WO2023171299A1 - Electrochemical cell - Google Patents

Electrochemical cell 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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WO
WIPO (PCT)
Prior art keywords
electrode layer
main surface
hydrogen electrode
average thickness
metal support
Prior art date
Application number
PCT/JP2023/005529
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French (fr)
Japanese (ja)
Inventor
春香 千葉
俊之 中村
玄太 寺澤
誠 大森
Original Assignee
日本碍子株式会社
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Priority to JP2024506001A priority Critical patent/JPWO2023171299A1/ja
Publication of WO2023171299A1 publication Critical patent/WO2023171299A1/en

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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

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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Abstract

An electrolyte layer (7) comprises an inner part (71), an outer part (72) and a middle part (73). The inner part (71) covers the surface of a hydrogen electrode layer (6) and is estranged from the tip (P6) of the hydrogen electrode layer (6) in the surface direction by at least a set distance (D1). The outer part (72) covers approximately all of a region of a first main surface (20S) that is exposed from the hydrogen electrode layer (6) and is estranged from the tip (P6) of the hydrogen electrode layer (6) in the surface direction by at least the set distance (D1). The middle part (73) lies between the inner part (71) and the outer part (72), in the surface direction. The average thickness of the middle part (73) is greater than the average thickness of the inner part (71).

Description

電気化学セルelectrochemical cell
　本発明は、電気化学セルに関する。 The present invention relates to an electrochemical cell.
　電気化学セル（電解セル、燃料電池など）において、金属支持体によってセル本体部を支持する構造が知られている。例えば、特許文献１に記載された電気化学セルは、第１電極層、電解質層、及び第２電極層がこの順で金属支持体の主面上に積層されたセル本体部を備える。電解質層は、第１電極層を覆っており、その端部はセル本体部の主面に接続されている。 In electrochemical cells (electrolytic cells, fuel cells, etc.), a structure in which the cell body is supported by a metal support is known. For example, 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.
特開２０２０－１５５３３７号JP2020-155337
　しかしながら、特許文献１に記載の電気化学セルでは、金属支持体の外周部が電解質層から露出しているため、電気化学セルの外周部の剛性は、金属支持体だけの剛性に委ねられている。 However, in the electrochemical cell described in Patent Document 1, the outer periphery of the metal support is exposed from the electrolyte layer, so the rigidity of the outer periphery of the electrochemical cell is left to the rigidity of the metal support alone. .
　本発明の課題は、剛性を向上可能な電気化学セルを提供することにある。 An object of the present invention is to provide an electrochemical cell whose rigidity can be improved.
　本発明の第１の側面に係る電気化学セルは、主面に形成された複数の供給孔を有する金属支持体と、主面上に形成され複数の供給孔を覆う第１電極層と、第２電極層と、第１電極層及び第２電極層の間に配置される電解質層とを有するセル本体部とを備える。電解質層は、主面に垂直な断面において、第１電極層の表面を覆い、主面に平行な面方向において第１電極層の先端から所定距離以上離れた内側部と、金属支持体の主面のうち第１電極層から露出する領域の略全部を覆い、面方向において第１電極層の先端から所定距離以上離れた外側部と、面方向において内側部と外側部の間に挟まれる中間部とを有する。中間部の平均厚みは、内側部の平均厚みより大きい。 An electrochemical cell according to a first aspect of the present invention 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.
　本発明の第２の側面に係る電気化学セルは、第１の側面に係り、中間部の平均厚みは、外側部の平均厚みより大きい。 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.
　本発明の第３の側面に係る電気化学セルは、第１又は第２の側面に係り、所定距離は、金属支持体の厚みの２分の１である。 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.
　本発明の第４の側面に係る電気化学セルは、第１乃至第３いずれかの側面に係り、中間部の平均厚みは、面方向において中間部を４等分する３か所における厚みの平均値であり、内側部の平均厚みは、内側部のうち面方向において中間部から所定距離までの部分を４等分する３か所における厚みの平均値である。 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.
　本発明の第５の側面に係る電気化学セルは、第２乃至第４いずれかの側面に係り、中間部の平均厚みは、面方向において中間部を４等分する３か所における厚みの平均値であり、外側部の平均厚みは、面方向において外側部を４等分する３か所における厚みの平均値である。 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.
　本発明の第６の側面に係る電気化学セルは、第１乃至第５いずれかの側面に係り、第１電極層は、面方向に垂直な厚み方向に沿って形成される側面を有し、側面には凹凸が形成されている。 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.
　本発明によれば、剛性を向上可能な電気化学セルを提供することができる。 According to the present invention, it is possible to provide an electrochemical cell whose rigidity can be improved.
