WO2024084981A1 - Unité d'anode de type cartouche pour pile à combustible zinc-air - Google Patents

Unité d'anode de type cartouche pour pile à combustible zinc-air Download PDF

Info

Publication number
WO2024084981A1
WO2024084981A1 PCT/JP2023/036331 JP2023036331W WO2024084981A1 WO 2024084981 A1 WO2024084981 A1 WO 2024084981A1 JP 2023036331 W JP2023036331 W JP 2023036331W WO 2024084981 A1 WO2024084981 A1 WO 2024084981A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
cartridge
type anode
fuel cell
main body
Prior art date
Application number
PCT/JP2023/036331
Other languages
English (en)
Inventor
Satoshi Ogawa
Yoshiharu Ajiki
Original Assignee
Sojitz Institute Of Innovative Technologies, Ltd.
Suwa University Of Science
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 Sojitz Institute Of Innovative Technologies, Ltd., Suwa University Of Science filed Critical Sojitz Institute Of Innovative Technologies, Ltd.
Publication of WO2024084981A1 publication Critical patent/WO2024084981A1/fr

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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode

Definitions

  • the present invention relates to a cartridge-type anode unit for a zinc-air fuel cell.
  • a zinc-air battery is attracting attention as high energy density and a high-capacity battery superior to a currently widely used lithium ion battery because the zinc-air battery can be charged and discharged by using oxygen in the air as a positive electrode active material to cause an oxidation-reduction reaction of the oxygen in a positive electrode (air electrode) and by causing an oxidation-reduction reaction of zinc constituting a negative electrode at the negative electrode.
  • Zinc-air batteries as primary batteries have already been put into practical use and distributed, have high energy density, and many studies have been conducted with the aim of converting zinc-air batteries into secondary batteries.
  • a flow-type zinc-air battery has been proposed for large-capacity energy storage (PTL 1 and Non-PTL 1).
  • the flow-type zinc-air battery has a configuration in which zinc is used as an active material, and a cell responsible for charging and discharging the storage battery and a storage section of the energy-storage material comprising the electrolytic solution are each independent and connected to each other by a pipe.
  • zinc fuel can be continuously supplied, stable output is easily obtained, and energy density is easily maximized.
  • a cartridge-type anode unit for a zinc-air fuel cell comprising a main body portion having an opening portion and a separator disposed in the opening portion, wherein the main body portion comprises a first coupling portion configured to be attachable to and detachable from a cathode unit of the zinc-air fuel cell, an anode current collecting portion, and a stirring portion, and an electrolyte solution containing zinc particles is provided inside the main body portion.
  • the stirring portion is a stirrer configured to be rotatable by a magnetic stirrer.
  • An electric motor comprising the cathode unit according to (3) above.
  • An electric heater comprising the cathode unit according to (3) above.
  • a light source comprising the cathode unit according to (3) above.
  • a vehicle comprising the cathode unit according to (3) above.
  • An aircraft comprising the cathode unit according to (3) above.
  • a ship comprising the cathode unit according to (3) above.
  • An electric apparatus comprising the cathode unit according to (3) above.
  • (11) A power supply system comprising the cathode unit according to (3) above.
  • a zinc fuel regeneration apparatus comprising a water electrolysis tank configured to reductively treat the cartridge-type anode unit according to (1) or (2) above.
  • a zinc-air fuel cell comprising the cartridge-type anode unit according to (1) or (2) above and the cathode unit according to (3) above.
  • a power supply system comprising the zinc-air fuel cell according to (13) above connected in series.
  • a cartridge-type anode unit for obtaining a zinc-air fuel cell which does not have flow loss, is easily miniaturized, and can be connected in series.
  • FIG. 1 is a cross-sectional schematic drawing of an example of the cartridge-type anode unit.
  • FIG. 2 is a schematic cross-sectional drawing of the cartridge-type anode unit having a first coupling portion coupled to a second coupling portion of a cathode unit of a zinc-air fuel cell.
  • FIG. 3 is a schematic cross-sectional drawing of the cartridge-type anode unit 1 having a first coupling portion with external threads coupled to a second coupling portion with internal threads of a cathode unit of a zinc-air fuel cell.
  • FIG. 1 is a cross-sectional schematic drawing of an example of the cartridge-type anode unit.
  • FIG. 2 is a schematic cross-sectional drawing of the cartridge-type anode unit having a first coupling portion coupled to a second coupling portion of a cathode unit of a zinc-air fuel cell.
  • FIG. 3 is a schematic cross-sectional drawing of the cartridge-type anode unit 1 having a first
  • FIG. 4 is a schematic cross-sectional drawing of the cartridge-type anode unit having a first coupling portion with a convex portion coupled to a second coupling portion with a concave portion of a cathode unit of a zinc-air fuel cell.
  • FIG. 5 is a cross-sectional schematic drawing of an insertion-type cap-shaped opening/closing portion which covers a separator of the cartridge-type anode unit.
  • FIG. 6 is a cross-sectional schematic drawing of a rotary cap-shaped opening/closing portion which covers a separator of the cartridge-type anode unit.
  • FIG. 7 is a cross-sectional schematic drawing of an insertion-type cap-shaped opening/closing portion which covers a separator of the cartridge-type anode unit.
  • FIG. 8 is a front schematic drawing of a sliding-type cap-shaped opening/closing portion having an opening and capable of sliding and rotating.
  • FIG. 9 is a cross-sectional schematic drawing of the zinc-air fuel cell in which the cartridge-type anode unit and the cathode unit are coupled, during discharge.
  • FIG. 10 is a cross-sectional schematic drawing of the cartridge-type anode unit 1 during the regeneration process (charging) in a zinc fuel regeneration apparatus.
  • FIG. 11 is a graph showing the air electrode potential and the discharge power density with respect to the discharge current density of the zinc-air fuel cell configured by connecting the charged cartridge-type anode unit to the cathode unit.
  • the present disclosure is directed to a cartridge-type anode unit for a zinc-air fuel cell, comprising a main body portion having an opening portion and a separator disposed in the opening portion, wherein the main body portion comprises a first coupling portion configured to be attachable to and detachable from a cathode unit of the zinc-air fuel cell, an anode current collecting portion, and a stirring portion, and an electrolyte solution containing zinc particles is provided inside the main body portion.
