WO2024010094A1 - Corps lié et son procédé de fabrication - Google Patents

Corps lié et son procédé de fabrication Download PDF

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Publication number
WO2024010094A1
WO2024010094A1 PCT/JP2023/025350 JP2023025350W WO2024010094A1 WO 2024010094 A1 WO2024010094 A1 WO 2024010094A1 JP 2023025350 W JP2023025350 W JP 2023025350W WO 2024010094 A1 WO2024010094 A1 WO 2024010094A1
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Prior art keywords
solid electrolyte
electrolyte membrane
electrode
metal element
proton conductive
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PCT/JP2023/025350
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English (en)
Japanese (ja)
Inventor
美紀 呉羽
勉 樋口
暁 茂木
祐之輔 中原
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三井金属鉱業株式会社
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Publication of WO2024010094A1 publication Critical patent/WO2024010094A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/047—Ceramics
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—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
    • 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
    • H01M8/124—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
    • H01M8/126—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 cerium oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a joined body and a method for manufacturing the same.
  • BZY barium zirconate added with yttrium
  • Patent Document 1 proposes the use of a mixture of barium zirconate and barium cerate to which a rare earth element is added.
  • Patent Document 2 proposes that in an electrolyte layer represented by Ba x Zr 1-y Y y O 3- ⁇ , x is set to 0.95 or more and 1 or less, and y is set to more than 0 and 0.5 or less. has been done.
  • an object of the present invention is to provide a bonded body in which the reaction between nickel element and barium or yttrium in proton conductive ceramics is suppressed, and a method for manufacturing the same.
  • the present invention has a compositional formula AB 1-x M x O 3- ⁇ (A represents at least one metal element selected from the group consisting of metal elements that can become divalent cations, and B represents a metal element selected from Ce and Zr. M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, ⁇ represents the amount of oxygen vacancies, and 0 ⁇ x ⁇ 1, 0.0 ⁇ ⁇ ⁇ 0.5); An electrode located on one side of the solid electrolyte membrane and containing a nickel element, the bonded body comprising: In an image obtained when a cross section along the thickness direction of the bonded body is elementally mapped using a scanning electron microscope-energy dispersive X-ray spectroscopy, the following ranges (a) or (b) are observed:
  • the present invention provides a bonded body in which the total area ratio of an oxide represented by the compositional formula AM 2 NiO 5 and an oxide represented by M 2 O 3 to the entire observed field of view is 30.0% or less.
  • the present invention has a compositional formula AB 1-x M x O 3- ⁇ (A represents at least one metal element selected from the group consisting of metal elements that can become divalent cations, and B represents a metal element selected from Ce and Zr. M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, ⁇ represents the amount of oxygen vacancies, and 0 ⁇ x ⁇ 1, 0.0 ⁇ ⁇ ⁇ 0.5); An electrode located on one side of the solid electrolyte membrane and containing a nickel element, the bonded body comprising: Metals contained in the solid electrolyte membrane in the range of (a) or (b) below calculated by the following formula (1) when a cross section along the thickness direction of the bonded body is measured with an electron beam microanalyzer.
  • the present invention provides a joined body in which the atomic ratio of the nickel element to the elements is 0.00% or more and 2.00% or less.
  • (a) A range of up to 5 ⁇ m in the thickness direction from the outermost surface of the solid electrolyte membrane toward the electrode side.
  • (b) When the thickness of the solid electrolyte membrane is T, a range of up to 0.3T in the thickness direction from the outermost surface of the solid electrolyte membrane toward the electrode side.
  • Atomic ratio of nickel element (number of atoms of nickel element) / ⁇ (number of atoms of metal element represented by A) + (number of atoms of metal element represented by B) + (metal element represented by M (number of atoms of nickel element) + (number of atoms of nickel element) ⁇ (1)
  • the present invention provides a solid electrolyte membrane containing proton-conducting ceramics;
  • a method for manufacturing a bonded body comprising: an electrode located on one side of the solid electrolyte membrane and containing a nickel element; mixing the proton conductive ceramic and an additive to form an electrode; forming a coating film by applying a slurry containing a proton conductive ceramic of the same kind or a different kind to the proton conductive ceramic on one side of the electrode; firing the coating film in an oxygen-containing atmosphere to form a solid electrolyte membrane,
  • the present invention provides a method for producing a bonded body in which the additive includes a core portion and a coating portion made of an oxide and located on the surface of the core portion.
  • FIG. 1 is a backscattered electron image obtained by observing a cross section along the thickness direction of the joined body manufactured in Example 1 using a scanning electron microscope.
  • the present invention relates to an assembly including a solid electrolyte membrane and an electrode located on one side of the solid electrolyte membrane.
  • the solid electrolyte membrane and the electrode may be placed so that they are in direct contact with each other, or may be placed indirectly through another layer.
  • the solid electrolyte membrane has a first surface and a second surface located opposite to the first surface, and at least a portion of the first surface is covered with an electrode, and preferably the entire first surface is covered with an electrode. is covered by the electrode.
  • the second surface of the solid electrolyte membrane may be exposed to the outside, or another layer may be laminated on the second surface.
  • the electrode has a substantially uniform thickness and is located on one side of the solid electrolyte membrane.