図１は、実施形態に係る電解セルの平面図である。FIG. 1 is a plan view of an electrolysis cell according to an embodiment. 図２は、図１のＡ－Ａ断面図である。FIG. 2 is a sectional view taken along line AA in FIG. 図３は、図２の部分拡大図である。FIG. 3 is a partially enlarged view of FIG. 2. 図４は、変形例１に係る電解セルの断面図である。FIG. 4 is a cross-sectional view of an electrolytic cell according to Modification Example 1.
　（電解セル１）
　図１は、実施形態に係る電解セル１の平面図である。図２は、図１のＡ－Ａ断面図である。電解セル１は、本発明に係る「電気化学セル」の一例である。 (Electrolysis cell 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.
　電解セル１は、Ｘ軸方向及びＹ軸方向に広がる板状に形成される。本実施形態において、電解セル１は、平面視においてＹ軸方向に延びる長方形に形成される。ただし、電解セル１の平面形状は特に限られず、長方形以外の多角形、楕円形、円形などであってもよい。 The electrolytic cell 1 is formed into a plate shape that extends in the X-axis direction and the Y-axis direction. In this embodiment, the electrolytic cell 1 is formed into a rectangle extending in the Y-axis direction in plan view. However, 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.
　図２に示すように、電解セル１は、セル本体部１０、金属支持体２０、及び流路部材３０を備える。 As shown in FIG. 2, the electrolytic cell 1 includes a cell main body 10, a metal support 20, and a channel member 30.
　［セル本体部１０］
　セル本体部１０は、水素極層６（カソード）、電解質層７、反応防止層８、及び酸素極層９（アノード）を有する。水素極層６、電解質層７、反応防止層８、及び酸素極層９は、Ｘ軸方向及びＹ軸方向に垂直なＺ軸方向において、この順で金属支持体２０側から積層されている。水素極層６、電解質層７、及び酸素極層９は必須の構成であり、反応防止層８は任意の構成である。 [Cell body part 10]
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.
　［水素極層６］
　水素極層６は、金属支持体２０及び電解質層７の間に配置される。水素極層６は、金属支持体２０によって支持される。詳細には、水素極層６は、金属支持体２０の第１主面２０Ｓ上に配置される。水素極層６は、金属支持体２０の第１主面２０Ｓに形成された複数の供給孔２１を覆う。水素極層６の一部は、各供給孔２１内に入り込んでいてよい。水素極層６は、本発明に係る「第１電極層」の一例である。 [Hydrogen pole layer 6]
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.
　水素極６には、各供給孔２１を介して原料ガスが供給される。原料ガスは、少なくともＨ２Ｏを含む。 Raw material gas is supplied to the hydrogen electrode 6 through each supply hole 21 . The source gas contains at least H 2 O.
　原料ガスがＨ２Ｏのみを含む場合、水素極６は、下記（１）式に示す水電解の電気化学反応に従って、原料ガスからＨ２を生成する。
　・水素極６：Ｈ２Ｏ＋２ｅ－→Ｈ２＋Ｏ２－・・・（１） 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)
　原料ガスがＨ２Ｏに加えてＣＯ２を含む場合、水素極６は、下記（２）、（３）、（４）式に示す共電解の電気化学反応に従って、原料ガスからＨ２、ＣＯ及びＯ２－を生成する。
　・水素極６：ＣＯ２＋Ｈ２Ｏ＋４ｅ－→ＣＯ＋Ｈ２＋２Ｏ２－・・・（２）
　・Ｈ２Ｏの電気化学反応：Ｈ２Ｏ＋２ｅ－→Ｈ２＋Ｏ２－・・・（３）
　・ＣＯ２の電気化学反応：ＣＯ２＋２ｅ－→ＣＯ＋Ｏ２－・・・（４） When the raw material gas contains CO 2 in addition to H 2 O, 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-... (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)
　水素極層６は、電子伝導性を有する多孔質材料によって構成される。水素極層６は、酸化物イオン伝導性を有していてよい。水素極層６は、例えば、８ｍｏｌ％イットリア安定化ジルコニア（８ＹＳＺ）、カルシア安定化ジルコニア（ＣＳＺ）、スカンジア安定化ジルコニア（ＳｃＳＺ）、ガドリニウムドープセリア（ＧＤＣ）、サマリウムドープセリア（ＳＤＣ）、（Ｌａ，Ｓｒ）（Ｃｒ，Ｍｎ）Ｏ３、（Ｌａ，Ｓｒ）ＴｉＯ３、Ｓｒ２（Ｆｅ,Ｍｏ）２Ｏ６、（Ｌａ，Ｓｒ）ＶＯ３、（Ｌａ，Ｓｒ）ＦｅＯ３、及びこれらのうち２つ以上を組み合わせた混合材料、或いは、これらのうち１つ以上とＮｉＯとの複合物によって構成することができる。 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.
　水素極層６の熱膨張係数の値は特に限られないが、例えば１２×１０―６／℃以上２０×１０－６／℃以下とすることができる。 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.
