WO2023171299A1 - 電気化学セル - Google Patents

電気化学セル Download PDF

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Publication number
WO2023171299A1
WO2023171299A1 PCT/JP2023/005529 JP2023005529W WO2023171299A1 WO 2023171299 A1 WO2023171299 A1 WO 2023171299A1 JP 2023005529 W JP2023005529 W JP 2023005529W WO 2023171299 A1 WO2023171299 A1 WO 2023171299A1
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WIPO (PCT)
Prior art keywords
electrode layer
main surface
hydrogen electrode
average thickness
metal support
Prior art date
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PCT/JP2023/005529
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English (en)
French (fr)
Japanese (ja)
Inventor
春香 千葉
俊之 中村
玄太 寺澤
誠 大森
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2024506001A priority Critical patent/JP7604715B2/ja
Publication of WO2023171299A1 publication Critical patent/WO2023171299A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/63—Holders for electrodes; Positioning of the electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • 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
    • 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 an electrochemical cell.
  • the electrochemical cell described in Patent Document 1 includes a cell main body in which a first electrode layer, an electrolyte layer, and a second electrode layer are laminated in this order on the main surface of a metal support.
  • the electrolyte layer covers the first electrode layer and has an end connected to the main surface of the cell body.
  • An object of the present invention is to provide an electrochemical cell whose rigidity can be improved.
  • An electrochemical cell includes: a metal support having a plurality of supply holes formed on a main surface; a first electrode layer formed on the main surface and covering the plurality of supply holes;
  • the cell body includes two electrode layers and an electrolyte layer disposed between the first electrode layer and the second electrode layer.
  • the electrolyte layer covers the surface of the first electrode layer in a cross section perpendicular to the main surface, and covers the inner part at least a predetermined distance from the tip of the first electrode layer in the direction parallel to the main surface, and the main part of the metal support.
  • An outer portion that covers substantially the entire area of the surface exposed from the first electrode layer and is located a predetermined distance or more from the tip of the first electrode layer in the surface direction, and an intermediate portion that is sandwiched between the inner portion and the outer portion in the surface direction. It has a department.
  • the average thickness of the middle part is greater than the average thickness of the inner part.
  • the electrochemical cell according to the second aspect of the present invention is related to the first aspect, and the average thickness of the middle part is larger than the average thickness of the outer part.
  • the electrochemical cell according to the third aspect of the present invention relates to the first or second side, and the predetermined distance is one-half the thickness of the metal support.
  • the electrochemical cell according to the fourth aspect of the present invention relates to any one of the first to third aspects, and the average thickness of the intermediate part is the average thickness of three places dividing the intermediate part into four in the surface direction.
  • the average thickness of the inner part is the average value of the thicknesses at three points that equally divide the part of the inner part up to a predetermined distance from the middle part in the surface direction into four parts.
  • the electrochemical cell according to the fifth aspect of the present invention relates to any one of the second to fourth aspects, and the average thickness of the intermediate portion is the average thickness of three places dividing the intermediate portion into four in the surface direction.
  • the average thickness of the outer portion is the average value of the thicknesses at three locations dividing the outer portion into four equal parts in the surface direction.
  • An electrochemical cell according to a sixth aspect of the present invention relates to any one of the first to fifth aspects, and the first electrode layer has a side surface formed along the thickness direction perpendicular to the surface direction, The sides are uneven.
  • FIG. 1 is a plan view of an electrolysis cell according to an embodiment.
  • FIG. 2 is a sectional view taken along line AA in FIG.
  • FIG. 3 is a partially enlarged view of FIG. 2.
  • FIG. 4 is a cross-sectional view of an electrolytic cell according to Modification Example 1.
  • FIG. 1 is a plan view of an electrolytic cell 1 according to an embodiment.
  • FIG. 2 is a sectional view taken along line AA in FIG.
  • the electrolytic cell 1 is an example of an "electrochemical cell" according to the present invention.
  • the electrolytic cell 1 is formed into a plate shape that extends in the X-axis direction and the Y-axis direction.
  • the electrolytic cell 1 is formed into a rectangle extending in the Y-axis direction in plan view.
  • the planar shape of the electrolytic cell 1 is not particularly limited, and may be a polygon other than a rectangle, an ellipse, a circle, or the like.
  • the electrolytic cell 1 includes a cell main body 10, a metal support 20, and a channel member 30.
