WO2024176929A1 - 電気化学セル - Google Patents

電気化学セル Download PDF

Info

Publication number
WO2024176929A1
WO2024176929A1 PCT/JP2024/005134 JP2024005134W WO2024176929A1 WO 2024176929 A1 WO2024176929 A1 WO 2024176929A1 JP 2024005134 W JP2024005134 W JP 2024005134W WO 2024176929 A1 WO2024176929 A1 WO 2024176929A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
protrusion
hole
holes
electrode layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/005134
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
敬司 白鳥
俊之 中村
玄太 寺澤
誠 大森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP2024552416A priority Critical patent/JP7692538B2/ja
Publication of WO2024176929A1 publication Critical patent/WO2024176929A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrochemical cell.
  • the electrochemical cell disclosed in Patent Document 1 has an electrode layer, an electrolyte layer, and a counter electrode layer stacked in that order on a metal plate.
  • the metal plate has through holes to supply raw material gas to the electrode layer.
  • an object of the present invention is to improve the diffusibility of the raw material gas supplied to the cell body.
  • the electrochemical cell according to the first aspect comprises a metal plate, a cell body, a first oxide protrusion, and a first non-oxide protrusion.
  • the metal plate has a first main surface, a second main surface, a first through hole, and a second through hole.
  • the cell body is disposed on the first main surface of the metal plate.
  • the cell body has a first electrode layer, a second electrode layer, and an electrolyte layer.
  • the electrolyte layer is disposed between the first electrode layer and the second electrode layer.
  • the first oxide protrusion is made of a material containing an oxide.
  • the first oxide protrusion is disposed on the inner wall surface of the first through hole.
  • the first non-oxide protrusion is made of a material containing a non-oxide.
  • the first non-oxide protrusion is disposed on the inner wall surface of the second through hole.
  • the raw material gas flowing through each through hole collides with the first oxide protrusions or the first non-oxide protrusions, generating a turbulent flow.
  • the diffusibility of the raw material gas supplied to the cell main body through each through hole can be improved.
  • the first oxide protrusions are made of a material containing an oxide and do not undergo phase transformation, so a turbulent flow can be generated stably.
  • the first non-oxide protrusions are made of a material containing a non-oxide and do not undergo phase transformation, so a turbulent flow can be generated stably.
  • the electrochemical cell according to the second embodiment is configured as follows in the electrochemical cell according to the first embodiment. At least one of the first oxide protrusions and the first non-oxide protrusions is annular and extends circumferentially on the inner wall surface. With this configuration, by making at least one of the first oxide protrusions and the first non-oxide protrusions annular, symmetry is increased, and mechanical reliability against thermal stress generated between each protrusion and the metal plate is improved.
  • the electrochemical cell according to the third aspect is the electrochemical cell according to the first or second aspect, and is configured as follows. At least one of the first oxide protrusions and the first non-oxide protrusions is made of a material having a higher Young's modulus than the metal plate. This configuration makes it possible to prevent deformation of each protrusion due to thermal stress and maintain the effect of improving gas diffusion.
  • the electrochemical cell according to the fourth aspect is an electrochemical cell according to any one of the first to third aspects, and is configured as follows.
  • the first oxide protrusions and the first non-oxide protrusions are arranged at the second main surface side end on the inner wall surface. With this configuration, the raw material gas flowing through the raw material gas flow passage formed on the second main surface side can be efficiently introduced into each through hole of the metal plate.
  • the electrochemical cell according to the fifth aspect is the electrochemical cell according to any one of the first to fourth aspects, further comprising a second oxide protrusion.
  • the second oxide protrusion is made of a material containing an oxide.
  • the second oxide protrusion is disposed on the inner wall surface of the first through hole closer to the first main surface than the first oxide protrusion.
  • the electrochemical cell according to the sixth aspect is the electrochemical cell according to any one of the first to fifth aspects, further comprising a second non-oxide protrusion.
  • the second non-oxide protrusion is made of a material containing a non-oxide.
  • the second non-oxide protrusion is disposed on the inner wall surface of the second through hole closer to the first principal surface than the first non-oxide protrusion.
  • the electrochemical cell according to the seventh aspect is the electrochemical cell according to any one of the first to sixth aspects, further comprising a second oxide protrusion.
  • the second oxide protrusion is made of a material containing an oxide.
  • the second oxide protrusion is disposed on the inner wall surface of the second through hole closer to the first main surface than the first non-oxide protrusion.
  • the electrochemical cell according to the eighth aspect is an electrochemical cell according to any one of the first to seventh aspects, further comprising a second non-oxide protrusion.
