WO2022203011A1 - Electrochemical cell - Google Patents

Electrochemical cell 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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Prior art keywords
electrolyte
electrode layer
layer
electrochemical cell
cell
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PCT/JP2022/014063
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French (fr)
Japanese (ja)
Inventor
広重 松本
ライ・チーウェン
和輝 平尾
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京セラ株式会社
国立大学法人九州大学
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Publication of WO2022203011A1 publication Critical patent/WO2022203011A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for 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
    • 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
    • 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
    • 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
    • H01M8/1016—Fuel 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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Abstract

In the present invention, an electrochemical cell comprises an electrolyte layer, and a first electrode layer and a second electrode layer. The electrolyte layer contains an ion-conductive first electrolyte. The first electrode layer and the second electrode layer face each other across the electrolyte layer. The first electrode layer contains a metal hydroxide, an electron conductor, and an ion-conductive second electrolyte. The second electrode layer has water-repellent properties.

Description

電気化学セルelectrochemical cell
　開示の実施形態は、電気化学セルに関する。 The disclosed embodiments relate to electrochemical cells.
　従来、単一のセルで水電解と発電とを可逆的に切り替える技術が提案されている。 Conventionally, technology has been proposed to reversibly switch between water electrolysis and power generation in a single cell.
国際公開第２０１８／０８４１７５号WO2018/084175
　実施形態の一態様に係る電気化学セルは、電解質層と、第１電極層および第２電極層とを備える。電解質層は、イオン伝導性を有する第１電解質を含有する。第１電極層および第２電極層は、電解質層を挟んで対向する。第１電極層は、金属水酸化物と、電子伝導体と、イオン伝導性を有する第２電解質とを含有する。第２電極層は、撥水性を有する。 An electrochemical cell according to one aspect of an embodiment 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.
図１は、第１の実施形態に係る電気化学セルの概略を示す図である。FIG. 1 is a schematic diagram of an electrochemical cell according to a first embodiment. 図２は、第１の実施形態に係る電気化学セルを備える蓄電・水素発生装置の概略を示す図である。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. 図３は、第２の実施形態に係る電気化学セルの概略を示す図である。FIG. 3 is a schematic diagram of an electrochemical cell according to a second embodiment.
　以下、添付図面を参照して、本願の開示する電気化学セルの実施形態を詳細に説明する。なお、以下に示す実施形態によりこの発明が限定されるものではない。 Hereinafter, embodiments of the electrochemical cell disclosed in the present application will be described in detail with reference to the accompanying drawings. In addition, this invention is not limited by embodiment shown below.
＜第１の実施形態＞
　図１は、第１の実施形態に係る電気化学セルの概略を示す図である。以下、電気化学セルを単にセルという場合がある。図１に示すように、セル１は、対向する第１面および第２面を有する電解質層４、電解質層４の第１面に位置する第１電極層３、第１電極層３上に位置する第１集電体２、電解質層４の第２面に位置する第２電極層５、および第２電極層５上に位置する第２集電体６を備える。 <First Embodiment>
FIG. 1 is a schematic diagram of an electrochemical cell according to a first embodiment. Hereinafter, an electrochemical cell may be simply called a cell. As shown in FIG. 1, 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 , and a second current collector 6 located on the second electrode layer 5 .
　電解質層４は、イオン伝導性を有する第１電解質を含有する。イオン伝導性を有する第１電解質としては、例えば、固体高分子電解質、高分子ゲル電解質、無機固体電解質などを使用することができる。固体高分子電解質としては、例えば、水酸化物イオン（ＯＨ－）伝導性を有する電解質、すなわちアルカリ性の電解質であるアルカリイオン交換樹脂（膜）、キトサンなどを使用することができる。 Electrolyte layer 4 contains a first electrolyte having ionic conductivity. As the 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. Examples of 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.
　また、例えば、プロトン（Ｈ＋）伝導性を有する電解質、すなわち酸性の電解質であるナフィオン（登録商標）などのパーフルオロスルホン酸系の材料などを使用してもよい。また、電解質層４は水を含有してもよい。なお、電解質層４は緻密質であり、第１面と第２面との間で水素（Ｈ２）などの気体を通しにくい。電解質層４は、さらにバインダを含有してもよい。 Also, for example, 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. Moreover, 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.