  • the cell main body 10 includes a hydrogen electrode layer 6 (cathode), an electrolyte layer 7, a reaction prevention layer 8, and an oxygen electrode layer 9 (anode).
  • the hydrogen electrode layer 6, the electrolyte layer 7, the reaction prevention layer 8, and the oxygen electrode layer 9 are laminated in this order from the metal support 20 side in the Z-axis direction perpendicular to the X-axis direction and the Y-axis direction.
  • the hydrogen electrode layer 6, the electrolyte layer 7, and the oxygen electrode layer 9 are essential structures, and the reaction prevention layer 8 is an optional structure.
  • Hydrogen electrode layer 6 is arranged between metal support 20 and electrolyte layer 7. Hydrogen electrode layer 6 is supported by metal support 20 . Specifically, the hydrogen electrode layer 6 is arranged on the first main surface 20S of the metal support 20. The hydrogen electrode layer 6 covers the plurality of supply holes 21 formed in the first main surface 20S of the metal support 20. A portion of the hydrogen electrode layer 6 may enter into each supply hole 21 .
  • the hydrogen electrode layer 6 is an example of the "first electrode layer" according to the present invention.
  • Raw material gas is supplied to the hydrogen electrode 6 through each supply hole 21 .
  • the source gas contains at least H 2 O.
  • the hydrogen electrode 6 When the source gas contains only H 2 O, the hydrogen electrode 6 generates H 2 from the source gas according to the electrochemical reaction of water electrolysis shown in equation (1) below.
  • ⁇ Hydrogen electrode 6 H 2 O + 2e - ⁇ H 2 + O 2 - (1)
  • the hydrogen electrode 6 extracts H 2 and CO from the raw material gas according to the electrochemical reaction of co-electrolysis shown in the following equations (2), (3), and (4). and O 2- is produced.
  • ⁇ Hydrogen electrode 6 CO 2 +H 2 O+4e - ⁇ CO+H 2 +2O 2-...
  • ⁇ Electrochemical reaction of H 2 O H 2 O + 2e - ⁇ H 2 + O 2 - (3)
  • ⁇ Electrochemical reaction of CO 2 CO 2 +2e - ⁇ CO + O 2 -... (4)
  • the hydrogen electrode layer 6 is made of a porous material having electron conductivity.
  • the hydrogen electrode layer 6 may have oxide ion conductivity.
  • the hydrogen electrode layer 6 is made of, for example, 8 mol% yttria-stabilized zirconia (8YSZ), calcia-stabilized zirconia (CSZ), scandia-stabilized zirconia (ScSZ), gadolinium-doped ceria (GDC), samarium-doped ceria (SDC), (La ,Sr)(Cr, Mn)O3, (La,Sr)TiO3, Sr2(Fe,Mo)2O6 , ( La , Sr) VO3 , (La,Sr) FeO3 , and among these It can be composed of a mixed material combining two or more of them, or a composite of one or more of these and NiO.
  • the value of the thermal expansion coefficient of the hydrogen electrode layer 6 is not particularly limited, but can be, for example, 12 ⁇ 10 ⁇ 6 /°C or more and 20 ⁇ 10 ⁇ 6 /°C or less.
  • the porosity of the hydrogen electrode layer 6 is not particularly limited, but can be, for example, 5% or more and 70% or less.
  • the thickness of the hydrogen electrode layer 6 is not particularly limited, but may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the method for forming the hydrogen electrode layer 6 is not particularly limited, and may include a baking method, a spray coating method (thermal spray method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spray method, etc.) ), PVD method (sputtering method, pulsed laser deposition method, etc.), CVD method, etc. can be used.
  • a baking method a spray coating method (thermal spray method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spray method, etc.)
  • PVD method sputtering method, pulsed laser deposition method, etc.
  • CVD method etc.
  • Electrolyte layer 7 is arranged between hydrogen electrode layer 6 and oxygen electrode layer 9.
  • the reaction prevention layer 8 is arranged between the electrolyte layer 7 and the oxygen electrode layer 9
  • the electrolyte layer 7 is arranged between the hydrogen electrode layer 6 and the reaction prevention layer 8
  • the reaction prevention layer 8 is arranged between the hydrogen electrode layer 6 and the reaction prevention layer 8. 6 and reaction prevention layer 8, respectively.
