US20200014051A1 - Manufacturing Method for Electrochemical Element and Electrochemical Element - Google Patents

Manufacturing Method for Electrochemical Element and Electrochemical Element Download PDF

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US20200014051A1
US20200014051A1 US16/495,231 US201816495231A US2020014051A1 US 20200014051 A1 US20200014051 A1 US 20200014051A1 US 201816495231 A US201816495231 A US 201816495231A US 2020014051 A1 US2020014051 A1 US 2020014051A1
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layer
electrode layer
electrochemical element
over
metal substrate
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Mitsuaki Echigo
Hisao Ohnishi
Yuji Tsuda
Kyohei Manabe
Kazuyuki Minami
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Osaka Gas Co Ltd
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Osaka Gas Co Ltd
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Assigned to OSAKA GAS CO., LTD. reassignment OSAKA GAS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ECHIGO, MITSUAKI, MANABE, KYOHEI, MINAMI, KAZUYUKI, OHNISHI, HISAO, TSUDA, YUJI
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • 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
    • H01M8/1286—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 manufacturing method for an electrochemical element, and an electrochemical element.
  • a conventional metal-supported solid oxide fuel cell is obtained by forming an anode electrode layer on/over a porous metal support obtained by sintering Fe—Cr based alloy powder, and forming an electrolyte layer on/over the anode electrode layer.
  • Non-Patent Document 1 it is necessary to prepare an anode electrode layer subjected to heating treatment at a high temperature of 1300° C. in order to form a zirconia-based electrolyte in a low temperature range. Accordingly, damage to the metal support is unavoidable, and it is necessary to provide, through heating treatment at 1200° C., an expensive LST (LaSrTiO 3 ) diffusion preventing layer for preventing elements that poison a cell from diffusing from the metal support, and this poses problems of reliability, durability, and cost.
  • LST LaSrTiO 3
  • the present invention was achieved in light of the foregoing problems, and an object of the present invention is to provide a low-cost electrochemical element that has excellent performance, reliability, and durability.
  • a characteristic configuration of a manufacturing method for an electrochemical element for achieving the object is a manufacturing method for an electrochemical element including a metal support and an electrode layer formed on/over the metal support, the method including an electrode layer forming step of forming an electrode layer having a region with a surface roughness (Ra) of 1.0 ⁇ m or less on/over the metal support, and an electrolyte layer forming step of forming an electrolyte layer by spraying aerosolized metal oxide powder onto the electrode layer.
  • Ra surface roughness
  • the electrode layer is suitable for an electrolyte layer formation process performed in a low temperature range, thus making it possible to form an electrochemical element including an electrode layer and an electrolyte layer on/over a metal support without providing an expensive LST diffusion preventing layer. It is also possible to manufacture an electrochemical element that has excellent reliability and durability as well as high adhesion strength between the electrode layer and the electrolyte layer.
  • a characteristic configuration of a manufacturing method for an electrochemical element for achieving the object is a manufacturing method for an electrochemical element including a metal support, an electrode layer formed on/over the metal support, and an intermediate layer formed on/over the electrode layer, the method including an intermediate layer forming step of forming an intermediate layer having a region with a surface roughness (Ra) of 1.0 ⁇ m or less on/over the electrode layer, and an electrolyte layer forming step of forming an electrolyte layer by spraying aerosolized metal oxide powder onto the intermediate layer.
  • Ra surface roughness
  • the intermediate layer is suitable for an electrolyte layer formation process performed in a low temperature range, thus making it possible to form an electrochemical element including an electrode layer, an intermediate layer, and an electrolyte layer on/over a metal support without providing an expensive LST diffusion preventing layer. It is also possible to manufacture an electrochemical element that has excellent reliability and durability as well as high adhesion strength between the intermediate layer and the electrolyte layer.
  • the electrolyte layer contains stabilized zirconia.
  • the electrolyte layer contains stabilized zirconia, thus making it possible to realize an electrochemical element having excellent performance that can be used in a high temperature range of about 650° C. or higher, for example.
  • a dense electrolyte layer is formed by spraying aerosolized metal oxide powder onto an electrode layer that is formed on/over a metal support and has a region with a surface roughness (Ra) of 1.0 ⁇ m or less.
  • the electrode layer is suitable for an electrolyte layer formation process performed in a low temperature range, thus making it possible to form an electrochemical element including an electrode layer and an electrolyte layer on/over a metal support without providing an expensive LST diffusion preventing layer. It is also possible to configure an electrochemical element that has excellent reliability and durability as well as high adhesion strength between the electrode layer and the electrolyte layer.
  • a dense electrolyte layer is formed by spraying aerosolized metal oxide powder onto an intermediate layer that is formed on/over an electrode layer on/over a metal support and has a region with a surface roughness (Ra) of 1.0 ⁇ m or less.
  • the intermediate layer is suitable for an electrolyte layer formation process performed in a low temperature range, thus making it possible to form an electrochemical element including an electrode layer, an intermediate layer, and an electrolyte layer on/over a metal support without providing an expensive LST diffusion preventing layer. It is also possible to configure an electrochemical element that has excellent reliability and durability as well as high adhesion strength between the intermediate layer and the electrolyte layer.
  • FIG. 1 is a schematic diagram showing a configuration of an electrochemical element.
  • FIG. 2 is an electron micrograph of a cross section of the electrochemical element.
  • the electrochemical element E is used as a constituent element of a solid oxide fuel cell that receives a supply of air and fuel gas containing hydrogen and generates power, for example.
