WO2022203011A1 - Cellule électrochimique - Google Patents

Cellule électrochimique Download PDF

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Publication number
WO2022203011A1
WO2022203011A1 PCT/JP2022/014063 JP2022014063W WO2022203011A1 WO 2022203011 A1 WO2022203011 A1 WO 2022203011A1 JP 2022014063 W JP2022014063 W JP 2022014063W WO 2022203011 A1 WO2022203011 A1 WO 2022203011A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
electrode layer
layer
electrochemical cell
cell
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PCT/JP2022/014063
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English (en)
Japanese (ja)
Inventor
広重 松本
ライ・チーウェン
和輝 平尾
Original Assignee
京セラ株式会社
国立大学法人九州大学
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Application filed by 京セラ株式会社, 国立大学法人九州大学 filed Critical 京セラ株式会社
Publication of WO2022203011A1 publication Critical patent/WO2022203011A1/fr

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031Porous electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material

Definitions

  • the disclosed embodiments relate to electrochemical cells.
  • An electrochemical cell includes an electrolyte layer, a first electrode layer, and a second electrode layer.
  • the electrolyte layer contains a first electrolyte having ionic conductivity.
  • the first electrode layer and the second electrode layer face each other with the electrolyte layer interposed therebetween.
  • the first electrode layer contains a metal hydroxide, an electronic conductor, and a second electrolyte having ionic conductivity.
  • the second electrode layer has water repellency.
  • FIG. 1 is a schematic diagram of an electrochemical cell according to a first embodiment.
  • FIG. 2 is a diagram showing an outline of a power storage/hydrogen generation device provided with an electrochemical cell according to the first embodiment.
  • FIG. 3 is a schematic diagram of an electrochemical cell according to a second embodiment.
  • FIG. 1 is a schematic diagram of an electrochemical cell according to a first embodiment.
  • an electrochemical cell may be simply called a cell.
  • the cell 1 comprises an electrolyte layer 4 having first and second opposing surfaces, a first electrode layer 3 located on the first surface of the electrolyte layer 4, and a first electrode layer 3 located on the first electrode layer 3.
  • a first current collector 2 a second electrode layer 5 located on the second surface of the electrolyte layer 4
  • a second current collector 6 located on the second electrode layer 5 .
  • Electrolyte layer 4 contains a first electrolyte having ionic conductivity.
  • a first electrolyte having ionic conductivity for example, a solid polymer electrolyte, a polymer gel electrolyte, an inorganic solid electrolyte, or the like can be used.
  • solid polymer electrolytes that can be used include electrolytes having hydroxide ion (OH ⁇ ) conductivity, that is, alkali ion exchange resins (membrane), chitosan, etc., which are alkaline electrolytes.
  • an electrolyte having proton (H + ) conductivity that is, a perfluorosulfonic acid-based material such as Nafion (registered trademark), which is an acidic electrolyte
  • the electrolyte layer 4 may contain water. Note that the electrolyte layer 4 is dense, and it is difficult for gases such as hydrogen (H 2 ) to pass between the first surface and the second surface. Electrolyte layer 4 may further contain a binder.
  • the first electrode layer 3 contains a metal hydroxide such as nickel hydroxide (Ni(OH) 2 ) as an active material.
  • the first electrode layer 3 may also contain a metal oxyhydroxide such as nickel oxyhydroxide (NiOOH).
  • the first electrode layer 3 may contain both a metal hydroxide and a metal oxyhydroxide.
  • Metal hydroxides and metal oxyhydroxides include nickel (Ni), cobalt (Co), iron (Fe), and the like. Of these, Ni hydroxide is particularly suitable as an active material for the first electrode layer 3 because high battery performance can be obtained when used as the active material for the first electrode layer 3 .
  • the first electrode layer 3 contains an electronic conductor.
  • the electron conductor for example, an electron conductive material such as a carbon material, an inorganic compound material, or a metal material having conductivity can be used.
  • the electronic conductor may be dispersed as particles in the first electrode layer 3 or may have a porous structure. Also, the electron conductor may cover the surface of the active material. Carbon black, for example, may be used as the carbon material.
  • the electron conductor is not limited to a carbon material, and may be a conductive inorganic compound material, a metal material, or the like that is resistant to acid or alkali.
  • the electron conductor may have properties such that when it is used as the first electrode layer 3, the electrolysis of water is less likely to occur and the reaction of the metal hydroxide, which is the active material, is less affected.
