WO2021205847A1 - 金属空気電池装置 - Google Patents

金属空気電池装置 Download PDF

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Publication number
WO2021205847A1
WO2021205847A1 PCT/JP2021/011427 JP2021011427W WO2021205847A1 WO 2021205847 A1 WO2021205847 A1 WO 2021205847A1 JP 2021011427 W JP2021011427 W JP 2021011427W WO 2021205847 A1 WO2021205847 A1 WO 2021205847A1
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WIPO (PCT)
Prior art keywords
metal
air battery
air
negative electrode
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/011427
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English (en)
French (fr)
Japanese (ja)
Inventor
俊輔 佐多
吉田　章人
宏隆 水畑
知 北川
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Sharp Corp
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Sharp Corp
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Publication date
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Priority to JP2022514370A priority Critical patent/JP7465340B2/ja
Publication of WO2021205847A1 publication Critical patent/WO2021205847A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/211—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/253—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders adapted for specific cells, e.g. electrochemical cells operating at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
    • H01M50/291—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by their shape
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a metal-air battery device.
  • This disclosure claims priority based on Japanese Patent Application No. 2020-60947 filed in Japan on April 7, 2020, the contents of which are incorporated herein by reference.
  • Patent Document 1 describes an example of a metal-air battery device in which a plurality of metal-air batteries are housed.
  • the metal-air battery described in Patent Document 1 has a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode, an electrolytic solution, and an exterior body containing the positive electrode, the negative electrode, the separator, and the electrolytic solution. ..
  • An opening is formed on the surface of the exterior body on the positive electrode side, and a water-repellent film is arranged between the exterior body and the positive electrode.
  • each metal-air battery provided in the metal-air battery device expands with discharge, and there is a concern that the battery characteristics may deteriorate, such as a decrease in discharge capacity and rate characteristics. Can be done.
  • a main object of the present disclosure is to provide a metal-air battery device in which deterioration of battery characteristics is suppressed.
  • the metal-air battery device of one embodiment of the present invention includes at least one metal-air battery having a positive electrode, a negative electrode arranged to face the positive electrode, and an exterior body accommodating the positive electrode and the negative electrode inside.
  • a regulating member that comes into contact with the at least one metal-air battery from the outside to partially regulate the at least one metal-air battery to a predetermined thickness or less.
  • FIG. 1 is a cross-sectional view taken along the line AA in FIG. It is a figure which shows another example of a metal-air battery. It is a schematic cross-sectional view which shows an example of the metal-air battery apparatus of Embodiment 1.
  • FIG. It is a top view which shows an example of the regulation member in FIG. It is a front view which shows an example of the state which provided the regulation member in a metal-air battery. It is a front view which shows the state which provided the regulation member of another example in a metal-air battery. It is a front view which shows the state which provided the regulation member of another example to a metal-air battery.
  • FIG. 1 is a front view of the metal-air battery 10.
  • FIG. 2 is a cross-sectional view taken along the line AA in FIG.
  • the metal-air battery 10 includes an exterior body formed by laminating a first resin film 11 and a second resin film 12. Further, the metal-air battery 10 includes an air electrode (positive electrode) 13, a metal negative electrode (negative electrode) 14, a separator 25, and a water-repellent film 16 housed inside the exterior body. Further, the inside of the exterior body is filled with an electrolytic solution (not shown) such as an alkaline aqueous solution (for example, a KOH aqueous solution). The electrolytic solution contains an electrolyte that is interposed between the air electrode 13 and the metal negative electrode 14 and transfers an electric charge between the air electrode 13 and the metal negative electrode 14.
  • an electrolytic solution such as an alkaline aqueous solution (for example, a KOH aqueous solution).
  • the electrolytic solution contains an electrolyte that is interposed between the air electrode 13 and the metal negative electrode 14 and transfers an electric charge between the air electrode 13 and the metal negative electrode 14.
