WO2023176242A1 - 電気化学セル - Google Patents

電気化学セル Download PDF

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Publication number
WO2023176242A1
WO2023176242A1 PCT/JP2023/004783 JP2023004783W WO2023176242A1 WO 2023176242 A1 WO2023176242 A1 WO 2023176242A1 JP 2023004783 W JP2023004783 W JP 2023004783W WO 2023176242 A1 WO2023176242 A1 WO 2023176242A1
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WO
WIPO (PCT)
Prior art keywords
electrode layer
metal plate
pores
pore
hole
Prior art date
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Ceased
Application number
PCT/JP2023/004783
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English (en)
French (fr)
Japanese (ja)
Inventor
玄太 寺澤
明浩 杉江
俊之 中村
誠 大森
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NGK Insulators Ltd
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NGK Insulators Ltd
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Publication date
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Priority to JP2024507592A priority Critical patent/JP7576206B2/ja
Publication of WO2023176242A1 publication Critical patent/WO2023176242A1/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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • 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
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • H01M8/1226—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 characterised by the supporting layer

Definitions

  • the present invention relates to an electrochemical cell.
  • an electrochemical cell such as an electrolytic cell or a fuel cell
  • a structure in which a cell body is supported by a metal plate is known.
  • an electrode layer, an electrolyte layer, and a counter electrode layer are laminated in this order on a metal plate.
  • the metal plate has through holes for supplying gas to the electrode layer.
  • the electrode layer is arranged on a metal plate with through holes, the electrode layer is not supported on the through holes, so if the electrode layer is formed thin, cracks may occur in the electrode layer. There is a problem that occurs.
  • an object of the present invention is to suppress cracking of an electrode layer formed on a metal plate.
  • An electrochemical cell includes a cell main body and a metal plate.
  • the cell main body includes a first electrode layer, a second electrode layer, and an electrolyte layer.
  • An electrolyte layer is disposed between the first electrode layer and the second electrode layer.
  • the metal plate supports the cell body.
  • the metal plate has a first main surface, a second main surface, and a through hole.
  • the first electrode layer has a main body portion, a filling portion, at least one first pore, and at least one second pore.
  • the main body portion is arranged on the first main surface of the metal plate.
  • the filling part is arranged within the through hole.
  • the first pore is arranged within the main body.
  • the second pores are arranged within the filling part.
  • the equivalent circle diameter of the largest second pore among the second pores is larger than the equivalent circle diameter of the largest second pore among the first pores.
  • the filling portion of the first electrode layer is arranged within the through hole of the metal plate, cracking of the first electrode layer formed on the metal plate can be suppressed.
  • the filling part contracts during the reduction process, for example.
  • the maximum second pores which are larger than the maximum first pores, are arranged within the filling part. Therefore, the second pores stop the cracks generated within the filled portion from expanding. As a result, cracks can be prevented from extending and penetrating the electrolyte layer.
  • the largest second pores are arranged on the second main surface side within the filling part.
  • the largest second pores are spaced apart from the inner wall surface defining the through hole.
  • the largest second pores contact the inner wall surface defining the through hole.
  • FIG. 7 is an enlarged sectional view showing details of an electrolytic cell according to a modification.
  • FIG. 7 is an enlarged sectional view showing details of an electrolytic cell according to a modification.
  • FIG. 7 is an enlarged sectional view showing details of an electrolytic cell according to a modification.
  • FIG. 1 is a sectional view showing an electrolytic cell.
  • the solid oxide electrolytic cell will be abbreviated as "cell”.
  • the cell 1 includes a cell main body 10 and a metal plate 4. Further, the cell 1 further includes a flow path member 3.
  • the flow path member 3 is joined to the metal plate 4.
  • the channel member 3 has a channel 31 .
  • the flow path 31 is formed on the surface of the flow path member 3 that faces the metal plate 4 .
  • a flow path 31 is formed on the upper surface of the flow path member 3.
  • the flow path 31 is open toward the metal plate 4.
  • the flow path 31 is connected to a manifold (not shown) or the like. In this embodiment, raw material gas is supplied to the flow path 31.
  • the flow path member 3 can be made of an alloy material, for example.
  • the flow path member 3 may be formed of the same material as the metal plate 4.
  • the flow path member 3 has a frame 32 and an interconnector 33.
  • the frame body 32 is an annular member that surrounds the sides of the flow path 31 .
  • the frame body 32 is joined to the metal plate 4.
  • the interconnector 33 is a plate-like member that electrically connects the electrolytic cell 1 to an external power source or other electrolytic cells in series.
  • the interconnector 33 is joined to the frame 32.
  • the frame 32 and the interconnector 33 are separate members, but the frame 32 and the interconnector 33 may be composed of one member.