  • the first electrode layer 3 contains a second electrolyte having ionic conductivity.
  • the electrolyte the same electrolyte as the first electrolyte contained in the electrolyte layer 4 may be used, or an electrolyte different from the first electrolyte may be used.
  • the second electrolyte contained in the first electrode layer 3 may have properties (proton conductivity or hydroxide ion conductivity) in common with the first electrolyte contained in the electrolyte layer 4 .
  • the first electrode layer 3 may contain an electrolyte dispersion (ionomer solution) in which a solid polymer electrolyte (ionomer) is dispersed as a second electrolyte. When the second electrolyte having hydroxide ion conductivity is used, even an active material such as nickel hydroxide, which is susceptible to acid attack, is less likely to corrode.
  • the second electrolyte examples include proton-conducting materials such as Nafion (registered trademark), zeolite, layered proton-conducting nanoparticles, alkali ion exchange resins, chitosan, and layered double hydroxide (LDH). ) and other hydroxide ion conductive materials.
  • the layered proton-conducting nanoparticles include GDC (Gd-Doped Ceria), SDC (Sm-Doped Ceria), YSZ (Yttria-Stabilized Zirconia), TiO 2 (titania), etc., each having a particle size of several nanometers. be done.
  • LDH examples include Mg (magnesium)--Al (aluminum)-based layered double hydroxide (Mg--AlCO 3 2- ).
  • the first electrode layer 3 may further contain a binder.
  • the first electrode layer 3 may contain water.
  • the water contained in the first electrode layer 3 contains a base such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) as a second electrolyte, or an acid such as hydrochloric acid (HCl) and sulfuric acid (H 2 SO 4 ). It may be a water-based electrolyte solution.
  • the first current collector 2 is, for example, a dense metal material such as stainless steel.
  • the material of the first current collector 2 may be any metal that has electronic conductivity and resistance to acid or alkali and water.
  • the shape of the first current collector 2 may be, for example, plate-like or columnar.
  • the first current collector 2 may be made of a metal material whose surface is plated with, for example, Pt having high corrosion resistance.
  • the second electrode layer 5 contains an electrode catalyst. Platinum (Pt), for example, can be used as the electrode catalyst.
  • the electrolyte layer 4 contains a hydroxide ion conductive first electrolyte, a material containing iron (Fe), nickel (Ni), cobalt (Co), silver (Ag) or a carbon-based material is used as the electrode catalyst.
  • the second electrode layer 5 has water repellency. Since the second electrode layer 5 has water repellency, for example, entry of water into the second current collector 6 is suppressed. That is, the second electrode layer 5 does not necessarily need to be water-repellent over the entire area, and for example, only a part near the second current collector 6 may be water-repellent.
  • the second electrode layer 5 may contain polytetrafluoroethylene (PTFE (eg, Teflon (registered trademark), etc.)), polyvinylidene fluoride (PVDF), or the like that imparts water repellency. Sufficient water repellency can be given to the 2nd electrode layer 5 by containing these.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • the second electrode layer having water repellency is described, for example, in Patent Document 1 and JP-A-2012-041578.
  • the second electrode layer 5 may further contain an electronically conductive material such as that contained in the first electrode layer 3 .
  • the second electrode layer 5 may be a mixture of an electrode catalyst and a water-repellent material, or may be a laminate of an electrode catalyst layer and a water-repellent material layer.
  • a laminated structure may be used in which a water-repellent material as described above is applied on carbon paper having electron conductivity, and an electrode catalyst is sprayed thereon to form a laminated structure.
  • the second current collector 6 is a metal material having gas permeability, such as a metal mesh material, a metal plate having through holes, or a porous metal obtained by sintering metal powder.
  • the material of the second current collector 6 may be any metal that has electronic conductivity and resistance to water, hydrogen and air.
  • the shape of the second current collector 6 may be, for example, plate-like or columnar.
  • the second current collector 6 may be made of a metal material whose surface is plated with, for example, Pt having high corrosion resistance.
  • the electrode reaction in the cell 1 will be described, taking as an example the cell 1 in which an OH - conductive alkaline electrolyte is applied as the electrolyte.