  • the electrode contains nickel (Ni) element. Nickel element breaks the bonds of hydrogen molecules and converts them into protons. As a result, the amount of protons supplied to the zygote of the present invention can be increased.
  • Ni nickel
  • the form of the nickel element during production is, for example, NiO.
  • NiO is stable in an air atmosphere, it becomes Ni with high hydrogen activity in a reducing atmosphere and functions to convert hydrogen molecules into protons.
  • the electrode preferably contains NiO.
  • the content of the nickel element in the electrode is preferably 40% or more and 90% or less, more preferably 50% or more and 80% or less, and 60% or more and 70% or less, as a mass ratio to all atoms contained in the electrode. % or less is more preferable.
  • the content of the nickel element in the electrode can be measured by, for example, an ICP emission spectrometer.
  • the electrode contains a proton conductive ceramic of the same kind or a different kind to the proton conductive ceramic contained in the solid electrolyte membrane described below. It is particularly preferable that the electrode includes a proton conductive ceramic represented by the same compositional formula as the proton conductive ceramic contained in the solid electrolyte membrane. By including proton conductive ceramics having such a compositional formula, it is possible to reduce the difference in thermal expansion coefficient between the electrode and the solid electrolyte membrane, thereby suppressing the occurrence of cracks in the solid electrolyte membrane during high-temperature treatment.
  • the content of proton conductive ceramics in the electrode is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and 30% by mass or more and 40% by mass or less. More preferably.
  • the content of proton conductive ceramics in the electrode can be measured, for example, by quantifying the elements contained in the ceramics using an ICP emission spectrometer.
  • the electrode may contain elements other than the elements constituting proton conductive ceramics and nickel. Examples of such elements include other elements that can be included in the solid electrolyte membrane described below. When the electrode contains such an element, for example, when the assembled body of the present invention is manufactured by firing, diffusion of the nickel compound into the electrolyte membrane during firing can be suppressed.
  • the thickness of the electrode can be adjusted as appropriate depending on the electrochemical device including the conjugate, but for example, by setting the average thickness to 500 ⁇ m or more, it is possible to impart sufficient strength and rigidity to the electrode as an electrochemical cell. Can be done. Further, from the viewpoint of manufacturing cost, the average thickness of the electrode is preferably 10,000 ⁇ m or less, but is not particularly limited. The thickness of the electrode is measured in the same manner as the thickness T of the solid electrolyte membrane described later.
  • the solid electrolyte membrane has a layered structure having a first surface and a second surface located opposite thereto, and having a substantially uniform thickness.
  • the solid electrolyte membrane has a composition formula AB 1-x M x O 3- ⁇ (A represents at least one metal element selected from the group consisting of metal elements that can become divalent cations, and B represents Ce and Zr.
  • M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, ⁇ represents the amount of oxygen vacancies, and 0 ⁇ x ⁇ 1, 0.0 ⁇ 0.5).
  • the trivalent rare earth element represented by M includes Sc, Y, La, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. It will be done. From the viewpoint of proton conductivity and proton transfer number, M is preferably at least one selected from the group consisting of Y, Yb, Lu, and In, and more preferably Y.
  • the proton conductive ceramic represented by the compositional formula AB 1-x M x O 3- ⁇ preferably has a perovskite structure.
  • the ratio of the total number of atoms of the metal element represented by B and the number of atoms of the metal element represented by M to the number of atoms of the metal element represented by A is 0.9 or more and 1.1 or less. You can.
  • x is preferably 0.05 or more and 0.5 or less, more preferably 0.1 or more and 0.3 or less, and even more preferably 0.15 or more and 0.2 or less. .
  • x is preferably 0.05 or more and 0.5 or less, more preferably 0.1 or more and 0.3 or less, and even more preferably 0.15 or more and 0.2 or less.
  • ⁇ is more than 0.0 and less than 0.5, preferably more than 0.0 and less than 0.4, and more preferably more than 0.0 and less than 0.3.
  • the proton conductive ceramic represented by the compositional formula AB 1-x M x O 3- ⁇ contained in the solid electrolyte membrane has the following properties: A is barium and B is zirconium, that is, its compositional formula is BaZr 1 -x M x O 3- ⁇ is preferred.
  • A is barium and B is zirconium, that is, its compositional formula is BaZr 1 -x M x O 3- ⁇ is preferred.
  • M is yttrium, that is, the compositional formula of the proton conductive ceramic is represented by BaZr 1-x Y x O 3- ⁇ .
  • Particularly preferred proton conductive ceramics include, for example, BaZr 0.8 Y 0.2 O 2.9 .
  • the content of proton conductive ceramics in the solid electrolyte membrane is preferably 70% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less. It is more preferable that By setting the content of proton conductive ceramics to 70% by mass or more, the proton conductivity of the electrode can be sufficiently increased.
  • the content of proton conductive ceramics in the solid electrolyte membrane can be measured in the same manner as the content of proton conductive ceramics in the electrodes.
  • the solid electrolyte membrane may contain other elements than the elements constituting the proton conductive ceramic. It is preferable that the other elements include at least one element selected from the group consisting of Zr, Mo, and Ce.
  • the solid electrolyte membrane contains the other elements mentioned above, for example, when the solid electrolyte membrane is manufactured by the method described below, by-products generated by the reaction between the proton conductive ceramics and the nickel element in the solid electrolyte membrane during firing are reduced. generation can be suppressed.