  • the metal plate 4 supports the cell main body part 10.
  • the metal plate 4 is formed into a plate shape.
  • the metal plate 4 may be flat or curved.
  • the thickness of the metal plate 4 is not particularly limited as long as it can maintain the strength of the cell 1, and may be, for example, 0.1 mm or more and 2.0 mm or less.
  • the metal plate 4 has a first main surface 41, a second main surface 42, and a plurality of through holes 43.
  • the first main surface 41 of the metal plate 4 supports the cell main body part 10.
  • the second main surface 42 of the metal plate 4 faces the flow path 31.
  • the upper surface of the metal plate 4 is the 1st main surface 41
  • the lower surface of the metal plate 4 is the 2nd main surface 42.
  • the frame 32 of the channel member 3 is connected to the second main surface 42 of the metal plate 4 .
  • the metal plate 4 has a rectangular shape in plan view. Note that the metal plate 4 may have other shapes such as a circular shape.
  • the plurality of through holes 43 are arranged along the longitudinal direction and the lateral direction of the metal plate 4.
  • the plurality of through holes 43 are formed in a region of the metal plate 4 that is joined to a hydrogen electrode layer 5, which will be described later.
  • the through hole 43 is open to the first main surface 41 .
  • the through hole 43 is also open to the second main surface 42 . That is, the through hole 43 penetrates the metal plate 4 in the thickness direction.
  • the through hole 43 communicates with the flow path 31 of the flow path member 3.
  • the through hole 43 has a substantially circular shape in plan view.
  • the area of the through hole 43 in plan view can be, for example, 0.00005 mm 2 or more and 1 mm 2 or less. Further, the diameter of the through hole 43 can be, for example, 10 ⁇ m or more and 1000 ⁇ m or less. Note that the through hole 43 may have a rectangular shape in plan view.
  • the source gas flowing through the flow path 31 is supplied to the hydrogen electrode layer 5 via the through hole 43.
  • a portion of the cell main body 10 is inserted into the through hole 43. Specifically, a part of the hydrogen electrode layer 5 of the cell main body 10 enters into the through hole 43.
  • the through hole 43 can be formed by mechanical processing (eg, punching), laser processing, chemical processing (eg, etching), or the like.
  • the metal plate 4 may also be made of porous metal in order to have gas permeability.
  • the metal plate 4 is made of a metal material.
  • the metal plate 4 is made of an alloy material containing Cr (chromium).
  • Cr chromium
  • Fe--Cr alloy steel stainless steel, etc.
  • Ni--Cr alloy steel etc.
  • the content of Cr in the metal plate 4 is not particularly limited, but may be 4% by mass or more and 30% by mass or less.
  • the metal plate 4 may contain Ti (titanium) or Zr (zirconium). Although the content rate of Ti in the metal plate 4 is not particularly limited, it can be set to 0.01 mol% or more and 1.0 mol% or less. Although the Zr content in the metal plate 4 is not particularly limited, it can be set to 0.01 mol% or more and 0.4 mol% or less.
  • the metal plate 4 may contain Ti as TiO 2 (titania), or may contain Zr as Zr (zirconium).
  • the metal plate 4 may have a chromium oxide film on its surface.
  • the chromium oxide film covers at least a portion of the surface of the metal plate 4.
  • the chromium oxide film only needs to cover at least a portion of the surface of the metal plate 4, but may cover substantially the entire surface. Further, the chromium oxide film may cover the inner wall surface of the through hole 43.
  • the chromium oxide film contains chromium oxide as a main component.
  • composition X "contains substance Y as a main component” means that substance Y accounts for 70% by weight or more of the entire composition X.
  • the thickness of the chromium oxide film is not particularly limited, but may be, for example, 0.1 ⁇ m or more and 20 ⁇ m or less.
  • the cell main body 10 is arranged on the first main surface 41 of the metal plate 4.
  • the cell main body 10 includes a hydrogen electrode layer 5 (cathode), an electrolyte layer 7, a reaction prevention layer 8, and an oxygen electrode layer 9 (anode).
  • the hydrogen electrode layer 5, the electrolyte layer 7, the reaction prevention layer 8, and the oxygen electrode layer 9 are laminated in this order from the metal plate 4 side. Note that the cell main body 10 does not need to have the reaction prevention layer 8.
  • the hydrogen electrode layer 5 is an example of the first electrode layer of the invention
  • the oxygen electrode layer 9 is an example of the second electrode layer of the invention.
  • Hydrogen electrode layer 5 is supported by metal plate 4 . Specifically, the hydrogen electrode layer 5 is arranged on the first main surface 41 of the metal plate 4. As shown in FIG. 2, the hydrogen electrode layer 5 is provided so as to cover a region of the metal plate 4 in which the plurality of through holes 43 are provided.
  • the hydrogen electrode layer 5 has a main body portion 51 and a plurality of filling portions 52.
  • the main body portion 51 is arranged on the first main surface 41 of the metal plate 4.
  • the thickness t of the main body portion 51 can be, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the main body portion 51 is thinner than the metal plate 4.
  • the filling part 52 is arranged within the through hole 43.
  • the filling portion 52 may fill the entire through hole 43 as shown in FIG. 3, or may fill only a part of the through hole 43 as shown in FIG. Further, as shown in FIG. 5, the filling portion 52 may protrude from the through hole 43 toward the second main surface 42 side. In this case, the filling portion 52 may be joined to the second main surface 42.