　第１電極層３は、活物質として金属水酸化物、例えば水酸化ニッケル（Ｎｉ（ＯＨ）２）を含有する。また、第１電極層３は、オキシ水酸化金属、例えばオキシ水酸化ニッケル（ＮｉＯＯＨ）を含有してもよい。また、第１電極層３は、金属水酸化物およびオキシ水酸化金属の両方を含有してもよい。金属水酸化物、オキシ水酸化金属の金属としては、ニッケル（Ｎｉ）のほか、例えばコバルト（Ｃｏ）、鉄（Ｆｅ）等が挙げられる。このうち、特にＮｉの水酸化物は、第１電極層３の活物質として用いると高い電池性能を得ることができ、第１電極層３の活物質として適している。 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). Also, 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 .
　第１電極層３は、電子伝導体を含有する。電子伝導体としては、例えば、導電性を有する炭素材料、無機化合物材料、金属材料などの電子伝導性材料を使用することができる。電子伝導体は、第１電極層３内に粒子として分散していてもよいし、多孔質の構造を有していてもよい。また、電子伝導体は、活物質の表面を被覆していてもよい。炭素材料としては、例えばカーボンブラックなどを用いてもよい。電子伝導体は、炭素材料に限らず、酸、アルカリに侵されにくい導電性の無機化合物材料、金属材料などを用いてもよい。電子伝導体は、第１電極層３として用いたときに水の電解を起こしにくく、活物質である水酸化物金属の反応に影響が少ない性質を有していてもよい。 The first electrode layer 3 contains an electronic conductor. As 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.
　また、第１電極層３は、イオン伝導性を有する第２電解質を含有する。電解質としては、電解質層４に含まれる第１電解質と同じものを使用してもよいし、第１電解質とは異なる電解質を使用してもよい。また、第１電極層３に含まれる第２電解質は、電解質層４に含まれる第１電解質と共通する性質（プロトン伝導性または水酸化物イオン伝導性）を有していてもよい。第１電極層３は、第２電解質として固体高分子電解質（ionomer）が分散した電解質分散液（ionomer　solution）を含有してもよい。なお、水酸化物イオン伝導性の第２電解質を用いると、例えば水酸化ニッケルなどの酸に侵されやすい活物質でも腐食しにくくなる。 In addition, the first electrode layer 3 contains a second electrolyte having ionic conductivity. As 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. Also, 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.
　第２電解質の具体例としては、例えばナフィオン（登録商標）、ゼオライト、層状プロトン伝導性ナノ粒子などのプロトン伝導性材料、およびアルカリイオン交換樹脂、キトサン、層状複水酸化物（ＬＤＨ：Layered　Double　Hydroxide）などの水酸化物イオン伝導性材料が挙げられる。層状プロトン伝導性ナノ粒子としては、例えば数ｎｍ程度の粒径を有するＧＤＣ（Gd-Doped　Ceria）、ＳＤＣ（Sm-Doped　Ceria）、ＹＳＺ（Yttria-Stabilized　Zirconia）、ＴｉＯ２（チタニア）などが挙げられる。ＬＤＨとしては、例えばＭｇ（マグネシウム）－Ａｌ（アルミニウム）系層状複水酸化物（Ｍｇ－ＡｌＣＯ３ ２－）などが挙げられる。第１電極層３は、さらにバインダを含有してもよい。 Specific examples of the second electrolyte 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. Examples of 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. Examples of LDH include Mg (magnesium)--Al (aluminum)-based layered double hydroxide (Mg--AlCO 3 2- ). The first electrode layer 3 may further contain a binder.
　また、第１電極層３は、水を含有してもよい。第１電極層３に含まれる水は、第２電解質として水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）などの塩基、または塩酸（ＨＣｌ）、硫酸（Ｈ２ＳＯ４）等の酸を含有する水系電解液であってもよい。 Moreover, 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.
