WO2023148903A1 - 電気化学セル - Google Patents

電気化学セル Download PDF

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Publication number
WO2023148903A1
WO2023148903A1 PCT/JP2022/004329 JP2022004329W WO2023148903A1 WO 2023148903 A1 WO2023148903 A1 WO 2023148903A1 JP 2022004329 W JP2022004329 W JP 2022004329W WO 2023148903 A1 WO2023148903 A1 WO 2023148903A1
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Prior art keywords
porous
conducting layer
electrochemical cell
layer
ion
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Ceased
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PCT/JP2022/004329
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English (en)
French (fr)
Japanese (ja)
Inventor
雄太郎 三由
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Filing date
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Application filed by Nissan Motor Co Ltd filed Critical Nissan Motor Co Ltd
Priority to EP22924813.3A priority Critical patent/EP4475238A4/en
Priority to US18/835,456 priority patent/US20250140886A1/en
Priority to CN202280090744.XA priority patent/CN118648145A/zh
Priority to PCT/JP2022/004329 priority patent/WO2023148903A1/ja
Priority to JP2023578290A priority patent/JP7831500B2/ja
Publication of WO2023148903A1 publication Critical patent/WO2023148903A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
    • 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
    • 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
    • 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
    • C25B9/60—Constructional parts of 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to electrochemical cells.
  • An electrochemical cell having a solid electrolyte such as a solid oxide fuel cell (SOFC) or a solid oxide electrolysis cell (SOEC), comprising a metal support for supporting an electrode (air electrode) exposed to an oxidizing atmosphere
  • SOFC solid oxide fuel cell
  • SOEC solid oxide electrolysis cell
  • the air electrode and its peripheral metal support are likely to be oxidized and deteriorated. Therefore, the mechanical strength is lowered, which may cause cell damage.
  • JP2009-59697A discloses a solid oxide fuel cell having a metal support layer that supports a cathode (air electrode) layer.
  • a barrier layer is formed on the surfaces of the cathode layer and the metal support layer to prevent oxidative deterioration of the cathode layer and the metal support layer.
  • a cathode layer precursor and a metal support layer are laminated and impregnated with a barrier material to form a barrier layer. Therefore, a barrier layer cannot be formed at the bonding interface between the cathode layer and the metal support layer. Therefore, when oxygen ions are conducted from the cathode layer to the metal support layer, oxidative deterioration is accelerated at the bonding interface between the cathode layer and the metal support layer. As a result, peeling or cracking occurs between the cathode layer and the metal support layer at the bonding interface, possibly damaging the cell.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an electrochemical cell that prevents cell damage due to oxidation deterioration.
  • an electrochemical cell in which a pair of electrodes are connected via a solid electrolyte and at least one of the electrodes is supported by a metal support.
  • the solid electrolyte is configured as a dense ion-conducting layer
  • at least one of the electrodes is configured as a porous ion-conducting layer having oxygen ion conductivity
  • the metal support is a porous electron layer supporting the porous ion-conducting layer. Constructed as a conductive layer.
  • a porous antioxidant layer is disposed between the porous ion-conducting layer and the porous electronically-conducting layer, and the catalyst material is used to connect the porous ion-conducting layer, the porous antioxidant layer, and the porous electronically-conducting layer. is carried.
  • FIG. 1 is a schematic configuration diagram of an electrochemical cell according to an embodiment of the invention.
  • FIG. 2 is an enlarged view of the porous antioxidant layer.
  • FIG. 3 is a schematic diagram illustrating conduction of electrons and oxygen ions in a porous electron-conducting layer, a porous antioxidant layer, and a porous ion-conducting layer.
  • FIG. 1 is a schematic configuration diagram of an electrochemical cell 100 according to this embodiment.
  • An electrochemical cell 100 has a pair of electrodes 20 and 30 connected via a solid electrolyte 10 .
  • the electrochemical cell 100 is described as a solid oxide fuel cell (SOFC) that extracts electricity from air (oxygen) and fuel (hydrogen), but is not limited to this.
  • electrochemical cell 100 may be a solid oxide electrolysis cell (SOEC) in which electricity is applied to electrolyze water to produce oxygen and hydrogen.