  • the cartridge-type anode (negative electrode) unit of the present disclosure (hereinafter, also referred to as the cartridge-type anode unit), it is possible to obtain a zinc-air fuel cell which does not have a flow loss due to deposition of an active material in the flow mechanism path, is easily miniaturized, and can be connected both in parallel and in series.
  • a conventional general secondary battery is connected to an electric motor or the like during use, and is charged by being connected to a charger during charging, or is charged by being directly supplied with power in a state of being connected to an electric motor or the like. Therefore, there is a problem in that it takes a long charging time.
  • the cartridge-type anode unit since it can be used as a cartridge, it is used (discharged) by being connected to a zinc-air fuel cell having a cathode unit (air electrode unit), and after use, it can be removed from the cathode unit and charged by subjecting the zinc active material to a reduction treatment. Further, according to the cartridge-type anode unit, since it can be used as a cartridge, it is not necessary to disassemble the anode unit in order to regenerate zinc oxide. Since another charged cartridge-type anode unit can be connected and used in the cathode unit of the zinc-air fuel cell from which the cartridge-type anode unit is removed, a charging time is not required. The cartridge-type anode unit can be replaced in this manner and used in an electric motor or the like.
  • the cartridge-type anode unit can be delivered (conveyed) as a single cartridge-type unit. Therefore, the cartridge-type anode unit has a very high energy density based on the volume of the cartridge-type unit, and a very high energy density with respect to the cost of delivery and storage.
  • the cartridge-type anode unit preferably has an energy density of 30 Wh/L to 7000 Wh/L or 10 to 950 Wh/kg.
  • the cartridge-type anode unit since miniaturization is easy and zinc fuel can be handled in units of cartridge-type units, the cartridge-type anode can be suitably used for a small power supply system, can be suitably used in an electric motor, an electric heater, a light source, or the like, and can be easily mounted on a vehicle, an aircraft, a ship, or an electric apparatus. Further, according to the cartridge-type anode unit, since the zinc-air fuel cell to which the cartridge-type anode unit is coupled can be easily connected in series, the cartridge-type anode unit can be applied to a medium-sized or large-sized stationary power supply system.
  • the waste fuel after use can be recovered in units of cartridges and subjected to a reduction treatment (regeneration treatment).
  • FIG. 1 shows a cross-sectional schematic drawing of an example of the cartridge-type anode unit.
  • the cartridge-type anode unit 1 has a main body portion 10 having an opening portion 11 and a separator 12 disposed in the opening portion 11.
  • the main body portion 10 comprises a first coupling portion 13 configured to be attachable to and detachable from a cathode unit of a zinc-air fuel cell, an anode current collecting portion 14, and a stirring portion 16, and an electrolytic solution 15 containing zinc particles is provided inside the main body portion 10.
  • the main body portion 10 is a container that holds fuel, which is an electrolytic solution containing zinc particles, inside.
  • the material of the main body portion 10 is not particularly limited as long as it can hold the fuel inside, and can be preferably made of resin, metal, or a combination thereof.
  • the resin is preferably a thermoplastic resin, and more preferably polypropylene.
  • the metal is preferably stainless steel.
  • the main body portion 10 may be, for example, based on a vial made of polypropylene, or may be a metal container made of stainless steel.
  • the main body portion 10 comprises the anode current collecting portion 14.
  • the anode current collecting portion 14 may be a current collector extending from the inside of the main body portion 10 to the outside as illustrated in FIG. 1.
  • the metal portion may function as the anode current collecting portion 14.
  • the anode current collecting portion 14 may extend so as to be electrically connected to the anode contact provided on the cathode unit side via the first coupling portion.
  • the material of the anode current collecting portion 14 is not particularly limited as long as it is a material conventionally used as a current collector of the secondary battery, and may be, for example, a conductive metal plate, a metal rod, or the like composed of copper, SUS, nickel, or the like, or a plate, a rod, or the like composed of a carbon material.
  • the main body portion 10 comprises the opening portion 11 for disposing the separator 12.
  • the size of the opening portion 11 may be any size as long as it does not substantially inhibit the battery characteristics as internal resistance when the cartridge-type anode unit 1 is combined with a cathode unit to be described later to operate as an air-zinc fuel cell.
  • the size of the opening 11 may be the same as or less than the cross-sectional area in the direction perpendicular to the longitudinal direction in which the cartridge-type anode unit 1 and the cathode unit are connected, and is preferably 50 to 100%, more preferably 60 to 90%, and still more preferably 70 to 80% of the cross-sectional area.
  • the separator 12 may be a conventionally used separator, and may be, for example, a polymer nonwoven fabric such as a nonwoven fabric made of polypropylene or a nonwoven fabric made of polyphenylene sulfide, a microporous film such as an olefin-based resin including polyethylene or polypropylene, or a combination thereof.
  • the separator 12 can be impregnated with an electrolytic solution to function as an ion conductor. In the separator 12, the zinc active material does not flow out, and only ions can be passed through.
  • the separator 12 may be impregnated with an electrolytic solution to form an electrolyte layer.
  • the separator 12 preferably has a thickness of 10 to 500 ⁇ m.
  • the separator 12 When the main body portion 10 has the separator having the preferable thickness, it becomes easy to suppress the outflow of the electrolytic solution during storage or conveyance while suppressing a substantial increase in the internal resistance when the cartridge-type anode unit 1 is connected to the cathode unit to constitute the zinc-air fuel cell.
  • the separator 12 may be any one as long as it is physically stable in the electrolytic solution and has ion conductivity, and has an ion conductivity of preferably 1 mS/cm or more, more preferably 10 mS/cm or more.
  • the separator 12 has such preferable ion conductivity, the zinc-air fuel cell to which the cartridge-type anode unit 1 is connected can exhibit good cell characteristics, and the reduction treatment (charging) of the cartridge-type anode unit 1 can be favorably performed.
  • the separator 12 may have a Gurley air permeability of, for example, 1 sec/100 mL to 10000 sec/100 mL or more.
  • the separator 12 has a Gurley air permeability of preferably 3 to 2000 sec/100 mL, more preferably 5 to 1000 sec/100 mL, still more preferably 7 to 500 sec/100 mL, and still more preferably 10 to 250 sec/100 mL.