  • a counter electrode layer 6 side may be referred to as “upper portion” or “upper side”
  • an electrode layer 2 side may be referred to as “lower portion” or “lower side”
  • an electrolyte layer 4 for example.
  • a surface on/over which the electrode layer 2 is formed may be referred to as “front side”
  • a surface on/over an opposite side may be referred to as “back side”.
  • the electrochemical element E includes a metal substrate 1 (metal support), an electrode layer 2 formed on/over the metal substrate 1 , an intermediate layer 3 formed on/over the electrode layer 2 , and an electrolyte layer 4 formed on/over the intermediate layer 3 .
  • the electrochemical element E further includes a reaction preventing layer 5 formed on/over the electrolyte layer 4 , and a counter electrode layer 6 formed on/over the reaction preventing layer 5 .
  • the counter electrode layer 6 is formed above the electrolyte layer 4
  • the reaction preventing layer 5 is formed between the electrolyte layer 4 and the counter electrode layer 6 .
  • the electrode layer 2 is porous, and the electrolyte layer 4 is dense.
  • the metal substrate 1 plays a role as a support that supports the electrode layer 2 , the intermediate layer 3 , the electrolyte layer 4 , and the like and maintains the strength of the electrochemical element E.
  • a material that has excellent electron conductivity, thermal resistance, oxidation resistance, and corrosion resistance is used as the material for forming the metal substrate 1 . Examples thereof include ferrite-based stainless steel, austenite-based stainless steel, and nickel-based alloys. In particular, alloys containing chromium are favorably used. It should be noted that although a plate-shaped metal substrate 1 is used as the metal support in this embodiment, a metal support having another shape such as a box shape or cylindrical shape can also be used.
  • the metal substrate 1 need only have a strength sufficient for serving as the support for forming the electrochemical element, and can have a thickness of approximately 0.1 mm to 2 mm, preferably approximately 0.1 mm to 1 mm, and more preferably approximately 0.1 mm to 0.5 mm, for example.
  • the metal substrate 1 is provided with a plurality of through holes 1 a that penetrate the surface on the front side and the surface on the back side.
  • the through holes 1 a can be provided in the metal substrate 1 through mechanical, chemical, or optical piercing processing, for example.
  • the through holes 1 a have a function of transmitting gas from the surface on the back side of the metal substrate 1 to the surface on the front side thereof.
  • Porous metal can also be used to impart gas permeability to the metal substrate 1 .
  • a metal sintered body, a metal foam, or the like can also be used as the metal substrate 1 , for example.
  • a metal oxide thin layer 1 b serving as a diffusion suppressing layer is provided on/over the surfaces of the metal substrate 1 . That is, the diffusion suppressing layer is formed between the metal substrate 1 and the electrode layer 2 , which will be described later.
  • the metal oxide thin layer 1 b is provided not only on/over the surface of the metal substrate 1 exposed to the outside but also the surface (interface) that is in contact with the electrode layer 2 and the inner surfaces of the through holes 1 a . Element interdiffusion that occurs between the metal substrate 1 and the electrode layer 2 can be suppressed due to this metal oxide thin layer 1 b .
  • the metal oxide thin layer 1 b is mainly made of a chromium oxide.
  • the metal oxide thin layer 1 b containing the chromium oxide as the main component suppresses diffusion of chromium atoms and the like of the metal substrate 1 to the electrode layer 2 and the electrolyte layer 4 .
  • the metal oxide thin layer 1 b need only have such a thickness that allows both high diffusion preventing performance and low electric resistance to be achieved.
  • the thickness is on the order of submicrons, and specifically, it is more preferable that the average thickness is approximately 0.3 ⁇ m or more and 0.7 ⁇ m or less. It is more preferable that the minimum thickness is about 0.1 ⁇ m or more.
  • the maximum thickness is about 1.1 ⁇ m or less.
  • the metal oxide thin layer 1 b can be formed using various techniques, but it is favorable to use a technique of oxidizing the surface of the metal substrate 1 to obtain a metal oxide. Also, the metal oxide thin layer 1 b may be formed on/over the surface of the metal substrate 1 by using a PVD technique such as a sputtering technique or PLD technique, a CVD technique, or a spray coating technique (a technique such as thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), or may be formed by plating and oxidation treatment. Furthermore, the metal oxide thin layer 1 b may also contain a spinel phase that has high electron conductivity, or the like.
  • a ferrite-based stainless steel material When a ferrite-based stainless steel material is used to form the metal substrate 1 , its thermal expansion coefficient is close to that of YSZ (yttria-stabilized zirconia), GDC (gadolinium-doped ceria; also called CGO), or the like, which is used as the material for forming the electrode layer 2 and the electrolyte layer 4 . Accordingly, even if low and high temperature cycling is repeated, the electrochemical element E is not likely to be damaged. Therefore, this is preferable due to being able to realize an electrochemical element E that has excellent long-term durability.
  • YSZ yttria-stabilized zirconia
  • GDC gadolinium-doped ceria
  • the electrode layer 2 can be provided as a thin layer in a region that is larger than the region provided with the through holes 1 a , on/over the front surface of the metal substrate 1 .
  • the thickness can be set to approximately 1 ⁇ m to 100 ⁇ m, and preferably 5 ⁇ m to 50 ⁇ m, for example. This thickness makes it possible to ensure sufficient electrode performance while also achieving cost reduction by reducing the used amount of expensive electrode layer material.
  • the region provided with the through holes 1 a is entirely covered with the electrode layer 2 . That is, the through holes 1 a are formed inside the region of the metal substrate 1 in which the electrode layer 2 is formed. In other words, all the through holes 1 a are provided facing the electrode layer 2 .