  • the filling part 52 is formed integrally with the main body part 51.
  • the diameter of the filling part 52 is substantially the same as the diameter of the through hole 43.
  • the height h of the filling part 52 is greater than the thickness t of the main body part 51.
  • the height h of the filling portion 52 can be, for example, 100 ⁇ m or more and 1000 ⁇ m or less. Note that the height h of the filling portion 52 means the dimension in the vertical direction in FIG.
  • the hydrogen electrode layer 5 has a plurality of first pores 53 and a plurality of second pores 54.
  • the first pores 53 are arranged within the main body portion 51 . That is, the first pores 53 are arranged on the electrolyte layer 7 side with respect to the first main surface 41 of the metal plate 4.
  • the second pores 54 are arranged within the filling part 52. That is, the second pores 54 are arranged within the through holes 43 of the metal plate 4.
  • a plurality of second pores 54 are arranged within one filling part 52.
  • the largest second pore 54 is referred to as the largest second pore 54. Note that when only one second pore 54 is formed in one filling part 52, that one second pore 54 is the maximum second pore 54.
  • the largest second pores 54 are spaced apart from the inner wall surface defining the through hole 43. Moreover, it is preferable that the largest second pores 54 are arranged on the second main surface 42 side within the filling part 52 . Note that the largest second pores 54 may be arranged on the first main surface 41 side within the filling part 52. Further, the largest second pores 54 may be in contact with the inner wall surface defining the through hole 43.
  • a plurality of first pores 53 are arranged within the main body portion 51.
  • the largest first pore 53 is referred to as the largest first pore 53.
  • the equivalent circle diameter of the maximum second pores 54 is larger than the equivalent circle diameter of the maximum first pores 53.
  • the maximum equivalent circle diameter of the second pores 54 can be twice or more the equivalent circle diameter of the maximum first pores 53.
  • the maximum equivalent circle diameter of the second pores 54 can be 80 times or less the equivalent circle diameter of the maximum first pores 53.
  • the average value of the equivalent circle diameters of the plurality of second pores 54 arranged in one filling part 52 is larger than the average value of the equivalent circle diameters of the first pores 53.
  • the equivalent circular diameter of the maximum second pores 54 is measured as follows. First, as shown in FIG. 1, a cut surface is formed so that the through hole 43 can be confirmed. At this cut surface, the inside of the through hole 43 is photographed with a SEM (scanning electron microscope) at a magnification of 200, and the SEM photograph is subjected to image processing to measure the area of each second pore 54 in the filling portion 52.
  • the second pore 54 with the largest area is defined as the largest second pore 54, and the diameter of a circle having the same area as the largest second pore 54 is defined as the equivalent circular diameter of the largest second pore 54.
  • the equivalent circular diameter of the maximum first pore 53 is measured as follows. First, the cell main body 10 is filled with resin and cut near the center. The main body portion 51 is brought into a mirror state by mechanical polishing, and 20 SEM photographs are taken at a magnification of 1000. Then, each SEM photograph is subjected to image processing, and the largest pore among them is determined as the largest first pore 53. Then, the diameter of a circle having the same area as the maximum first pore 53 is defined as the circle equivalent diameter of the maximum first pore 53.
  • the equivalent circle diameter of the maximum second pore 54 formed in any one of the plurality of filling parts 52 is larger than the equivalent circle diameter of the maximum first pore 53. That is, all of the equivalent circle diameters of the maximum second pores 54 formed in each filling portion 52 do not need to be larger than the equivalent circle diameters of the maximum first pores 53.
  • the equivalent circle diameter of the maximum second pores 54 is larger than the equivalent circle diameter of the maximum first pores 53 in 10% or more of the plurality of filling portions 52 .
  • the above ratio is confirmed, for example, as follows. First, the maximum equivalent circle diameter of the second pores 54 in each of the 100 arbitrary filling portions 52 is measured. Then, among the 100 filled portions 52, the ratio of the filled portions 52 having the maximum second pores 54 having an equivalent circle diameter larger than the equivalent circle diameter of the maximum first pores 53 is checked. It is preferable that this ratio is 10% or more.
  • the maximum equivalent circle diameter of the second pores 54 is preferably 10% or more and 70% or less of the diameter of the through hole 43.
  • the hydrogen electrode layer 5 is porous. Although the porosity of the hydrogen electrode layer 5 is not particularly limited, it can be, for example, 20% or more and 70% or less.
  • Raw material gas is supplied to the hydrogen electrode layer 5 through the through hole 43 .
  • the source gas contains CO 2 and H 2 O.
  • the hydrogen electrode layer 5 generates H 2 , CO, and O 2 ⁇ from the raw material gas according to the electrochemical reaction of co-electrolysis shown in equation (1) below.
  • ⁇ Hydrogen electrode layer 5 CO 2 +H 2 O+4e - ⁇ CO+H 2 +2O 2 -...(1)
  • the hydrogen electrode layer 5 is made of a porous material having electron conductivity.
  • the hydrogen electrode layer 5 may have oxide ion conductivity.
  • the hydrogen electrode layer 5 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.