  • the total content thereof is preferably 1.0% or more and 10.0% or less, and 2.0% or more as an atomic ratio to all atoms contained in the solid electrolyte membrane. It is more preferably 9.5% or less, and even more preferably 3.0% or more and 9.0% or less.
  • the total content of other elements is 1.0% or more in atomic ratio, for example, when the solid electrolyte membrane is manufactured by the method described below, the proton conductive ceramics and nickel in the solid electrolyte membrane are It is possible to suppress the production of by-products caused by reactions of elements. Further, by setting the total content of other elements to 10.0% or less in terms of atomic ratio, it is possible to suppress the generation of by-products while maintaining the proton conductivity of the solid electrolyte membrane.
  • the content of each element in the solid electrolyte membrane can be measured using, for example, an electron beam microanalyzer.
  • the solid electrolyte membrane may contain nickel element in addition to the above-mentioned elements, but in order to make the solid electrolyte membrane have low resistance to proton conduction, the content of nickel element is preferably as low as possible. .
  • the outermost surface of the solid electrolyte membrane is calculated by the following formula (2).
  • the atomic ratio of the nickel element to the metal element contained in the range up to 1 ⁇ m in the thickness direction from the starting point toward the electrode side (hereinafter also simply referred to as the "atomic ratio of the nickel element”) is the solid electrolyte membrane.
  • the atomic ratio of the nickel element to the metal element is smaller than the atomic ratio of the nickel element to the metal element within a range of up to 1 ⁇ m in the thickness direction from the electrode interface toward the solid electrolyte membrane side.
  • Atomic ratio of nickel element (number of atoms of nickel element) / ⁇ (number of atoms of metal element represented by A) + (number of atoms of metal element represented by B) + (metal element represented by M (number of atoms of nickel element) + (number of atoms of nickel element) ⁇ (2)
  • the solid electrolyte membrane can have low resistance to proton conduction.
  • the outermost surface of the solid electrolyte membrane refers to the surface of the solid electrolyte membrane that does not face the electrode.
  • the outermost surface of the solid electrolyte membrane may be a flat surface or a curved surface.
  • the thickness T of the solid electrolyte membrane is preferably 1 ⁇ m or more and 300 ⁇ m or less, more preferably 2 ⁇ m or more and 100 ⁇ m or less, even more preferably 5 ⁇ m or more and 50 ⁇ m or less, and most preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • the film thickness T is preferably 1 ⁇ m or more and 300 ⁇ m or less, more preferably 2 ⁇ m or more and 100 ⁇ m or less, even more preferably 5 ⁇ m or more and 50 ⁇ m or less, and most preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • the thickness T of the solid electrolyte membrane is measured as follows. First, a cross section of the joined body along the thickness direction is observed using a scanning electron microscope (SEM) to obtain a backscattered electron image. Among the points indicating the presence of nickel oxide (NiO) in the backscattered electron image, the straight line passing through the point closest to the outermost surface of the solid electrolyte membrane and perpendicular to the thickness direction of the bonded body is defined as straight line L. . In this specification, the straight line L is regarded as the boundary (interface) between the electrode and the solid electrolyte membrane in the assembly.
  • SEM scanning electron microscope
  • the solid electrolyte membrane may contain an oxide represented by the composition formula AM 2 NiO 5 or M 2 O 3 .
  • the oxide represented by AM 2 NiO 5 or M 2 O 3 is mixed with the proton conductive ceramics contained in the solid electrolyte membrane and the nickel element thermally diffused from the electrode in the firing process of the assembly manufacturing process. It is produced by the reaction of Among the nickel oxides contained in the solid electrolyte membrane, oxides represented by the compositional formula AM 2 NiO 5 or M 2 O 3 are generally high resistance substances for proton conduction, so it is possible to make the bonded body with low resistance. In order to achieve this, it is necessary to suppress the content of the oxide in the solid electrolyte membrane as low as possible.
  • the content of the oxide in the solid electrolyte membrane can be measured, for example, by X-ray diffraction (XRD), but may also be measured by scanning electron microscopy-energy dispersive X-ray spectroscopy (hereinafter also referred to as "SEM-EDS"). ) is preferable because even trace amounts of elements can be detected.
  • XRD X-ray diffraction
  • SEM-EDS scanning electron microscopy-energy dispersive X-ray spectroscopy
  • the following range (a) or (b) is observed using an image obtained by elemental mapping of a cross section along the thickness direction of the bonded body by SEM-EDS.
  • the total area ratio of the oxide represented by the compositional formula AM 2 NiO 5 and the oxide represented by M 2 O 3 is 30.0% or less.
  • (a) A range of up to 5 ⁇ m in the thickness direction from the outermost surface of the solid electrolyte membrane toward the electrode side.
  • the range is up to 0.3T in the thickness direction from the outermost surface of the solid electrolyte membrane toward the electrode side. Note that a method for calculating the area ratio using an image obtained by elemental mapping using SEM-EDS will be explained in Examples below.
  • the area ratio is 30.0% or less, the content of the oxide represented by the compositional formula AM 2 NiO 5 or M 2 O 3 in the solid electrolyte membrane will be sufficiently low, resulting in poor bonding.