  • a composite material such as NiO-GDC, Ni-GDC, NiO—YSZ, Ni—YSZ, CuO—CeO 2 , or Cu—CeO 2 can be used as the material for forming the electrode layer 2 , for example.
  • GDC, YSZ, and CeO 2 can be called the aggregate of the composite material.
  • the electrode layer 2 it is preferable to form the electrode layer 2 using low-temperature heating (not performing heating treatment in a high temperature range of higher than 1100° C., but rather performing a wet process using heating treatment in a low temperature range, for example), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like.
  • a spray coating technique a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique
  • PVD technique e.g., a sputtering technique or a pulse laser deposition technique
  • CVD technique or the like.
  • a favorable electrode layer 2 is obtained without using heating in a high temperature range of higher than 1100° C., for example. Therefore, this is preferable due to being able to prevent damage to the metal substrate 1 , suppress element interdiffusion between the metal substrate 1 and the electrode layer 2 , and realize an electrochemical element that has excellent durability. Furthermore, using low-temperature heating makes it possible to facilitate handling of raw materials and is thus more preferable.
  • the inside and the surface of the electrode layer 2 are provided with a plurality of pores in order to impart gas permeability to the electrode layer 2 .
  • the electrode layer 2 is formed as a porous layer.
  • the electrode layer 2 is formed to have a denseness of 30% or more and less than 80%, for example.
  • a size suitable for smooth progress of an electrochemical reaction can be selected as appropriate.
  • the “denseness” is a ratio of the material of the layer to the space and can be represented by a formula “1 ⁇ porosity”, and is equivalent to relative density.
  • the intermediate layer 3 can be formed as a thin layer on/over the electrode layer 2 so as to cover the electrode layer 2 .
  • the thickness can be set to approximately 1 ⁇ m to 100 ⁇ m, preferably approximately 2 ⁇ m to 50 ⁇ m, and more preferably approximately 4 ⁇ m to 25 ⁇ m, for example. This thickness makes it possible to ensure sufficient performance while also achieving cost reduction by reducing the used amount of expensive intermediate layer material.
  • YSZ yttria-stabilized zirconia
  • SSZ scandium-stabilized zirconia
  • GDC gallium-doped ceria
  • YDC yttrium-doped ceria
  • SDC sinarium-doped ceria
  • ceria-based ceramics are favorably used.
  • the intermediate layer 3 it is preferable to form the intermediate layer 3 using low-temperature heating (not performing heating treatment in a high temperature range of higher than 1100° C., but rather performing a wet process using heating treatment in a low temperature range, for example), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like.
  • a spray coating technique a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique
  • PVD technique e.g., a sputtering technique or a pulse laser deposition technique
  • CVD technique or the like.
  • an intermediate layer 3 is obtained without using heating in a high temperature range of higher than 1100° C., for example. Therefore, it is possible to prevent damage to the metal substrate 1 , suppress element interdiffusion between the metal substrate 1 and the electrode layer 2 , and realize an electrochemical element E that has excellent durability. Furthermore, using low-temperature heating makes it possible to facilitate handling of raw materials and is thus more preferable.
  • the intermediate layer 3 has oxygen ion (oxide ion) conductivity. It is more preferable that the intermediate layer 3 has both oxygen ion (oxide ion) conductivity and electron conductivity, namely mixed conductivity.
  • the intermediate layer 3 that has these properties is suitable for application to the electrochemical element E.
  • the intermediate layer 3 has a region with a surface roughness (Ra) of 1.0 ⁇ m or less. This region may correspond to all or a part of the surface of the intermediate layer 3 .
  • An electrochemical element E that has excellent reliability and durability as well as high adhesion strength between the intermediate layer 3 and the electrolyte layer 4 can be configured due to the intermediate layer 3 having a region with a surface roughness (Ra) of 1.0 ⁇ m or less.
  • the intermediate layer 3 more preferably has a region with a surface roughness (Ra) of 0.5 ⁇ m or less, and even more preferably 0.3 ⁇ m or less. The reason for this is that an electrochemical element E that has excellent reliability and durability as well as higher adhesion strength between the intermediate layer 3 and the electrolyte layer 4 can be configured if the intermediate layer 3 is smoother in terms of the surface roughness.
  • the electrolyte layer 4 is formed as a thin layer on/over the intermediate layer 3 so as to cover the electrode layer 2 and the intermediate layer 3 .
  • the electrolyte layer 4 is provided on/over both the intermediate layer 3 and the metal substrate 1 (spanning the intermediate layer 3 and the metal substrate 1 ). Configuring the electrolyte layer 4 in this manner and joining the electrolyte layer 4 to the metal substrate 1 make it possible to allow the electrochemical element to have excellent toughness as a whole.
  • the electrolyte layer 4 is provided in a region that is larger than the region provided with the through holes 1 a , on/over the front surface of the metal substrate 1 . That is, the through holes 1 a are formed inside the region of the metal substrate 1 in which the electrolyte layer 4 is formed.
  • the leakage of gas from the electrode layer 2 and the intermediate layer 3 can be suppressed in the vicinity of the electrolyte layer 4 .
  • a description of this will be given.
  • gas is supplied from the back side of the metal substrate 1 through the through holes 1 a to the electrode layer 2 during the operation of the SOFC.
  • leakage of gas can be suppressed without providing another member such as a gasket.
  • YSZ yttria-stabilized zirconia
  • SSZ scandium-stabilized zirconia
  • GDC gallium-doped ceria
  • YDC yttrium-doped ceria
  • SDC samarium-doped ceria
  • LSGM strontium- and magnesium-doped lanthanum gallate
  • zirconia-based ceramics are favorably used.