  • the first resin film 11 has an air intake port 111 as an opening for taking in air into the first accommodating portion S11 described later.
  • a resin film used in a known metal-air battery can be used as the first resin film 11. More specifically, the first resin film 11 is preferably formed of a thermoplastic resin that can be welded to the second resin film 12 and has excellent alkali resistance, and is preferably a polyolefin-based film such as polypropylene or polyethylene. Resin film can be used.
  • a resin film layer such as nylon (registered trademark) or polyethylene terephthalate or a metal film layer such as aluminum foil or stainless foil is applied to the outside air side of the first resin film 11 and the second resin film 12. It may be a laminated structure.
  • the thickness of the first resin film 11 is not particularly limited, but is preferably 0.02 mm to 0.25 mm. If the thickness of the first resin film 11 is less than 0.02 mm, it may not be sufficiently welded at the time of welding and the bonding strength may be insufficient, while if the thickness of the first resin film 11 exceeds 0.25 mm. Since the film is difficult to stretch, stress is concentrated on the welded portion when the battery expands, and the welded portion may be peeled off. Further, the opening ratio of the air intake port 111 with respect to the first resin film 11 is preferably 10% to 70%.
  • the second resin film 12 is arranged so as to face the first resin film 11.
  • the second resin film 12 can be appropriately used from the resin film used in the first resin film 11.
  • the thickness of the second resin film 12 is preferably 0.02 mm to 0.25 mm for the same reason as that of the first resin film 11.
  • the separator 15 is arranged so as to face the first resin film 11 and the second resin film 12. That is, the separator 15 is provided between the first resin film 11 and the second resin film 12.
  • the peripheral edge of the separator 15 is welded to the peripheral edge of the first resin film 11.
  • the peripheral edge portion of the separator 15 may be welded to the peripheral edge portion of the second resin film 12, or may be welded to both the peripheral edge portion of the first resin film 11 and the peripheral edge portion of the second resin film.
  • a separator material generally used in the field of metal-air batteries can be used as long as it is a material that can be welded to the first resin film 11 and the second resin film 12.
  • the thickness of the separator 15 is not particularly limited, but is preferably 0.05 mm to 0.4 mm.
  • the separator 15 may break due to the volume expansion of the negative electrode active material during discharge, while if the thickness of the separator 15 exceeds 0.4 mm, the separator 15 may break. As a result of the increase in internal resistance, the battery output may decrease.
  • the space between the first resin film 11 and the separator 15 is the first accommodating portion S11.
  • the air electrode 13 and the water-repellent film 16 are accommodated in the first accommodating portion S11. More specifically, the water-repellent film 16 is one size larger than the air intake port 111, and is welded to the first resin film 11 so as to cover the air intake port 111 from the inside.
  • the air electrode 13 is arranged between the water repellent film 16 and the separator 15.
  • the water-repellent film 16 is provided to take in air from the air intake port 111 to the air electrode 13 and prevent leakage of the electrolytic solution from the air intake port 111, and provides air permeability and a gas-liquid separation function. Have.
  • the water-repellent film 16 is fixed to the first resin film 11 by welding or the like so as to cover the air intake port 111 from the inside.
  • the material of the water-repellent film 16 is generally used in the field of metal-air batteries, and is not particularly limited as long as it can be fixed to the first resin film 11.
  • the thickness of the water-repellent film 16 is preferably 0.05 mm to 0.5 mm.
  • the water-repellent film 16 in the present embodiment is exposed to the outside of the metal-air battery 10, and can be said to be a part of the exterior body.
  • the air electrode 13 is composed of, for example, a catalyst layer 132 and a positive electrode current collector 131 arranged inside the catalyst layer 132. A part of the positive electrode current collector 131 is extended to the outside of the exterior body to form a lead portion 133 of the metal-air battery 10.
  • the positive electrode current collector 131 is not particularly limited as long as it is a conductive material such as a metal generally used in the field of a metal-air battery.