  • the body has a sufficiently low resistance to proton conduction.
  • the area ratio is preferably 20.0% or less, more preferably 10.0% or less, and even more preferably 5.0% or less. . Ideally, the area ratio is zero.
  • the area ratio is 30.0% or less in either range (a) or (b) above, but in both ranges (a) and (b).
  • the area ratio may be 30.0% or less.
  • the thickness T of the solid electrolyte membrane is preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 6 ⁇ m or more and 30 ⁇ m or less, and still more preferably 7 ⁇ m or more and 15 ⁇ m or less.
  • the solid electrolyte membrane has a thickness T of 5 ⁇ m or more and 50 ⁇ m or less, a sufficient area can be evaluated under the condition (a).
  • the thickness T of the solid electrolyte membrane is less than 5 ⁇ m or more than 50 ⁇ m, more preferably less than 6 ⁇ m or more than 30 ⁇ m, even more preferably less than 7 ⁇ m or more than 15 ⁇ m, the evaluation area is insufficient under condition (a). Therefore, it is preferable to measure the area ratio in the range (b).
  • the solid electrolyte membrane in the range of (a) or (b) below is calculated by the following formula (1).
  • the atomic ratio of the nickel element to the metal element contained in the metal element is preferably 0.00% or more and 2.00% or less, more preferably 0.00% or more and 1.00% or less, and 0.00% More preferably, the content is 0.50% or less.
  • a method for measuring the average content of nickel element using an electron beam microanalyzer will be explained in Examples below. Furthermore, when making measurements using an electron beam microanalyzer, data obtained from measurements using SEM or SEM-EDS (for example, the film thickness T of the solid electrolyte membrane, etc.) can be referred to as necessary.
  • the atomic ratio of the nickel element is 2.00% or less in either of the above ranges (a) or (b); In both ranges, the atomic ratio of the nickel element may be 2.00% or less.
  • the thickness T of the solid electrolyte membrane is preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 6 ⁇ m or more and 30 ⁇ m or less, and even more preferably 7 ⁇ m or more and 15 ⁇ m or less.
  • the solid electrolyte membrane has a thickness T of 5 ⁇ m or more and 50 ⁇ m or less, a sufficient area can be evaluated under the condition (a).
  • the thickness T of the solid electrolyte membrane is less than 5 ⁇ m or more than 50 ⁇ m, more preferably less than 6 ⁇ m or more than 30 ⁇ m, even more preferably less than 7 ⁇ m or more than 15 ⁇ m, the evaluation area is insufficient under condition (a). Therefore, it is preferable to measure the atomic ratio of the nickel element in the range (b).
  • the joined body of the present invention may satisfy only one of the two embodiments described above, or may satisfy both embodiments.
  • the joined body of the present invention can be suitably used in electrochemical cells such as fuel cells and water electrolysis cells because the proton conductivity and proton transfer number of proton conductive ceramics are suppressed from decreasing. Furthermore, an electrochemical cell containing the conjugate of the present invention can be suitably used in various electrochemical devices.
  • a preferred method for manufacturing the joined body of the present invention is roughly divided into the following steps. ⁇ Process of forming electrodes. ⁇ Process of forming a coating film that is a precursor of a solid electrolyte membrane. - A step of firing the coating film to form a solid electrolyte membrane.
  • Step of forming electrodes In this step, proton conductive ceramics and additives are mixed to form an electrode. There is no particular restriction on the type of proton conductive ceramic, and various conventionally known proton conductive ceramics can be used. From the viewpoint of increasing the proton conductivity of the bonded body, it is preferable to select from the above-mentioned proton conductive ceramics that may be included in the solid electrolyte membrane constituting the bonded body of the present invention.
  • the additive includes a core portion and a coating portion located on the surface of the core portion and made of an oxide.
  • the core portion of the additive consists of a transition metal oxide.
  • oxides of first transition elements such as nickel and cobalt or oxides of noble metal elements such as silver and iridium are preferred, and NiO is more preferred. This is because these metal oxides have an effect as a sintering aid for the solid electrolyte membrane during firing and an effect of improving proton conductivity.
  • the oxide constituting the coating portion of the additive examples include various metal oxides. More specifically, it is further preferable that the coating portion of the additive contains an oxide of at least one metal element selected from the group consisting of Zr, Mo, and Ce. By containing oxides of these metal elements in the coating portion of the additive, thermal diffusion of the nickel element contained in the core portion of the additive into the solid electrolyte membrane is suppressed during firing, and as a result, the solid electrolyte The amount of a high-resistance Ni compound, for example, an oxide represented by the composition formula AM 2 NiO 5 produced in the film can be suppressed.
  • a high-resistance Ni compound for example, an oxide represented by the composition formula AM 2 NiO 5 produced in the film can be suppressed.
  • the number of moles of the metal element constituting the coating portion per gram of the transition metal oxide constituting the additive core portion must be 5.0 ⁇ It is preferably 10 ⁇ 7 mol or more and 3.0 ⁇ 10 ⁇ 4 mol or less, preferably 1.0 ⁇ 10 ⁇ 6 mol or more and 5.0 ⁇ 10 ⁇ 5 mol or less, and 5.0 ⁇ 10 ⁇ More preferably, the amount is 6 mol or more and 3.0 ⁇ 10 ⁇ 5 mol or less.