  • the air permeability can be measured by a Gurley-type air permeability tester (Gurley densometer).
  • the main body portion 10 has a first coupling portion 13 configured to be attachable to and detachable from the cathode unit of the zinc-air fuel cell.
  • the cartridge-type anode unit 1 can be used as a cartridge-type by providing the main body portion 10 with the first coupling portion 13 configured to be attachable to and detachable from the cathode unit of the zinc-air fuel cell.
  • the main body portion 10 may comprise the first coupling portion 13 on an outer peripheral surface close to the separator 12, a bottom portion in the vicinity of the separator 12, or both of them.
  • the first coupling portion 13 may be inserted or fitted into a second coupling portion 23 of the cathode unit 20 of the zinc-air fuel cell such that the cartridge-type anode unit 1 and the cathode unit 20 are electrically coupled to each other.
  • FIG. 2 is a schematic cross-sectional drawing of the cartridge-type anode unit 1 having the first coupling portion 13 coupled to the second coupling portion 23 of the cathode unit 20 of the zinc-air fuel cell.
  • the second coupling portion 23 may have a concave shape capable of receiving the surface shape of the first coupling portion 13.
  • the cartridge-type anode unit 1 and the cathode unit 20 may be electrically coupled to each other via the separator 12.
  • the first coupling portion 13 may comprises an external thread 131 on the surface of the first coupling portion.
  • the second coupling portion 23 may comprise an internal thread that can be screwed to the external thread 131.
  • FIG. 3 is a schematic cross-sectional drawing of the cartridge-type anode unit 1 having the first coupling portion 13 with the external threads 131 coupled to the second coupling portion 23 with the internal threads of the cathode unit 20 of the zinc-air fuel cell.
  • the first coupling portion 13 can be coupled to the second coupling portion 23 by relatively rotating the main body portion 10 of the cartridge-type anode unit 1 so that the external thread 131 of the first coupling portion 13 is screwed into the internal thread of the second coupling portion 23.
  • the first coupling portion 13 may have an internal thread
  • the second coupling portion 23 may have an external thread.
  • the first coupling portion 13 may comprise a convex portion 132 on a surface thereof.
  • the second coupling portion 23 may have a concave portion that can be fitted into the convex portion 132.
  • FIG. 4 is a schematic cross-sectional drawing of the cartridge-type anode unit 1 having the first coupling portion 13 with the convex portion 132 coupled to the second coupling portion 23 with the concave portion of the cathode unit 20 of the zinc-air fuel cell.
  • the first coupling portion 13 can be coupled to the second coupling portion 23 by pushing the main body portion 10 of the cartridge-type anode unit 1 so as to fit the convex portion 132 in the concave portion of the second coupling portion 23.
  • the number of the convex portions 132 and the concave portions may be one or more.
  • the first coupling portion 13 may have a concave portion, and the second coupling portion 23 may have a convex portion.
  • the main body portion 10 may have an opening/closing portion that is configured to be openable/closable at a position covering the separator 12.
  • the opening/closing portion can be closed during storage or conveyance of the cartridge-type anode unit 1 and the opening/closing portion can be opened when connected to the cathode unit of the zinc-air fuel cell or the zinc fuel regeneration apparatus.
  • the main body portion 10 comprises the opening/closing portion, even when a separator having a low air permeability is used, it is possible to suppress the outflow or the evaporation of the electrolytic solution from the separator during storage and conveyance.
  • the opening/closing portion may be provided at a position in contact with the first coupling portion 13 of the main body portion 10. When the opening/closing portion is closed, the opening/closing portion may be in contact with the separator 12, or may be adjacent to the separator with a gap therebetween, and preferably the opening/closing portion is in contact with the separator 12. By bringing the opening/closing portion into contact with the separator 12 when the opening/closing portion is closed, it is possible to further suppress the outflow and the evaporation of the electrolytic solution.
  • the opening/closing portion is configured to be openable and closable in any manner, such as an insertion-type, a rotation-type, or a slide-type. When the opening/closing portion is closed, it may be closed by gravity, and is preferably fitted and closed.
  • the opening/closing portion 30 may be separated from the main body portion 10 when opened, or may be coupled to the main body portion 10 by a band, a string, a chain, or the like so as not to fall off.
  • FIG. 5 shows a cross-sectional schematic drawing of the insertion-type cap-shaped opening/closing portion 30 covering the separator 12 of the cartridge-type anode unit 1.
  • FIG. 6 is a cross-sectional schematic drawing of the rotary cap-shaped opening/closing portion 30 covering the separator 12 of the cartridge-type anode unit 1.
  • the separator 12 By rotating the opening/closing portion 30 in a direction of relatively tightening the opening/closing portion 30 so as to screw the internal thread of the cap-shaped opening/closing portion 30 into the external thread 131 of the first coupling portion 13, the separator 12 can be covered with the opening/closing portion 30.
  • the opening/closing portion When the opening/closing portion is opened, the opening/closing portion can be removed from the main body portion 10 by rotating the opening/closing portion 30 in the loosening direction.
  • the first coupling portion 13 may have an internal thread
  • the cap-shaped opening/closing portion 30 may have an external thread.
  • the opening/closing portion 30 When the opening/closing portion has a rotatable cap shape in which the external thread and the internal thread are screwed to each other, the opening/closing portion 30 can be firmly fitted to the main body portion 10, and it is possible to further prevent the opening/closing portion from falling off when the opening/closing portion is closed. Further, since it is a rotary type, a strong force is not required when opening the opening/closing portion, and wear of the external thread and the internal thread which are the fitting members is also small.
  • FIG. 7 is a cross-sectional schematic drawing of the insertion-type cap-shaped opening/closing portion 30 covering the separator 12 of the cartridge-type anode unit 1.
  • the separator 12 By pushing the main body portion 10 of the cartridge-type anode unit 1 so that the concave portion of the cap-shaped opening/closing portion 30 is fitted to the convex portion 132 of the first coupling portion 13, the separator 12 can be covered with the opening/closing portion 30.