  • the second non-oxide protrusion is made of a material containing a non-oxide.
  • the second non-oxide protrusion is disposed on the inner wall surface of the first through hole closer to the first main surface than the first oxide protrusion.
  • the electrochemical cell according to the ninth aspect is an electrochemical cell according to any one of the first to eighth aspects, and is configured as follows:
  • the first oxide protrusion is made of ceramics.
  • the electrochemical cell according to the tenth aspect is an electrochemical cell according to any one of the first to ninth aspects, and is configured as follows:
  • the first non-oxide protrusion is configured of a metal.
  • the electrochemical cell according to the eleventh aspect is an electrochemical cell according to any one of the first to tenth aspects, and is configured as follows.
  • the electrochemical cell includes a plurality of first through holes in which the first oxide protrusions are formed, and a plurality of second through holes in which the first non-oxide protrusions are formed.
  • the metal plate has a supply port side region and an exhaust port side region.
  • the supply port side region is disposed on the supply port side of the flow path of the raw material gas supplied to the cell body through the first through hole and the second through hole.
  • the exhaust port side region is disposed on the exhaust port side of the flow path.
  • the ratio of the first through holes to the second through holes is larger in the supply port side region than in the exhaust port side region.
  • the electrochemical cell is an electrolytic cell.
  • the supply port side of the raw material gas has a higher oxygen partial pressure than the exhaust port side of the raw material gas, as in the electrolytic cell, by providing many first oxide protrusions on the supply port side and many first non-oxide protrusions on the exhaust port side, the occurrence of phase transformation of the protrusions can be suppressed, and a stable gas diffusion effect can be obtained.
  • the electrochemical cell according to the twelfth aspect is an electrochemical cell according to any one of the first to tenth aspects, and is configured as follows.
  • the electrochemical cell includes a plurality of first through holes in which the first oxide protrusions are formed, and a plurality of second through holes in which the first non-oxide protrusions are formed.
  • the metal plate has a supply port side region and an exhaust port side region.
  • the supply port side region is disposed on the supply port side of the flow path of the raw material gas supplied to the cell body through the first through hole and the second through hole.
  • the exhaust port side region is disposed on the exhaust port side of the flow path.
  • the ratio of the first through holes to the second through holes is smaller in the supply port side region than in the exhaust port side region.
  • the electrochemical cell is preferably a fuel cell.
  • the exhaust port side of the raw material gas has a higher oxygen partial pressure than the supply port side of the raw material gas, as in a fuel cell, by providing more first oxide protrusions on the exhaust port side and more first non-oxide protrusions on the supply port side, the occurrence of phase transformation of the protrusions can be suppressed, and a stable gas diffusion effect can be obtained.
  • FIG. 4 A top view of a metal plate.
  • FIG. 4 is an enlarged cross-sectional view showing the periphery of a first through hole.
  • FIG. 4 is an enlarged bottom view showing the periphery of a first through hole.
  • FIG. 4 is a plan view of a metal plate showing each region.
  • FIG. 4 is an enlarged cross-sectional view showing the periphery of a second through hole.
  • FIG. 4 is an enlarged bottom view showing the periphery of a second through hole.
  • FIG. 11 is a cross-sectional view showing an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a first through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a second through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a second through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a first through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a through hole of an electrolysis cell according to a modified example.
  • FIG. 11 is an enlarged cross-sectional view showing the periphery of a through hole of an electrolysis cell according to a modified example.
  • electrolytic cell an example of an electrochemical cell
  • SOEC solid oxide electrolytic cell
  • Figure 1 is a cross-sectional view of an electrolytic cell.
  • the solid oxide electrolytic cell may be abbreviated to "cell.”
  • the cell 100 has a metal plate 2, a cell body 3, a first oxide protrusion 4, and a first non-oxide protrusion 5.
  • the cell 100 further includes a flow path member 6.
  • the flow path member 6 is joined to the metal plate 2.
  • the flow path member 6 has a flow path 61.
  • the flow path 61 is formed on a surface of the flow path member 6 that faces the metal plate 2.
  • the flow path 61 is formed on an upper surface of the flow path member 6.
  • the flow path 61 opens toward the metal plate 2.
  • the flow path 61 is connected to a manifold (not shown) or the like. In this embodiment, for example, a raw material gas is supplied from left to right in the flow path 61.
  • the flow path member 6 can be made of, for example, an alloy material.
  • the flow path member 6 may be made of the same material as the metal plate 2.
  • the flow path member 6 has a frame body 62 and an interconnector 63.
  • the frame body 62 is an annular member that surrounds the side of the flow path 61.
  • the frame body 62 is joined to the metal plate 2.