　水素極層６の気孔率は特に制限されないが、例えば５％以上７０％以下とすることができる。水素極層６の厚みは特に制限されないが、例えば１μｍ以上１００μｍ以下とすることができる。 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 μm or more and 100 μm or less.
　水素極層６の形成方法は特に制限されず、焼成法、スプレーコーティング法（溶射法、エアロゾルデポジション法、エアロゾルガスデポジッション法、パウダージェットデポジッション法、パーティクルジェットデポジション法、コールドスプレー法など）、ＰＶＤ法（スパッタリング法、パルスレーザーデポジション法など）、ＣＶＤ法などを用いることができる。 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.
　［電解質層７］
　電解質層７は、水素極層６及び酸素極層９の間に配置される。本実施形態では、電解質層７及び酸素極層９の間に反応防止層８が配置されているので、電解質層７は、水素極層６及び反応防止層８の間に配置され、水素極層６及び反応防止層８それぞれに接続される。 [Electrolyte layer 7]
Electrolyte layer 7 is arranged between hydrogen electrode layer 6 and oxygen electrode layer 9. In this embodiment, since 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, and 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.
　電解質層７は、水素極層６を覆うとともに、金属支持体２０の第１主面２０Ｓのうち水素極層６から露出する領域を覆う。図１に示すように、電解質層７は、平面視において、水素極層６の表面の全体を覆っている。図１に示すように、電解質層７は、平面視において、第１主面２０Ｓのうち水素極層６から露出する領域の全体を覆っていることが好ましいが、第１主面２０Ｓの一部が電解質層７から露出していてもよい。電解質層７の詳細な構成については後述する。 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.
　電解質層７は、水素極層６において生成されたＯ２－を酸素極層９側に伝達させる。電解質層７は、酸化物イオン伝導性を有する緻密質材料によって構成される。電解質層７は、例えば、ＹＳＺ（イットリア安定化ジルコニア、例えば８ＹＳＺ）、ＧＤＣ（ガドリニウムドープセリア）、ＳｃＳＺ（スカンジア安定化ジルコニア）、ＳＤＣ（サマリウム固溶セリア）、ＬＳＧＭ（ランタンガレート）などによって構成することができる。 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.
　電解質層７の熱膨張係数の値は特に限られないが、例えば１０×１０―６／℃以上１２×１０―６／℃以下とすることができる。 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.
　電解質層７の気孔率は特に制限されないが、例えば０．１％以上７％以下とすることができる。電解質層７の厚みは特に制限されないが、例えば１μｍ以上１００μｍ以下とすることができる。 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 μm or more and 100 μm or less.
　電解質層７の形成方法は特に制限されず、焼成法、スプレーコーティング法、ＰＶＤ法、ＣＶＤ法などを用いることができる。 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.
　［反応防止層８］
　反応防止層８は、電解質層７及び酸素極層９の間に配置される。反応防止層８は、電解質層７を基準として水素極層６の反対側に配置される。反応防止層８は、電解質層７の構成元素が酸素極層９の構成元素と反応して電気抵抗の大きい層が形成されることを抑制する。 [Reaction prevention layer 8]
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.
　反応防止層８は、酸化物イオン伝導性材料によって構成される。反応防止層８は、ＧＤＣ、ＳＤＣなどによって構成することができる。 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.
　反応防止層８の気孔率は特に制限されないが、例えば０．１％以上５０％以下とすることができる。反応防止層８の厚みは特に制限されないが、例えば１μｍ以上５０μｍ以下とすることができる。 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 μm or more and 50 μm or less.
　反応防止層８の形成方法は特に制限されず、焼成法、スプレーコーティング法、ＰＶＤ法、ＣＶＤ法などを用いることができる。 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.
　［酸素極層９］
　酸素極層９は、電解質層７を基準として水素極層６の反対側に配置される。本実施形態では、電解質層７及び酸素極層９の間に反応防止層８が配置されているので、酸素極層９は反応防止層８に接続される。電解質層７及び酸素極層９の間に反応防止層８が配置されない場合、酸素極層９は電解質層７に接続される。酸素極層９は、本発明に係る「第２電極層」の一例である。 [Oxygen electrode layer 9]
The oxygen electrode layer 9 is arranged on the opposite side of the hydrogen electrode layer 6 with respect to the electrolyte layer 7. In this embodiment, 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. When 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.
