. A LaCrO 3 -based material was used as the ceramic material for the mixed layer. SUS was used as the metal material of the mixed layer.
  • a first support green sheet, a first mixed layer green sheet, an anode green sheet, an electrolyte green sheet, a cathode green sheet, a second mixed layer green sheet, and a second support green sheet are laminated in this order and subjected to a firing process, A single cell with a symmetrical structure was fabricated.
  • the cathode porous body was impregnated with PrOx as a cathode catalyst.
  • the anode porous body was impregnated with Ni and GDC as an anode catalyst.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below. A single cell and an interconnector were connected by laser welding without providing a current collector. As a result of power generation evaluation, each resistance value was separated by impedance measurement. The ohmic resistance of the single cell was 0.5 ⁇ cm 2 and the reaction resistance was 0.4 ⁇ cm 2 .
  • Example 2 In Example 2, the cathode porous body was impregnated with LSM. Other conditions were the same as in Example 1.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below. A single cell and an interconnector were connected by laser welding without providing a current collector. As a result of power generation evaluation, each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.3 ⁇ cm 2 and the reaction resistance was 0.7 ⁇ cm 2 . It is believed that the difference in ohmic resistance and reaction resistance from Example 1 is due to the difference in the cathode catalyst. From the results of Examples 1 and 2, it can be seen that it is preferable to use LSM from the viewpoint of reducing ohmic resistance, and it is preferable to use PrOx from the viewpoint of reducing reaction resistance.
  • Example 3 the cathode porous body was impregnated with GDC and LSC. In order to suppress the reaction between ScYSZ and LSC, GDC was first impregnated and then LSC was impregnated. Other conditions were the same as in Example 1.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below. A single cell and an interconnector were connected by laser welding without providing a current collector. As a result of power generation evaluation, each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.3 ⁇ cm 2 and the reaction resistance was 0.6 ⁇ cm 2 . It is believed that the difference in ohmic resistance and reaction resistance from Example 1 is due to the difference in the cathode catalyst. From the results of Examples 2 and 3, it can be seen that it is preferable to use LSC from the viewpoint of reducing the reaction resistance.
  • Example 4 The manufacturing conditions for the single cell were the same as in Example 3. When the amount of warpage of the single cell was evaluated, it was less than 1% as in Example 3. It is considered that this is because of the symmetrical structure.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • the single cell and the interconnector were connected by laser welding without providing a current collector.
  • no current collector was provided between the single cell and the interconnector, and no laser welding was performed.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.4 ⁇ cm 2 and the reaction resistance was 0.6 ⁇ cm 2 .
  • Comparative example 1 In Comparative Example 1, an asymmetric structure was adopted without providing a support on the cathode side. Other conditions were the same as in Example 3. When the warp amount of the single cell was evaluated, it was 3%. It is considered that this is because the asymmetric structure made the difference in the coefficient of thermal expansion of each material remarkable.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • the single cell and the interconnector were connected by laser welding without providing a current collector. Attempts were made to weld the mixed layer on the cathode side to the interconnector, but it was found to be unweldable. It is considered that this is because the ceramic material is mixed in the mixed layer. Therefore, instead of welding on the cathode side, the current collector was installed between the single cell and the interconnector, and evaluated in a sandwiched state.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the cell was 0.7 ⁇ cm 2 and the reaction resistance was 0.6 ⁇ cm 2 . Compared with Example 3, the ohmic resistance increased because the cathode side was not connected by welding.
  • Comparative example 2 In Comparative Example 2, a support green sheet, a mixed layer green sheet, an anode green sheet, and an electrolyte green sheet were laminated in this order, and a firing process was performed to produce a half cell. Thereafter, a GDC layer having a thickness of about 700 nm was formed on the solid electrolyte layer by PVD film formation, a cathode was printed using LSC paste, and the layer was fired to complete a single cell. Other conditions were the same as in Example 1.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • the single cell and the interconnector were connected by laser welding without providing a current collector.