  • the first coupling portion 13 may have a concave portion
  • the cap-shaped opening/closing portion 30 may have a convex portion.
  • the opening/closing portion 30 can be firmly fitted to the main body portion 10, and it is possible to further prevent the opening/closing portion from falling off when the opening/closing portion is closed. Further, since it is an insertion type, it can be easily connected to the main body portion with a band or the like, and can be more easily prevented from falling off from the main body portion 10 when opened.
  • FIG. 8 shows a schematic front view of the sliding-type cap-shaped opening/closing portion 30 having an opening 301 and capable of sliding and rotating. The arrow indicates a direction in which the opening/closing portion 30 can be slid and rotated.
  • the cap-shaped opening/closing portion 30 which covers the separator 12, has the opening portion 301 and is slidable and rotatable can be rotated to be fixed at a position where the separator 12 is closed during storage and conveyance, and to be fixed at a position where the separator 12 is exposed during use.
  • the main body portion 10 of the cartridge-type anode unit 1 comprises the stirring portion.
  • the stirring portion can stir the electrolytic solution accommodated in the main body portion 10.
  • zinc particles in the electrolytic solution may be coarsened and dendrites may grow during charge and discharge
  • the stirring of the electrolytic solution by the stirring portion can prevent the coarsening of zinc particles and the growth of dendrites.
  • coarsening of zinc may occur during repeated oxidation and reduction of zinc in the electrolytic solution, and zinc oxide, which may be precipitated, may be included in the coarse particles. Since zinc tends to be in a lower energy state as a crystal, zinc formed into a dendritic structure during charging may be reduced in surface area and coarsened when oxidized and reduced at the solid-liquid interface.
  • the stirring portion may be configured to be capable of stirring operation with electric energy or magnetic energy supplied from the outside of the main body portion 10.
  • the stirring portion may be configured to be capable of adjusting the stirring strength by the intensity of the energy supplied from the outside.
  • the stirring portion may be configured to be capable of controlling the stirring operation by a wireless signal or a wired signal from the outside of the main body portion 10.
  • the stirring portion provides a mechanical stirring action to the electrolytic solution, and may be a stirrer rotated by a magnetic force, an ultrasonic stirrer, a screw-type stirrer, a mechanism having a fixed blade inside the main body portion 10 and providing a stirring action by rotating the cartridge-type anode unit 1, or the like.
  • the stirring portion is preferably disposed between the anode current collecting portion 14 and the separator 12 and more preferably is disposed close to or in contact with the surface of the separator 12, at least during the reduction treatment (charging).
  • FIG. 1 schematically shows an embodiment in which the stirring portion 16 is disposed in contact with the surface of the separator 12.
  • the stirring portion 16 is preferably positioned between the anode current collecting portion 14 and the separator 12, more preferably close to or in contact with the surface of the separator 12, the growth of the dendrites stops in the vicinity of the stirring portion 16, and thus it is possible to suppress the dendrites from coming out of the separator 12.
  • the stirring by the stirring portion 16 is mechanical stirring, the growth suppressing effect of the dendrites is very large as compared with the chemical action of the complexing agent conventionally used. Since the complexing agent diffuses also to the cathode (positive electrode) side at the stage of dissolving in the electrolytic solution and oxidatively deteriorates during the oxygen generation reaction of the cathode, it is difficult to apply the complexing agent to a cycle of long-term regeneration and utilization.
  • the stirring portion 16 is preferably a stirrer of a magnetic stirrer.
  • the stirrer can be rotated by a magnetic force generated by the magnetic stirrer.
  • the stirrer can be rotated by the magnetic force applied from the magnetic stirrer disposed outside the main body portion 10, and can easily adjust the position in the main body portion 10.
  • the magnetic stirrer can be arranged at a position opposed to the stirring portion 16 with the separator 12 outside the main body portion 10 interposed therebetween, the cartridge-type anode unit 1 can be arranged in the central region of the magnetic stirrer so that the separator 12 is on the lower side, and the stirrer can be arranged and rotated at the center on the separator 12 by a magnetic force.
  • the stirring bar is also preferable from the viewpoint of cost and maintenance because it is not necessary to provide a complicated mechanical structure or wiring in the main body portion 10.
  • the electrolytic solution held in the main body portion 10 may be an electrolytic solution commonly used as an electrolytic solution of a secondary battery, and is not particularly limited, and may be an aqueous electrolytic solution, an organic electrolytic solution, or a combination thereof.
  • the electrolyte may be any fluid electrolyte, and may be a liquid electrolyte, a gel electrolyte, a polymer electrolyte, or a combination thereof. From the viewpoint of safety, the electrolyte solution is preferably an aqueous electrolyte solution or an electrolyte solution in which an aqueous electrolyte solution is used as a main component and an organic electrolyte or an organic electrolyte solution is mixed.
  • Examples of the organic electrolytic solution include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, benzonitrile, ionic liquids, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, and fluorine-containing polyethylene glycols.
  • the organic electrolytic solution can be used in one type or in two or more types.
  • aqueous electrolytic solution examples include an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, an aqueous solution of lithium hydroxide, an aqueous solution of zinc sulfate, an aqueous solution of zinc nitrate, an aqueous solution of zinc phosphate, and an aqueous solution of zinc acetate.
  • an alkaline electrolyte such as an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, and an aqueous solution of lithium hydroxide, is preferred.
  • the aqueous electrolyte solution may be used in one type or in two or more types.
  • the aqueous electrolytic solution may include the organic solvent-based electrolytic solution described above.
  • the concentration of the electrolyte in the electrolyte solution is not particularly limited, and may be any concentration.
  • the electrolytic solution may be weakly acidic, neutral, or alkaline, and the pH of the electrolytic solution is preferably 6 to 14, more preferably 6 to 12, and still more preferably 7 to 10.
  • the electrolytic solution contains zinc particles as the negative electrode active material.