　酸素極層９は、下記（２）式の化学反応に従って、水素極層６から電解質層７を介して伝達されるＯ２－からＯ２を生成する。
　・酸素極層９：２Ｏ２－→Ｏ２＋４ｅ－・・・（２） 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)
　酸素極層９は、酸化物イオン伝導性及び電子伝導性を有する多孔質材料によって構成される。酸素極層９は、例えば（Ｌａ，Ｓｒ）（Ｃｏ，Ｆｅ）Ｏ３、（Ｌａ，Ｓｒ）ＦｅＯ３、Ｌａ（Ｎｉ，Ｆｅ）Ｏ３、（Ｌａ，Ｓｒ）ＣｏＯ３、及び（Ｓｍ，Ｓｒ）ＣｏＯ３のうち１つ以上と酸化物イオン伝導材料（ＧＤＣなど）との複合材料によって構成することができる。 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.).
　酸素極層９の気孔率は特に制限されないが、例えば２０％以上６０％以下とすることができる。酸素極層９の厚みは特に制限されないが、例えば１μｍ以上１００μｍ以下とすることができる。 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 μm or more and 100 μm or less.
　酸素極層９の形成方法は特に制限されず、焼成法、スプレーコーティング法、ＰＶＤ法、ＣＶＤ法などを用いることができる。 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.
　［金属支持体２０］
　金属支持体２０は、セル本体部１０を支持する。金属支持体２０は、板状に形成される。金属支持体２０は、平板状であってもよいし、曲板状であってもよい。金属支持体２０は電解セル１の強度を保つことができればよく、その厚みは特に制限されないが、例えば０．１ｍｍ以上２．０ｍｍ以下とすることができる。 [Metal support 20]
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.
　図２に示すように、金属支持体２０は、複数の供給孔２１、第１主面２０Ｓ及び第２主面２０Ｔを有する。第１主面２０Ｓは、本発明に係る「主面」の一例である。 As shown in FIG. 2, 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.
　各供給孔２１は、第１主面２０Ｓに形成される。各供給孔２１は、第１主面２０Ｓから第２主面２０Ｔまで金属支持体２０を貫通する。各供給孔２１は、第１主面２０Ｓ及び第２主面２０Ｔそれぞれに開口する。各供給孔２１の第１主面２０Ｓの開口は、水素極層６によって覆われる。すなわち、各供給孔２１は、第１主面２０Ｓのうち水素極層６に接合される領域に形成される。各供給孔２１は、金属支持体２０及び流路部材３０の間の流路３０ａに繋がる。 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.
　各供給孔２１は、機械加工（例えば、パンチング加工）、レーザ加工、或いは、化学加工（例えば、エッチング加工）などによって形成することができる。また、金属支持体２０が多孔質金属によって構成される場合、各供給孔２１は多孔質金属の開気孔であってよい。各供給孔２１は、第１主面２０Ｓに対して垂直であってもよいし、第１主面２０Ｓに対して垂直でなくてもよいし、直線状でなくてもよい。 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.
　第１主面２０Ｓには、セル本体部１０が接合される。第２主面２０Ｔには、流路部材３０が接合される。第１主面２０Ｓは、第２主面２０Ｔの反対側に設けられる。 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.
　金属支持体２０は、金属材料によって構成される。例えば、金属支持体２０は、Ｃｒ（クロム）を含有する合金材料によって構成される。このような金属材料としては、Ｆｅ－Ｃｒ系合金鋼（ステンレス鋼など）やＮｉ－Ｃｒ系合金鋼などが挙げられる。金属支持体２０におけるＣｒの含有率は特に制限されないが、４質量％以上３０質量％以下とすることができる。 The metal support 20 is made of a metal material. For example, 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.
　金属支持体２０は、Ｔｉ（チタン）やＺｒ（ジルコニウム）を含有していてもよい。金属支持体２０におけるＴｉの含有率は特に制限されないが、０．０１ｍｏｌ％以上１．０ｍｏｌ％以下とすることができる。金属支持体２０におけるＡｌの含有率は特に制限されないが、０．０１ｍｏｌ％以上０．４ｍｏｌ％以下とすることができる。金属支持体２０は、ＴｉをＴｉＯ２（チタニア）として含有していてもよいし、ＺｒをＺｒＯ２（ジルコニア）として含有していてもよい。 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).
　金属支持体２０の熱膨張係数の値は特に限られないが、例えば１０×１０―６／℃以上２０×１０―６／℃以下とすることができる。 Although 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.
　金属支持体２０は、金属支持体２０の構成元素が酸化することによって形成される酸化皮膜を表面に有していてよい。酸化膜としては、例えば酸化クロム膜が代表的である。酸化クロム膜は、金属支持体２０の表面の少なくとも一部を覆う。また、酸化クロム膜は、各供給孔２１の内壁面の少なくとも一部を覆っていてもよい。 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.
　［流路部材３０］
　流路部材３０は、金属支持体２０の第２主面２０Ｔに接合される。流路部材３０は、金属支持体２０との間に流路３０ａを形成する。流路３０ａには、原料ガスが供給される。流路３０ａに供給された原料ガスは、金属支持体２０の各供給孔２１を介して、セル本体部１０の水素極層６に供給される。 [Flow path member 30]
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.