  • SOEC solid oxide electrolysis cell
  • the electrochemical cell 100 of the present embodiment is mainly mounted on a vehicle or the like, but is not limited to this.
  • an electrochemical cell 100 includes a solid electrolyte 10, a pair of electrodes 20 and 30 connected via the solid electrolyte 10, and a metal support 40 provided to support one electrode 20. , an antioxidant layer 50 disposed between the electrode 20 and the metal support 40 . Further, the electrochemical cell 100 carries a catalyst material 60 .
  • the solid electrolyte 10 is configured as a dense ion-conducting layer formed of an oxide having oxygen ion conductivity (hereinafter, the solid electrolyte 10 is also referred to as the dense ion-conducting layer 10), and a pair of electrodes 20, 30 is sandwiched between Examples of the oxide include yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SSZ), samarium-doped ceria (SDC), gadolinium-doped ceria (GDC), lanthanum strontium magnesium gallate (LSGM), and the like. can be used, but is not limited to these.
  • YSZ yttria-stabilized zirconia
  • SSZ scandia-stabilized zirconia
  • SDC samarium-doped ceria
  • GDC gadolinium-doped ceria
  • LSGM lanthanum strontium magnesium gallate
  • the electrode 20 is an oxidant electrode (air electrode, cathode electrode) exposed to an oxygen atmosphere, and is configured as a porous ion-conducting layer having oxygen ion conductivity (hereinafter, the electrode 20 is referred to as a porous ion-conducting layer). Also referred to as layer 20).
  • the porous ion-conducting layer 20 is provided so as to be in contact with one surface of the dense ion-conducting layer 10 .
  • oxides of lanthanum, strontium, manganese, cobalt, zirconium, cerium, etc. can be used, but the material is not limited to these.
  • a reduction reaction occurs in the porous ion-conducting layer 20 to reduce oxygen in the cathode gas (air).
  • the electrode 30 is a fuel electrode (anode electrode) and is made of a porous material.
  • the electrode 30 can be formed of, for example, a mixed cermet material such as a noble metal material having a catalytic function such as nickel and yttria-stabilized zirconia (YSZ), but is not limited thereto.
  • the electrode 30 is provided so as to be in contact with the other surface of the dense ion conductive layer 10 .
  • an oxidation reaction occurs to oxidize the anode gas containing hydrogen or the like by the oxide ions that have been conducted through the dense ion-conducting layer 10 .
  • the electrochemical cell 100 generates power based on electrode reactions at a cathode (electrode 20) and an anode (electrode 30).
  • the electrochemical cell 100 is a solid oxide electrolysis cell (SOEC)
  • electricity is applied to the electrochemical cell 100 to electrolyze water, thereby producing hydrogen (fuel) at the electrode 30 (fuel electrode).
  • Oxygen is taken out at the electrode 20 (air electrode).
  • the metal support 40 is provided so as to be in contact with one surface of the antioxidant layer 50 to be described later, and supports the porous ion-conducting layer 20 and the antioxidant layer 50 . That is, the metal support 40 functions as a structural member for reinforcing the strength of the electrochemical cell 100 .
  • the metal support 40 is configured as a porous electron-conducting layer having electron conductivity (hereinafter, the metal support 40 is also referred to as the porous electron-conducting layer 40).
  • specific materials for forming the porous electron-conducting layer 40 for example, metals such as stainless steel, iron, and nickel can be used, but the materials are not limited to these.
  • the antioxidant layer 50 is a porous member for preventing oxidation of the porous ion-conducting layer 20 and the porous electron-conducting layer 40, and separates the porous ion-conducting layer 20 and the porous electron-conducting layer 40. , is arranged between the porous ion-conducting layer 20 and the porous electron-conducting layer 40 (hereinafter, the antioxidant layer 50 is also referred to as the porous antioxidant layer 50).
  • the porous antioxidant layer 50 has no oxygen ion conductivity or has oxygen ion conductivity higher than that of the other layers (the dense ion-conducting layer 10, the porous ion-conducting layer 20, the electrode 30, the porous electron-conducting layer 40). are made of materials with low This prevents the oxygen ions in the porous ion-conducting layer 20 from conducting to the porous electron-conducting layer 40 .