  • the interconnector 63 is a plate-like member that electrically connects the electrolysis cell 100 in series with an external power source or another electrolysis cell.
  • the interconnector 63 is joined to the frame body 62.
  • the frame body 62 and the interconnector 63 are separate members, but the frame body 62 and the interconnector 63 may be formed from a single member.
  • the metal plate 2 supports the cell main body 3.
  • the metal plate 2 is formed in a plate shape.
  • the metal plate 2 may be flat or curved.
  • the metal plate 2 may have any thickness as long as it can maintain the strength of the cell 100, and the thickness is not particularly limited, but may be, for example, 0.1 mm or more and 2.0 mm or less.
  • the metal plate 2 has a first main surface 21, a second main surface 22, and a plurality of through holes 23.
  • the first main surface 21 of the metal plate 2 supports the cell body 3.
  • the second main surface 22 of the metal plate 2 faces the flow path 61.
  • the upper surface of the metal plate 2 is the first main surface 21, and the lower surface of the metal plate 2 is the second main surface 22.
  • the frame 62 of the flow path member 6 is connected to the second main surface 22 of the metal plate 2.
  • the metal plate 2 is rectangular in plan view.
  • the metal plate 2 may be circular or of another shape.
  • the through holes 23 are arranged along the longitudinal and lateral directions of the metal plate 2.
  • the through holes 23 are formed in a region of the metal plate 2 that is joined to the hydrogen electrode layer 31 described later.
  • the through holes 23 open to the first main surface 21.
  • the through holes 23 also open to the second main surface 22. That is, the through holes 23 extend from the first main surface 21 to the second main surface 22 of the metal plate 2 in the thickness direction of the metal plate 2.
  • the through holes 23 penetrate the metal plate 2 in the thickness direction.
  • the through holes 23 communicate with the flow path 61 of the flow path member 6.
  • the raw material gas flowing through the flow path 61 is supplied to the hydrogen electrode layer 31 via the through holes 23.
  • the through hole 23 has a substantially circular shape in a plan view.
  • the area of the through hole 23 in a plan view can be, for example, 0.00005 mm2 or more and 1 mm2 or less.
  • the diameter of the through hole 23 can be, for example, 10 ⁇ m or more and 1000 ⁇ m or less.
  • the through hole 23 may have a rectangular shape in a plan view.
  • the height of the through hole 23 is greater than the thickness of the hydrogen electrode layer 31.
  • the height of the through hole 23 can be, for example, 100 ⁇ m or more and 2000 ⁇ m or less.
  • the height of the through hole 23 means the dimension in the vertical direction in FIG. 1.
  • the through holes 23 can be formed by mechanical processing (e.g., punching), laser processing, or chemical processing (e.g., etching).
  • the metal plate 2 can also be made of a porous metal to provide gas permeability.
  • the multiple through holes 23 include multiple first through holes 23a and multiple second through holes 23b.
  • the first through hole 23a is a through hole among the multiple through holes 23 that has a first oxide protrusion 4 formed on its inner wall surface.
  • the second through hole 23b is a through hole among the multiple through holes 23 that has a first non-oxide protrusion 5 formed on its inner wall surface.
  • the metal plate 2 is made of a metal material.
  • the metal plate 2 is made of an alloy material containing Cr (chromium).
  • Examples of such metal materials that can be used include Fe-Cr alloy steel (stainless steel, etc.) and Ni-Cr alloy steel.
  • Cr content in the metal plate 2 can be 4% by mass or more and 30% by mass or less.
  • the metal plate 2 may contain Ti (titanium) and Zr (zirconium).
  • the Ti content in the metal plate 2 is not particularly limited, but may be 0.01 mol% or more and 1.0 mol% or less.
  • the Zr content in the metal plate 2 is not particularly limited, but may be 0.01 mol% or more and 0.4 mol% or less.
  • the metal plate 2 may contain Ti as TiO2 (titania) and may contain Zr as ZrO2 (zirconia).
  • the metal plate 2 may have an oxide film on its surface. Specifically, the metal plate 2 may have a chromium oxide film on its surface. The oxide film covers at least a portion of the surface of the metal plate 2. The oxide film may cover at least a portion of the surface of the metal plate 2, but may also cover substantially the entire surface. The oxide film may also cover the inner wall surface of the through hole 23.
  • the thickness of the oxide film is not particularly limited, but may be, for example, 0.1 ⁇ m or more and 20 ⁇ m or less.
  • the cell body 3 is disposed on the first main surface 21 of the metal plate 2.
  • the cell body 3 has a hydrogen electrode layer 31 (cathode), an electrolyte layer 32, a reaction prevention layer 33, and an oxygen electrode layer 34 (anode).
  • the hydrogen electrode layer 31, the electrolyte layer 32, the reaction prevention layer 33, and the oxygen electrode layer 34 are laminated in this order from the metal plate 2 side. Note that the cell body 3 does not necessarily have to have the reaction prevention layer 33.
  • the hydrogen electrode layer 31 is an example of a first electrode layer of the present invention
  • the oxygen electrode layer 34 is an example of a second electrode layer of the present invention.
  • the hydrogen electrode layer 31 is supported by the metal plate 2.
  • the hydrogen electrode layer 31 is disposed on the first main surface 21 of the metal plate 2.