　流路部材３０は、例えば、合金材料によって構成することができる。流路部材３０は、金属支持体２０と同様の材料によって形成されていてよい。この場合、流路部材３０は、金属支持体２０と実質的に一体であってよい。 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. In this case, the channel member 30 may be substantially integral with the metal support 20.
　流路部材３０は、枠体３１及びインターコネクタ３２を有する。枠体３１は、流路３０ａの側方を取り囲む環状部材である。枠体３１は、金属支持体２０の第２主面２０Ｔに接合される。インターコネクタ３２は、外部電源又は他の電解セルを電解セル１と電気的に直列に接続するための板状部材である。インターコネクタ３２は、枠体３１に接合される。 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.
　本実施形態では、枠体３１とインターコネクタ３２が別部材となっているが、枠体３１とインターコネクタ３２は一体の部材であってよい。 In this embodiment, the frame 31 and the interconnector 32 are separate members, but the frame 31 and the interconnector 32 may be an integrated member.
　［電解質層７の構成］
　図３は、図２の部分拡大図である。図３は、金属支持体２０の第１主面２０Ｓに垂直な断面である。図３では、電解セル１の外周部の断面が図示されている。 [Configuration of electrolyte layer 7]
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. In FIG. 3, a cross section of the outer peripheral portion of the electrolytic cell 1 is illustrated.
　図３に示すように、電解質層７は、内側部７１、外側部７２及び中間部７３を有する。金属支持体２０の第１主面２０Ｓに平行な面方向（図３に示すＸ軸方向）において、内側部７１は中間部７３によって取り囲まれ、中間部７３は外側部７２によって取り囲まれている。 As shown in FIG. 3, the electrolyte layer 7 has an inner part 71, an outer part 72, and an intermediate part 73. In the plane direction parallel to the first main surface 20S of the metal support 20 (X-axis direction shown in FIG. 3), the inner part 71 is surrounded by the intermediate part 73, and the intermediate part 73 is surrounded by the outer part 72.
　内側部７１は、水素極層６の表面を覆い、かつ、面方向において水素極層６の先端Ｐ６から所定距離Ｄ１以上離れている。内側部７１は、電解質層７のうち、第１基準線Ｌ１上及び第１基準線Ｌ１より内側の部分である。本明細書において、内側とは、面方向において第１主面２０Ｓの先端Ｐ２０から水素極層６の先端Ｐ６に向かう側を意味する。 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. In this specification, 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.
　第１基準線Ｌ１は、第２基準線Ｌ２と平行であり、かつ、第２基準線Ｌ２から所定距離Ｄ１だけ内側に設定される直線である。第２基準線Ｌ２は、水素極層６の先端Ｐ６を通り、かつ、第１主面２０Ｓに垂直な直線である。所定距離Ｄ１は、第２基準線Ｌ２上における金属支持体２０の厚みＴａの２分の１である。金属支持体２０の厚みＴａを基準として所定距離Ｄ１を規定するのは、水素極層６の先端Ｐ６に近接する部分を中間部７３として特定するためである。 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.
　なお、第２基準線Ｌ２を規定する場合、断面画像（例えば、ＳＥＭ画像）上において、第１主面２０Ｓを最小二乗法により直線化して得られる直線を第１主面２０Ｓとして用いる。また、図３では、水素極層６の先端Ｐ６が第１主面２０Ｓ上に位置しているが、水素極層６の先端Ｐ６は第１主面２０Ｓから離れていてもよい。 Note that when defining 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. Further, in FIG. 3, 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.
　外側部７２は、第１主面２０Ｓのうち水素極層６から露出する領域の略全部を覆い、かつ、面方向において水素極層６の先端Ｐ６から所定距離Ｄ１以上離れている。第１主面２０Ｓのうち水素極層６から露出する領域の略全部を覆うとは、外側部７２が第１主面２０Ｓの先端Ｐ２０まで覆っていることを意味する。外側部７２は、電解質層７のうち、第３基準線Ｌ３上及び第３基準線Ｌ３より外側の部分である。本明細書において、外側とは、面方向において水素極層６の先端Ｐ６から第１主面２０Ｓの先端Ｐ２０に向かう側を意味する。第３基準線Ｌ３は、第２基準線Ｌ２と平行であり、かつ、第２基準線Ｌ２から所定距離Ｄ１だけ外側に設定される直線である。 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. In this specification, 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.
　中間部７３は、面方向において内側部７１と外側部７２の間に挟まれている。中間部７３は、電解質層７のうち、第１基準線Ｌ１と第３基準線Ｌ３の間の部分である。中間部７３は、内側部７１の外側かつ外側部７２の内側に配置される。中間部７３は、内側部７１と外側部７２の両方に連なる。中間部７３と内側部７１の境界は、第１基準線Ｌ１によって規定される。中間部７３と外側部７２の境界は、第３基準線Ｌ３によって規定される。面方向における中間部７３の中央は、第２基準線Ｌ２によって規定される。 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.