  • This hydrogen electrode layer 5 can be formed as follows. First, a paste for the main body portion 51 and a paste for the filling portion 52 are prepared.
  • the paste for the main body portion 51 includes any of the above-mentioned materials and a pore-forming material containing an organic component.
  • the paste for the filling part 52 is prepared in the same way as the paste for the main body part 51. Note that the pore-forming material contained in the paste for the filling portion 52 is larger than the pore-forming material contained in the paste for the main body portion 51 .
  • paste for the filling portion 52 is screen printed into the through hole 43 of the metal plate 4, and squeegeeing is performed to push the paste into the through hole 43 and remove the paste from above the first main surface 41. do.
  • a paste for the main body portion 51 is formed on the first main surface 41 of the metal plate 4 by a screen printing method.
  • the pore-forming material is removed by heating in an electric furnace to form pores, and then fired.
  • the hydrogen electrode layer 5 is formed on the metal plate 4.
  • the electrolyte layer 7 is arranged between the hydrogen electrode layer 5 and the oxygen electrode layer 9. In this embodiment, since the cell main body 10 has the reaction prevention layer 8 , the electrolyte layer 7 is interposed between the hydrogen electrode layer 5 and the reaction prevention layer 8 .
  • the thickness of the electrolyte layer 7 is not particularly limited, but may be, for example, 3 ⁇ m or more and 50 ⁇ m or less.
  • the electrolyte layer 7 is arranged to cover the entire hydrogen electrode layer 5.
  • the outer peripheral portion of the electrolyte layer 7 is joined to the first main surface 41 of the metal plate 4 . This ensures airtightness between the hydrogen electrode layer 5 side and the oxygen electrode layer 9 side, so there is no need to separately seal between the metal plate 4 and the electrolyte layer 7.
  • the electrolyte layer 7 transmits O 2 ⁇ generated in the hydrogen electrode layer 5 to the oxygen electrode layer 9.
  • Electrolyte layer 7 has oxide ion conductivity.
  • the electrolyte layer 7 is made of a dense material.
  • the porosity of the electrolyte layer 7 is about 0% or more and 7% or less.
  • the electrolyte layer 7 is a fired body made of a dense material that has ionic conductivity and no electronic conductivity.
  • the electrolyte layer 7 can be made of, for example, 8YSZ, GDC, ScSZ, SDC, LSGM (lanthanum gallate), or the like.
  • the method for forming the electrolyte layer 7 is not particularly limited, and can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.
  • Reaction prevention layer 8 is arranged on electrolyte layer 7 . Reaction prevention layer 8 is interposed between electrolyte layer 7 and oxygen electrode layer 9.
  • the thickness of the reaction prevention layer 8 is not particularly limited, but may be, for example, 3 ⁇ m or more and 50 ⁇ m or less.
  • the reaction prevention layer 8 prevents the constituent materials of the oxygen electrode layer 9 and the constituent materials of the electrolyte layer 7 from reacting to form a reaction layer with high electrical resistance.
  • the reaction prevention layer 8 is made of a material having oxide ion conductivity.
  • the reaction prevention layer 8 can be made of a ceria-based material such as GDC or SDC.
  • the porosity of the reaction prevention layer 8 is not particularly limited, but may be, for example, 0% or more and 50% or less.
  • the method for forming the reaction prevention layer 8 is not particularly limited, and can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.
  • the oxygen electrode layer 9 is arranged on the opposite side of the hydrogen electrode layer 5 with respect to the electrolyte layer 7. In this embodiment, since the cell 1 has the reaction prevention layer 8 , the oxygen electrode layer 9 is arranged on the reaction prevention layer 8 .
  • the oxygen electrode layer 9 is preferably porous.
  • the porosity of the oxygen electrode layer 9 is not particularly limited, but may be, for example, 20% or more and 70% or less.
  • the thickness of the oxygen electrode layer 9 is not particularly limited, but may be, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • 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 method for forming the oxygen electrode layer 9 is not particularly limited, and can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.
  • the oxygen electrode layer 9 generates O 2 from O 2 ⁇ transmitted from the hydrogen electrode layer 5 via the electrolyte layer 7 according to the chemical reaction of equation (2) below.
  • ⁇ Oxygen electrode layer 9 2O 2- ⁇ O 2 +4e - (2)
  • the hydrogen electrode layer 5 was described as an example of the first electrode layer, and the oxygen electrode layer 9 was described as an example of the second electrode layer, but the reverse may be used. That is, as shown in FIG. 6, the first electrode layer may be the oxygen electrode layer 9, and the second electrode layer may be the hydrogen electrode layer 5. In this case, the oxygen electrode layer 9 is placed on the metal plate 4. Further, the oxygen electrode layer 9 has a main body portion 91 , a filling portion 92 , first pores 93 , and second pores 94 . Further, a reaction prevention layer 8 is disposed between the oxygen electrode layer 9 and the electrolyte layer 7.
  • the electrolytic cell 1 was described as an example of an electrochemical cell, but the electrochemical cell may be other than an electrolytic cell.
  • the electrochemical cell may be a fuel cell such as a solid oxide fuel cell.
  • the first electrode layer can be used as a fuel electrode (anode), and the second electrode layer can be used as an air electrode (cathode).