　第１集電体２は、例えば、ステンレス鋼など、緻密質の金属材料である。第１集電体２の材料は、電子伝導性を有し、酸またはアルカリおよび水に対し耐久性を有する金属であればよい。第１集電体２の形状は、例えば、板状または柱状であってもよい。また、表面を例えば耐食性の高いＰｔなどでメッキ処理した金属材料を第１集電体２としてもよい。 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. Alternatively, the first current collector 2 may be made of a metal material whose surface is plated with, for example, Pt having high corrosion resistance.
　第２電極層５は、電極触媒を含有する。電極触媒としては、例えば、白金（Ｐｔ）を使用することができる。電解質層４が水酸化物イオン伝導性の第１電解質を含む場合は、電極触媒として鉄（Ｆｅ）、ニッケル（Ｎｉ）、コバルト（Ｃｏ）、銀（Ａｇ）を含む材料または炭素系材料を使用してもよい。また、第２電極層５は、撥水性を有する。第２電極層５が撥水性を有することにより、例えば、第２集電体６への水の進入が抑えられる。すなわち、第２電極層５は、全体にわたる撥水性を必ずしも要さず、例えば、第２集電体６に近い一部にのみ撥水性が付与されていてもよい。第２電極層５は、撥水性を付与するポリテトラフルオロエチレン（ＰＴＦＥ（例えば、テフロン（登録商標）など））、ポリフッ化ビニリデン（ＰＶＤＦ）、などを含有してもよい。これらを含有することで第２電極層５に充分な撥水性を付与することができる。撥水性を有する第２電極層については、例えば特許文献１、特開２０１２－０４１５７８などに記載されている。 The second electrode layer 5 contains an electrode catalyst. Platinum (Pt), for example, can be used as the electrode catalyst. When 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. You may Moreover, 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. The second electrode layer having water repellency is described, for example, in Patent Document 1 and JP-A-2012-041578.
　第２電極層５は、さらに第１電極層３に含まれるような電子伝導性材料を含有してもよい。第２電極層５は、電極触媒および撥水材料の混合物であってもよいし、電極触媒層、撥水材料層などの積層体であってもよい。第２電極層５として、例えば電子伝導性を有するカーボンペーパー上に上記のような撥水性材料を塗布し、さらにその上に電極触媒をスプレーし、積層構造を形成したものを用いてもよい。 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. As the second electrode layer 5, for example, 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.
　第２集電体６は、例えば金属メッシュ材料、貫通孔を有する金属板、金属粉末を焼成した多孔質金属など、ガス透過性を有する金属材料である。第２集電体６の材料は、電子伝導性を有し、水、水素および空気に対し耐久性を有する金属であればよい。第２集電体６の材料としては、具体的には例えばチタン、ステンレス鋼などを用いることができる。第２集電体６の形状は、例えば、板状または柱状であってもよい。また、表面を例えば耐食性の高いＰｔなどでメッキ処理した金属材料を第２集電体６としてもよい。 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. As the material of the second current collector 6, specifically, for example, titanium, stainless steel, or the like can be used. The shape of the second current collector 6 may be, for example, plate-like or columnar. Alternatively, the second current collector 6 may be made of a metal material whose surface is plated with, for example, Pt having high corrosion resistance.
　ここで、セル１における電極反応について、電解質としてＯＨ－伝導性のアルカリ性電解質を適用したセル１を例に挙げて説明する。充電時における第１電極層３および第２電極層５での反応式はそれぞれ、以下のとおりである。 Here, 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.
　第１電極層：Ｎｉ（ＯＨ）２　＋　ＯＨ－　→　ＮｉＯＯＨ　＋　Ｈ２Ｏ　＋　ｅ－
　　　　　　　０．５２Ｖ（ｖｓ．ＳＨＥ：標準水素電極）
　第２電極層：Ｈ２Ｏ　＋　ｅ－　→　１／２Ｈ２　＋ＯＨ－
　　　　　　　－０．８３Ｖ（ｖｓ．ＳＨＥ：標準水素電極） 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)
　このように、充電時には、第２電極層５で水素が生成する。これにより、セル１は、水素生成装置として利用することができる。 Thus, hydrogen is generated in the second electrode layer 5 during charging. Thereby, the cell 1 can be used as a hydrogen generator.