　ここで、中間部７３の平均厚みは、内側部７１の平均厚みより大きい。 Here, the average thickness of the intermediate portion 73 is greater than the average thickness of the inner portion 71.
　中間部７３の平均厚みは、面方向において中間部７３を４等分する３か所における厚みＴ１，Ｔ２，Ｔ３の平均値である。中間部７３の厚みＴ１，Ｔ２，Ｔ３は、第１基準線Ｌ１及び第３基準線Ｌ３の間を面方向に４等分する３か所において測定される厚みである。本明細書において、厚みとは、Ｚ軸方向（厚み方向）における厚みを意味する。 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. In this specification, thickness means thickness in the Z-axis direction (thickness direction).
　内側部７１の平均厚みは、内側部７１のうち面方向において第１基準線Ｌ１から所定距離Ｄ１までの部分を４等分する３か所における厚みＴ４、Ｔ５，Ｔ６の平均値である。内側部７１の厚みＴ４、Ｔ５，Ｔ６は、第１基準線Ｌ１及び第４基準線Ｌ４の間を面方向に４等分する３か所において測定される厚みである。第４基準線Ｌ４は、第１基準線Ｌ１を基準として、第２基準線Ｌ２と線対称な線である。第４基準線Ｌ４は、第１基準線Ｌ１と平行であり、かつ、第２基準線Ｌ２から所定距離Ｄ１の２倍だけ内側に設定される直線である。上述の通り、所定距離Ｄ１は、第１基準線Ｌ１上における金属支持体２０の厚みＴａの２分の１である。 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. As described above, the predetermined distance D1 is one half of the thickness Ta of the metal support 20 on the first reference line L1.
　中間部７３の平均厚みは特に限られないが、例えば１０μｍ以上１００μｍ以下とすることができる。内側部７１の平均厚みは特に限られないが、例えば３μｍ以上５０μｍ以下とすることができる。また、中間部７３の平均厚みは、外側部７２の平均厚みより大きい。中間部７３の平均厚みは、上述した通りに測定される。 The average thickness of the intermediate portion 73 is not particularly limited, but may be, for example, 10 μm or more and 100 μm or less. The average thickness of the inner portion 71 is not particularly limited, but may be, for example, 3 μm or more and 50 μm 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.
　外側部７２の平均厚みは、外側部７２を４等分する３か所における厚みＴ７、Ｔ８，Ｔ９の平均値である。外側部７２の厚みＴ７、Ｔ８，Ｔ９は、第３基準線Ｌ３から電解質層７の先端Ｐ７までを面方向に４等分する３か所において測定される厚みである。本実施形態では、面方向において、電解質層７の先端Ｐ７は、第１主面２０Ｓの先端Ｐ２０より外側に位置しているが、第１主面２０Ｓの先端Ｐ２０上、又は、第１主面２０Ｓの先端Ｐ２０より内側に位置していてもよい。 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. In this embodiment, 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.
　外側部７２の平均厚みは特に限られないが、例えば３μｍ以上５０μｍ以下とすることができる。外側部７２の平均厚みは、内側部７１の平均厚みより大きくても小さくてもよく、また、内側部７１の平均厚みと同じであってもよい。 The average thickness of the outer portion 72 is not particularly limited, but may be, for example, 3 μm or more and 50 μm 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.
　図３に示すように、外側部７２は、突出部７２ａを有していてもよい。突出部７２ａは、外側部７２のうち金属支持体２０の第１主面２０Ｓの外側にはみ出た部分である。すなわち、突出部７２ａは、外側部７２のうち第１主面２０Ｓの先端Ｐ２０より外側に位置する部分である。 As shown in FIG. 3, 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.
　図示しないが、外側部７２の突出部７２ａは、金属支持体２０の側面２０Ｕの少なくとも一部を覆っていることが好ましい。これによって、側面２０Ｕを突出部７２ａで被覆できるため、金属支持体２０からの放熱をさらに抑制することができる。 Although not shown, it is preferable that 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.
　（特徴） (Features)
　（１）電解質層７は、図３に示すように、内側部７１、外側部７２及び中間部７３を有する。内側部７１は、水素極層６の表面を覆い、かつ、面方向において水素極層６の先端Ｐ６から所定距離Ｄ１以上離れている。外側部７２は、第１主面２０Ｓのうち水素極層６から露出する領域の略全部を覆い、かつ、面方向において水素極層６の先端Ｐ６から所定距離Ｄ１以上離れている。中間部７３は、面方向において内側部７１と外側部７２の間に挟まれている。中間部７３の平均厚みは、内側部７１の平均厚みより大きい。 (1) As shown in FIG. 3, 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.