  • Whether or not the additive has a coating made of metal oxide as described above can be determined by, for example, using a transmission electron microscope and observing the cross section of the additive at an acceleration voltage of 20 kV and a magnification of 4000 times. It can be carried out.
  • the additive in which a coating made of a metal oxide is formed on the surface of the core portion is preferably manufactured by applying a solution containing a metal element to the surface of the core portion and then heating the solution.
  • the metal element contained in the solution may be contained as a metal oxide, or may be contained as a metal compound other than a metal oxide, and may be converted into a metal oxide upon heating. Examples of this include ZrO(CH 3 COO) 2 , (NH 4 ) 6 Mo 7 O 24 , Ce(CH 3 COO) 3 ⁇ xH 2 O, and the like.
  • the solvent contained in the solution is preferably capable of dissolving the metal compound contained in the solution, from the viewpoint of making the thickness of the coating formed on the surface of the additive core more uniform.
  • solvents include water; alcohols such as methanol, ethanol, and ethylene glycol; aprotic polar solvents such as N,N-dimethylformamide and dimethyl sulfoxide; and ether solvents such as tetrahydrofuran and polyethylene glycol. These can be used alone or in combination.
  • the solvent contained in the solution has not only solubility but also a boiling point that evaporates when heated. More specifically, the boiling point of the solvent contained in the solution is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower. On the other hand, it is preferable that the boiling point of the solvent is 70° C. or higher from the viewpoint of facilitating handling.
  • Examples of methods for attaching the solution to the surface of the core portion of the additive include a method in which a coating liquid is impregnated with a transition metal oxide that will become the core portion of the additive.
  • the heating temperature when heating the additive with the solution attached to the surface of the core part depends on the type of metal element contained in the solution, but is preferably 200°C or more and 1300°C or less, and 300°C or more and 1200°C or less.
  • the temperature is more preferably 400°C or higher and 1100°C or lower.
  • the heating atmosphere when heating the additive whose solution is applied to the surface of the core part, and it may be an oxidizing atmosphere such as air, a reducing atmosphere such as hydrogen, or an inert atmosphere such as nitrogen or argon. Good too. From the viewpoint of cost and safety, an air atmosphere or a nitrogen atmosphere is preferable.
  • an air atmosphere or a nitrogen atmosphere is preferable.
  • the heating time when heating the additive whose solution is applied to the surface of the core part is preferably 0.25 hours or more and 3 hours or less, more preferably 0.5 hours or more and 2 hours or less, and even more preferably 0.25 hours or more and 3 hours or less, more preferably 0.5 hours or more and 2 hours or less, .75 hours or more and 1 hour or less.
  • the heating time is set to 0.25 hours or more, the solvent contained in the solution can be sufficiently volatilized and removed, and the metal compound contained in the solution can be converted into a metal oxide.
  • setting the heating time to 3 hours or less is advantageous in terms of economy.
  • the particle size of the additive is preferably 0.2 ⁇ m or more and 20.0 ⁇ m or less, more preferably 0.3 ⁇ m or more and 7.0 ⁇ m or less, and even more preferably 0.5 ⁇ m or more and 5.0 ⁇ m or less. From the viewpoint of handling properties, it is preferable that the particle size of the additive is 0.2 ⁇ m or more. In addition, when the particle size of the additive is 20.0 ⁇ m or less, irregularities on the electrode surface are reduced.
  • the particle size of the core part of the additive is preferably 0.2 ⁇ m or more and 20.0 ⁇ m or less, more preferably 0.3 ⁇ m or more and 7.0 ⁇ m or less, and preferably 0.5 ⁇ m or more and 5.0 ⁇ m or less. More preferred.
  • the particle size of the core portion is 0.2 ⁇ m or more, the solution can easily adhere to the surface of the core portion. Further, since the particle size of the core portion is 20.0 ⁇ m or less, irregularities on the electrode surface are reduced.
  • the above-mentioned additive and the particle size of its core portion refer to MA (area average diameter) obtained by laser diffraction scattering particle size distribution measurement. Note that the thickness of the coating portion is smaller than the particle size of the additive, and there is no difference in particle size before and after coating.
  • the proton conductive ceramics and additives can be mixed in a wet or dry manner, but it is preferable to do it in a dry manner from the viewpoint of simplicity. Further, mixing can be performed using, for example, a ball mill.
  • the mixing ratio of proton conductive ceramics and additives is preferably 0.11 or more and 1.50 or less, and 0.25 or more and 1.00 or less. is more preferable, and even more preferably 0.40 or more and 0.70 or less. By setting the mixing ratio within the above-mentioned range, the thickness of the covering portion can be easily set within the above-mentioned preferable range.
  • an electrode is formed by firing.
  • the firing temperature is preferably 900°C or more and 1300°C or less, more preferably 950°C or more and 1250°C or less, and even more preferably 1000°C or more and 1200°C or less.
  • the firing time is preferably 1 hour or more and 20 hours or less, more preferably 5 hours or more and 18 hours or less, and even more preferably 10 hours or more and 15 hours or less.