  • the thickness of the positive electrode current collector 131 is not particularly limited, but is preferably 0.05 mm to 0.5 mm.
  • the catalyst layer 132 contains at least an air electrode catalyst.
  • the air electrode catalyst is a catalyst having at least a redox ability.
  • the air electrode catalyst include conductive carbons such as Ketjen black, acetylene black, denka black, carbon nanotubes, and fullerene, metals such as platinum, metal oxides such as manganese oxide, metal hydroxides, and metal sulfides. And one or more of these can be used. This makes it possible to form a three-phase interface in which oxygen gas, water, and electrons coexist on the air electrode catalyst, and the discharge reaction can proceed.
  • the catalyst layer 132 may include a catalyst such as manganese dioxide.
  • the metal air battery 10 may be a secondary battery, and in this case, the catalyst layer 132 may contain not only an air electrode catalyst having an oxygen reducing ability but also a catalyst having an oxygen generating ability, and oxygen. It may contain a Bi-functional catalyst having both an ability to generate and an ability to reduce oxygen.
  • the mass ratio of the air electrode catalyst contained in the catalyst layer 132 is preferably 5% by mass or more of the catalyst layer 132.
  • the air electrode catalyst layer may contain a binder in addition to the air electrode catalyst. Further, a binder such as polytetrafluoroethylene can be used for the catalyst layer 132.
  • the thickness of the catalyst layer 132 is preferably 0.1 mm or more and 1.0 mm or less.
  • a second accommodating portion S12 is formed between the second resin film 12 and the separator 15.
  • the metal negative electrode 14 is accommodated in the second accommodating portion S12.
  • the peripheral edge portion of the separator 15 may be welded to the peripheral edge portion of the second resin film 12.
  • it is the welding of the first resin film 11 and the second resin film 12 that forms the outer periphery of the second accommodating portion S12. It is a department.
  • the metal negative electrode 14 is arranged so as to face the air electrode 13, for example, and includes the negative electrode current collector 141 and the negative electrode active material layer 142.
  • the negative electrode active material layer 142 contains at least the negative electrode active material. More specifically, the negative electrode current collector 141 and the particulate negative electrode active material (for example, zinc or zinc oxide) are separately charged into the second accommodating portion S12 to form the metal negative electrode 14. A part of the negative electrode current collector 141 is extended to the outside of the exterior body to form a lead portion 143 of the metal-air battery 10.
  • the thickness of the negative electrode current collector 141 is not particularly limited, but is preferably 0.05 mm to 0.50 mm. Further, a resin additive for improving the binding property and rheological characteristics of the negative electrode active material may be appropriately contained.
  • the negative electrode active material is appropriately adopted from materials generally used in the field of metal-air batteries.
  • metal types such as cadmium type, lithium type, sodium type, magnesium type, lead type, zinc type, tin type, aluminum type, and iron type can be used.
  • the metal-air battery 10 is a secondary battery, the negative electrode active material is reduced by being charged, so that it may be in the state of a metal oxide.
  • the negative electrode active material preferably has an average particle size of 1 nm to 500 ⁇ m. It is more preferably 5 nm to 300 ⁇ m, further preferably 100 nm to 250 ⁇ m, and particularly preferably 200 nm to 200 ⁇ m.
  • the average particle size can be measured using a particle size distribution measuring device.
  • an electrolytic solution (not shown) appropriately selected depending on the metal type used for the negative electrode active material is accommodating.
  • the metal negative electrode 14 may be in the form of a slurry in which the negative electrode active material is dispersed in the electrolytic solution (in other words, the slurry-like negative electrode active material layer 142).
  • the ratio of the weight of the electrolytic solution to the weight of the negative electrode active material is preferably 0.3 to 2.0.
  • the particle size of the negative electrode active material is preferably 10 ⁇ m to 800 ⁇ m, and more preferably 75 ⁇ m to 425 ⁇ m.