  • the zinc particles include particles of metal zinc particles, zinc compound particles, or a combination thereof.
  • the zinc particles have an average particle size (diameter) which is preferably in the range of 1 nm to 500 ⁇ m, more preferably 5 nm to 200 ⁇ m, even more preferably 10 nm to 100 ⁇ m, and even more preferably 10 nm to 60 ⁇ m.
  • the electrolytic solution may further comprise particles of other metals or other metal compounds, such as magnesium particles, aluminum particles, iron particles, copper particles, and the like, in addition to the zinc particles.
  • the above average particle size can be measured as D50 using a particle size distribution measuring apparatus.
  • the electrolytic solution may further comprise a catalyst and/or a complexing agent.
  • the catalyst contained in the electrolytic solution may be a conventionally used catalyst, and is preferably carbon particles.
  • the carbon particles can be graphite, carbon fiber, carbon black, carbon nanoparticles, or the like.
  • the ratio of the carbon particles to the zinc particles is preferably in the range of 2.5 to 10% by mass.
  • the proportion of the electrolyte in the electrolytic solution containing zinc is preferably in the range of 50 to 80% by volume.
  • the complexing agent may be a complexing agent conventionally used to suppress dendrite formation of a negative electrode, and may be, for example, ethylenediaminetetraacetic acid (EDTA), citric acid, ammonium hydroxide, or the like.
  • EDTA ethylenediaminetetraacetic acid
  • citric acid citric acid
  • ammonium hydroxide or the like.
  • the separator 12 can be impregnated with the electrolytic solution to function as an electrolyte layer.
  • the electrolyte layer 24 may include a nonwoven fabric impregnated with the electrolytic solution.
  • the electrolyte layer exhibits ionic conductivity between the cathode and the anode.
  • the nonwoven fabric contained in the electrolyte layer 24 may be the same as the nonwoven fabric that can be used for the separator 12.
  • the shape of the main body portion 10 of the cartridge-type anode unit 1 may be any shape, such as a cylindrical shape, a rectangular parallelepiped shape, or a combination thereof, and is preferably a cylindrical shape.
  • the cartridge When the cartridge has a cylindrical shape, the cartridge can be moved by being rolled from the upper side to the lower side.
  • a cassette such as a beverage vending machine, in which the cartridge can be moved from above to below by gravity, the charged cartridge-type anode unit 1 can be sequentially fed and connected to the cathode unit of the zinc-air fuel cell from which the used cartridge-type anode unit 1 has been removed.
  • the present disclosure is also directed to a cathode unit (air electrode unit) having a second coupling portion configured to be attachable to and detachable from the first coupling portion of the cartridge-type anode unit 1 described above.
  • the cartridge-type anode unit 1 described above can be coupled to the cathode unit to form a zinc-air fuel cell.
  • the used cartridge-type anode unit 1 can be removed from the cathode unit, and a reduced (charged) cartridge-type anode unit 1 can be attached to the cathode unit and used as a zinc-air fuel cell.
  • the used cartridge-type anode unit 1 can be subjected to a reduction treatment (charging).
  • FIG. 2 shows a cross-sectional schematic drawing of a zinc-air fuel cell in which the cartridge-type anode unit 1 is connected to the cathode unit 20.
  • the housing of the cathode unit 20 can be made of a resin, such as acrylic, for example.
  • the material of the second coupling portion 23 is not particularly limited as long as the first coupling portion 13 can be inserted or fitted into the second coupling portion 23, and can be made of a resin, such as acrylic, for example.
  • the cathode unit 20 is not particularly limited as long as it comprises the second coupling portion 23 and functions as an air electrode, and may have a configuration of an air electrode conventionally used.
  • the cathode unit 20 may comprise an air electrode layer 22, an electrolyte layer 24, and a cathode current collector.
  • the air electrode layer 22 may have a configuration in which the water-repellent layer and the catalyst layer are held by a metal mesh. By pressure-bonding the water-repellent layer and the catalyst layer to the metal mesh, the water-repellent layer and the catalyst layer can be held in a cathode current collecting portion such as the metal mesh.
  • the water-repellent layer may be a conventionally used water-repellent layer, and may be a porous film of polytetrafluoroethylene (PTFE), for example.
  • the catalyst layer may be a conventionally used catalyst layer, and may be a mixed layer of carbon and a catalyst, for example.
  • the catalyst contained in the catalyst layer is not particularly limited as long as it is a material conventionally used for an air electrode, and may be a conductive carbon, such as Ketjen black, acetylene black, Denka black, carbon nanotubes, or fullerenes, a metal, a metal oxide, a metal hydroxide, a metal sulfide, or the like, and one or more of these may be used.
  • a conductive carbon such as Ketjen black, acetylene black, Denka black, carbon nanotubes, or fullerenes, a metal, a metal oxide, a metal hydroxide, a metal sulfide, or the like, and one or more of these may be used.
  • the mass ratio of the catalyst contained in the catalyst layer is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, based on 100% by mass of the catalyst layer.
  • the mass ratio of the catalyst contained in the catalyst layer is preferably 98% by mass or less, more preferably 95% by mass or less. When the ratio of the catalyst is within the preferable range, the function of the air electrode can be more sufficient.
  • the catalyst layer may further comprise a binder.
  • the binder is not particularly limited as long as it is a material conventionally used for an air electrode, and may be either thermoplastic or thermosetting, and examples of the binder include halogen atom-containing polymers such as polyvinylidene fluoride and polytetrafluoroethylene, hydrocarbon site-containing polymers such as polyolefin, aromatic group-containing polymers such as polystyrene; ether group-containing polymers such as alkylene glycol; hydroxyl group-containing polymers such as polyvinyl alcohol; amide bond-containing polymers such as polyamide and polyacrylamide; imide group-containing polymers such as polymaleimide; carboxyl group-containing polymers such as poly (meth) acrylic acid; carboxylic acid salt-containing polymers such as poly (meth) acrylate; sulfonic acid salt site-containing polymers; quaternary ammonium salt-containing polymers and quaternary phosphonium salt-containing polymers; i
  • the mass ratio of the binder in the catalyst layer is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 to 5% by mass.
  • the thickness of the catalyst layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more.
  • the air electrode layer 22 may further comprise a gas diffusion layer (GDL).
  • GDL gas diffusion layer