  • Reaction formulas in the first electrode layer 3 and the second electrode layer 5 during charging are as follows.
  • First electrode layer Ni(OH) 2 + OH - ⁇ NiOOH + H 2 O + e - 0.52 V (vs. SHE: standard hydrogen electrode)
  • Second electrode layer H 2 O + e ⁇ ⁇ 1/2H 2 +OH ⁇ -0.83 V (vs. SHE: standard hydrogen electrode)
  • the cell 1 can be used as a hydrogen generator.
  • the cell 1 according to the present embodiment has a lower electrolysis voltage than a water electrolysis cell in which oxygen is generated. Thereby, according to the cell 1 according to the present embodiment, performance can be improved.
  • the reaction proceeds in the opposite direction to the reaction formula described above. That is, the second electrode layer 5 generates electricity using hydrogen supplied from the outside. Thereby, the cell 1 can be used as a fuel cell.
  • the cell 1 according to the present embodiment has a higher power generation voltage than a fuel cell that uses oxygen gas to generate power. Thereby, according to the cell 1 according to the present embodiment, performance can be improved.
  • the first electrode layer 3 is in an alkaline environment and the active material is not attacked by acid, so good performance can be maintained.
  • reaction formulas in the first electrode layer 3 and the second electrode layer 5 during charging are as follows.
  • First electrode layer Ni(OH) 2 ⁇ NiOOH + H + + e ⁇
  • Second electrode layer H + + e ⁇ ⁇ 1/2H 2
  • FIG. 1 The cell 1 shown in FIG. 1 can be used reversibly as a power storage/hydrogen generator.
  • FIG. 2 is a diagram showing an outline of a power storage/hydrogen generation device provided with an electrochemical cell according to the first embodiment.
  • the electricity storage/hydrogen generator 10 includes a cell 1, a water tank 7, a hydrogen gas flow path 8, and lead wires 9a and 9b.
  • the water tank 7 is filled with water or electrolyte.
  • the electrolytic solution for example, a solution containing a base such as sodium hydroxide (NaOH) or potassium hydroxide (KOH), or a solution containing an acid such as hydrochloric acid (HCl) or sulfuric acid (H 2 SO 4 ) can be used. can.
  • the electrolytic solution can be appropriately selected according to the properties (proton conductivity or hydroxide ion conductivity) of the second electrolyte.
  • the insides of the first electrode layer 3 and the electrolyte layer 4 are wet by facing the water tank 7 .
  • the inside of the water tank 7 may be pressurized. By appropriately pressurizing the inside of the water tank 7, for example, the electrode reaction in the cell 1 is promoted.
  • the water tank 7 may be connected to a water channel that supplies or drains water or electrolyte to the water tank 7 .
  • hydrogen gas supplied from the outside through the hydrogen gas flow path 8 is used to generate power.
  • Excess water generated in the first electrode layer 3 and the electrolyte layer 4 is discharged to the water tank 7, so that the insides of the first electrode layer 3 and the electrolyte layer 4 can be maintained in a moderately moist state.
  • FIG. 3 is a schematic diagram of an electrochemical cell according to a second embodiment. As shown in FIG. 3, the cell 1A differs from the cell 1 according to the first embodiment in that it includes a first electrode layer 13 and an electrolyte layer 14 instead of the first electrode layer 3 and the electrolyte layer 4 .
  • the electrolyte layer 14 contains a solid electrolyte having ionic conductivity as the first electrolyte.
  • the electrolyte layer 14 may contain a porous solid electrolyte, or may contain a green compact obtained by compressing solid electrolyte powder.
  • a solid polymer electrolyte, an inorganic solid electrolyte, or the like can be used as the solid electrolyte contained in the electrolyte layer 14.
  • solid polymer electrolytes that can be used include electrolytes having hydroxide ion (OH ⁇ ) conductivity, that is, alkali ion exchange resins (membrane), chitosan, etc., which are alkaline electrolytes.
  • an electrolyte having proton (H + ) conductivity that is, a perfluorosulfonic acid-based material such as Nafion (registered trademark), which is an acidic electrolyte, may be used.
  • inorganic solid electrolyte examples include layered double hydroxide (LDH) having hydroxide ion (OH ⁇ ) conductivity, zeolite having proton (H + ) conductivity, layered proton conductive nanoparticles, and the like. be able to.
  • LDH layered double hydroxide
  • zeolite having proton (H + ) conductivity
  • H + layered proton conductive nanoparticles
  • a porous solid electrolyte has pores.
  • the compact of solid electrolyte has voids between particles.
  • the electrolyte layer 14 has water or electrolyte inside such pores or voids.