  • the details of the anti-oxidation layer 50 will be described later.
  • the catalytic material 60 catalyzes the reduction reaction of oxygen, for example platinum, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, copper, silver, chromium, cobalt, nickel, manganese, vanadium, It can be selected from metals such as molybdenum, gallium, and aluminum, and alloys thereof, but is not limited to these.
  • the catalyst material 60 has electronic conductivity, and is carried so as to connect the porous electron-conducting layer 40 , the antioxidant layer 50 and the porous ion-conducting layer 20 .
  • an electrode exposed to an oxidizing atmosphere and a support for this are used.
  • the metal support to be used is easily oxidized and deteriorated.
  • oxygen ions are conducted from the air electrode to the metal support, oxidative deterioration is accelerated at the bonding interface between the air electrode and the metal support, causing peeling and cracking of the air electrode and the metal support at the bonding interface, resulting in cell may be damaged.
  • an antioxidant layer 50 is provided between the porous ion-conducting layer 20 (air electrode) and the porous electron-conducting layer 40 (metal support), and the porous ion-conducting layer 20 ( air electrode) and the porous electron-conducting layer 40 (metal support). Therefore, conduction of oxygen ions in the porous ion-conducting layer 20 to the porous electron-conducting layer 40 is inhibited.
  • porous antioxidant layer 50 The details of the porous antioxidant layer 50 will be described below.
  • FIG. 2 is an enlarged view of the porous antioxidant layer 50.
  • the porous antioxidant layer 50 is prepared, for example, by kneading raw material particles and a binder, and as shown in FIG. It is carried in contact with the conductive layer 40 and the porous ion-conducting layer 20 .
  • One surface of the porous antioxidant layer 50 is sintered to the porous ion-conducting layer 20 and the other surface is sintered to the porous electron-conducting layer 40, thereby forming the porous ion-conducting layer 20 and the porous It is arranged between the electron conducting layer 40 and the electron conducting layer 40 .
  • the porous antioxidant layer 50 is not oxygen-ion conductive or oxygen-ion conductive to other layers (the dense ion-conducting layer 10, the porous ion-conducting layer 20, the electrode 30, the porous electron-conducting layer). It is made of a lower material than layer 40). Specifically, for example, it is made of zirconia doped with 3 mol % or less of yttria as an additive material (doped zirconia). By setting the content of the additive material to 3 mol % or less, oxygen ion conductivity can be kept low while maintaining sufficient strength.
  • the porous antioxidant layer 50 contains 70% or more of a material that has no oxygen ion conductivity or has a lower oxygen ion conductivity than other layers at the interface connecting to the porous ion conductive layer 20. is formed as
  • the porous antioxidant layer 50 contains 70% or more of a material formed of zirconia doped with 3 mol % or less of yttria as an additive material (doped zirconia) at the interface connecting to the porous ion-conducting layer 20 .
  • the porous anti-oxidation layer 50 contains the same metal component (for example, zirconium, cerium, etc.) as the material forming the porous ion-conducting layer 20, and the thermal expansion of the material forming the porous anti-oxidation layer 50 is minimized.
  • the difference between the coefficient of thermal expansion and the coefficient of thermal expansion of the material forming the porous ion-conducting layer 20 is set to 20% or less. By setting the difference in coefficient of thermal expansion to 20% or less, it is possible to prevent the porous antioxidant layer 50 and the porous ion-conducting layer 20 from being separated when they are sintered.
  • the porous anti-oxidation layer 50 contains the same metal component as the porous ion-conducting layer 20, the sintering strength of both layers is improved.
  • the porous antioxidant layer 50 has a thermal expansion coefficient difference of 20% or less from that of the material forming the porous ion-conducting layer 20 at the interface connecting to the porous ion-conducting layer 20, and is porous. It is configured to contain 70% or more of a material containing the same kind of metal component as the material constituting the ion-conducting layer 20 . As a result, separation of the porous antioxidant layer 50 and the porous ion-conducting layer 20 during sintering can be prevented, the sintering strength of both layers can be improved, and the interface with the porous ion-conducting layer 20 can be Since other materials can be used for the other portions, the degree of freedom in material selection is increased.