  • zirconia-based ceramics for the electrolyte layer 4 makes it possible to increase the operation temperature of the SOFC in which the electrochemical element E is used compared with the case where ceria-based ceramics are used.
  • the electrochemical element E is used in the SOFC, by adopting a system configuration in which a material such as YSZ that can exhibit high electrolyte performance even in a high temperature range of approximately 650° C.
  • a hydrocarbon-based raw fuel material such as city gas or LPG is used as the raw fuel for the system, and the raw fuel material is reformed into anode gas of the SOFC through steam reforming or the like, it is thus possible to construct a high-efficiency SOFC system in which heat generated in a cell stack of the SOFC is used to reform raw fuel gas.
  • the electrolyte layer 4 it is preferable to form the electrolyte layer 4 using an aerosol deposition technique. Due to such a film formation process that can be used in a low temperature range, an electrolyte layer 4 that is dense and has high gas-tightness and gas barrier properties is obtained without using heating in a high temperature range of higher than 1100° C., for example. Therefore, it is possible to prevent damage to the metal substrate 1 , suppress element interdiffusion between the metal substrate 1 and the electrode layer 2 , and realize an electrochemical element E that has excellent performance and durability.
  • the electrolyte layer 4 is given a dense configuration in order to block gas leakage of anode gas and cathode gas and exhibit high ion conductivity.
  • the electrolyte layer 4 preferably has a denseness of 90% or more, more preferably 95% or more, and even more preferably 98% or more.
  • the denseness is preferably 95% or more, and more preferably 98% or more.
  • the electrolyte layer 4 has a multilayer configuration, at least a portion thereof preferably includes a layer (dense electrolyte layer) having a denseness of 98% or more, and more preferably a layer (dense electrolyte layer) having a denseness of 99% or more.
  • an electrolyte layer that is dense and has high gas-tightness and gas barrier properties can be easily formed due to such a dense electrolyte layer being included as a portion of the electrolyte layer even when the electrolyte layer has a multilayer configuration.
  • the reaction preventing layer 5 can be formed as a thin layer on/over the electrolyte layer 4 .
  • the thickness can be set to approximately 1 ⁇ m to 100 ⁇ m, preferably approximately 2 ⁇ m to 50 ⁇ m, and more preferably approximately 4 ⁇ m to 25 ⁇ m, for example. This thickness makes it possible to ensure sufficient performance while also achieving cost reduction by reducing the used amount of expensive reaction preventing layer material.
  • the material for forming the reaction preventing layer 5 need only be capable of preventing reactions between the component of the electrolyte layer 4 and the component of the counter electrode layer 6 . For example, a ceria-based material or the like is used.
  • reaction preventing layer 5 between the electrolyte layer 4 and the counter electrode layer 6 effectively suppresses reactions between the material constituting the counter electrode layer 6 and the material constituting the electrolyte layer 4 and makes it possible to improve long-term stability in the performance of the electrochemical element E.
  • Forming the reaction preventing layer 5 using, as appropriate, a method through which the reaction preventing layer 5 can be formed at a treatment temperature of 1100° C. or lower makes it possible to suppress damage to the metal substrate 1 , suppress element interdiffusion between the metal substrate 1 and the electrode layer 2 , and realize an electrochemical element E that has excellent performance and durability, and is thus preferable.
  • the reaction preventing layer 5 can be formed using, as appropriate, low-temperature heating (not performing heating treatment in a high temperature range of higher than 1100° C., but rather performing a wet process using heating treatment in a low temperature range, for example), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like.
  • low-temperature heating an aerosol deposition technique, or the like makes it possible to realize a low-cost element and is thus preferable.
  • using low-temperature heating makes it possible to facilitate handling of raw materials and is thus more preferable.
  • the counter electrode layer 6 can be formed as a thin layer on/over the electrolyte layer 4 or the reaction preventing layer 5 .
  • the thickness can be set to approximately 1 ⁇ m to 100 ⁇ m, and preferably approximately 5 ⁇ m to 50 ⁇ m, for example. This thickness makes it possible to ensure sufficient electrode performance while also achieving cost reduction by reducing the used amount of expensive counter electrode layer material.
  • a complex oxide such as LSCF or LSM can be used as the material for forming the counter electrode layer 6 , for example.
  • the counter electrode layer 6 constituted by the above-mentioned material functions as a cathode.
  • forming the counter electrode layer 6 using, as appropriate, a method through which the counter electrode layer 6 can be formed at a treatment temperature of 1100° C. or lower makes it possible to suppress damage to the metal substrate 1 , suppress element interdiffusion between the metal substrate 1 and the electrode layer 2 , and realize an electrochemical element E that has excellent performance and durability, and is thus preferable.
  • the counter electrode layer 6 can be formed using, as appropriate, low-temperature heating (not performing heating treatment in a high temperature range of higher than 1100° C., but rather performing a wet process using heating treatment in a low temperature range, for example), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like.
  • low-temperature heating a spray coating technique, or the like makes it possible to realize a low-cost element and is thus preferable.
  • using low-temperature heating makes it possible to facilitate handling of raw materials and is thus more preferable.
  • the electrochemical element E configured as described above can be used as a power generating cell for a solid oxide fuel cell.
  • fuel gas containing hydrogen is supplied from the back surface of the metal substrate 1 through the through holes 1 a to the electrode layer 2 , air is supplied to the counter electrode layer 6 serving as a counter electrode of the electrode layer 2 , and the operation is performed at a temperature of 600° C. or higher and 850° C. or lower, for example.