  • the electrolyte layer 14 has water or an electrolytic solution inside the pores or voids, so that gas such as hydrogen (H 2 ) is basically impermeable between the first surface and the second surface.
  • the electrolyte layer 14 may further contain a binder.
  • the first electrode layer 13 contains a metal hydroxide such as nickel hydroxide (Ni(OH) 2 ) as an active material.
  • the first electrode layer 13 may also contain a metal oxyhydroxide such as nickel oxyhydroxide (NiOOH).
  • the first electrode layer 13 may contain both a metal hydroxide and a metal oxyhydroxide.
  • the metal of the metal hydroxide and the metal oxyhydroxide the same materials as those mentioned as the material of the first electrode layer 3 according to the first embodiment can be used.
  • the first electrode layer 13 contains an electronic conductor.
  • the electron conductor for example, an electron conductive material such as a carbon material, an inorganic compound material, or a metal material having conductivity can be used.
  • the electronic conductor may be dispersed as particles in the first electrode layer 3 or may have a porous structure. Also, the electron conductor may cover the surface of the active material.
  • the carbon material, the inorganic compound material, and the metal material the same materials as those mentioned as the material of the first electrode layer 3 according to the first embodiment can be used.
  • the first electrode layer 13 contains a second electrolyte having ionic conductivity.
  • the second electrolyte the same solid electrolyte as that contained in the electrolyte layer 14 may be used, or an electrolyte different from the solid electrolyte may be used.
  • the second electrolyte contained in the first electrode layer 13 may have properties (proton conductivity or hydroxide ion conductivity) in common with the solid electrolyte contained in the electrolyte layer 14 .
  • the same materials as the materials of the first electrode layer 3 according to the first embodiment can be used.
  • the first electrode layer 13 may further contain a binder.
  • the first electrode layer 13 may contain water.
  • the water contained in the first electrode layer 13 contains a base such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) or an acid such as hydrochloric acid (HCl) or sulfuric acid (H 2 SO 4 ) as a second electrolyte. It may be a water-based electrolyte solution.
  • the water contained in the first electrode layer 13 exists between the pores of the electrolyte or the active material, the electronic conductor, and the electrolyte that constitute the first electrode layer 13, so that the first electrode layer 13 is ionically conductive. have a sexuality.
  • the cell 1A can be used as a hydrogen generator.
  • the cell 1A according to the present embodiment has a lower electrolysis voltage than a water electrolysis cell in which oxygen is generated. Thereby, according to the cell 1A according to the present embodiment, performance can be improved.
  • the second electrode layer 5 generates power using hydrogen supplied from the outside.
  • the cell 1A can be used as a fuel cell.
  • the cell 1A according to this embodiment has a higher power generation voltage than a fuel cell that generates power using oxygen gas. Thereby, according to the cell 1A according to the present embodiment, performance can be improved.
  • the present disclosure is not limited to the above embodiments, and various modifications are possible without departing from the gist thereof.
  • the cell 1A shown in FIG. 3 may be applied instead of the cell 1 included in the electricity storage and hydrogen generation device 10 shown in FIG.
  • the water tank 7 shown in FIG. 2 may be filled with water.
  • the electricity storage and hydrogen generation device 10 may include a cell stack in which a plurality of cells 1 or cells 1A are stacked instead of the cells 1 or 1A.
  • the electrochemical cell (cell 1) includes the electrolyte layer 4, the first electrode layer 3 and the second electrode layer 5.
  • Electrolyte layer 4 contains a first electrolyte having ionic conductivity.
  • the first electrode layer 3 and the second electrode layer 5 face each other with the electrolyte layer 4 interposed therebetween.
  • the first electrode layer 3 contains a metal hydroxide, an electronic conductor, and a second electrolyte having ionic conductivity.
  • the second electrode layer 5 has water repellency. Thereby, the performance of the cell 1 can be improved.
  • first electrolyte and the second electrolyte according to the embodiment contain a solid electrolyte having hydroxide ion conductivity. Thereby, the performance of the cell 1 can be improved.
  • Reference Signs List 1 1A cell 2 first current collector 3, 13 first electrode layer 4, 14 electrolyte layer 5 second electrode layer 6 second current collector 7 water tank 10 power storage/hydrogen generator