  • all of the first resin film 11, the second resin film 12, the air electrode 13, the metal negative electrode 14, the separator 15, the water-repellent film 16 and the electrolytic solution are in the field of the metal-air battery. Conventionally used ones can be used in.
  • the air intake port 111 is formed in the first resin film 11 (the first resin film 11 in which the air intake port 111 is formed is prepared).
  • the water-repellent film 16 is adhered to the first resin film 11 so as to cover the air intake port 111.
  • the water-repellent film 16 has a size one size larger than that of the air intake port 111, and the water-repellent film 16 is laminated at the edge portion (adhesive region) of the air intake port 111 and heat-welded.
  • the catalyst layer 132 is laminated on the surface of the water repellent film 16 opposite to the air intake port 111.
  • the positive electrode current collector 131 is laminated on the catalyst layer 132 so that one side extends from the adhesive region, and these are pressure-bonded by a press.
  • a lead portion 133 electrically connected to the stretched portion of the positive electrode current collector 131 may be further provided, and tab films may be attached to both sides of the lead portion 133.
  • the separator 15 is laminated on the positive electrode current collector 131, and the separator 15 is heat-welded to the first resin film 11.
  • the separator 15 has a size one size larger than that of the water-repellent film 16, and is welded at a portion where the separator 15 overlaps the first resin film 11.
  • the separator 15 is heat-welded at a portion overlapping the tab film.
  • the negative electrode current collector 141 is laminated on the separator 15.
  • a lead portion 143 electrically connected to the negative electrode current collector 141 may be further provided, and tab films may be attached to both sides of the lead portion 143.
  • the second resin film 12 is laminated on the negative electrode current collector 141, and the lower side (the side where the lead portion 133 and the lead portion 143 are not extended to the outside of the exterior body, for example, the lead portion 133 and the lead portion 143 are the exterior
  • Each of the three sides is heat-welded except for the side extending to the outside of the body and the side facing the side).
  • at least the portion where the first resin film 11 and the second resin film 12 overlap each other is heat-welded on the two side surfaces.
  • at least the portion where the first resin film 11 and the second resin film 12 overlap is heat-welded.
  • an electrolytic solution composed of, for example, zinc powder as a negative electrode active material and a 7M-KOH aqueous solution is put through the opening on one side (lower side) that is not welded, and then the side is adhered.
  • the separator 15 has already been welded to the first resin film 11.
  • the portion where the resin films (the first resin film 11 and the second resin film 12) overlap each other is heat-welded so that the welding width is, for example, 4 mm.
  • the metal-air battery 10 in the present embodiment is not limited to the above configuration.
  • the negative electrode is sandwiched between the portions where the second resin film is provided.
  • the structure may also have a second air electrode in which a separator 15, a positive electrode current collector 131, a catalyst layer 132, a water repellent film 16, and a first resin film 11 are further laminated.
  • a positive electrode for charging having an oxygen evolution catalytic ability may be used instead of the second air electrode.
  • the positive electrode for charging is, for example, an electrode containing Ni having an oxygen evolution catalytic ability.
  • FIG. 4 is a schematic side view of the metal-air battery device 1.
  • FIG. 5 is a plan view showing an example of the regulating member 21.
  • FIG. 6 is a front view of the metal-air battery to which the regulation member 21 is mounted.
  • the metal-air battery device 1 has at least one metal-air battery 10 in which an air electrode 13 and a metal negative electrode 14 are arranged in a laminated direction in a housing 20. Be prepared.
  • a case where three metal-air batteries 10 are arranged in the housing 20 is illustrated, but the number of the metal-air batteries 10 is not particularly limited and may be a plurality.
  • the regulating member 21 includes, for example, linear rod-shaped portions 21a, 21b, 21c, 21d, and connecting portions 21e, 21f.