  • the oxygen O 2 included in air reacts with electrons e ⁇ in the counter electrode layer 6 , thus producing oxygen ions O 2 ⁇ .
  • the oxygen ions O 2 ⁇ move through the electrolyte layer 4 to the electrode layer 2 .
  • the hydrogen H 2 included in the supplied fuel gas reacts with the oxygen ions O 2 ⁇ , thus producing water H 2 O and electrons e ⁇ . With these reactions, electromotive force is generated between the electrode layer 2 and the counter electrode layer 6 .
  • the electrode layer 2 functions as a fuel electrode (anode) of the SOFC
  • the counter electrode layer 6 functions as an air electrode (cathode).
  • the electrode layer 2 is formed as a thin film in a region that is broader than the region provided with the through holes 1 a , on/over the front surface of the metal substrate 1 .
  • the through holes of the metal substrate 1 can be provided through laser processing or the like.
  • the electrode layer 2 can be formed using low-temperature heating (a wet process using heating treatment in a low temperature range of 1100° C.
  • a spray coating technique a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique
  • a PVD technique e.g., a sputtering technique or a pulse laser deposition technique
  • CVD technique e.g., a CVD technique, or the like. Regardless of which technique is used, it is desirable to perform the technique at a temperature of 1100° C. or lower in order to suppress deterioration of the metal substrate 1 .
  • a material paste is produced by mixing powder of the material for forming the electrode layer 2 and a solvent (dispersion medium), and is applied to the front surface of the metal substrate 1 .
  • the electrode layer 2 is obtained through compression shape forming (electrode layer smoothing step) and heating at a temperature of 1100° C. or lower (electrode layer heating step).
  • compression shape forming of the electrode layer 2 include CIP (Cold Isostatic Pressing) shape forming, roll pressing shape forming, and RIP (Rubber Isostatic Pressing) shape forming. It is favorable to perform heating of the electrode layer 2 at a temperature of 800° C.
  • the electrode layer smoothing step and the electrode layer heating step are performed can be changed. It should be noted that, when an electrochemical element including an intermediate layer is formed, the electrode layer smoothing step and the electrode layer heating step may be omitted, and an intermediate layer smoothing step and an intermediate layer heating step, which will be described later, may include the electrode layer smoothing step and the electrode layer heating step.
  • lapping shape forming, leveling treatment, surface cutting treatment, surface polishing treatment, or the like can also be performed as the electrode layer smoothing step.
  • the metal oxide thin layer 1 b (diffusion suppressing layer) is formed on/over the surface of the metal substrate 1 during the heating step in the above-described electrode layer forming step.
  • the above-mentioned heating step includes a heating step in which the heating atmosphere satisfies the atmospheric condition that the oxygen partial pressure is low because a high-quality metal oxide thin layer 1 b (diffusion suppressing layer) that has a high element interdiffusion suppressing effect and has a low resistance value is formed.
  • a separate diffusion suppressing layer forming step may also be included.
  • the metal oxide thin layer 1 b may be formed on/over the surface of the metal substrate 1 during the heating step in an intermediate layer forming step, which will be described later.
  • the intermediate layer 3 is formed as a thin layer on/over the electrode layer 2 so as to cover the electrode layer 2 .
  • the intermediate layer 3 can be formed using low-temperature heating (a wet process using heating treatment in a low temperature range of 1100° C. or lower), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like. Regardless of which technique is used, it is desirable to perform the technique at a temperature of 1100° C. or lower in order to suppress deterioration of the metal substrate 1 .
  • low-temperature heating a wet process using heating treatment in a low temperature range of 1100° C. or lower
  • a spray coating technique a technique such as a thermal spraying technique, an aerosol de
  • a material paste is produced by mixing powder of the material for forming the intermediate layer 3 and a solvent (dispersion medium), and is applied to the front surface of the metal substrate 1 .
  • the intermediate layer 3 is obtained through compression shape forming (intermediate layer smoothing step) and heating at a temperature of 1100° C. or lower (intermediate layer heating step).
  • compression shape forming to be performed on the intermediate layer 3 include CIP (Cold Isostatic Pressing) shape forming, roll pressing shape forming, and RIP (Rubber Isostatic Pressing) shape forming. It is favorable to perform heating of the intermediate layer 3 at a temperature of 800° C.
  • this temperature makes it possible to form an intermediate layer 3 that has high strength while suppressing damage to and deterioration of the metal substrate 1 . It is more preferable to perform heating of the intermediate layer 3 at a temperature of 1050° C. or lower, and more preferably 1000° C. or lower. The reason for this is that the lower the heating temperature of the intermediate layer 3 is, the more likely it is to further suppress damage to and deterioration of the metal substrate 1 when forming the electrochemical element E. It should be noted that the order in which the intermediate layer smoothing step and the intermediate layer heating step are performed can be changed.
  • lapping shape forming, leveling treatment, surface cutting treatment, surface polishing treatment, or the like can also be performed as the intermediate layer smoothing step.
  • the electrolyte layer 4 is formed as a thin layer on/over the intermediate layer 3 so as to cover the electrode layer 2 and the intermediate layer 3 .
  • aerosol deposition technique as the electrolyte layer forming step in order to form a high-quality electrolyte layer 4 that is dense and has high gas-tightness and gas barrier properties in a temperature range of 1100° C. or lower.
  • aerosolized powder of the material for forming the electrolyte layer 4 is sprayed onto the intermediate layer 3 on/over the metal substrate 1 , and the electrolyte layer 4 is thus formed.
  • the reaction preventing layer 5 is formed as a thin layer on/over the electrolyte layer 4 .