  • the current collector was installed between the unit cell and the interconnector, and the evaluation was performed in a sandwiched state.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.7 ⁇ cm 2 and the reaction resistance was 0.6 ⁇ cm 2 . Compared with Example 3, the ohmic resistance increased because the cathode side was not connected by welding.
  • Comparative Example 3 In Comparative Example 3, an all-ceramic single cell was produced instead of a metal-supported single cell. A mixture of NiO/YSZ was used for the support. A NiO/ScYSZ cermet electrode was used as the anode. A dense layer of ScYSZ was used as the solid electrolyte layer. A GDC layer having a thickness of about 700 nm was formed on the solid electrolyte layer by PVD film formation, a cathode was printed using LSC paste, and a single cell was completed by firing. No mixed layer was provided.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • the single cell and the interconnector were connected by laser welding without providing a current collector.
  • the current collector was installed between the unit cell and the interconnector, and the evaluation was performed in a sandwiched state.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.9 ⁇ cm 2 and the reaction resistance was 0.6 ⁇ cm 2 .
  • an increase in ohmic resistance was observed because none of the electrodes were connected by welding.
  • Comparative Example 4 Comparative Example 4, LSM paste was printed instead of LSC paste for the cathode. Other conditions were the same as in Comparative Example 3.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • the single cell and the interconnector were connected by laser welding without providing a current collector.
  • the current collector was installed between the unit cell and the interconnector, and the evaluation was performed in a sandwiched state.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.9 ⁇ cm 2 and the reaction resistance was 1.2 ⁇ cm 2 .
  • an increase in ohmic resistance was observed because none of the electrodes were connected by welding.
  • an increase in reaction resistance was observed. It is believed that this is because the catalytic activity of LSM is lower than that of LSC.
  • Example 5 A single cell having a symmetrical structure was produced by carrying out the firing process in the same manner as in Example 1.
  • the size of the single cell in plan view was 100 mm ⁇ 100 mm.
  • An insulating member was applied to the outer peripheral surface of the cell by dipping. The dip depth was set to 1 mm.
  • the cathode porous body was impregnated with LSM as a cathode catalyst for an area of 98 mm ⁇ 98 mm.
  • the porous body of the anode was impregnated with Ni and GDC as an anode catalyst for an area of 98 mm ⁇ 98 mm.
  • the warp amount of the single cell was evaluated, it was less than 1%. It is considered that this is because of the symmetrical structure.
  • the impregnating liquid did not seep into the electrode on the opposite side. It is considered that this is because the insulating member is provided.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below. A single cell and an interconnector were connected by laser welding without providing a current collector. As a result of power generation evaluation, each resistance value was separated by impedance measurement. The ohmic resistance of the single cell was 0.3 ⁇ cm 2 and the reaction resistance was 0.7 ⁇ cm 2 . The current that flowed when the terminal voltage was 0.9V was 19.1A.
  • Example 6 A single cell having a symmetrical structure was produced by carrying out the firing process in the same manner as in Example 1.
  • the size of the single cell in plan view was 100 mm ⁇ 100 mm.
  • An insulating member was applied to the outer peripheral surface of the cell by dipping. The dip depth was set to 2 mm.
  • the cathode porous body was impregnated with LSM as a cathode catalyst for an area of 96 mm ⁇ 96 mm.
  • the anode porous body was impregnated with Ni and GDC as an anode catalyst for an area of 96 mm ⁇ 96 mm.
  • the warp amount of the single cell was evaluated, it was less than 1%. It is considered that this is because of the symmetrical structure.
  • the impregnating liquid did not seep into the electrode on the opposite side. It is considered that this is because the insulating member is provided.
  • Example 5 a single cell power generation evaluation was performed.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • a single cell and an interconnector were connected by laser welding without providing a current collector.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.3 ⁇ cm 2 and the reaction resistance was 0.7 ⁇ cm 2 .
  • the current that flowed when the terminal voltage was 0.9V was 18.3A. From the results of comparison between Example 5 and Example 6, it can be seen that the higher the effective power generation area utilization rate, the larger the current.