  • the electrolyte layer 7 covers the hydrogen electrode layer 6 and also covers the region of the first main surface 20S of the metal support 20 that is exposed from the hydrogen electrode layer 6. As shown in FIG. 1, the electrolyte layer 7 covers the entire surface of the hydrogen electrode layer 6 in plan view. As shown in FIG. 1, it is preferable that the electrolyte layer 7 covers the entire region of the first main surface 20S exposed from the hydrogen electrode layer 6 in plan view, but a part of the first main surface 20S may be exposed from the electrolyte layer 7. The detailed structure of the electrolyte layer 7 will be described later.
  • the electrolyte layer 7 transmits O 2 ⁇ generated in the hydrogen electrode layer 6 to the oxygen electrode layer 9 side.
  • the electrolyte layer 7 is made of a dense material having oxide ion conductivity.
  • the electrolyte layer 7 is made of, for example, YSZ (yttria-stabilized zirconia, e.g. 8YSZ), GDC (gadolinium-doped ceria), ScSZ (scandia-stabilized zirconia), SDC (samarium solid solution ceria), LSGM (lanthanum gallate), or the like. be able to.
  • the value of the thermal expansion coefficient of the electrolyte layer 7 is not particularly limited, but may be, for example, 10 ⁇ 10 ⁇ 6 /°C or more and 12 ⁇ 10 ⁇ 6 /°C or less.
  • the porosity of the electrolyte layer 7 is not particularly limited, but can be, for example, 0.1% or more and 7% or less.
  • the thickness of the electrolyte layer 7 is not particularly limited, but may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the method for forming the electrolyte layer 7 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, etc. can be used.
  • Reaction prevention layer 8 is arranged between electrolyte layer 7 and oxygen electrode layer 9.
  • the reaction prevention layer 8 is arranged on the opposite side of the hydrogen electrode layer 6 with respect to the electrolyte layer 7.
  • the reaction prevention layer 8 prevents the constituent elements of the electrolyte layer 7 from reacting with the constituent elements of the oxygen electrode layer 9 to form a layer with high electrical resistance.
  • the reaction prevention layer 8 is made of an oxide ion conductive material.
  • the reaction prevention layer 8 can be made of GDC, SDC, or the like.
  • the porosity of the reaction prevention layer 8 is not particularly limited, but may be, for example, 0.1% or more and 50% or less.
  • the thickness of the reaction prevention layer 8 is not particularly limited, but may be, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the method for forming the reaction prevention layer 8 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, etc. can be used.
  • the oxygen electrode layer 9 is arranged on the opposite side of the hydrogen electrode layer 6 with respect to the electrolyte layer 7.
  • the reaction prevention layer 8 since the reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9, the oxygen electrode layer 9 is connected to the reaction prevention layer 8.
  • the reaction prevention layer 8 is not disposed between the electrolyte layer 7 and the oxygen electrode layer 9, the oxygen electrode layer 9 is connected to the electrolyte layer 7.
  • the oxygen electrode layer 9 is an example of the "second electrode layer" according to the present invention.
  • the oxygen electrode layer 9 generates O 2 from O 2 ⁇ transmitted from the hydrogen electrode layer 6 through the electrolyte layer 7 according to the chemical reaction of equation (2) below.
  • ⁇ Oxygen electrode layer 9 2O 2- ⁇ O 2 +4e - (2)
  • the oxygen electrode layer 9 is made of a porous material having oxide ion conductivity and electron conductivity.
  • the oxygen electrode layer 9 is made of, for example, (La,Sr)(Co,Fe) O3 , (La,Sr) FeO3 , La(Ni,Fe) O3 , (La,Sr) CoO3 , and (Sm,Sr). ) CoO 3 and an oxide ion conductive material (GDC, etc.).
  • the porosity of the oxygen electrode layer 9 is not particularly limited, but can be, for example, 20% or more and 60% or less.
  • the thickness of the oxygen electrode layer 9 is not particularly limited, but may be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the method of forming the oxygen electrode layer 9 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, etc. can be used.
  • the metal support 20 supports the cell main body 10 .
  • the metal support 20 is formed into a plate shape.
  • the metal support 20 may have a flat plate shape or a curved plate shape.
  • the thickness of the metal support 20 is not particularly limited as long as it can maintain the strength of the electrolytic cell 1, and may be, for example, 0.1 mm or more and 2.0 mm or less.