  • the thickness t of the hydrogen electrode layer 31 may be, for example, not less than 1 ⁇ m and not more than 100 ⁇ m.
  • the hydrogen electrode layer 31 is thinner than the metal plate 2.
  • the hydrogen electrode layer 31 is provided so as to cover a region of the metal plate 2 in which the multiple through holes 23 are provided.
  • the hydrogen electrode layer 31 is preferably porous. There are no particular limitations on the porosity of the hydrogen electrode layer 31, but it can be, for example, 20% or more and 70% or less.
  • the hydrogen electrode layer 31 is made of a porous material having electronic conductivity.
  • the hydrogen electrode layer 31 may have oxide ion conductivity.
  • the hydrogen electrode layer 31 may be 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) O 3 , (La, Sr) TiO 3 , Sr 2 (Fe, Mo) 2 O 6 , (La, Sr) VO 3 , (La, Sr) FeO 3 , a mixed material of two or more of these, or a composite of one or more of these and NiO.
  • 8YSZ 8 mol % yttria-stabilized zirconia
  • CSZ calcia-
  • the method for forming the hydrogen electrode layer 31 is not particularly limited, and it can be formed by a firing method, a spray coating method, a PVD method, a CVD method, etc.
  • the hydrogen electrode layer 31 is configured to generate hydrogen by an electrolytic reaction.
  • a source gas is supplied to the hydrogen electrode layer 31 through the through-holes 23.
  • the source gas contains at least H2O .
  • the hydrogen electrode layer 31 produces H 2 from the source gas in accordance with the electrochemical reaction of water electrolysis shown in the following formula (1).
  • Hydrogen electrode layer 31 H 2 O+2e ⁇ ⁇ H 2 +O 2 ⁇ (1)
  • the hydrogen electrode layer 31 When the source gas contains CO 2 in addition to H 2 O, the hydrogen electrode layer 31 produces H 2 , CO, and O 2 ⁇ from the source gas in accordance with the co-electrochemical reactions shown in the following formulas (2), (3), and (4).
  • Hydrogen electrode layer 31 CO 2 + H 2 O + 4e ⁇ ⁇ CO + H 2 + 2O 2 ⁇ (2)
  • Electrochemical reaction of CO2 CO2 + 2e- ⁇ CO + O2 -... (4)
  • the electrolyte layer 32 is disposed between the hydrogen electrode layer 31 and the oxygen electrode layer 34.
  • the electrolyte layer 32 is interposed between the hydrogen electrode layer 31 and the reaction prevention layer 33.
  • the thickness of the electrolyte layer 32 is not particularly limited, but may be, for example, 3 ⁇ m or more and 50 ⁇ m or less.
  • the electrolyte layer 32 is disposed so as to cover the entire hydrogen electrode layer 31.
  • the outer periphery of the electrolyte layer 32 is bonded to the first main surface 21 of the metal plate 2. This ensures airtightness between the hydrogen electrode layer 31 side and the oxygen electrode layer 34 side, eliminating the need for a separate seal between the metal plate 2 and the electrolyte layer 32.
  • the electrolyte layer 32 transmits O 2- generated in the hydrogen electrode layer 31 to the oxygen electrode layer 34.
  • the electrolyte layer 32 has oxide ion conductivity.
  • the electrolyte layer 32 is made of a dense material.
  • the porosity of the electrolyte layer 32 is approximately 0% or more and 7% or less.
  • the electrolyte layer 32 is a sintered body made of a dense material that has ion conductivity but no electronic conductivity.
  • the electrolyte layer 32 can be made of, for example, 8YSZ, GDC, ScSZ, SDC, LSGM (lanthanum gallate), or the like.
  • the method for forming the electrolyte layer 32 is not particularly limited, and it can be formed by a baking method, a spray coating method, a PVD method, a CVD method, etc.
  • the reaction prevention layer 33 is disposed on the electrolyte layer 32.
  • the reaction prevention layer 33 is interposed between the electrolyte layer 32 and the oxygen electrode layer 34.
  • the thickness of the reaction prevention layer 33 is not particularly limited, but may be, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the reaction prevention layer 33 suppresses the formation of a reaction layer with high electrical resistance caused by a reaction between the constituent material of the oxygen electrode layer 34 and the constituent material of the electrolyte layer 32.
  • the reaction prevention layer 33 is made of a material having oxide ion conductivity.
  • the reaction prevention layer 33 can be made of a ceria-based material such as GDC or SDC.
  • the porosity of the reaction prevention layer 33 is not particularly limited, but can be, for example, 0.1% to 50%.
  • the method of forming the reaction prevention layer 33 is not particularly limited, and it can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.
  • the oxygen electrode layer 34 is disposed on the opposite side of the hydrogen electrode layer 31 with respect to the electrolyte layer 32. In this embodiment, since the cell 100 has the reaction prevention layer 33, the oxygen electrode layer 34 is disposed on the reaction prevention layer 33.
  • the oxygen electrode layer 34 is preferably porous.
  • the porosity of the oxygen electrode layer 34 is not particularly limited, but can be, for example, 20% to 70%.
  • the thickness of the oxygen electrode layer 34 is not particularly limited, but can be, for example, 1 ⁇ m to 100 ⁇ m.
  • the oxygen electrode layer 34 is made of a porous material having oxide ion conductivity and electron conductivity, and may be made of a composite of one or more of (La,Sr)(Co,Fe) O3 , (La,Sr) FeO3 , La(Ni,Fe) O3 , (La,Sr) CoO3 , and (Sm,Sr) CoO3 with an oxide ion conductive material (such as GDC).
  • an oxide ion conductive material such as GDC
  • the method for forming the oxygen electrode layer 34 is not particularly limited, and it can be formed by a baking method, a spray coating method, a PVD method, a CVD method, etc.