  • Example 7 A first support green sheet, a first mixed layer green sheet, an anode green sheet, and an electrolyte green sheet were laminated in this order to obtain a laminate. Next, on the electrolyte green sheet, a cathode layer is printed in an area smaller than that of the laminate by 2 to 3 mm from the outer periphery and dried, a mixed layer is printed and dried, and a second support layer is printed.
  • the cathode porous body was impregnated with LSM as a cathode catalyst for an area of 96 mm ⁇ 96 mm.
  • the anode porous body was impregnated with Ni and GDC as an anode catalyst for an area of 96 mm ⁇ 96 mm.
  • the warp amount of the single cell was evaluated, it was less than 1%. It is considered that this is because of the symmetrical structure.
  • the impregnating liquid did not seep into the electrode on the opposite side. It is considered that this is because the cathode was formed in a small area by carrying out the slurry rebuild.
  • Example 6 did not use a slurry build, it is advantageous in terms of cost.
  • Example 8 A single cell having a symmetrical structure was produced by carrying out the firing process in the same manner as in Example 1.
  • the size of the single cell in plan view was 100 mm ⁇ 100 mm. No insulating member was formed on the outer peripheral surface of the cell.
  • the anode porous body was impregnated with Ni and GDC for an area of 80 mm ⁇ 80 mm.
  • the cathode porous body was impregnated with LSM over an area of 80 mm ⁇ 80 mm.
  • the warp amount of the single cell was evaluated, it was less than 1%. It is considered that this is because of the symmetrical structure.
  • the impregnating liquid did not seep into the electrode on the opposite side. It is believed that this is because the area impregnated with the catalyst was reduced.
  • Example 5 a single cell power generation evaluation was performed.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • a single cell and an interconnector were connected by laser welding without providing a current collector.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.3 ⁇ cm 2 and the reaction resistance was 0.7 ⁇ cm 2 .
  • the current that flowed when the terminal voltage was 0.9V was 12.7A. From the results of comparison between Example 5 and Example 8, it can be seen that the higher the effective power generation area utilization rate, the larger the current.
  • Example 9 A single cell having a symmetrical structure was produced by carrying out the firing process in the same manner as in Example 1.
  • the size of the single cell in plan view was 100 mm ⁇ 100 mm. No insulating member was formed on the outer peripheral surface of the cell.
  • the anode porous body was impregnated with Ni and GDC for an area of 96 mm ⁇ 96 mm.
  • the cathode porous body was impregnated with LSM over an area of 96 mm x 96 mm.
  • Comparative Example 5 In Comparative Example 5, a support green sheet, a mixed layer green sheet, an anode green sheet, and an electrolyte green sheet were laminated in this order, followed by firing to produce a half cell. No insulating member was formed on the outer peripheral surface of the cell. The size of the half-cell in plan view was 100 mm ⁇ 100 mm. The anode porous body was impregnated with Ni and GDC for an area of 96 mm ⁇ 96 mm. After that, LSM was printed on an area of 96 mm ⁇ 96 mm on the solid electrolyte layer and baked at a temperature of 900° C. or lower.
  • the single cell was evaluated in a state in which it was sandwiched between interconnectors from above and below.
  • the single cell and the interconnector were connected by laser welding without providing a current collector.
  • the current collector was installed between the unit cell and the interconnector, and the evaluation was performed in a sandwiched state.
  • each resistance value was separated by impedance measurement.
  • the ohmic resistance of the single cell was 0.7 ⁇ cm 2 and the reaction resistance was 0.7 ⁇ cm 2 .
  • the current that flowed when the terminal voltage was 0.9V was 13.2A.
  • the effective power generation area was the same as that of Example 6, the current obtained by power generation decreased by the amount corresponding to the increase in ohmic resistance.

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JP2008502113A (ja) * 2004-06-10 2008-01-24 テクニカル ユニバーシティ オブ デンマーク 固体酸化物型燃料電池
JP2006321706A (ja) * 2005-03-01 2006-11-30 Air Products & Chemicals Inc 酸素回収のための電気化学装置製作方法
JP2013501330A (ja) * 2009-08-03 2013-01-10 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 金属支持型電気化学電池およびその製造方法

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