  • the metal support 20 has a plurality of supply holes 21, a first main surface 20S, and a second main surface 20T.
  • the first main surface 20S is an example of the "main surface” according to the present invention.
  • Each supply hole 21 is formed on the first main surface 20S.
  • Each supply hole 21 penetrates the metal support 20 from the first main surface 20S to the second main surface 20T.
  • Each supply hole 21 opens on the first main surface 20S and the second main surface 20T, respectively.
  • the opening of the first main surface 20S of each supply hole 21 is covered with the hydrogen electrode layer 6. That is, each supply hole 21 is formed in a region of the first main surface 20S that is joined to the hydrogen electrode layer 6.
  • Each supply hole 21 is connected to a flow path 30a between the metal support 20 and the flow path member 30.
  • Each supply hole 21 can be formed by mechanical processing (for example, punching process), laser processing, chemical processing (for example, etching process), or the like. Furthermore, when the metal support 20 is made of porous metal, each supply hole 21 may be an open pore of the porous metal. Each supply hole 21 may be perpendicular to the first main surface 20S, may not be perpendicular to the first main surface 20S, and may not be linear.
  • the cell main body portion 10 is joined to the first main surface 20S.
  • the flow path member 30 is joined to the second main surface 20T.
  • the first main surface 20S is provided on the opposite side of the second main surface 20T.
  • the metal support 20 is made of a metal material.
  • the metal support 20 is made of an alloy material containing Cr (chromium).
  • Examples of such metal materials include Fe--Cr alloy steel (such as stainless steel) and Ni--Cr alloy steel.
  • the content of Cr in the metal support 20 is not particularly limited, but can be 4% by mass or more and 30% by mass or less.
  • the metal support 20 may contain Ti (titanium) or Zr (zirconium).
  • the content of Ti in the metal support 20 is not particularly limited, but can be set to 0.01 mol% or more and 1.0 mol% or less.
  • the Al content in the metal support 20 is not particularly limited, but can be set to 0.01 mol% or more and 0.4 mol% or less.
  • the metal support 20 may contain Ti as TiO 2 (titania) or Zr as ZrO 2 (zirconia).
  • the value of the thermal expansion coefficient of the metal support 20 is not particularly limited, it can be, for example, 10 ⁇ 10 ⁇ 6 /°C or more and 20 ⁇ 10 ⁇ 6 /°C or less.
  • the metal support 20 may have an oxide film formed by oxidation of the constituent elements of the metal support 20 on its surface.
  • a typical example of the oxide film is a chromium oxide film.
  • the chromium oxide film covers at least a portion of the surface of the metal support 20. Further, the chromium oxide film may cover at least a portion of the inner wall surface of each supply hole 21.
  • the flow path member 30 is joined to the second main surface 20T of the metal support 20.
  • the channel member 30 forms a channel 30a between it and the metal support 20.
  • a raw material gas is supplied to the flow path 30a.
  • the raw material gas supplied to the flow path 30a is supplied to the hydrogen electrode layer 6 of the cell main body 10 via each supply hole 21 of the metal support 20.
  • the flow path member 30 can be made of an alloy material, for example.
  • the flow path member 30 may be formed of the same material as the metal support 20.
  • the channel member 30 may be substantially integral with the metal support 20.
  • the flow path member 30 has a frame 31 and an interconnector 32.
  • the frame body 31 is an annular member that surrounds the sides of the flow path 30a.
  • the frame 31 is joined to the second main surface 20T of the metal support 20.
  • the interconnector 32 is a plate-like member for electrically connecting an external power source or another electrolytic cell to the electrolytic cell 1 in series.
  • the interconnector 32 is joined to the frame 31.
  • the frame 31 and the interconnector 32 are separate members, but the frame 31 and the interconnector 32 may be an integrated member.
  • FIG. 3 is a partially enlarged view of FIG. 2.
  • FIG. 3 is a cross section perpendicular to the first main surface 20S of the metal support 20.
  • FIG. 3 a cross section of the outer peripheral portion of the electrolytic cell 1 is illustrated.
  • the electrolyte layer 7 has an inner part 71, an outer part 72, and an intermediate part 73.
  • the inner part 71 is surrounded by the intermediate part 73, and the intermediate part 73 is surrounded by the outer part 72.