  • the porous antioxidant layer 50 is configured to contain a metal material.
  • the bonding between the porous antioxidant layer 50 and the porous electron-conducting layer 40 (metal support) is metal-to-metal bonding, thereby improving the bonding strength.
  • the porous antioxidant layer 50 is configured so that the metal material ratio is 30% or more at the interface connecting with the porous electron-conducting layer 40 .
  • the metal material ratio can be reduced to further lower the oxygen ion conductivity.
  • the metal material used in the porous antioxidant layer 50 for example, stainless containing 2 to 6 wt% of aluminum (Al) (aluminum-containing SUS) can be used.
  • Al aluminum
  • the oxidation resistance of the metal in the porous anti-oxidation layer 50 can be enhanced, and deterioration of the porous anti-oxidation layer 50 can be prevented.
  • the porous antioxidant layer 50 is configured such that the thickness t is 50% or more of the average particle size of the metal particles contained in the porous electron-conducting layer 40 . If the thickness t of the porous electron-conducting layer 50 is less than 50% of the average particle size of the metal particles contained in the porous electron-conducting layer 40, the porous electron-conducting layer 40 will undergo porous oxidation during fabrication of the electrochemical cell 100. There is a possibility that the prevention layer 50 is penetrated and connected to the porous ion-conducting layer 20 .
  • the thickness t of the porous anti-oxidation layer 50 is configured to be 50% or more of the average particle size of the metal particles contained in the porous electron-conducting layer 40, thereby improving the electrochemical cell 100.
  • the porous electron-conducting layer 40 is prevented from penetrating through the porous antioxidant layer 50 and connecting to the porous ion-conducting layer 20 .
  • FIG. 2 is a diagram schematically showing the porous antioxidant layer 50, and the thickness t of the porous antioxidant layer 50 is actually different than the particle size of the metal particles contained in the porous electron-conducting layer 40. shown to be considerably larger than
  • the porous antioxidant layer 50 is made of a material that has an affinity with the porous ion-conducting layer 20 and further inhibits the conduction of oxygen ions in the vicinity of the interface connecting to the porous ion-conducting layer 20.
  • the vicinity of the interface connected to the porous electron-conducting layer 40 is composed of a material having an affinity with the porous electron-conducting layer 40 .
  • the porous antioxidant layer 50 is configured to have a thickness such that the porous electron-conducting layer 40 does not penetrate through the porous antioxidant layer 50 when the electrochemical cell 100 is fabricated.
  • a method for changing the ratio of each material near the interface for example, a method of dividing the porous antioxidant layer 50 into a plurality of layers having different material ratios and joining the layers can be used. However, it is not limited to this.
  • FIG. 3 is a schematic diagram illustrating conduction of electrons and oxygen ions in the porous electron-conducting layer 40, the porous antioxidant layer 50, and the porous ion-conducting layer 20.
  • FIG. 3 is a schematic diagram illustrating conduction of electrons and oxygen ions in the porous electron-conducting layer 40, the porous antioxidant layer 50, and the porous ion-conducting layer 20.
  • the porous ion-conducting layer 20, the porous antioxidant layer 50, and the porous electron-conducting layer 40 support a catalyst material 60 having electron conductivity so as to connect these three layers. ing. Therefore, when electrons are supplied to the porous electron-conducting layer 40 side from a circuit or the like, the electrons are conducted from the porous electron-conducting layer 40 having electron conductivity to the catalyst material 60, and the catalyst material 60 and the porous It is supplied to the three-phase interface exposed to the ion-conducting layer 20 and the gas phase. That is, electrons supplied from the porous electron-conducting layer 40 side are conducted to the porous ion-conducting layer 20 without being hindered by the porous antioxidant layer 50 .
  • a porous antioxidant layer 50 that inhibits conduction of oxygen ions is provided between the porous electron-conducting layer 40 and the porous ion-conducting layer 20. are arranged to separate the Therefore, oxygen ions in the porous ion-conducting layer 20 are conducted only to the dense ion-conducting layer 10 (see FIG. 1) side, and are not conducted to the porous electron-conducting layer 40 . Therefore, oxidative deterioration of the bonding interface between the porous ion-conducting layer 20 and the porous electron-conducting layer 40 due to conduction of oxygen ions is suppressed.