  • the oxygen electrode layer 34 produces O 2 from O 2 ⁇ transferred from the hydrogen electrode layer 31 via the electrolyte layer 32 in accordance with the chemical reaction of the following formula (5).
  • FIG. 3 is a cross-sectional view showing the details of the first through hole 23a in which the first oxide protrusion 4 is formed
  • FIG. 4 is a bottom view of the first through hole 23a viewed from the second main surface side.
  • the first oxide protrusion 4 is disposed on the inner wall surface of the first through hole 23a.
  • the first oxide protrusion 4 is annular and extends along the circumferential direction on the inner wall surface of the first through hole 23a. That is, the first oxide protrusion 4 extends continuously along the circumferential direction.
  • the first oxide protrusion 4 may extend intermittently along the circumferential direction.
  • the first oxide protrusion 4 may not extend along the circumferential direction.
  • the first oxide protrusion 4 may not be formed directly on the inner wall surface of the first through hole 23a. For example, when an oxide film is formed on the inner wall surface of the first through hole 23a, the first oxide protrusion 4 is formed on the oxide film.
  • the first oxide protrusion 4 is disposed on the inner wall surface of the first through hole 23a at the end on the second main surface 22 side.
  • the first through hole 23a has an end on the first main surface 21 side and an end on the second main surface 22 side in the axial direction.
  • the first oxide protrusion 4 is not formed on the end on the first main surface 21 side of both axial ends of the first through hole 23a, but is formed on the end on the second main surface 22 side.
  • the first oxide protrusion 4 may be disposed on the first main surface 21 side.
  • the first oxide protrusion 4 protrudes from the inner wall surface of the first through hole 23a toward the center.
  • the height of the first oxide protrusion 4 is, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the height of the first oxide protrusion 4 is the dimension from the inner wall surface of the first through hole 23a toward the center.
  • the first oxide protrusions 4 are made of a material having a higher Young's modulus than the metal plate 2.
  • the first oxide protrusions 4 are made of a material containing an oxide. More specifically, the first oxide protrusions 4 are made of a material consisting of only an oxide.
  • the first oxide protrusions 4 are made of oxide ceramics. More specifically, the first oxide protrusions 4 can be made of Cr2O3 , (Mn, Cr) 3O4 , (Mn, Cr, Fe ) 3O4 , (Cr, Fe ) 2O3 , Fe2O3 , Fe3O4 , Al2O3 , ZrO2 , CeO2 , or the like.
  • the first oxide protrusions 4 may be made of the same material as the oxide film formed on the inner wall surface of the first through hole 23a.
  • the part that protrudes from the other parts is the first oxide protrusions 4.
  • the height of the first oxide protrusions 4 is greater than the thickness of the oxide film.
  • the height of the first oxide protrusions 4 refers to the height from the inner wall surface of the first through hole 23a.
  • the first oxide protrusion 4 can be formed by applying an oxide paste to the inner wall surface of the first through hole 23a in the circumferential direction using a precision nozzle dispenser, and then firing the oxide paste.
  • the first oxide protrusion 4 can be formed by locally laser-heating the inner wall surface of the first through hole 23a in the circumferential direction to form a thick oxide film.
  • the first oxide protrusions 4 are preferably formed in the through holes 23 located in the supply port side region A1.
  • the region A in which the through holes 23 are formed in the metal plate 2 is divided into thirds along the direction in which the raw material gas flows (supply direction).
  • the raw material gas flows from left to right, so the region A is divided into thirds along the left-right direction.
  • the region close to the supply port of the raw material gas (the region on the left side in FIG. 5) is the supply port side region A1.
  • the region close to the exhaust port of the raw material gas (the region on the right side in FIG. 5) is the exhaust port side region A2, and the region between the supply port side region A1 and the exhaust port side region A2 is the central region A3.
  • the first oxide protrusions 4 are preferably formed in all the through holes 23 in the supply port side region A1, but are not required to be formed in all the through holes 23 in the supply port side region A1.
  • the first oxide protrusions 4 are preferably formed in 50% or more of the through holes 23 in the supply port side region A1.
  • the first oxide protrusions 4 are preferably formed in at least 10% or more of the through holes 23 in the supply port side region A1.
  • the first oxide protrusions 4 may be formed in the through holes 23 in the discharge port side region A2 or the central region A3.
  • FIG. 6 is a cross-sectional view showing the details of the periphery of the second through-hole 23b in which the first non-oxide projection 5 is formed
  • FIG. 7 is a cross-sectional view showing the second through-hole 23b in which the first non-oxide projection 5 is formed.
  • the first non-oxide protrusion 5 is disposed on the inner wall surface of the second through hole 23b.
  • the first non-oxide protrusion 5 is annular and extends circumferentially on the inner wall surface of the second through hole 23b. That is, the first non-oxide protrusion 5 extends continuously in the circumferential direction.