  • the inner part 71 covers the surface of the hydrogen electrode layer 6 and is spaced from the tip P6 of the hydrogen electrode layer 6 by a predetermined distance D1 or more in the plane direction.
  • the inner part 71 is a part of the electrolyte layer 7 on the first reference line L1 and inside the first reference line L1.
  • the inside means the side from the tip P20 of the first main surface 20S toward the tip P6 of the hydrogen electrode layer 6 in the planar direction.
  • the first reference line L1 is a straight line that is parallel to the second reference line L2 and set a predetermined distance D1 inward from the second reference line L2.
  • the second reference line L2 is a straight line that passes through the tip P6 of the hydrogen electrode layer 6 and is perpendicular to the first main surface 20S.
  • the predetermined distance D1 is one half of the thickness Ta of the metal support 20 on the second reference line L2. The reason why the predetermined distance D1 is defined based on the thickness Ta of the metal support 20 is to specify the portion of the hydrogen electrode layer 6 close to the tip P6 as the intermediate portion 73.
  • the second reference line L2 a straight line obtained by straightening the first main surface 20S using the least squares method on a cross-sectional image (for example, a SEM image) is used as the first main surface 20S.
  • a cross-sectional image for example, a SEM image
  • the tip P6 of the hydrogen electrode layer 6 is located on the first main surface 20S, but the tip P6 of the hydrogen electrode layer 6 may be separated from the first main surface 20S.
  • the outer portion 72 covers substantially the entire region of the first main surface 20S that is exposed from the hydrogen electrode layer 6, and is spaced from the tip P6 of the hydrogen electrode layer 6 by a predetermined distance D1 or more in the surface direction. Covering substantially the entire region of the first main surface 20S exposed from the hydrogen electrode layer 6 means that the outer portion 72 covers the first main surface 20S up to the tip P20.
  • the outer portion 72 is a portion of the electrolyte layer 7 on and outside the third reference line L3.
  • the outer side means the side from the tip P6 of the hydrogen electrode layer 6 toward the tip P20 of the first main surface 20S in the plane direction.
  • the third reference line L3 is a straight line that is parallel to the second reference line L2 and set outward from the second reference line L2 by a predetermined distance D1.
  • the intermediate portion 73 is sandwiched between the inner portion 71 and the outer portion 72 in the plane direction.
  • the intermediate portion 73 is a portion of the electrolyte layer 7 between the first reference line L1 and the third reference line L3.
  • the intermediate part 73 is arranged outside the inner part 71 and inside the outer part 72.
  • the intermediate portion 73 is continuous with both the inner portion 71 and the outer portion 72.
  • the boundary between the intermediate portion 73 and the inner portion 71 is defined by the first reference line L1.
  • the boundary between the intermediate portion 73 and the outer portion 72 is defined by the third reference line L3.
  • the center of the intermediate portion 73 in the surface direction is defined by the second reference line L2.
  • the average thickness of the intermediate portion 73 is greater than the average thickness of the inner portion 71.
  • the average thickness of the intermediate portion 73 is the average value of the thicknesses T1, T2, and T3 at three locations that divide the intermediate portion 73 into four equal parts in the surface direction.
  • the thicknesses T1, T2, and T3 of the intermediate portion 73 are the thicknesses measured at three locations that equally divide the area between the first reference line L1 and the third reference line L3 into four in the surface direction.
  • thickness means thickness in the Z-axis direction (thickness direction).
  • the average thickness of the inner portion 71 is the average value of the thicknesses T4, T5, and T6 at three points that equally divide the portion of the inner portion 71 from the first reference line L1 to a predetermined distance D1 in the surface direction into four parts.
  • the thicknesses T4, T5, and T6 of the inner side portion 71 are the thicknesses measured at three locations that equally divide the space between the first reference line L1 and the fourth reference line L4 into four in the surface direction.
  • the fourth reference line L4 is a line symmetrical to the second reference line L2 with respect to the first reference line L1.
  • the fourth reference line L4 is a straight line that is parallel to the first reference line L1 and is set inward from the second reference line L2 by twice the predetermined distance D1.
  • the predetermined distance D1 is one half of the thickness Ta of the metal support 20 on the first reference line L1.