　このように、外側部７２が第１主面２０Ｓのうち水素極層６から露出する領域の略全部を覆っていることによって、金属支持体２０の剛性だけでなく緻密質な電解質層７の剛性をも電解セル１の外周部に付与することができる。従って、電解セル１全体の剛性を向上させることができる。 In this way, by covering substantially the entire region of the first main surface 20S that is exposed from the hydrogen electrode layer 6, 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.
　また、中間部７３の平均厚みが内側部７１の平均厚みより大きいため、水素極層６の先端Ｐ６付近を起点とするクラックが電解質層７に発生することを抑制できる。具体的には、次の通りである。 Furthermore, since 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.
　電解セル１の起動時、金属材料によって構成される金属支持体２０は、セラミックスによって構成されるセル本体部１０よりも昇温しやすい。このとき、金属支持体２０と接触する水素極層６の温度は上昇しやすいが、電解質層７のうち水素極層６上に配置される部分の温度は上昇しにくい。そのため、電解質層７のうち水素極層６上に配置される部分と水素極層６との間に熱応力が生じる。また、電解質層７のうち金属支持体２０と接触する部分の温度は上昇しやすいが、電解質層７のうち水素極層６上に配置される部分の温度は上昇しにくい。そのため、水素極層６の先端Ｐ６付近に熱応力が集中しやすいが、上述の通り、中間部７３の平均厚みを内側部７１の平均厚みより大きくすることによって中間部７３の強度が増大されている。従って、水素極層６の先端Ｐ６付近を起点とするクラックが中間部７３に発生することを抑制できる。中間部７３にクラックが生じれば電解質層７の機能の一部が失われてしまうため、中間部７３のクラックを抑制することは重要である。 When the electrolytic cell 1 is started, 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. At this time, 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. Therefore, 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.
　（２）中間部７３の平均厚みは、外側部７２の平均厚みより大きい。従って、中間部７３の厚みをより厚くしやすいため、中間部７３の強度を十分増大できる。そのため、水素極層６の先端Ｐ６付近を起点とするクラックが中間部７３に発生することをより抑制できる。 (2) 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.
　（実施形態の変形例）
　以上、本発明の実施形態について説明したが、本発明はこれらに限定されるものではなく、本発明の趣旨を逸脱しない限りにおいて種々の変更が可能である。 (Modified example of embodiment)
Although the embodiments of the present invention have been described above, the present invention is not limited to these, and various changes can be made without departing from the spirit of the present invention.
　［変形例１］
　上記実施形態において、水素極層６の厚みは、図３に示したように、先端Ｐ６に近づくほど徐々に薄くなることとしたが、これに限られない。例えば、図４に示すように、水素極層６の厚みは全体的に略一定であってもよい。この場合であっても、水素極層６の先端Ｐ６を基準として第１乃至第４基準線Ｌ１～Ｌ４を設定することによって、内側部７１、外側部７２及び中間部７３を規定するとともに、これらの平均厚みを求めることができる。 [Modification 1]
In the above embodiment, as shown in FIG. 3, 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. For example, as shown in FIG. 4, 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.
　図４に示すように、水素極層６がＺ軸方向に沿って形成される側面６Ｓを有する場合、側面６Ｓには凹凸が形成されていることが好ましい。これによって、水素極層６と電解質層７の界面強度を高めることができるため、昇降温時の熱応力による破損を低減することができる。 As shown in FIG. 4, when 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.
　［変形例２］
　上記実施形態では、図３に示した一断面において、中間部７３の平均厚みが内側部７１の平均厚みより大きいことを説明した。図３に示した構成は、電解セル１の外周部の全ての断面において観察されることが好ましいが、電解セル１の外周部の少なくとも一断面において観察できればよい。図３に示した構成が一断面でも観察されるのであれば、少なくとも当該箇所では中間部７３にクラックが発生することを抑制できるからである。 [Modification 2]
In the above embodiment, it has been explained that 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.
　［変形例３］
　上記実施形態において、水素極層６はカソードとして機能し、酸素極層９はアノードとして機能することとしたが、水素極層６がアノードとして機能し、酸素極層９がカソードとして機能してもよい。この場合、水素極層６と酸素極層９の構成材料を入れ替えるとともに、水素極層６の外表面に原料ガスを流す。 [Modification 3]
In the above embodiment, 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. In this case, 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.
　［変形例４］
　上記実施形態では、電気化学セルの一例として電解セル１について説明したが、電気化学セルは電解セルに限られない。電気化学セルとは、電気エネルギーを化学エネルギーに変えるため、全体的な酸化還元反応から起電力が生じるように一対の電極が配置された素子と、化学エネルギーを電気エネルギーに変えるための素子との総称である。従って、電気化学セルには、例えば、酸化物イオン或いはプロトンをキャリアとする燃料電池が含まれる。 [Modification 4]
In the above embodiment, 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.