　また、充電時には、第１電極層３で水が生成するが、酸素はＮｉ（ＯＨ）２と反応してＮｉＯＯＨを生成し、酸素ガスは生成しない。このため、本実施形態に係るセル１は、酸素が発生する水電解セルと比較して電解電圧が低下する。これにより、本実施形態に係るセル１によれば、性能を向上することができる。 Also, water is generated in the first electrode layer 3 during charging, but oxygen reacts with Ni(OH) 2 to generate NiOOH, and oxygen gas is not generated. Therefore, 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.
　一方、放電（発電）時には、上記した反応式とは逆方向に反応が進行する。すなわち、第２電極層５は、外部から供給された水素を利用して発電する。これにより、セル１は、燃料電池として利用することができる。 On the other hand, during discharge (power generation), 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.
　また、放電時には、第１電極層３でＮｉＯＯＨが酸化されてＮｉ（ＯＨ）２を生成するが、酸素ガスは反応に寄与しない。このため、本実施形態に係るセル１は、酸素ガスを利用して発電する燃料電池と比較して発電電圧が上昇する。これにより、本実施形態に係るセル１によれば、性能を向上することができる。ＯＨ－伝導性のアルカリ性電解質を適用したセル１では、第１電極層３がアルカリ性の環境下にあり、活物質が酸に侵されないため、良好な性能を維持できる。 Also, during discharge, NiOOH is oxidized in the first electrode layer 3 to form Ni(OH) 2 , but oxygen gas does not contribute to the reaction. Therefore, 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. In the cell 1 to which the OH - conductive alkaline electrolyte is applied, 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.
　なお、電解質としてプロトン伝導性の酸性電解質を適用したセル１では、充電時における第１電極層３および第２電極層５での反応式はそれぞれ、以下のとおりである。
　第１電極層：Ｎｉ（ＯＨ）２　→　ＮｉＯＯＨ　＋　Ｈ＋　＋　ｅ－
　第２電極層：Ｈ＋　＋　ｅ－　→　１／２Ｈ２ In addition, in the cell 1 in which a proton-conducting acidic 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 →NiOOH + H + + e −
Second electrode layer: H + + e − → 1/2H 2
　図１に示すセル１は、蓄電・水素発生装置として可逆的に使用することができる。図２は、第１の実施形態に係る電気化学セルを備える蓄電・水素発生装置の概略を示す図である。 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.
　図２に示すように、蓄電・水素発生装置１０は、セル１と、水槽７と、水素ガス流路８と、リード線９ａ，９ｂとを備える。 As shown in FIG. 2, 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.
　水槽７は、水または電解液で満たされている。電解液としては、例えば、水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）等の塩基を含む溶液、塩酸（ＨＣｌ）、硫酸（Ｈ２ＳＯ４）等の酸を含む溶液を使用することができる。電解液は、第２電解質の性質（プロトン伝導性または水酸化物イオン伝導性）に応じ、適宜選択できる。第１電極層３および電解質層４の内部は、水槽７に面することにより湿潤している。水槽７の内部は、加圧されてもよい。水槽７の内部を適度に加圧することにより、例えば、セル１における電極反応が促進される。水槽７は、水または電解液を水槽７に供給、または水槽７から排出する水路と接続されていてもよい。 The water tank 7 is filled with water or electrolyte. As 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 .
　水電解モードでは、リード線９ａ，９ｂを介して第１集電体２および第２集電体６に電圧を印加する。その結果、第２電極層５で発生した水素ガスは、水素ガス流路８から外部へ排出される。 In the water electrolysis mode, voltage is applied to the first current collector 2 and the second current collector 6 via the lead wires 9a and 9b. As a result, the hydrogen gas generated in the second electrode layer 5 is discharged from the hydrogen gas channel 8 to the outside.