  • the average thickness of the intermediate portion 73 is not particularly limited, but may be, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • the average thickness of the inner portion 71 is not particularly limited, but may be, for example, 3 ⁇ m or more and 50 ⁇ m or less. Further, the average thickness of the intermediate portion 73 is greater than the average thickness of the outer portion 72. The average thickness of the intermediate portion 73 is measured as described above.
  • the average thickness of the outer portion 72 is the average value of the thicknesses T7, T8, and T9 at three locations that divide the outer portion 72 into four equal parts.
  • the thicknesses T7, T8, and T9 of the outer portion 72 are the thicknesses measured at three locations that equally divide the area from the third reference line L3 to the tip P7 of the electrolyte layer 7 into four in the surface direction.
  • the tip P7 of the electrolyte layer 7 is located outside the tip P20 of the first main surface 20S in the plane direction, but is located on the tip P20 of the first main surface 20S or on the first main surface It may be located inside the tip P20 of 20S.
  • the average thickness of the outer portion 72 is not particularly limited, but may be, for example, 3 ⁇ m or more and 50 ⁇ m or less.
  • the average thickness of the outer part 72 may be larger or smaller than the average thickness of the inner part 71, or may be the same as the average thickness of the inner part 71.
  • the outer part 72 may have a protrusion 72a.
  • the protruding portion 72a is a portion of the outer portion 72 that protrudes to the outside of the first main surface 20S of the metal support 20. That is, the protruding portion 72a is a portion of the outer portion 72 located outside the tip P20 of the first main surface 20S.
  • the protruding portion 72a of the outer portion 72 covers at least a portion of the side surface 20U of the metal support 20. Thereby, the side surface 20U can be covered with the protrusion 72a, so that heat radiation from the metal support 20 can be further suppressed.
  • the electrolyte layer 7 has an inner part 71, an outer part 72, and an intermediate part 73.
  • the inner part 71 covers the surface of the hydrogen electrode layer 6 and is spaced from the tip P6 of the hydrogen electrode layer 6 by a predetermined distance D1 or more in the plane direction.
  • the outer portion 72 covers substantially the entire region of the first main surface 20S that is exposed from the hydrogen electrode layer 6, and is spaced from the tip P6 of the hydrogen electrode layer 6 by a predetermined distance D1 or more in the surface direction.
  • the intermediate portion 73 is sandwiched between the inner portion 71 and the outer portion 72 in the plane direction. The average thickness of the intermediate portion 73 is greater than the average thickness of the inner portion 71.
  • the outer portion 72 improves not only the rigidity of the metal support 20 but also the rigidity of the dense electrolyte layer 7. can also be applied to the outer periphery of the electrolytic cell 1. Therefore, the rigidity of the electrolytic cell 1 as a whole can be improved.
  • the average thickness of the intermediate portion 73 is larger than the average thickness of the inner portion 71, it is possible to suppress the occurrence of cracks in the electrolyte layer 7 starting near the tip P6 of the hydrogen electrode layer 6. Specifically, it is as follows.
  • the temperature of the metal support 20 made of a metal material increases more easily than that of the cell main body 10 made of ceramic.
  • the temperature of the hydrogen electrode layer 6 in contact with the metal support 20 tends to rise, but the temperature of the portion of the electrolyte layer 7 disposed on the hydrogen electrode layer 6 is difficult to rise. Therefore, thermal stress is generated between the portion of the electrolyte layer 7 disposed on the hydrogen electrode layer 6 and the hydrogen electrode layer 6 . Further, the temperature of the portion of the electrolyte layer 7 that contacts the metal support 20 tends to rise, but the temperature of the portion of the electrolyte layer 7 disposed on the hydrogen electrode layer 6 does not easily rise.
  • thermal stress tends to concentrate near the tip P6 of the hydrogen electrode layer 6, but as mentioned above, by making the average thickness of the intermediate part 73 larger than the average thickness of the inner part 71, the strength of the intermediate part 73 is increased. There is. Therefore, it is possible to suppress the occurrence of cracks starting in the vicinity of the tip P6 of the hydrogen electrode layer 6 in the intermediate portion 73. If cracks occur in the intermediate portion 73, part of the function of the electrolyte layer 7 will be lost, so it is important to suppress cracks in the intermediate portion 73.