  • the reaction preventing layer 5 can be formed using low-temperature heating (not performing heating treatment in a high temperature range of higher than 1100° C., but rather performing a wet process using heating treatment in a low temperature range, for example), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like. Regardless of which technique is used, it is desirable to perform the technique at a temperature of 1100° C. or lower in order to suppress deterioration of the metal substrate 1 .
  • the counter electrode layer 6 is formed as a thin layer on/over the reaction preventing layer 5 .
  • the counter electrode layer 6 can be formed using low-temperature heating (not performing heating treatment in a high temperature range of higher than 1100° C., but rather performing a wet process using heating treatment in a low temperature range, for example), a spray coating technique (a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique), a PVD technique (e.g., a sputtering technique or a pulse laser deposition technique), a CVD technique, or the like. Regardless of which technique is used, it is desirable to perform the technique at a temperature of 1100° C. or lower in order to suppress deterioration of the metal substrate 1 .
  • the manufacturing method for an electrochemical element is a manufacturing method for an electrochemical element including a metal substrate 1 (metal support), an electrode layer 2 formed on/over the metal substrate 1 , an intermediate layer 3 formed on/over the electrode layer 2 , and an electrolyte layer 4 on/over the intermediate layer 3 , and the method includes an intermediate layer forming step of forming the intermediate layer 3 with a surface roughness (Ra) of 1.0 ⁇ m or less on/over the electrode layer 2 , and an electrolyte layer forming step of forming the electrolyte layer 4 by spraying aerosolized metal oxide powder onto the intermediate layer 3 .
  • a surface roughness Ra
  • the electrochemical element E does not include both or either of the intermediate layer 3 and the reaction preventing layer 5 is also possible. That is, a configuration in which the electrode layer 2 and the electrolyte layer 4 are in contact with each other, or a configuration in which the electrolyte layer 4 and the counter electrode layer 6 are in contact with each other is also possible.
  • the intermediate layer forming step and the reaction preventing layer forming step are omitted. It should be noted that it is also possible to add a step of forming another layer or to form a plurality of layers of the same type one on/over top of another, but in any case, it is desirable to perform these steps at a temperature of 1100° C. or lower.
  • a metal substrate 1 was produced by providing a plurality of through holes 1 a through laser processing in a region with a radius of 2.5 mm from the center of a crofer 22 APU metal plate having a circular shape with a thickness of 0.3 mm and a diameter of 25 mm. It should be noted that, at this time, the through holes 1 a on the surface of the metal substrate 1 were provided through laser processing.
  • a paste was produced by mixing 60 wt % of NiO powder and 40 wt % of GDC powder and adding an organic binder and an organic solvent (dispersion medium) thereto.
  • the paste was used to form an electrode layer 2 on/over a region with a radius of 3 mm from the center of the metal substrate 1 . It should be noted that the electrode layer 2 was formed using screen printing. Then, heating treatment was performed at 950° C. on the metal substrate 1 on/over which the electrode layer 2 was formed (electrode layer forming step, diffusion suppressing layer forming step).
  • a paste was produced by adding an organic binder and an organic solvent (dispersion medium) to fine powder of GDC.
  • the paste was used to form an intermediate layer 3 , through screen printing, on/over a region with a radius of 5 mm from the center of the metal substrate 1 on which the electrode layer 2 was formed.
  • the intermediate layer 3 having a flat surface was formed by performing CIP shape forming with a pressure of 300 MPa on the metal substrate 1 on/over which the intermediate layer 3 was formed and then performing heating treatment at 1000° C. (intermediate layer forming step).
  • the electrode layer 2 and the intermediate layer 3 obtained through the above-described steps had a thickness of about 20 ⁇ m and about 10 ⁇ m, respectively. Moreover, the He leakage amount of metal substrate 1 on/over which the electrode layer 2 and the intermediate layer 3 were formed in this manner was 11.5 mL/minute ⁇ cm 2 under a pressure of 0.2 MPa.
  • powder of 8YSZ yttria-stabilized zirconia
  • a mode diameter of about 0.7 ⁇ m was aerosolized using dry air at a flow rate of 13 L/min.
  • the aerosol was introduced into a chamber in which the pressure was set to 250 Pa, and then an electrolyte layer 4 was formed by spraying the aerosol onto 15 mm ⁇ 15 mm region on/over the metal substrate 1 on/over which the electrode layer 2 and the intermediate layer 3 was formed, so as to cover the intermediate layer 3 (aerosol deposition technique). It should be noted that, at this time, the metal substrate 1 was not heated (electrolyte layer forming step).
  • the electrolyte layer 4 obtained through the above-described step had a thickness of approximately 3 to 4 ⁇ m.
  • the He leakage amount of the metal substrate 1 on/over which the electrode layer 2 , the intermediate layer 3 , and the electrolyte layer 4 were formed was measured under a pressure of 0.2 MPa.
  • the determined He leakage amount was smaller than the lower detection limit (1.0 mL/minute ⁇ cm 2 ). That is, compared with the He leakage amount after forming the intermediate layer 3 , the He leakage amount after forming the electrolyte layer 4 decreased significantly and was smaller than the lower detection limit. It was thus confirmed that a high-quality electrolyte layer 4 that was dense and had increased gas barrier properties was formed.
  • a paste was produced by adding an organic binder and an organic solvent (dispersion medium) to fine powder of GDC.
  • the paste was used to form a reaction preventing layer 5 on/over the electrolyte layer 4 of the electrochemical element E using screen printing.
  • reaction preventing layer 5 was formed by performing heating treatment at 1000° C. on the electrochemical element E on/over which the reaction preventing layer 5 was formed (reaction preventing layer forming step).