　一方、発電モードでは、外部から水素ガス流路８を介して供給される水素ガスを利用して発電する。第１電極層３および電解質層４で生成された余剰な水は、水槽７に排出され、第１電極層３および電解質層４の内部は適度な湿潤状態を維持することができる。 On the other hand, in the power generation mode, 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.
＜第２の実施形態＞
　図３は、第２の実施形態に係る電気化学セルの概略を示す図である。図３に示すように、セル１Ａは、第１電極層３および電解質層４に代えて、第１電極層１３および電解質層１４を備える点で第１の実施形態に係るセル１と相違する。 <Second embodiment>
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 .
　電解質層１４は第１電解質としてイオン伝導性を有する固体電解質を含有する。電解質層１４は、多孔質の固体電解質を含有してもよいし、固体電解質の粉末を圧縮成形した圧粉体を含有してもよい。 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.
　電解質層１４が含有する固体電解質としては、固体高分子電解質、無機固体電解質などを使用することができる。固体高分子電解質としては、例えば、水酸化物イオン（ＯＨ－）伝導性を有する電解質、すなわちアルカリ性の電解質であるアルカリイオン交換樹脂（膜）、キトサンなどを使用することができる。また、例えば、プロトン（Ｈ＋）伝導性を有する電解質、すなわち酸性の電解質であるナフィオン（登録商標）などのパーフルオロスルホン酸系の材料などを使用してもよい。 As the solid electrolyte contained in the electrolyte layer 14, a solid polymer electrolyte, an inorganic solid electrolyte, or the like can be used. Examples of 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. Also, for example, 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.
　無機固体電解質としては、例えば、水酸化物イオン（ＯＨ－）伝導性を有する層状複水酸化物（ＬＤＨ）、プロトン（Ｈ＋）伝導性を有するゼオライト、層状プロトン伝導性ナノ粒子などを使用することができる。 Examples of the inorganic solid electrolyte 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.
　多孔質の固体電解質は、細孔を有している。固体電解質の圧粉体は、粒子間に空隙を有している。電解質層１４は、このような細孔または空隙の内部に、水または電解液を有している。電解質層１４は、細孔または空隙の内部に、水または電解液を有することにより、第１面と第２面との間で水素（Ｈ２）などの気体を基本的に通さない。電解質層１４は、さらにバインダを含有してもよい。 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.
　第１電極層１３は、活物質として金属水酸化物、例えば水酸化ニッケル（Ｎｉ（ＯＨ）２）を含有する。また、第１電極層１３は、オキシ水酸化金属、例えばオキシ水酸化ニッケル（ＮｉＯＯＨ）を含有してもよい。また、第１電極層１３は、金属水酸化物およびオキシ水酸化金属の両方を含有してもよい。金属水酸化物、オキシ水酸化金属の金属としては、第１の実施形態に係る第１電極層３の材料として挙げたものと同じものを使用できる。 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). Also, the first electrode layer 13 may contain both a metal hydroxide and a metal oxyhydroxide. As 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.
　第１電極層１３は、電子伝導体を含有する。電子伝導体としては、例えば、導電性を有する炭素材料、無機化合物材料、金属材料などの電子伝導性材料を使用することができる。電子伝導体は、第１電極層３内に粒子として分散していてもよいし、多孔質の構造を有していてもよい。また、電子伝導体は、活物質の表面を被覆していてもよい。炭素材料、無機化合物材料、金属材料としては、第１の実施形態に係る第１電極層３の材料として挙げたものと同じものを使用できる。 The first electrode layer 13 contains an electronic conductor. As 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. As 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.
　また、第１電極層１３は、イオン伝導性を有する第２電解質を含有する。第２電解質としては、電解質層１４に含まれる固体電解質と同じものを使用してもよいし、固体電解質とは異なる電解質を使用してもよい。また、第１電極層１３に含まれる第２電解質は、電解質層１４に含まれる固体電解質と共通する特性（プロトン伝導性または水酸化物イオン伝導性）を有していてもよい。第２電解質としては、第１の実施形態に係る第１電極層３の材料として挙げたものと同じものを使用できる。第１電極層１３は、さらにバインダを含有してもよい。 In addition, the first electrode layer 13 contains a second electrolyte having ionic conductivity. As 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. Also, 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 . As the second electrolyte, 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.