  • the GDL may take in air from the outside and may comprise a layer of carbon particles and platinum particles with some hydrophobic agents, such as Teflon.
  • a separation film may be provided between the catalyst layer and the adjacent electrolyte layer 24.
  • the cathode current collecting portion is not particularly limited as long as it is a material conventionally used as a current collector, such as a porous structure such as carbon paper or a metal mesh, a mesh structure, a fiber, or a nonwoven fabric, and for example, a metal mesh formed of SUS, nickel, aluminum, iron, titanium, or the like can be used.
  • a metal foil having an oxygen supply hole can also be used.
  • the cathode unit may be provided in a machine requiring electricity.
  • the cathode unit can be provided in an electric motor, an electric heater, or a light source.
  • the electric motor include a belt conveyor, a chain saw, a crane, a power shovel, a pump, an electric toy (including an electric skateboard), a polisher, an electric grass mower, and the like.
  • the electric heater include a heater, an air conditioner (including cooling and dehumidifying), and the like.
  • the light source include a flashlight, an outdoor lighting device for construction or the like, a laser, a camping light, a tent light, and an underground shelter light.
  • the cathode unit can also preferably be provided in a vehicle, an aircraft, a ship, an electrical apparatus, or a power supply system.
  • vehicle examples include an electric passenger car including a hybrid car, a bus, a truck, an electric motor bicycle, a wheelchair, a tractor, an agricultural machine, a snow motorcycle, a train, and the like.
  • the cathode unit can also be used as an auxiliary power source for a vehicle, an alternative power source for a lead storage battery, or the like.
  • the cathode unit is disposed on the left side of the vehicle in the case of a domestic vehicle, and on the right side of the vehicle in the case of a vehicle in the United States, and that an inlet/outlet for the cartridge-type anode unit is provided.
  • the aircraft include a general jet plane (passenger plane, cargo plane), an electric propeller plane (passenger plane, cargo plane), a drone, an artificial satellite, a space station, and the like.
  • the ship include a leisure motor boat, a personal watercraft, a submarine, and a general ship.
  • the electric apparatus can be an electric apparatus that can be generally used, and examples thereof include a communication apparatus, a household electric appliance, a measurement apparatus, an air cleaner, an apparatus that collects water from air, a robot, an external power supply for a personal computer, and the like.
  • Examples of the power supply system include, for example, emergency power supplies for buildings or hospitals, stationary power supplies, and the like, such as commercial and industrial power storage, residential solar power storage, microgrid construction, alternative power storage of peaking plant, backup power supplies of renewable energy, power storage for integration of renewable energy system, seasonal energy storage, and power storage of grid service (particularly, for demand response, ancillary services, governor free operation, frequency regulation, and the like), and may be portable power supplies.
  • emergency power supplies for buildings or hospitals stationary power supplies, and the like, such as commercial and industrial power storage, residential solar power storage, microgrid construction, alternative power storage of peaking plant, backup power supplies of renewable energy, power storage for integration of renewable energy system, seasonal energy storage, and power storage of grid service (particularly, for demand response, ancillary services, governor free operation, frequency regulation, and the like), and may be portable power supplies.
  • the cathode units may be connected in series, parallel, or series and parallel.
  • the present disclosure is also directed to a zinc fuel regeneration apparatus having a water electrolysis tank configured to reductively treat the cartridge-type anode unit 1 described above.
  • FIG. 9 shows a cross-sectional schematic drawing of the zinc-air fuel cell in which the cartridge-type anode unit 1 and the cathode unit 20 are coupled to each other during discharge.
  • zinc contained in the electrolytic solution 15 in the main body portion 10 is oxidized during discharge, and an electrolytic solution 18 containing zinc oxide is generated from the cathode unit side.
  • the waste fuel containing the generated zinc oxide is recovered while being mounted on the cartridge-type anode unit 1.
  • the zinc oxide in the recovered waste fuel is electrochemically reduced to zinc by the zinc fuel regeneration apparatus, and can be reused as a fuel.
  • zinc may be coarsened during the electrochemical reaction in the zinc-air fuel cell or the zinc fuel regeneration apparatus, the coarsening of zinc and growth of dendrites can be suppressed by stirring the electrolytic solution with the stirring portion.
  • FIG. 10 shows a cross-sectional schematic drawing of the cartridge-type anode unit 1 during the regeneration process (charging) by the zinc fuel regeneration apparatus 40.
  • the regeneration treatment charging
  • the zinc oxide contained in the electrolytic solution 18 in the main body portion 10 is reduced to zinc from the vicinity of the anode current collecting portion 14 extending from the inside of the main body portion 10 to the outside, and the electrolytic solution 15 containing zinc is generated.
  • the water electrolysis tank of the zinc fuel regeneration apparatus 40 may have a container 41 configured to contain an aqueous solution 43, and an electrode 42 for electrolyzing water.
  • the material of the container 41 is not particularly limited as long as it can accommodate the aqueous solution 43, and may be a container made of resin, for example, polypropylene.
  • the separator 12 side of the used cartridge-type anode unit 1 is immersed in the aqueous solution 43, and water is electrolyzed by the electrode 42 disposed in the aqueous solution 43, and the zinc oxide can be reduced to zinc by the generated hydrogen.
  • the zinc fuel regeneration apparatus 40 has a holding portion capable of holding the cartridge-type anode unit 1, and preferably, the container 41 has a holding portion capable of holding the cartridge-type anode unit 1.
  • the structure of the holding portion is not particularly limited as long as it can hold the cartridge-type anode unit 1, and may have a structure that holds the horizontal direction so that the cartridge-type anode unit 1 supported by the bottom of the container 41 by gravity does not fall down, or may have a structure that holds the horizontal direction and the vertical direction of the cartridge-type anode unit 1.
  • the container 41 may comprise a fixing jig having a hole with a diameter substantially the same as or slightly larger than the outer diameter of the cartridge-type anode unit 1 to hold the cartridge-type anode unit 1 in the horizontal direction.