  • the first non-oxide protrusion 5 may extend intermittently in the circumferential direction.
  • the first non-oxide protrusion 5 may not extend in the circumferential direction.
  • the first non-oxide protrusion 5 may not be formed directly on the inner wall surface of the second through hole 23b. For example, if an oxide film is formed on the inner wall surface of the second through hole 23b, the first non-oxide protrusion 5 is formed on the oxide film.
  • the first non-oxide protrusion 5 is disposed on the inner wall surface of the second through hole 23b at the end on the second main surface 22 side.
  • the second through hole 23b has an end on the first main surface 21 side and an end on the second main surface 22 side in the axial direction.
  • the first non-oxide protrusion 5 is not formed on the end on the first main surface 21 side of both axial ends of the second through hole 23b, but is formed on the end on the second main surface 22 side.
  • the first non-oxide protrusion 5 may be disposed on the first main surface 21 side.
  • the first non-oxide protrusion 5 protrudes from the inner wall surface of the second through hole 23b toward the center.
  • the height of the first non-oxide protrusion 5 is, for example, 1 ⁇ m or more and 100 ⁇ m or less.
  • the height of the first non-oxide protrusion 5 is the dimension from the inner wall surface of the second through hole 23b toward the center.
  • the first non-oxide protrusion 5 is made of a material containing a non-oxide. More specifically, the first non-oxide protrusion 5 is made of a material containing a metal. For example, the first non-oxide protrusion 5 is made of a metal.
  • the first non-oxide protrusion 5 may contain an oxide in addition to the metal. More specifically, the first non-oxide protrusion 5 may be configured such that the surface of an oxide is covered with a metal.
  • examples of the metal contained in the first non-oxide protrusion 5 include Fe , Co, Ni, and Cu.
  • Examples of the oxide contained in the first non-oxide protrusion 5 include Cr2O3, (Mn, Cr)3O4 , (Mn, Cr, Fe)3O4 , ( Cr , Fe) 2O3 , Fe3O4 , Al2O3 , ZrO2 , and CeO2 .
  • the first non-oxide projections 5 may be made of a material having a higher Young's modulus than the metal plate 2 .
  • the first non-oxide protrusion 5 can be formed by applying a non-oxide paste to the inner wall surface of the second through hole 23b in the circumferential direction using a precision nozzle dispenser, and then firing in a controlled atmosphere so that the non-oxide is not oxidized.
  • the first non-oxide protrusion 5 can be formed by selectively laser sintering the non-oxide paste applied to the inner wall surface of the second through hole 23b.
  • the first non-oxide protrusions 5 are preferably formed in the through holes 23 arranged in the outlet side region A2.
  • the first non-oxide protrusions 5 are preferably formed in all the through holes 23 in the outlet side region A2, but do not have to be formed in all the through holes 23 in the outlet side region A2.
  • the first non-oxide protrusions 5 are preferably formed in 50% or more of the through holes 23 in the outlet side region A2.
  • the first non-oxide protrusions 5 are preferably formed in at least 10% of the through holes 23 in the outlet side region A2.
  • the first non-oxide protrusions 5 may be formed in the through holes 23 in the supply port side region A1 or the central region A3.
  • the number of first through holes 23a is greater than the number of second through holes 23b in the supply port side region A1, and is less than the number of second through holes 23b in the exhaust port side region A2. That is, the ratio of the first through holes 23a to the second through holes 23b in the supply port side region A1 is greater than the ratio of the first through holes 23a to the second through holes 23b in the exhaust port side region A2.
  • This ratio can be calculated, for example, on the cut surface by cutting the metal plate 2 along the arrangement direction of the multiple through holes 23 and the supply direction of the raw material gas, as shown by the dashed line in FIG. 5. It is not necessary that the second through holes 23b are formed in the supply port side region A1. It is also not necessary that the first through holes 23a are formed in the exhaust port side region A2.
  • the hydrogen electrode layer 31 is disposed on the metal plate 2, but the configuration of the cell body 3 is not limited to this.
  • the oxygen electrode layer 34 may be disposed on the metal plate 2.
  • the oxygen electrode layer 34, the reaction prevention layer 33, the electrolyte layer 32, and the hydrogen electrode layer 31 are disposed in this order from the metal plate 2 side.
  • the electrolyte layer 32 is formed so as to cover the oxygen electrode layer 34 and the reaction prevention layer 33. Note that the reaction prevention layer 33 does not necessarily have to be formed.
  • the electrolysis cell 100 may further have a second oxide protrusion 7.
  • the second oxide protrusion 7 is arranged on the inner wall surface of the first through hole 23a closer to the first main surface 21 than the first oxide protrusion 4.
  • the second oxide protrusion 7 is arranged in the axial center of the first through hole 23a.
  • the second oxide protrusion 7 is arranged at a distance from the hydrogen electrode layer 31.
  • the second oxide protrusion 7 is also arranged at a distance from the first oxide protrusion 4.
  • the second oxide protrusions 7 are formed on the inner wall surface of the first through hole 23a, similar to the first oxide protrusions 4.
  • the height of the second oxide protrusions 7 may be formed to be lower than the height of the first oxide protrusions 4.