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Fuel Cell (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inert Electrodes (AREA)

Abstract

Dans la présente invention, une cellule électrochimique comprend une couche d'électrolyte, et une première couche d'électrode ainsi qu'une seconde couche d'électrode. La couche d'électrolyte contient un premier électrolyte conducteur d'ions. La première couche d'électrode et la seconde couche d'électrode se font face l'une à l'autre à travers la couche d'électrolyte. La première couche d'électrode contient un hydroxyde métallique, un conducteur d'électrons et un second électrolyte conducteur d'ions. La seconde couche d'électrode présente des propriétés hydrofuges.
PCT/JP2022/014063 2021-03-25 2022-03-24 Cellule électrochimique WO2022203011A1 (fr)

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JP2021052303A JP2022149943A (ja) 2021-03-25 2021-03-25 セル
JP2021-052303 2021-03-25

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001512186A (ja) * 1997-07-29 2001-08-21 ミクロリン・エル・シー 流体分配装置用貯蔵安定な電解ガス発生装置
JP2013191523A (ja) * 2012-03-15 2013-09-26 Osaka Prefecture Univ 全固体アルカリ燃料電池用電解質膜
CN106257729A (zh) * 2015-06-17 2016-12-28 中国科学院大连化学物理研究所 自呼吸式光助生物质燃料电池及其应用
JP2018106882A (ja) * 2016-12-26 2018-07-05 国立研究開発法人物質・材料研究機構 燃料電池および水電解装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001512186A (ja) * 1997-07-29 2001-08-21 ミクロリン・エル・シー 流体分配装置用貯蔵安定な電解ガス発生装置
JP2013191523A (ja) * 2012-03-15 2013-09-26 Osaka Prefecture Univ 全固体アルカリ燃料電池用電解質膜
CN106257729A (zh) * 2015-06-17 2016-12-28 中国科学院大连化学物理研究所 自呼吸式光助生物质燃料电池及其应用
JP2018106882A (ja) * 2016-12-26 2018-07-05 国立研究開発法人物質・材料研究機構 燃料電池および水電解装置

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