  • the container 41 may comprise a fixing jig having a hole with a diameter substantially the same as or slightly larger than the outer diameter of the outer diameter of the cartridge-type anode unit 1 and a fastening mechanism for the hole to hold the horizontal and vertical directions of the cartridge-type anode unit 1.
  • the zinc fuel regeneration apparatus may have a third coupling portion configured to be attachable to and detachable from the first coupling portion.
  • the configuration of the third coupling portion is not limited as long as it can conduct ions via the separator 12, and can have the same configuration as that of the second coupling portion described above.
  • the cartridge-type anode unit 1 is disposed in the aqueous solution 43 of the container 41 so as to have a gap between the separator 12 and the bottom surface of the container 41.
  • the gap may be formed by disposing a nonwoven fabric or the like at the bottom of the container 41.
  • the zinc fuel regeneration apparatus 40 preferably comprises a magnetic stirrer 44 that generates a magnetic force for rotating the stirring portion 16, which is a stirrer in the main body portion 10.
  • the magnetic stirrer 44 may comprise a magnet and a motor that rotates the magnet at a variable rotational speed.
  • the cathode unit may also comprise a magnetic stirrer.
  • the stirring portion 16 can be rotated by the magnetic stirrer 44 as indicated by an arrow in FIG. 10 to stir the electrolytic solution in the main body portion 10.
  • the present disclosure is also directed to a zinc-air fuel cell comprising the cartridge-type anode unit 1 described above and the cathode unit 20 described above.
  • the zinc-air fuel cell comprises the electrolytic solution containing the zinc active material as the zinc fuel in the main body portion 10.
  • the cartridge-type anode unit 1 is connected to the second coupling portion 23 of the cathode unit 20 to constitute the zinc-air fuel cell, which can be used for discharging.
  • a plurality of the zinc-air fuel cells can be used connected in series, in parallel, or in series and parallel.
  • a power supply system is a relatively large scale stationary facility that temporarily stores electricity, and can output a relatively high voltage when the zinc-air fuel cells are connected in series.
  • PTFE polytetrafluoroethylene
  • a opening portion was provided on a cap of the vial, the opening portion was sealed with a nonwoven fabric (thickness: 100 ⁇ m, Gurley value: 20 sec/100 mL), and the cap provided with the nonwoven fabric on the opening portion was attached to the vial, thereby producing the cartridge-type anode unit having the first coupling portion with a diameter of 25 mm schematically shown in FIG. 1.
  • Ketjen Black, PTFE aqueous dispersion (solid concentration Nv 60%), and water were mixed at a mass ratio of 10:1:2, and the mixture was placed in a polyethylene bag and rolled with a roll pressing apparatus in which a gap between the rolls was adjusted to 0.5 mm to obtain a flat plate-shaped paste.
  • the obtained flat plate-shaped paste was rolled on a Ni-plated SUS mesh used as a current collector to be integrated therewith, and a PTFE water-repellent film (thickness: 100 ⁇ m, Gurley value: 18 sec/100 mL) was further attached to one surface thereof by rolling to fabricate an air electrode layer (oxygen reduction electrode).
  • a housing made of acrylic resin with the second coupling portion with an inner diameter of 25 mm configured so as to fit the cartridge-type anode unit was prepared, a nonwoven fabric (thickness: 1 mm) was arranged at a position adjacent to the second coupling portion, and 3 g of a 3M aqueous potassium hydroxide solution was introduced so as to permeate the nonwoven fabric.
  • the fabricated oxygen reduction electrode was attached to an end surface of the housing made of acrylic resin facing the second coupling portion to fabricate a cathode unit schematically shown in FIG. 2.
  • the first coupling portion of the fabricated cartridge-type anode unit was fitted to the second coupling portion of the fabricated cathode unit so that the nonwoven fabric attached to the vial cap of the cartridge-type anode unit and the nonwoven fabric disposed in the cathode unit were in contact with each other, thereby fabricating a zinc-air fuel cell schematically shown in FIG. 2.
  • the electrolyte solutions impregnated in each of the nonwoven fabrics were mixed, whereby a path of ion conduction was formed to enable discharge.
  • a discharge test was conducted using the cartridge-type anode unit of the fabricated zinc-air fuel cell as a negative electrode and the oxygen reduction electrode of the cathode unit as a positive electrode.
  • a charge and discharge test device HJ1001SD8 manufactured by Hokuto Denko Corporation was used, and the discharge voltage was measured while changing the discharge current from 0.1 mA/cm 2 to 200 mA/cm 2 , and the discharge power at the respective discharge currents was calculated.
  • FIG. 11 shows a graph showing the air electrode potential and the discharge power density with respect to the discharge current density of the fabricated zinc-air fuel cell.
  • the current density could be increased to about 100 mA/cm 2 .
  • a cartridge-type anode unit was fabricated in the same manner as in Example 1 except that 1 g of metallic zinc powder was put in the vial, and a zinc-air fuel cell was fabricated in combination with the cathode unit in the same manner as in Example 1.
  • the fabricated zinc-air fuel cell exhibited a discharge capacity of 750 mAh/g at a discharge current of 10 mA/cm 2 with respect to a theoretical capacity of 820 mAh/g.
  • the cartridge-type anode unit was removed from the zinc-air fuel cell after discharge and introduced into the aqueous potassium hydroxide solution of the container of the zinc fuel regeneration apparatus with the magnetic stirrer as schematically shown in FIG. 10. While stirring the electrolyte solution by rotating the stirrer in the main body portion of the cartridge-type anode unit with a magnetic stirrer, water was electrolyzed using the electrodes, and a charging reaction was performed at the same current rate of 10 mA as that at the time of discharging, whereby a zinc oxide generated in the main body portion was regenerated. The regeneration treatment regenerated 748 mAh/g of zinc. When the cartridge-type anode unit subjected to the regeneration treatment was again connected to the cathode unit of the zinc-air fuel cell and discharged, and a discharge capacity of 720 mAh/g was confirmed.
  • cartridge-type anode unit 10 main body portion 11 opening portion of main body portion 12 separator 13 first coupling portion 131 external thread 132 convex portion 14 anode current collecting portion 15 electrolytic solution containing zinc 16 stirring portion 18 electrolytic solution containing zinc oxide 20 cathode unit of zinc-air fuel cell 22 air electrode layer 23 second coupling portion 24 electrolyte layer 30 opening-closing portion 301 opening portion of opening/closing portion 40 zinc fuel regeneration apparatus 41 container 42 electrode 43 aqueous solution 44 magnetic stirrer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)