  • the regulating member 21 has a structure in which rod-shaped portions 21a, 21b, 21c, and 21d are connected by connecting portions 21e and 21f.
  • the regulating member 21 has a ring-shaped portion 21g surrounded by adjacent rod-shaped portions 21a and 21b and connecting portions 21e and 21f.
  • the portion surrounded by the adjacent rod-shaped portions 21b / 21c and the connecting portions 21e / 21f, and the portion surrounded by the adjacent rod-shaped portions 21c / 21d and the connecting portions 21e / 21f are also ring-shaped portions.
  • Each ring-shaped portion is the same as the ring-shaped portion 21 g. Then, each metal-air battery 10 is inserted into each ring-shaped portion 21 g and each ring-shaped portion.
  • the material of the regulating member 21 is not particularly limited, and may have flexibility to follow the expansion of the metal-air battery 10, for example. Further, the thickness of the regulating member 21 is not particularly limited, and if it is too thin, the regulating member 21 is likely to be damaged, and if it is too thick, the air intake port 111 of the metal-air battery 10 is blocked, resulting in deterioration of battery performance. It leads to.
  • the thickness of the regulating member 21 is, for example, 0.5 mm or more and 5 mm or less. In the present embodiment, the structure is such that three ring-shaped portions are connected, but the present invention is not limited to this, and the ring-shaped portion may be a single or a plurality of connected rings.
  • the metal-air battery 10 (exterior body) in the metal-air battery device 1 is sandwiched by a rod-shaped portion 21a and a rod-shaped portion 21b from the outside in the stacking direction in which the air electrode 13 and the metal negative electrode 14 are laminated. ing.
  • the distance between the rod-shaped portion 21a and the rod-shaped portion 21b at this time is L1. That is, the metal-air battery 10 is regulated to a thickness corresponding to the distance L1 between the rod-shaped portion 21a and the rod-shaped portion 21b.
  • the metal-air battery 10 is formed with a curved portion 10a regulated by the rod-shaped portions 21a and 21b, and is divided into a first portion 10b and a second portion 10c with a contact portion with the rod-shaped portions 21a and 21b as a boundary. Be done.
  • the rod-shaped portions 21a and 21b bend the metal-air battery 10, that is, the exterior body.
  • the thickness of the curved portion 10a of the metal-air battery 10 in other words, the predetermined thickness is larger than the thickness of the metal-air battery 10 when not regulated by the rod-shaped portion 21a and the rod-shaped portion 21b. It's getting thinner.
  • the width of the rod-shaped portions 21a and 21b in the stacking direction is not particularly limited, but for example, when the metal-air battery 10 expands, the water-repellent films 16 of the adjacent metal-air batteries 10 come into contact with each other to take in air. It suffices to keep a distance that does not block the mouth 111, and it is preferable that the distance is as small as possible.
  • the metal-air battery device 1 can be made more compact. In other words, it can be said that the predetermined thickness is thinner than the maximum thickness when the metal-air battery 10 is expanded.
  • the present invention is not limited to this, and other shapes such as wavy may be used.
  • the regulation is performed between the rod-shaped portions 21a and 21b, but for example, the metal-air battery 10 may be fixed and regulated so as to regulate one of the rod-shaped portions 21a and 21b.
  • the metal-air battery 10 can expand with discharge.
  • the thickness of the metal-air battery 10 when not discharged that is, the thickness W1 of the metal-air battery 10 in the undischarged initial stage (for example, at the time of preparation) is smaller than the thickness W2 at the time of expansion. It becomes.
  • the thickness W2 at the time of expansion becomes larger than L1
  • the metal-air battery 10 is regulated by the regulating member 21 to form a curved portion.
  • the metal-air battery 10 can be used. It will have a curved portion.
  • the regulating member 21 comes into contact with a part of the metal-air battery 10 and suppresses an increase in the thickness of the part of the metal-air battery 10.