　また、第１電極層１３は、水を含有してもよい。第１電極層１３に含まれる水は、第２電解質として水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）などの塩基、または塩酸（ＨＣｌ）、硫酸（Ｈ２ＳＯ４）などの酸を含有する水系電解液であってもよい。第１電極層１３に含まれる水が、電解質の細孔、または第１電極層１３を構成する活物質、電子伝導体、電解質の間に存在することにより、第１電極層１３は、イオン伝導性を有することとなる。 Also, 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.
　このように構成されたセル１Ａであっても、充電時には、第２電極層５で水素が生成する。これにより、セル１Ａは、水素生成装置として利用することができる。 Even in the cell 1A configured in this way, hydrogen is generated in the second electrode layer 5 during charging. Thereby, the cell 1A can be used as a hydrogen generator.
　また、充電時には、第１電極層１３で水が生成するが、酸素はＮｉ（ＯＨ）２と反応してＮｉＯＯＨを生成し、酸素ガスは生成しない。このため、本実施形態に係るセル１Ａは、酸素が発生する水電解セルと比較して電解電圧が低下する。これにより、本実施形態に係るセル１Ａによれば、性能を向上することができる。 Also, water is generated in the first electrode layer 13 during charging, but oxygen reacts with Ni(OH) 2 to generate NiOOH, and oxygen gas is not generated. Therefore, 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.
　一方、放電（発電）時には、第２電極層５は、外部から供給された水素を利用して発電する。これにより、セル１Ａは、燃料電池として利用することができる。 On the other hand, during discharge (power generation), the second electrode layer 5 generates power using hydrogen supplied from the outside. Thereby, the cell 1A can be used as a fuel cell.
　また、放電時には、第１電極層１３でＮｉＯＯＨが酸化されてＮｉ（ＯＨ）２を生成するが、酸素ガスは反応に寄与しない。このため、本実施形態に係るセル１Ａは、酸素ガスを利用して発電する燃料電池と比較して発電電圧が上昇する。これにより、本実施形態に係るセル１Ａによれば、性能を向上することができる。 Also, during discharge, NiOOH is oxidized in the first electrode layer 13 to produce Ni(OH) 2 , but oxygen gas does not contribute to the reaction. For this reason, 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.
　以上、本開示の実施形態について説明したが、本開示は上記実施形態に限定されるものではなく、その趣旨を逸脱しない限りにおいて種々の変更が可能である。例えば、図２に示す蓄電・水素発生装置１０が有するセル１に代えて、図３に示すセル１Ａを適用してもよい。かかる場合、例えば、図２に示す水槽７には、水を満たせばよい。 Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments, and various modifications are possible without departing from the gist thereof. For example, 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. In such a case, for example, the water tank 7 shown in FIG. 2 may be filled with water.
　また、蓄電・水素発生装置１０は、セル１またはセル１Ａに代えて、複数のセル１またはセル１Ａを積層したセルスタックを備えてもよい。 Also, 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.
　以上のように、実施形態に係る電気化学セル（セル１）は、電解質層４と、第１電極層３および第２電極層５とを備える。電解質層４は、イオン伝導性を有する第１電解質を含有する。第１電極層３および第２電極層５は、電解質層４を挟んで対向する。第１電極層３は、金属水酸化物と、電子伝導体と、イオン伝導性を有する第２電解質とを含有する。第２電極層５は、撥水性を有する。これにより、セル１の性能を向上することができる。 As described above, the electrochemical cell (cell 1) according to the embodiment 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.
　また、実施形態に係る第１電解質および第２電解質は、水酸化物イオン伝導性を有する固体電解質を含有する。これにより、セル１の性能を向上することができる。 Also, the 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.