  • the average thickness of the intermediate portion 73 is greater than the average thickness of the outer portion 72. Therefore, it is easier to increase the thickness of the intermediate portion 73, so that the strength of the intermediate portion 73 can be sufficiently increased. Therefore, it is possible to further suppress the occurrence of cracks starting near the tip P6 of the hydrogen electrode layer 6 in the intermediate portion 73.
  • the thickness of the hydrogen electrode layer 6 gradually becomes thinner as it approaches the tip P6, but the thickness is not limited to this.
  • the thickness of the hydrogen electrode layer 6 may be substantially constant throughout. Even in this case, by setting the first to fourth reference lines L1 to L4 based on the tip P6 of the hydrogen electrode layer 6, the inner part 71, the outer part 72, and the intermediate part 73 are defined, and these lines are also defined. The average thickness of can be determined.
  • the hydrogen electrode layer 6 has a side surface 6S formed along the Z-axis direction, it is preferable that unevenness is formed on the side surface 6S. As a result, the strength of the interface between the hydrogen electrode layer 6 and the electrolyte layer 7 can be increased, so that damage caused by thermal stress during temperature rise and fall can be reduced.
  • the average thickness of the intermediate part 73 is larger than the average thickness of the inner part 71 in the cross section shown in FIG.
  • the configuration shown in FIG. 3 is preferably observed in all cross sections of the outer circumferential portion of the electrolytic cell 1, but it is sufficient if it can be observed in at least one cross section of the outer circumferential portion of the electrolytic cell 1. This is because if the configuration shown in FIG. 3 is observed even in one cross section, it is possible to suppress the occurrence of cracks in the intermediate portion 73 at least at that location.
  • the hydrogen electrode layer 6 functions as a cathode and the oxygen electrode layer 9 functions as an anode, but even if the hydrogen electrode layer 6 functions as an anode and the oxygen electrode layer 9 functions as a cathode, good.
  • the constituent materials of the hydrogen electrode layer 6 and the oxygen electrode layer 9 are exchanged, and the raw material gas is caused to flow over the outer surface of the hydrogen electrode layer 6.
  • the electrolytic cell 1 has been described as an example of an electrochemical cell, but the electrochemical cell is not limited to an electrolytic cell.
  • An electrochemical cell consists of an element with a pair of electrodes arranged so that an electromotive force is generated from the overall redox reaction, and an element that converts chemical energy into electrical energy. It is a generic term. Therefore, electrochemical cells include, for example, fuel cells that use oxide ions or protons as carriers.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005158297A (ja) * 2003-11-20 2005-06-16 Nissan Motor Co Ltd 固体電解質型燃料電池
JP2006324190A (ja) * 2005-05-20 2006-11-30 Shinko Electric Ind Co Ltd 固体酸化物型燃料電池およびその製造方法
JP2011204505A (ja) * 2010-03-26 2011-10-13 Ngk Insulators Ltd 燃料電池セル
JP2016072216A (ja) * 2014-09-30 2016-05-09 Toto株式会社 固体酸化物形燃料電池セルスタック
JP2016154096A (ja) * 2015-02-20 2016-08-25 三菱日立パワーシステムズ株式会社 固体酸化物形燃料電池及び固体酸化物形燃料電池の製造方法
JP2020095984A (ja) * 2020-03-23 2020-06-18 大阪瓦斯株式会社 電気化学素子、電気化学モジュール、電気化学装置、エネルギーシステム、固体酸化物形燃料電池、および電気化学素子製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005158297A (ja) * 2003-11-20 2005-06-16 Nissan Motor Co Ltd 固体電解質型燃料電池
JP2006324190A (ja) * 2005-05-20 2006-11-30 Shinko Electric Ind Co Ltd 固体酸化物型燃料電池およびその製造方法
JP2011204505A (ja) * 2010-03-26 2011-10-13 Ngk Insulators Ltd 燃料電池セル
JP2016072216A (ja) * 2014-09-30 2016-05-09 Toto株式会社 固体酸化物形燃料電池セルスタック
JP2016154096A (ja) * 2015-02-20 2016-08-25 三菱日立パワーシステムズ株式会社 固体酸化物形燃料電池及び固体酸化物形燃料電池の製造方法
JP2020095984A (ja) * 2020-03-23 2020-06-18 大阪瓦斯株式会社 電気化学素子、電気化学モジュール、電気化学装置、エネルギーシステム、固体酸化物形燃料電池、および電気化学素子製造方法

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