  • the second oxide protrusions 7 are made of a material containing an oxide.
  • the second oxide protrusions 7 are made of a material having a higher Young's modulus than the metal plate 2.
  • the second oxide protrusions 7 can be made of the same material as the first oxide protrusions 4.
  • the second oxide protrusions 7 can be formed in the same manner as the first oxide protrusions 4.
  • the second oxide protrusion 7 may be disposed on the inner wall surface of the second through-hole 23b closer to the first main surface 21 than the first non-oxide protrusion 5.
  • the second oxide protrusion 7 is disposed in the axial center of the second through-hole 23b.
  • the second oxide protrusion 7 is disposed at a distance from the hydrogen electrode layer 31.
  • the second oxide protrusion 7 is also disposed at a distance from the first non-oxide protrusion 5.
  • the electrolysis cell 100 may further have a second non-oxide protrusion 8.
  • the second non-oxide protrusion 8 is disposed on the inner wall surface of the second through-hole 23b closer to the first main surface 21 than the first non-oxide protrusion 5.
  • the second non-oxide protrusion 8 is disposed in the axial center of the second through-hole 23b.
  • the second non-oxide protrusion 8 is disposed at a distance from the hydrogen electrode layer 31.
  • the second non-oxide protrusion 8 is also disposed at a distance from the first non-oxide protrusion 5.
  • the second non-oxide protrusions 8 are formed on the inner wall surface of the second through hole 23b, similar to the first non-oxide protrusions 5.
  • the height of the second non-oxide protrusions 8 may be formed to be lower than the height of the first non-oxide protrusions 5.
  • the second non-oxide protrusions 8 are made of a material containing a non-oxide.
  • the second non-oxide protrusions 8 can be made of the same material as the first non-oxide protrusions 5. Furthermore, the second non-oxide protrusions 8 can be formed in the same manner as the first non-oxide protrusions 5.
  • the second non-oxide protrusion 8 may be disposed on the inner wall surface of the first through-hole 23a closer to the first main surface 21 than the first oxide protrusion 4.
  • the second non-oxide protrusion 8 is disposed in the axial center of the first through-hole 23a.
  • the second non-oxide protrusion 8 is disposed at a distance from the hydrogen electrode layer 31.
  • the second non-oxide protrusion 8 is also disposed at a distance from the first oxide protrusion 4.
  • the first oxide protrusions 4 and the first non-oxide protrusions 5 are not limited to the shapes described above.
  • the first oxide protrusions 4 and the first non-oxide protrusions 5 may have a triangular cross section as shown in FIG. 13, or may have another shape.
  • the second oxide protrusions 7 and the second non-oxide protrusions 8 are also not limited to the shapes described above, and may have a triangular cross section as shown in FIG. 14, or may have another shape.
  • the hydrogen electrode layer 31 may extend into the through hole 23.
  • the hydrogen electrode layer 31 may fill only a portion of the through hole 23 as shown in FIG. 15, may fill the entire through hole 23, or may protrude from the through hole 23 onto the second main surface 22.
  • the first oxide protrusion 4 and the first non-oxide protrusion 5 are disposed at the end of the through hole 23 on the second main surface 22 side, but the positions of the first oxide protrusion 4 and the first non-oxide protrusion 5 are not limited to this.
  • the first oxide protrusion 4 and the first non-oxide protrusion 5 may be disposed in the axial center of the through hole 23, or may be disposed in other positions.
  • the first oxide protrusions 4 and the first non-oxide protrusions 5 are not disposed on the second main surface 22 of the metal plate 2, but the configuration of the first oxide protrusions 4 is not limited to this.
  • the first oxide protrusions 4 and the first non-oxide protrusions 5 may be formed on the inner wall surface of the through hole 23 and also on the second main surface 22.
  • the first oxide protrusions 4 and the first non-oxide protrusions 5 are disposed so as to cover the corners 221 formed by the inner wall surface of the through hole 23 and the second main surface 22.
  • the electrolysis cell 100 has been described as an example of an electrochemical cell, but the electrochemical cell may be something other than an electrolysis cell.
  • the electrochemical cell may be a fuel cell such as a solid oxide fuel cell.
  • the first electrode layer may be a fuel electrode (anode)
  • the second electrode layer may be an air electrode (cathode).
  • the first oxide protrusions 4 are preferably formed in the through holes 23 arranged in the outlet side region A2.
  • the first non-oxide protrusions 5 are preferably formed in the through holes 23 arranged in the supply port side region A1.
  • the number of first through holes 23a is smaller than the number of second through holes 23b in the supply port side region A1 and is greater than the number of second through holes 23b in the outlet side region A2.
  • the ratio of first through holes 23a to second through holes 23b in the supply port side region A1 is smaller than the ratio of first through holes 23a to second through holes 23b in the outlet side region A2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Sustainable Development (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Fuel Cell (AREA)
PCT/JP2024/005134 2023-02-22 2024-02-15 電気化学セル Ceased WO2024176929A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024552416A JP7692538B2 (ja) 2023-02-22 2024-02-15 電気化学セル