  • the curved portion 10a is formed in a region in contact with the rod-shaped portions 21a and 21b in the exterior body including, for example, the first resin film 11, the second resin film 12, and the water-repellent film 16. It is preferable that at least a part of the rod-shaped portions 21a and 21b in contact with the exterior body is curved. As a result, it is possible to suppress damage to the exterior body, particularly the water-repellent film 16, with which the rod-shaped portions 21a and 21b come into contact.
  • the curved portion 10a is preferably curved in a state in which the first resin film 11, the water-repellent film 16, and the catalyst layer 132 are laminated, and further, the positive electrode current collector 131 and the slurry negative electrode active material layer 142 are formed.
  • the accommodated second accommodating portions S12 are curved in a laminated state.
  • the catalyst layer 132 and / or the positive electrode current collector 131 in advance in this way, it is possible to suppress the expansion of the metal-air battery 10 due to electric discharge. Therefore, it is possible to eliminate the non-uniformity of the discharge reaction due to the plane direction of the air electrode 13 caused by the change in the distance between the electrodes due to the expansion of the metal-air battery 10.
  • the metal-air battery 10 is restricted by the rod-shaped portions 21a and 21b to at least partially a predetermined thickness or less, that is, not more than the distance between the rod-shaped portions 21a and the rod-shaped portions 21b. Therefore, even if the negative electrode active material layer 142 or the like expands, the fluctuation of the distance between the positive electrode current collector 131 and the negative electrode current collector 141 is suppressed. In particular, in the regulating member 21, since the rod-shaped portions 21a and 21b are connected to each other by the connecting portions 21e and 21f, fluctuations in the distance between the rod-shaped portions 21a and the rod-shaped portions 21b can be further suppressed.
  • both ends of the rod-shaped portion 21a and the rod-shaped portion 21b are connected by the connecting portion 21e and the connecting portion 21f, but either the connecting portion 21e or the connecting portion 21f may be connected.
  • the connecting region 21h in which the rod-shaped portions 21a and 21b of the regulating member 21 and the connecting portions 21e and 21f are connected is configured to be a curved surface.
  • the positive electrode current collector 131 and the negative electrode current collector 141 in the metal-air battery 10 are preferably plate-shaped.
  • the plate-shaped positive electrode current collector 131 or the plate-shaped negative electrode current collector 141 is formed by arranging, knitting, and bending wire-shaped conductive materials constituting each of them into a plate shape. Also includes.
  • the positive electrode current collector 131 is preferably curved by the rod-shaped portions 21a and 21b of the regulating member 21. As a result, fluctuations in the distance between the positive electrode current collector 131 and the negative electrode current collector 141 can be further suppressed, the battery reaction in the metal-air battery 10 can be made more uniform, and the rate characteristics and the battery capacity can be further reduced. It can be suppressed.
  • the positive electrode current collector 131 and the negative electrode current collector 141 may be, for example, a porous body or a mesh shape.
  • the thickness of the negative electrode current collector 141 is not particularly limited, but is preferably such that it can be curved.
  • the rod-shaped portions 21a and 21b regulate the metal-air battery 10 across the central portion of the metal-air battery 10 in a direction substantially orthogonal to the stacking direction, for example.
  • substantially orthogonal means 90 ° ⁇ 5 ° with respect to a predetermined direction
  • the central portion is the peripheral edge of the air electrode in a direction substantially orthogonal to the stacking direction (that is, the plane direction of each component). It is an area located in the center rather than a quarter from the part.
  • the rod-shaped portions 21b / 21c and the rod-shaped portions 21c / 21d also have the same effect as the rod-shaped portions 21a / 21b.
  • a rod-shaped portion is arranged between the adjacent metal-air batteries 10, so that a gap is provided. This gap can prevent the water-repellent films 16 of the metal-air battery 10 from coming into contact with each other and block the air intake port 111, making it easier to supply air to the metal-air battery 10.