  • a barrier layer of a barrier material having electrical and electronic conductivity may be provided.
  • the barrier layer can be provided by impregnating the porous electron-conducting layer 40 and the porous ion-conducting layer 20 with a barrier material.
  • the electrochemical cell 100 includes a porous ion-conducting layer 20 and a porous electron-conducting layer 40 (metal support), and a porous antioxidant layer 50 disposed between the porous ion-conducting layer 20 and the porous antioxidant layer.
  • a catalyst material 60 is carried to connect 50 and the porous electron conducting layer 40 .
  • the catalyst material 60 is supported so as to connect the porous ion-conducting layer 20, the porous antioxidant layer 50, and the porous electron-conducting layer 40, the electrons supplied from the porous electron-conducting layer 40 side can be conducted to the porous ion-conducting layer 20 without being hindered by the porous antioxidant layer 50 .
  • the electrochemical cell 100 constitutes an air electrode in which the porous ion-conducting layer 20 is exposed to an oxidizing atmosphere.
  • a porous antioxidant layer 50 is disposed in between. In this way, by providing the porous anti-oxidation layer 50 on the air electrode side where there is a high risk of oxidation deterioration, it is possible to more effectively prevent damage to the electrochemical cell 100 due to oxidation deterioration.
  • the porous antioxidant layer 50 is composed of a material that has no or lower oxygen ion conductivity than other layers. As a result, diffusion of oxygen ions in the porous ion-conducting layer 20 toward the porous electron-conducting layer 40 can be further inhibited, and bonding between the porous ion-conducting layer 20 and the porous electron-conducting layer 40 Oxidative deterioration at the interface can be further prevented.
  • the porous antioxidant layer 50 is made of doped zirconia doped with an additive material containing 3 mol% or less of yttria. Thereby, the oxygen ion conductivity of the porous antioxidant layer 50 can be kept low while maintaining the strength of the porous antioxidant layer 50 .
  • the electrochemical cell 100 contains 70 percent or more of a material that has no or lower oxygen ion conductivity than the other layers at the interface where the porous antioxidant layer 50 connects with the porous ion-conducting layer 20 .
  • a material that has no or lower oxygen ion conductivity than the other layers at the interface where the porous antioxidant layer 50 connects with the porous ion-conducting layer 20 As a result, diffusion of oxygen ions in the porous ion-conducting layer 20 toward the porous antioxidant layer 50 can be further inhibited, and bonding between the porous ion-conducting layer 20 and the porous electron-conducting layer 40 can be prevented. Oxidative deterioration at the interface can be further prevented.
  • the degree of freedom in material selection increases.
  • the electrochemical cell 100 contains 70% or more of a material made of doped zirconia doped with 3 mol % or less of an additive material at the interface where the porous antioxidant layer 50 connects with the porous ion-conducting layer 20 .
  • a material made of doped zirconia doped with 3 mol % or less of an additive material at the interface where the porous antioxidant layer 50 connects with the porous ion-conducting layer 20 contains 70% or more of a material made of doped zirconia doped with 3 mol % or less of an additive material at the interface where the porous antioxidant layer 50 connects with the porous ion-conducting layer 20 .
  • the difference in thermal expansion coefficient between the material forming the porous antioxidant layer 50 and the material forming the porous ion-conducting layer 20 is 20% or less. In this way, by forming the porous antioxidant layer 50 from the material forming the porous ion-conducting layer 20 and the material having a thermal expansion coefficient difference of 20% or less, the porous antioxidant layer 50 and the porous ion When sintered with the conductive layer 20, both layers can be prevented from being separated.
  • the material forming the porous antioxidant layer 50 contains the same metal component as the material forming the porous ion-conducting layer 20 .
  • the sintering strength between the porous antioxidant layer 50 and the porous ion-conducting layer 20 is improved, and peeling or the like between the porous antioxidant layer 50 and the porous ion-conducting layer 20 is prevented.