  • the heating atmosphere when firing the mixed powder of proton conductive ceramics and additives may be an oxidizing atmosphere such as air, a reducing atmosphere such as hydrogen, or an inert atmosphere such as nitrogen or argon. good. From the viewpoint of cost and safety, an air atmosphere or a nitrogen atmosphere is preferable.
  • Firing may be carried out by directly placing a mixed powder of proton conductive ceramics and additives on a firing plate, or by spreading a powder other than the mixed powder on the firing plate and placing the powder on top of the mixed powder. It may also be carried out by placing a mixed powder.
  • Another powder is a mixture of a proton-conducting ceramic represented by the composition formula AB 1-x M x O 3- ⁇ and a salt containing element A, that is, a mixture containing element A in excess of the proton-conducting ceramic. It is preferable to use a mixture of This makes it possible to more effectively suppress the production of by-products such as AM 2 NiO 5 and M 2 O 3 during firing, as shown in Examples below.
  • carbonate can be preferably used as the salt containing element A.
  • element A is barium
  • the mixture contains element A in excess of 0.5 mol % or more than the proton conductive ceramic.
  • a slurry containing a proton conductive ceramic of the same kind or a different kind as the proton conductive ceramic is applied to one side of the electrode formed as described above to form a coating film.
  • various conventionally known methods can be used. Examples of such methods include spin coating, roll coating, curtain coating, spraying, and inkjet methods. Among these, it is preferable to use a spin coating method because it is simple and the film thickness can be easily controlled.
  • the proton conductive ceramics contained in the slurry may be of the same type as the proton conductive ceramics contained in the electrode or of a different type; however, it is preferable that the proton conductive ceramics are of the same type as the proton conductive ceramics contained in the electrode. This is preferable from the viewpoint of increasing conductivity.
  • the slurry is one in which proton conductive ceramics are dispersed in a dispersion medium.
  • ⁇ -terpineol is preferably used as the dispersion medium. This is because ⁇ -terpineol exhibits excellent solubility in resins such as ethyl cellulose, which will be described later.
  • the slurry may contain components other than the proton conductive ceramic and the dispersion medium.
  • components other than the proton conductive ceramic and the dispersion medium include resins such as ethyl cellulose. Adding a resin has the advantage of improving the density of the solid electrolyte membrane.
  • the rotation speed is not particularly limited and can be appropriately selected depending on the desired film thickness and the type of dispersion medium.
  • the time for the spin coating method is also not particularly limited.
  • heating and drying may be performed as necessary to volatilize the dispersion medium and resin.
  • the heating temperature and heating time can be appropriately selected depending on the type of dispersion medium and resin, but for example, it is preferably 200°C or more and 1000°C or less, and preferably 500°C or more and 800°C or less. More preferred.
  • the heating drying time is also not particularly limited, and can be, for example, 1 hour or more and 3 hours or less. Heating may be carried out in an atmosphere that does not contain moisture but contains oxygen, and is preferably carried out, for example, in a dry air atmosphere.
  • Step of baking the coating film to form a solid electrolyte membrane Next, the coating film obtained as described above is fired to form a solid electrolyte membrane. Firing is performed in an oxygen-containing atmosphere.
  • the oxygen-containing atmosphere is preferably carried out in an atmosphere containing 10% by volume or more and 30% by volume or less of oxygen.
  • the temperature at which the coating film is fired is preferably 500°C or more and 2000°C or less, more preferably 1000°C or more and 1800°C or less, and even more preferably 1400°C or more and 1600°C or less.
  • the time for baking the coating film is preferably 2 hours or more and 20 hours or less, more preferably 5 hours or more and 18 hours or less, and even more preferably 10 hours or more and 15 hours or less.
  • compositional formula AB 1-x M x O 3- ⁇ (A represents at least one metal element selected from the group consisting of metal elements that can become divalent cations, and B consists of Ce and Zr.
  • M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, ⁇ represents the amount of oxygen vacancies, and 0 ⁇ x ⁇ 1, 0.0 ⁇ 0.5.
  • Composition formula AB 1-x M x O 3- ⁇ (A represents at least one metal element selected from the group consisting of elements that can become divalent cations, B represents the group consisting of Ce and Zr M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, ⁇ represents the amount of oxygen vacancies, and 0 ⁇ x ⁇ 1, 0.0 ⁇ 0.5);
  • An electrode located on one side of the solid electrolyte membrane and containing a nickel element, the bonded body comprising: Metals contained in the solid electrolyte membrane in the range of (a) or (b) below calculated by the following formula (1) when a cross section along the thickness direction of the bonded body is measured with an electron beam microanalyzer.
  • a bonded body in which the atomic ratio of nickel element to elements is 0.00% or more and 2.00% or less (a) A range of up to 5 ⁇ m in the thickness direction from the outermost surface of the solid electrolyte membrane toward the electrode side. (b) When the thickness of the solid electrolyte membrane is T, a range of up to 0.3T in the thickness direction from the outermost surface of the solid electrolyte membrane toward the electrode side.
  • Atomic ratio of nickel element (number of atoms of nickel element) / ⁇ (number of atoms of metal element represented by A) + (number of atoms of metal element represented by B) + (metal element represented by M (number of atoms of nickel element) + (number of atoms of nickel element) ⁇ (1)
  • the cross section is calculated by the following formula (2), starting from the outermost surface of the solid electrolyte membrane and directed toward the electrode side.