  • a paste was produced by mixing GDC powder and LSCF powder and adding an organic binder and an organic solvent (dispersion medium) thereto. The paste was used to form a counter electrode layer 6 on/over the reaction preventing layer 5 using screen printing. Lastly, a final electrochemical element E was obtained by heating, at 900° C., the electrochemical element E on/over which the counter electrode layer 6 was formed (counter electrode layer forming step).
  • FIG. 2 shows an electron micrograph of a cross section of the electrochemical element E.
  • the dense electrolyte layer 4 was formed on/over the smooth surface with a surface roughness (Ra) of 1.0 ⁇ m or less of the intermediate layer 3 on the side facing the electrolyte layer, and it is thus clear that a cell for a solid oxide fuel cell (electrochemical element E) that had favorable performance was obtained.
  • the surface roughness (Ra) of the intermediate layer 3 was 1.0 ⁇ m or less, and a favorable electrolyte layer 4 could be formed on/over the intermediate layer 3 .
  • the surface roughness (Ra) of the intermediate layer 3 was greater than 1.0 ⁇ m.
  • An electrochemical element E according to this embodiment has a configuration in which the intermediate layer 3 is not provided, that is, the electrode layer 2 and the electrolyte layer 4 are in contact with each other. Therefore, in the manufacturing method for the electrochemical element E, the intermediate layer forming step is omitted.
  • the electrochemical element E includes the metal substrate 1 (metal support), the electrode layer 2 formed on/over the metal substrate 1 , and the electrolyte layer 4 formed on/over the electrode layer 2 .
  • the electrochemical element E further includes the reaction preventing layer 5 formed on/over the electrolyte layer 4 , and the counter electrode layer 6 formed on/over the reaction preventing layer 5 .
  • the counter electrode layer 6 is formed above the electrolyte layer 4
  • the reaction preventing layer 5 is formed between the electrolyte layer 4 and the counter electrode layer 6 .
  • the electrode layer 2 is porous, and the electrolyte layer 4 is dense.
  • the electrode layer 2 has a region with a surface roughness (Ra) of 1.0 ⁇ m or less. This region may correspond to all or a part of the surface of the electrode layer 2 .
  • An electrochemical element E that has excellent reliability and durability as well as high adhesion strength between the electrode layer 2 and the electrolyte layer 4 can be configured due to the electrode layer 2 having a region with a surface roughness (Ra) of 1.0 ⁇ m or less.
  • the electrode layer 2 more preferably has a region with a surface roughness (Ra) of 0.5 ⁇ m or less, and even more preferably 0.3 ⁇ m or less. The reason for this is that an electrochemical element E that has excellent reliability and durability as well as higher adhesion strength between the electrode layer 2 and the electrolyte layer 4 can be configured if the electrode layer 2 is smoother in terms of the surface roughness.
  • the electrochemical element E according to this embodiment does not include the intermediate layer 3 . Accordingly, in the manufacturing method for the electrochemical element E according to this embodiment, the electrode layer forming step (diffusion suppressing layer forming step), the electrolyte layer forming step, the reaction preventing layer forming step, and the counter electrode layer forming step are performed in the stated order.
  • the electrode layer 2 is formed as a thin film in a region that is broader than the region provided with the through holes 1 a , on/over the front surface of the metal substrate 1 .
  • the through holes of the metal substrate 1 can be provided through laser processing or the like.
  • the electrode layer 2 can be formed using low-temperature heating (a wet process using heating treatment in a low temperature range of 1100° C.
  • a spray coating technique a technique such as a thermal spraying technique, an aerosol deposition technique, an aerosol gas deposition technique, a powder jet deposition technique, a particle jet deposition technique, or a cold spraying technique
  • a PVD technique e.g., a sputtering technique or a pulse laser deposition technique
  • CVD technique e.g., a CVD technique, or the like. Regardless of which technique is used, it is desirable to perform the technique at a temperature of 1100° C. or lower in order to suppress deterioration of the metal substrate 1 .
  • a material paste is produced by mixing powder of the material for forming the electrode layer 2 and a solvent (dispersion medium), and is applied to the front surface of the metal substrate 1 .
  • the electrode layer 2 is obtained through compression shape forming (electrode layer smoothing step) and heating at a temperature of 1100° C. or lower (electrode layer heating step).
  • compression shape forming of the electrode layer 2 include CIP (Cold Isostatic Pressing) shape forming, roll pressing shape forming, and RIP (Rubber Isostatic Pressing) shape forming. It is favorable to perform heating of the electrode layer 2 at a temperature of 800° C.
  • this temperature makes it possible to form an electrode layer 2 that has high strength while suppressing damage to and deterioration/over of the metal substrate 1 . It is more preferable to perform heating of the electrode layer 2 at a temperature of 1050° C. or lower, and more preferably 1000° C. or lower. The reason for this is that the electrochemical element E can be formed with damage to and deterioration of the metal substrate 1 being further suppressed as the heating temperature of the electrode layer 2 is reduced.
  • lapping shape forming, leveling treatment, surface cutting treatment, surface polishing treatment, or the like can also be performed as the electrode layer smoothing step.
  • the manufacturing method for an electrochemical element is a manufacturing method for an electrochemical element including a metal substrate 1 (metal support), an electrode layer 2 formed on/over the metal substrate 1 , and an electrolyte layer 4 formed on/over the electrode layer 2 , and the method includes an electrode layer forming step of forming the electrode layer 2 with a surface roughness (Ra) of 1.0 ⁇ m or less on the metal substrate 1 , and an electrolyte layer forming step of forming the electrolyte layer 4 by spraying aerosolized metal oxide powder onto the electrode layer 2 .