  • the difference in thermal expansion coefficient from the material constituting the porous ion-conducting layer 20 is 20% or less at the interface where the porous antioxidant layer 50 connects to the porous ion-conducting layer 20, and the porous 70% or more of the material containing the same kind of metal component as the material constituting the ion-conducting layer 20 is included.
  • the porous antioxidant layer 50 and the porous ion-conducting layer 20 during sintering can be prevented, the sintering strength of both layers can be improved, and the interface with the porous ion-conducting layer 20 can be Since other materials can be used for the other portions, the degree of freedom in material selection is increased.
  • the porous antioxidant layer 50 contains a metal material.
  • the bonding between the porous antioxidant layer 50 and the porous electron-conducting layer 40 (metal support) is metal-to-metal bonding, thereby improving the bonding strength. Therefore, peeling or the like between the porous antioxidant layer 50 and the porous electron-conducting layer 40 is prevented.
  • the electrochemical cell 100 has a metal material ratio of 30% or more at the interface where the porous antioxidant layer 50 connects with the porous electron-conducting layer 40 . Thereby, the bonding strength between the porous antioxidant layer 50 and the porous electron-conducting layer 40 is further improved. In addition, in the portion of the porous antioxidant layer 50 other than the interface with the porous electron-conducting layer 40, the metal material ratio can be reduced to further lower the oxygen ion conductivity.
  • the porous antioxidant layer 50 contains a metal material containing 2-6 wt% aluminum. Thereby, the oxidation resistance of the metal in the porous antioxidant layer 50 can be improved, and deterioration of the porous antioxidant layer 50 can be prevented.
  • the thickness t of the porous antioxidant layer 50 is 50% or more of the average particle size of the metal particles that make up the porous electron-conducting layer 40. This prevents the porous electron-conducting layer 40 from penetrating through the porous antioxidant layer 50 and connecting to the porous ion-conducting layer 20 during fabrication of the electrochemical cell 100 .
  • the porous ion-conducting layer 20 is used as the air electrode, and the porous anti-oxidation layer 50 is provided on the air electrode side, but this is not necessarily the case. That is, a porous electron-conducting layer (metal support) having electron conductivity is provided on the fuel electrode (electrode 30) side, and a porous antioxidant layer is arranged between the electrode 30 and the porous electron-conducting layer. There may be. For example, when a vehicle equipped with the electrochemical cell 100 is stopped, oxygen may flow into the fuel electrode side. By providing the layer, damage due to oxidative deterioration of the electrochemical cell 100 can be prevented.
  • the porous antioxidant layer 50 is made of a material that has no oxygen ion conductivity or has lower oxygen ion conductivity than other layers, but it is not necessarily limited to this.
  • only a portion of the porous antioxidant layer 50 is made of a material that has no oxygen ion conductivity or is lower than the other layers, and the other portion is made of a material that has the same oxygen ion conductivity as the other layers. You may In this case as well, the conduction of oxygen ions can be inhibited, and oxidative deterioration at the bonding interface between the porous ion-conducting layer 20 and the porous electron-conducting layer 40 is suppressed.
  • the entire porous antioxidant layer 50 may be made of a material having oxygen ion conductivity equivalent to that of the other layers.
  • conduction of oxygen ions from the porous ion-conducting layer 20 to the porous electron-conducting layer 40 can be suppressed as compared with the case where the porous ion-conducting layer 20 and the porous electron-conducting layer 40 are directly bonded. can be done.
  • porous antioxidant layer 50 may have any structure as long as it can suppress the conduction of oxygen ions from the porous ion-conducting layer 20 to the porous electron-conducting layer 40 .

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PCT/JP2022/004329 2022-02-03 2022-02-03 電気化学セル Ceased WO2023148903A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP22924813.3A EP4475238A4 (en) 2022-02-03 2022-02-03 ELECTROCHEMICAL CELL
US18/835,456 US20250140886A1 (en) 2022-02-03 2022-02-03 Electrochemical cell
CN202280090744.XA CN118648145A (zh) 2022-02-03 2022-02-03 电化学单元电池
PCT/JP2022/004329 WO2023148903A1 (ja) 2022-02-03 2022-02-03 電気化学セル
JP2023578290A JP7831500B2 (ja) 2022-02-03 2022-02-03 電気化学セル

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