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PCT/JP2023/004783 2022-03-14 2023-02-13 電気化学セル Ceased WO2023176242A1 (ja)

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JP2022-039313 2022-03-14

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WO2025143244A1 (ja) * 2023-12-28 2025-07-03 京セラ株式会社 電気化学セル、電気化学セル装置、モジュールおよびモジュール収容装置

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JP2021158026A (ja) * 2020-03-27 2021-10-07 大阪瓦斯株式会社 電気化学素子の金属支持体、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、および固体酸化物形電解セル

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JP2004207088A (ja) * 2002-12-26 2004-07-22 Nissan Motor Co Ltd ガス透過性基体及びこれを用いた固体酸化物形燃料電池
JP2007173243A (ja) * 2005-12-21 2007-07-05 Samsung Electro Mech Co Ltd 燃料電池及びその製造方法
JP2008257885A (ja) * 2007-03-30 2008-10-23 Dainippon Printing Co Ltd 固体酸化物形燃料電池
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JP2021158026A (ja) * 2020-03-27 2021-10-07 大阪瓦斯株式会社 電気化学素子の金属支持体、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、および固体酸化物形電解セル

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WO2025143244A1 (ja) * 2023-12-28 2025-07-03 京セラ株式会社 電気化学セル、電気化学セル装置、モジュールおよびモジュール収容装置

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