  • a surface roughness Ra
  • a metal substrate 1 was produced by providing a plurality of through holes 1 a through laser processing in a region with a radius of 2.5 mm from the center of a crofer 22 APU metal plate having a circular shape with a thickness of 0.3 mm and a diameter of 25 mm. It should be noted that, at this time, the through holes 1 a on the surface of the metal substrate 1 were provided through laser processing.
  • a paste was produced by mixing 60 wt % of NiO powder and 40 wt % of YSZ powder and adding an organic binder and an organic solvent (dispersion medium) thereto.
  • the paste was used to form an electrode layer 2 on/over a region with a radius of 3 mm from the center of the metal substrate 1 . It should be noted that the electrode layer 2 was formed using screen printing.
  • CIP shape forming was performed with a pressure of 300 MPa on the metal substrate 1 on/over which the electrode layer 2 was formed, and then heating treatment was performed at 1050° C. (electrode layer forming step, diffusion suppressing layer forming step).
  • the electrode layer 2 obtained through the above-described step had a thickness of about 20 ⁇ m. Moreover, the He leakage amount of metal substrate 1 on/over which the electrode layer 2 was formed in this manner was 4.3 mL/minute ⁇ cm 2 under a pressure of 0.1 MPa.
  • powder of 8YSZ yttria-stabilized zirconia
  • a mode diameter of about 0.7 ⁇ m was aerosolized using dry air at a flow rate of 4 L/min.
  • the aerosol was introduced into a chamber in which the pressure was set to 60 Pa, and then an electrolyte layer 4 was formed by spraying the aerosol onto 15 mm ⁇ 15 mm region on/over the metal substrate 1 on/over which the electrode layer 2 was formed, so as to cover the electrode layer 2 (aerosol deposition technique). It should be noted that, at this time, the metal substrate 1 was not heated (electrolyte layer forming step).
  • the electrolyte layer 4 obtained through the above-described step had a thickness of approximately 5 to 6 ⁇ m.
  • the He leakage amount of the metal substrate 1 on/over which the electrode layer 2 and the electrolyte layer 4 were formed in this manner was measured under a pressure of 0.2 MPa.
  • the determined He leakage amount was smaller than the lower detection limit (1.0 mL/minute ⁇ cm 2 ). It was thus confirmed that a high-quality electrolyte layer 4 that was dense and had increased gas barrier properties was formed.
  • a paste was produced by adding an organic binder and an organic solvent (dispersion medium) to fine powder of GDC.
  • the paste was used to form a reaction preventing layer 5 on/over the electrolyte layer 4 of the electrochemical element E using screen printing.
  • reaction preventing layer 5 was formed by performing heating treatment at 1000° C. on the electrochemical element E on/over which the reaction preventing layer 5 was formed (reaction preventing layer forming step).
  • a paste was produced by mixing GDC powder and LSCF powder and adding an organic binder and an organic solvent thereto. The paste was used to form a counter electrode layer 6 on/over the reaction preventing layer 5 using screen printing. Lastly, a final electrochemical element E was obtained by heating, at 900° C., the electrochemical element E on/over which the counter electrode layer 6 was formed (counter electrode layer forming step).
  • the surface roughness (Ra) of the electrode layer 2 was 1.0 ⁇ m or less, and a favorable electrolyte layer 4 , a favorable reaction preventing layer 5 , and a favorable counter electrode layer 6 could be formed on/over the electrode layer 2 .
  • electrochemical elements E are used in a solid oxide fuel cell in the above-described embodiments, the electrochemical elements E can also be used in a solid oxide electrolytic cell, an oxygen sensor using a solid oxide, and the like.
  • the present application is applied to a metal-supported solid oxide fuel cell in which the metal substrate 1 serves as a support in the above-described embodiments
  • the present application can also be applied to an electrode-supported solid oxide fuel cell in which the electrode layer 2 or counter electrode layer 6 serves as a support, or an electrolyte-supported solid oxide fuel cell in which the electrolyte layer 4 serves as a support.
  • the functions of a support can be obtained by forming the electrode layer 2 , counter electrode layer 6 , or electrolyte layer 4 to have a required thickness.
  • a composite material such as NiO-GDC, Ni-GDC, NiO—YSZ, Ni—YSZ, CuO—CeO 2 , or Cu—CeO 2 is used as the material for forming the electrode layer 2
  • a complex oxide such as LSCF or LSM is used as the material for forming the counter electrode layer 6 .
  • the electrode layer 2 serves as a fuel electrode (anode) when hydrogen gas is supplied thereto
  • the counter electrode layer 6 serves as an air electrode (cathode) when air is supplied thereto, thus making it possible to use the electrochemical element E as a cell for a solid oxide fuel cell.
  • an electrochemical element E such that the electrode layer 2 can be used as an air electrode and the counter electrode layer 6 can be used as a fuel electrode. That is, a complex oxide such as LSCF or LSM is used as the material for forming the electrode layer 2 , and a composite material such as NiO-GDC, Ni-GDC, NiO—YSZ, Ni—YSZ, CuO—CeO 2 , or Cu—CeO 2 is used as the material for forming the counter electrode layer 6 .
  • the electrode layer 2 serves as an air electrode when air is supplied thereto
  • the counter electrode layer 6 serves as a fuel electrode when hydrogen gas is supplied thereto, thus making it possible to use the electrochemical element E as a cell for a solid oxide fuel cell.
  • the present invention can be applied to an electrochemical element and a cell for a solid oxide fuel cell.

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