  • the atomic ratio of the nickel element to the metal element included in the range of up to 1 ⁇ m in the thickness direction is included in the range of up to 1 ⁇ m from the interface between the solid electrolyte membrane and the electrode toward the solid electrolyte membrane side.
  • Atomic ratio of nickel element (number of atoms of nickel element) / ⁇ (number of atoms of metal element represented by A) + (number of atoms of metal element represented by B) + (metal element represented by M (number of atoms of nickel element) + (number of atoms of nickel element) ⁇ (2)
  • the proton conductive ceramic has a composition formula BaZr 1-x M x O 3- ⁇ (M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, and ⁇ is The zygote according to any one of [1] to [5], which represents the amount of oxygen vacancies and satisfies 0 ⁇ x ⁇ 1, 0.0 ⁇ 0.5.
  • M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In
  • ⁇ is The zygote according to any one of [1] to [5], which represents the amount of oxygen vacancies and satisfies 0 ⁇ x ⁇ 1, 0.0 ⁇ 0.5.
  • An electrochemical cell comprising the conjugate according to any one of [1] to [6].
  • An electrochemical device comprising the electrochemical cell according to [7].
  • a solid electrolyte membrane containing proton-conducting ceramics A method for manufacturing a bonded body comprising: an electrode located on one side of the solid electrolyte membrane and containing a nickel element; mixing the proton conductive ceramic and an additive to form an electrode; forming a coating film by applying a slurry containing a proton conductive ceramic of the same kind or a different kind to the proton conductive ceramic on one side of the electrode; firing the coating film in an oxygen-containing atmosphere to form the solid electrolyte membrane, A method for producing a bonded body, wherein the additive includes a core portion and a coating portion that is located on the surface of the core portion and is made of an oxide.
  • a solution containing a metal element is attached to the surface of the core portion and then heated to obtain the additive in which the coating portion made of a metal oxide is formed on the surface of the core portion.[9 The manufacturing method described in ]. [11] The manufacturing method according to [9] or [10], wherein the core portion contains nickel oxide. [12] The manufacturing method according to any one of [9] to [11], wherein the oxide contains an oxide of at least one metal element selected from the group consisting of Zr, Mo, and Ce.
  • the proton conductive ceramic has a composition formula BaZr 1-x M x O 3- ⁇ (M represents at least one metal element selected from the group consisting of trivalent rare earth elements and In, and ⁇ is The manufacturing method according to any one of [9] to [12], which represents the amount of oxygen vacancies and satisfies 0 ⁇ x ⁇ 1, 0.0 ⁇ 0.5.
  • Example 1 Manufacture of additives
  • Zirconium oxyacetate Zircosol ZA-30, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., 54.2 mg
  • water 9 mL
  • NiO 10 g
  • the residue thus obtained was heated at 550° C. for 1 hour in the air to obtain an additive powder having a coating portion made of zirconium oxide and a core portion made of NiO.
  • the particle size of the resulting additive powder was 1.98 ⁇ m, and the number of moles of the metal element constituting the coating per gram of transition metal oxide (NiO) constituting the additive core was 1.92 ⁇ 10 ⁇ It was 5 mol. (molding of electrode) 3 g of the additive thus obtained and 2 g of BaZr 0.8 Y 0.2 O 2.9 powder, which is a proton conductive ceramic having a perovskite structure, were mixed in a dry manner. This mixed powder was spread with a mixture of BaZr 0.8 Y 0.2 O 2.9 and barium carbonate (containing 1 mol% more Ba element than BaZr 0.8 Y 0.2 O 2.9 ).
  • the electrode was molded by placing it on a baking dish and baking it at 1000° C. for 10 hours in an air atmosphere.
  • a slurry consisting of BaZr 0.8 Y 0.2 O 2.9 powder (1 part by mass), ethyl cellulose (0.04 parts by mass), and ⁇ -terpineol (0.96 parts by mass) was placed on one side of the electrode. was applied to form a coating film. The slurry was applied by spin coating.
  • the area ratio (%) of the oxide represented by the compositional formula BaY 2 NiO 5 was calculated as follows. First, by translating the curve representing the outermost surface 4 of the solid electrolyte membrane observed in the backscattered electron image shown in FIG. 1 by 5 ⁇ m in the thickness direction toward the electrode side, a virtual curve 5 is obtained. Ta.
  • the range (range 6) sandwiched between the outermost surface 4 of the solid electrolyte membrane and the curve 5 is a range up to 5 ⁇ m in the thickness direction starting from the outermost surface 4 of the solid electrolyte membrane toward the electrode side, and this Within the range, the area ratio of the oxide represented by the compositional formula BaY 2 NiO 5 and the oxide represented by Y 2 O 3 was measured.
  • one measurement point was randomly selected from within a range of up to 1 ⁇ m in the thickness direction toward the electrode side.
  • the atomic ratio of the nickel element was measured at this measurement point, and the value was taken as the atomic ratio of the nickel element on the outermost surface of the solid electrolyte membrane.
  • the straight line L one measurement point was randomly selected from within the range up to 1 ⁇ m toward the solid electrolyte membrane side.