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-026500 2023-02-22
JP2023026500 2023-02-22

Publications (1)

Publication Number Publication Date
WO2024176929A1 true WO2024176929A1 (ja) 2024-08-29

Family

ID=92501193

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/005134 Ceased WO2024176929A1 (ja) 2023-02-22 2024-02-15 電気化学セル

Country Status (2)

Country Link
JP (1) JP7692538B2 (https=)
WO (1) WO2024176929A1 (https=)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013033617A (ja) * 2011-08-01 2013-02-14 Dainippon Printing Co Ltd 固体酸化物形燃料電池および固体酸化物形燃料電池の製造方法
JP2014049320A (ja) * 2012-08-31 2014-03-17 Nissan Motor Co Ltd 固体酸化物形燃料電池及びその製造方法
JP2020149970A (ja) * 2019-03-07 2020-09-17 日本碍子株式会社 電気化学セル
CN112952170A (zh) * 2021-02-09 2021-06-11 广东省科学院新材料研究所 一种燃料电池/电解池多孔金属支撑体及其增材制备方法
WO2023176241A1 (ja) * 2022-03-15 2023-09-21 日本碍子株式会社 電気化学セル
JP2023135460A (ja) * 2022-03-15 2023-09-28 日本碍子株式会社 電気化学セル

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017002264A1 (ja) 2015-07-02 2017-01-05 日産自動車株式会社 固体酸化物形燃料電池及びその製造方法
JP2017199570A (ja) 2016-04-27 2017-11-02 株式会社デンソー 燃料電池単セル
WO2018198352A1 (ja) 2017-04-28 2018-11-01 株式会社 東芝 固体酸化物電気化学セル及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013033617A (ja) * 2011-08-01 2013-02-14 Dainippon Printing Co Ltd 固体酸化物形燃料電池および固体酸化物形燃料電池の製造方法
JP2014049320A (ja) * 2012-08-31 2014-03-17 Nissan Motor Co Ltd 固体酸化物形燃料電池及びその製造方法
JP2020149970A (ja) * 2019-03-07 2020-09-17 日本碍子株式会社 電気化学セル
CN112952170A (zh) * 2021-02-09 2021-06-11 广东省科学院新材料研究所 一种燃料电池/电解池多孔金属支撑体及其增材制备方法
WO2023176241A1 (ja) * 2022-03-15 2023-09-21 日本碍子株式会社 電気化学セル
JP2023135460A (ja) * 2022-03-15 2023-09-28 日本碍子株式会社 電気化学セル

Also Published As

Publication number Publication date
JP7692538B2 (ja) 2025-06-13
JPWO2024176929A1 (https=) 2024-08-29

Similar Documents

Publication Publication Date Title
JP7637833B1 (ja) 電気化学セル
US20240332566A1 (en) Electrochemical cell
JP7696493B2 (ja) 電気化学セル
JP7280991B1 (ja) 電気化学セル
JP7692538B2 (ja) 電気化学セル
JP7641449B2 (ja) 電気化学セル
JP7670931B2 (ja) 電気化学セル
JP7576206B2 (ja) 電気化学セル
JP7649810B2 (ja) 電気化学セル
JP7659706B1 (ja) 電気化学セル
JP7577244B2 (ja) 電気化学セル
JP7604715B2 (ja) 電気化学セル
JP7696497B2 (ja) 電気化学セル
JP7668971B2 (ja) 電気化学セル
JP7668972B2 (ja) 電気化学セル
JP7649929B2 (ja) 電気化学セル
JP7657379B1 (ja) 電気化学セル
JP7659705B1 (ja) 電気化学セル
JP7657365B2 (ja) 電気化学セル
JP7625134B2 (ja) 電気化学セル
JP7700386B1 (ja) 流路構造体、及び電気化学セル
WO2025141900A1 (ja) 電気化学セル
WO2024143292A1 (ja) 電気化学セル
JP2024044532A (ja) 電気化学セル
WO2025141899A1 (ja) ガス流通容器及びメタルサポート形電気化学セル

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2024552416

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24760230

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 24760230

Country of ref document: EP

Kind code of ref document: A1