１　　　セル
６　　　水素極層
７　　　電解質層
７１　　内側部
７２　　外側部
７３　　中間部
８　　　反応防止層
９　　　酸素極層
１０　　セル本体部
２０　　金属支持体
２０Ｓ　第１主面
２１　　供給孔
３０　　流路部材
３０ａ　流路
Ｌ１～Ｌ４　　第１乃至第４基準線
Ｐ２０　　第１主面の先端
Ｐ６　　水素極層の先端
Ｄ１　　所定距離 1 Cell 6 Hydrogen electrode layer 7 Electrolyte layer 71 Inner part 72 Outer part 73 Intermediate part 8 Reaction prevention layer 9 Oxygen electrode layer 10 Cell body part 20 Metal support 20S First main surface 21 Supply hole 30 Channel member 30a Channel L1 ～L4 First to fourth reference line P20 Tip of first main surface P6 Tip of hydrogen electrode layer D1 Predetermined distance

Claims (6)

  1. 　主面に形成された複数の供給孔を有する金属支持体と、
    　前記主面上に形成され、前記複数の供給孔を覆う第１電極層と、第２電極層と、前記第１電極層及び前記第２電極層の間に配置される電解質層とを有するセル本体部と、
    を備え、
    　前記電解質層は、前記主面に垂直な断面において、
    　前記第１電極層の表面を覆い、前記主面に平行な面方向において前記第１電極層の先端から所定距離以上離れた内側部と、
    　前記金属支持体の前記主面のうち前記第１電極層から露出する領域の略全部を覆い、前記面方向において前記第１電極層の先端から所定距離以上離れた外側部と、
    　前記面方向において前記内側部と前記外側部の間に挟まれる中間部と、
    を有し、
    　前記中間部の平均厚みは、前記内側部の平均厚みより大きい、
    電気化学セル。     a metal support having a plurality of supply holes formed on the main surface;
    A cell having a first electrode layer formed on the main surface and covering the plurality of supply holes, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer. The main body and
    Equipped with
    The electrolyte layer has, in a cross section perpendicular to the main surface,
    an inner part that covers the surface of the first electrode layer and is spaced a predetermined distance or more from the tip of the first electrode layer in a plane direction parallel to the main surface;
    an outer portion that covers substantially the entire area of the main surface of the metal support that is exposed from the first electrode layer and is spaced a predetermined distance or more from the tip of the first electrode layer in the surface direction;
    an intermediate part sandwiched between the inner part and the outer part in the surface direction;
    has
    The average thickness of the intermediate part is greater than the average thickness of the inner part.
    electrochemical cell.
  2. 　前記中間部の平均厚みは、前記外側部の平均厚みより大きい、
    請求項１に記載の電気化学セル。     The average thickness of the intermediate portion is greater than the average thickness of the outer portion.
    An electrochemical cell according to claim 1.
  3. 　前記所定距離は、前記金属支持体の厚みの２分の１である、
    請求項１に記載の電気化学セル。     the predetermined distance is one-half the thickness of the metal support;
    An electrochemical cell according to claim 1.
  4. 　前記中間部の平均厚みは、前記面方向において前記中間部を４等分する３か所における厚みの平均値であり、
    　前記内側部の平均厚みは、前記内側部のうち前記面方向において前記中間部から前記所定距離までの部分を４等分する３か所における厚みの平均値である、
    請求項１に記載の電気化学セル。     The average thickness of the intermediate portion is the average value of the thickness at three locations dividing the intermediate portion into four equal parts in the surface direction,
    The average thickness of the inner part is the average value of the thickness at three places that equally divide the part of the inner part from the intermediate part to the predetermined distance in the surface direction,
    An electrochemical cell according to claim 1.
  5. 　前記中間部の平均厚みは、前記面方向において前記中間部を４等分する３か所における厚みの平均値であり、
    　前記外側部の平均厚みは、前記面方向において前記外側部を４等分する３か所における厚みの平均値である、
    請求項２に記載の電気化学セル。     The average thickness of the intermediate portion is the average value of the thickness at three locations dividing the intermediate portion into four equal parts in the surface direction,
    The average thickness of the outer portion is an average value of thicknesses at three locations dividing the outer portion into four equal parts in the surface direction.
    An electrochemical cell according to claim 2.
  6. 　前記第１電極層は、前記面方向に垂直な厚み方向に沿って形成される側面を有し、
    　前記側面には凹凸が形成されている、
    請求項１乃至５のいずれかに記載の電気化学セル。     The first electrode layer has a side surface formed along a thickness direction perpendicular to the surface direction,
    unevenness is formed on the side surface;
    An electrochemical cell according to any one of claims 1 to 5.
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