Abstract

La présente invention concerne une unité d'anode de type cartouche pour obtenir une pile à combustible zinc-air qui n'a pas de perte de flux, est facilement miniaturisée, et peut être connectée en série. La présente invention concerne une unité d'anode de type cartouche pour une pile à combustible zinc-air, comprenant une partie de corps principal ayant une partie d'ouverture et un séparateur disposé dans la partie d'ouverture, la partie de corps principal comprenant une première partie de couplage configurée pour pouvoir être fixée à une unité de cathode de la pile à combustible zinc-air et détachée de celle-ci, une partie de collecte de courant d'anode, et une partie d'agitation, et une solution électrolytique contenant des particules de zinc est disposée à l'intérieur de la partie de corps principal.
PCT/JP2023/036331 2022-10-20 2023-10-05 Unité d'anode de type cartouche pour pile à combustible zinc-air WO2024084981A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-168195 2022-10-20
JP2022168195 2022-10-20

Publications (1)

Publication Number Publication Date
WO2024084981A1 true WO2024084981A1 (fr) 2024-04-25

Family

ID=90737387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/036331 WO2024084981A1 (fr) 2022-10-20 2023-10-05 Unité d'anode de type cartouche pour pile à combustible zinc-air

Country Status (1)

Country Link
WO (1) WO2024084981A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110109141A (ko) * 2010-03-30 2011-10-06 주식회사 미트 카트리지 분리형 금속 공기 전지
JP2016024944A (ja) * 2014-07-18 2016-02-08 シャープ株式会社 化学電池
JP2016225213A (ja) * 2015-06-02 2016-12-28 シャープ株式会社 金属電極カートリッジ、及び、化学電池
JP2017079147A (ja) * 2015-10-20 2017-04-27 シャープ株式会社 金属空気電池、電解液槽、及び、金属空気電池の使用方法
JP2017147068A (ja) * 2016-02-16 2017-08-24 シャープ株式会社 化学電池、化学電池に用いる活物質、活物質生成装置、及び活物質生成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110109141A (ko) * 2010-03-30 2011-10-06 주식회사 미트 카트리지 분리형 금속 공기 전지
JP2016024944A (ja) * 2014-07-18 2016-02-08 シャープ株式会社 化学電池
JP2016225213A (ja) * 2015-06-02 2016-12-28 シャープ株式会社 金属電極カートリッジ、及び、化学電池
JP2017079147A (ja) * 2015-10-20 2017-04-27 シャープ株式会社 金属空気電池、電解液槽、及び、金属空気電池の使用方法
JP2017147068A (ja) * 2016-02-16 2017-08-24 シャープ株式会社 化学電池、化学電池に用いる活物質、活物質生成装置、及び活物質生成方法

Similar Documents

Publication Publication Date Title
EP3379625B1 (fr) Batterie secondaire, bloc-batterie et véhicule
JP6873767B2 (ja) 二次電池、電池パック及び車両
Toussaint et al. Development of a rechargeable zinc-air battery
JP3740323B2 (ja) 二次電池の充電方法及びその装置
US9941559B2 (en) Water enhanced ionic liquid electrolytes for metal-air batteries
Pei et al. A high-energy-density and long-stable-performance zinc-air fuel cell system
CN109524725B (zh) 二次电池、电池组以及车辆
CN102110839A (zh) 一种电池
US10411286B2 (en) Alkali/oxidant battery
JP7067985B2 (ja) 二次電池、電池パック、車両、及び定置用電源
US20050031919A1 (en) Hybrid fuel cell
EP2878035A1 (fr) Batterie à métal/oxygène ayant un système d'alimentation en oxygène
CN110299506B (zh) 二次电池、电池组、车辆和固定电源
US10074877B2 (en) Method for charging a zinc-air battery with limited potential
CN114141981B (zh) 一种正极极片及其制备方法和应用
JP5851624B2 (ja) リチウム空気電池用の水性電解液
US10211494B1 (en) Lithium hydrogen secondary electrochemical cell
WO2015079689A1 (fr) Batterie alcaline/oxydant à forte capacité
WO2024084981A1 (fr) Unité d'anode de type cartouche pour pile à combustible zinc-air
JP6945788B2 (ja) 二次電池、電池パック、車両、定置用電源及び負極
KR20080106839A (ko) 분말형 연료 전지
Lu et al. Introduction to Zinc–Air Batteries
Jain et al. History and Development of Zinc Batteries
US10629970B2 (en) Lithium air battery including negative electrode, positive electrode, nonaqueous lithium ion conductor, and copper ion
CN111183539A (zh) 二次电池、电池包、车辆和固定电源

Legal Events

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

Ref document number: 23879628

Country of ref document: EP

Kind code of ref document: A1