  • the atomic ratio of the nickel element was measured at this measurement point, and the value was taken as the atomic ratio of the nickel element at the interface between the solid electrolyte membrane and the electrode.
  • Example 2 The same procedure was carried out except that a solution was prepared using (NH 4 ) 6 Mo 7 O 24 (manufactured by Kishida Chemical Co., Ltd., 0.226 g) instead of zirconium oxyacetate, and the coating portion of the additive was made of molybdenum oxide. A zygote was obtained in the same manner as in Example 1. Table 1 shows various measured values of the obtained joined body. In addition, the particle size of the additive powder produced in Example 2 was 2.80 ⁇ m, and the number of moles of the metal element constituting the coating per 1 g of transition metal oxide (NiO) constituting the additive core was It was 1.34 ⁇ 10 ⁇ 4 mol.
  • Example 3 Except that a solution was prepared using Ce(CH 3 COO) 3.xH 2 O (manufactured by Kishida Chemical Co., Ltd., 0.061 g) instead of zirconium oxyacetate, and the coating portion of the additive was made of cerium oxide. A bonded body was obtained in the same manner as in Example 1. Table 1 shows various measured values of the obtained joined body. Note that "-" regarding the solid electrolyte membrane in Table 1 indicates that it has not been measured. Furthermore, the particle size of the additive powder produced in Example 3 was 2.49 ⁇ m, and the mol number of the metal element constituting the coating portion per 1 g of transition metal oxide constituting the additive core was 1.92. It was ⁇ 10 ⁇ 5 mol.
  • Example 4 The wet mixing of BaZr 0.8 Y 0.2 O 2.9 powder and an additive having a core made of NiO, and the wet mixing of BaZr 0.8 Y 0.2 O 2.9 powder and barium carbonate.
  • a bonded body was obtained in the same manner as in Example 1, except that the mixture was not spread over the baking dish.
  • Table 2 shows various measured values of the obtained joined body. Note that "-" regarding the solid electrolyte membrane in Table 2 indicates that it has not been measured.
  • Example 5 A joined body was obtained in the same manner as in Example 1, except that BaZr 0.8 Y 0.2 O 2.9 powder and an additive having a core made of NiO were wet mixed. Table 2 shows various measured values of the obtained joined body. Note that "-" regarding the solid electrolyte membrane in Table 2 indicates that it has not been measured.
  • Example 6 A bonded body was obtained in the same manner as in Example 1, except that the particle size of the additive having a core made of NiO was changed to 1.76 ⁇ m. Table 2 shows various measured values of the obtained joined body. Note that "-" regarding the solid electrolyte membrane in Table 2 indicates that it has not been measured.
  • Example 1 A bonded body was obtained in the same manner as in Example 1 except that NiO without a coating was used as an additive instead of the additive with a coating. Table 1 shows various measured values of the obtained joined body.
  • a bonded body that suppresses the reaction between proton conductive ceramics and nickel element in a solid electrolyte membrane, and a method for manufacturing the same.

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Abstract

La présente invention concerne un corps lié comprenant : une membrane à électrolyte solide contenant une céramique conductrice de protons représentée par la formule de composition AB1-xMxO3-δ ; et une électrode disposée sur l'une des surfaces de la membrane à électrolyte solide et contenant un élément de nickel. Dans une image obtenue par la réalisation d'un mappage élémentaire au moyen d'une spectroscopie à rayons X à dispersion d'énergie par microscope électronique à balayage sur une coupe transversale dans la direction de l'épaisseur du corps lié, la proportion surfacique totale d'un oxyde représenté par la formule de composition AM2NiO5 et d'un oxyde représenté par la formule de composition M2O3, observée dans une plage spécifique, est inférieure ou égale à 30,0 %, par rapport à l'ensemble du champ de vision observé.
PCT/JP2023/025350 2022-07-07 2023-07-07 Corps lié et son procédé de fabrication WO2024010094A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1021930A (ja) * 1996-06-27 1998-01-23 Tokyo Gas Co Ltd 固体電解質型燃料電池の燃料極
JP2011514644A (ja) * 2008-03-18 2011-05-06 テクニカル ユニヴァーシティー オブ デンマーク 全セラミックス固体酸化物形電池
JP2018088384A (ja) * 2016-04-19 2018-06-07 パナソニックＩｐマネジメント株式会社 電気化学デバイスの膜電極接合体、燃料電池、電気化学的水素ポンプ、および水素センサ
JP2020068195A (ja) * 2018-10-18 2020-04-30 パナソニックＩｐマネジメント株式会社 膜電極接合体および燃料電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1021930A (ja) * 1996-06-27 1998-01-23 Tokyo Gas Co Ltd 固体電解質型燃料電池の燃料極
JP2011514644A (ja) * 2008-03-18 2011-05-06 テクニカル ユニヴァーシティー オブ デンマーク 全セラミックス固体酸化物形電池
JP2018088384A (ja) * 2016-04-19 2018-06-07 パナソニックＩｐマネジメント株式会社 電気化学デバイスの膜電極接合体、燃料電池、電気化学的水素ポンプ、および水素センサ
JP2020068195A (ja) * 2018-10-18 2020-04-30 パナソニックＩｐマネジメント株式会社 膜電極接合体および燃料電池

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