　さらなる効果や変形例は、当業者によって容易に導き出すことができる。このため、本開示のより広範な態様は、以上のように表しかつ記述した特定の詳細および代表的な実施形態に限定されるものではない。したがって、添付の請求の範囲およびその均等物によって定義される総括的な発明の概念の精神または範囲から逸脱することなく、様々な変更が可能である。 Further effects and modifications can be easily derived by those skilled in the art. Therefore, the broader aspects of the disclosure are not limited to the specific details and representative embodiments so represented and described. Accordingly, various changes may be made without departing from the spirit or scope of the general inventive concept defined by the appended claims and equivalents thereof.
　　１，１Ａ　セル
　　２　第１集電体
　　３，１３　第１電極層
　　４，１４　電解質層
　　５　第２電極層
　　６　第２集電体
　　７　水槽
　１０　蓄電・水素発生装置 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

Claims (7)

  1. 　イオン伝導性を有する第１電解質を含有する電解質層と、
    　該電解質層を挟んで対向する第１電極層および第２電極層と
    　を備え、
    　前記第１電極層は、金属水酸化物と、電子伝導体と、イオン伝導性を有する第２電解質とを含有し、
    　前記第２電極層は、撥水性を有する
    　電気化学セル。     an electrolyte layer containing a first electrolyte having ionic conductivity;
    A first electrode layer and a second electrode layer facing 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 electrochemical cell, wherein the second electrode layer has water repellency.
  2. 　前記第１電解質および前記第２電解質は、水酸化物イオン伝導性を有する固体電解質を含有する
    　請求項１に記載の電気化学セル。     2. The electrochemical cell of claim 1, wherein said first electrolyte and said second electrolyte contain a solid electrolyte having hydroxide ion conductivity.
  3. 　前記第１電解質および前記第２電解質は、多孔質の固体電解質を含有する
    　請求項１または２に記載の電気化学セル。     3. The electrochemical cell according to claim 1, wherein the first electrolyte and the second electrolyte contain porous solid electrolytes.
  4. 　前記金属水酸化物は、水酸化ニッケルを含む
    　請求項１～３のいずれか１つに記載の電気化学セル。     The electrochemical cell of any one of claims 1-3, wherein the metal hydroxide comprises nickel hydroxide.
  5. 　前記電解質層および前記第１電極層は、水を含有する
    　請求項１～４のいずれか１つに記載の電気化学セル。     The electrochemical cell according to any one of claims 1 to 4, wherein the electrolyte layer and the first electrode layer contain water.
  6. 　前記第２電極層は、充電により水素を生成する
    　請求項１～５のいずれか１つに記載の電気化学セル。     The electrochemical cell according to any one of claims 1 to 5, wherein the second electrode layer generates hydrogen upon charging.
  7. 　前記第２電極層は、水素を消費して放電する
    　請求項１～６のいずれか１つに記載の電気化学セル。     The electrochemical cell according to any one of claims 1 to 6, wherein the second electrode layer discharges by consuming hydrogen.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001512186A (en) * 1997-07-29 2001-08-21 ミクロリン・エル・シー Storage stable electrolytic gas generator for fluid distributor
JP2013191523A (en) * 2012-03-15 2013-09-26 Osaka Prefecture Univ Electrolyte membrane for all-solid alkaline fuel cell
CN106257729A (en) * 2015-06-17 2016-12-28 中国科学院大连化学物理研究所 Self-respiration type light helps microbial fuel cell and application thereof
JP2018106882A (en) * 2016-12-26 2018-07-05 国立研究開発法人物質・材料研究機構 Fuel cell and water electrolysis device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001512186A (en) * 1997-07-29 2001-08-21 ミクロリン・エル・シー Storage stable electrolytic gas generator for fluid distributor
JP2013191523A (en) * 2012-03-15 2013-09-26 Osaka Prefecture Univ Electrolyte membrane for all-solid alkaline fuel cell
CN106257729A (en) * 2015-06-17 2016-12-28 中国科学院大连化学物理研究所 Self-respiration type light helps microbial fuel cell and application thereof
JP2018106882A (en) * 2016-12-26 2018-07-05 国立研究開発法人物質・材料研究機構 Fuel cell and water electrolysis device

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