  • the metal-air batteries 10 are adjacent to each other via a rod-shaped portion sandwiched between the metal-air batteries 10 and the adjacent metal-air batteries 10 as the metal-air batteries 10 expand. Power is applied to 10. Due to the applied force, the adjacent metal-air batteries 10 are pushed by the rod-shaped portion and expansion is suppressed.
  • the effect of suppressing expansion of the plurality of metal-air batteries 10 can be obtained in the same manner, which is particularly preferable.
  • the thickness of each of the plurality of metal-air batteries 10 can be made substantially uniform, the battery characteristics such as the rate characteristics of each of the plurality of metal-air batteries 10 can be made uniform, and the variation among the metal-air batteries 10 can be made. It can be suppressed.
  • the metal-air battery device 1 in the present embodiment can be easily manufactured by mounting the metal-air battery 10 on the regulation member 21 and storing it in the housing 20. It is preferable that a part of the regulating member 21 is inscribed in the housing 20. For example, it is more preferable that the rod-shaped portion 21a of the regulation member 21 arranged between the metal-air battery 10 and the housing 20 is inscribed in the housing 20. As a result, the thickness of each of the plurality of metal-air batteries 10 regulated by the regulating member 21 becomes more uniform. Therefore, the battery characteristics such as the rate characteristics of each of the plurality of metal-air batteries 10 included in the same housing 20 can be made uniform, and the variation among the metal-air batteries 10 can be suppressed.
  • the housing 20 is provided with holes in the direction in which the metal-air batteries 10 are arranged and / or in the direction substantially orthogonal to the direction in which the metal-air batteries 10 are arranged. By forming this hole, it becomes easy to supply air to the metal-air battery 10, and deterioration of battery characteristics can be suppressed.
  • the holes in the housing 20 in the direction substantially orthogonal to the direction in which the metal-air batteries 10 are arranged facilitate the flow of air in the direction parallel to the air intake port 111, so that air can be supplied to the metal-air batteries 10. It is easy and preferable.
  • the holes in the side walls facing in the direction in which the metal-air batteries 10 are arranged in the housing 20, that is, in the direction substantially orthogonal to the stacking direction, are formed in the space between the metal-air batteries 10 formed by the regulating member 21. It is preferable to provide them so as to face each other. Thereby, air can be easily supplied to each metal-air battery 10.
  • the number of holes in the side wall may be one or a plurality.
  • the rod-shaped portions 21a and 21b of the regulating member 21 regulate the central portion of the metal-air battery 10 in the vertical direction
  • the number of the regulating members 21 and the regulated parts are limited to this. It's not a thing.
  • the regulated portion regulates a portion that substantially equally divides the vertical direction and / or the horizontal direction of the air intake port 111 of the metal-air battery 10.
  • the two regulating members 21 are used to regulate only the vertical direction of the air intake port 111 of the metal-air battery 10.
  • a portion that divides the vertical direction of the inlet 111 into substantially three equal parts may be regulated, or as shown in FIG. 8, the vertical direction of the air intake 111 of the metal-air battery 10 and the vertical direction of the metal-air battery 10 using the four regulating members 21.
  • the portion of the metal-air battery 10 that divides the lateral direction into substantially three equal parts may be regulated.
  • the thickness W1 of the metal-air battery 10 can be regulated more efficiently.
  • the regulation member 21 and the housing 20 are provided separately, but they may be integrally formed.
  • a general material such as resin or metal can be used for the housing 20.
  • the same material may be used for the regulation member 21 and the housing 20, or different materials may be used.
  • Examples and Comparative Examples> A metal-air battery having substantially the same configuration as the metal-air battery 10 according to the above embodiment was produced in the following manner.
  • the resin film is a laminate of a nylon (registered trademark) film having a thickness of 15 ⁇ m and a polyethylene (PE) film having a thickness of 100 ⁇ m.
  • An air intake port having an opening having a size of 60 ⁇ 60 mm was formed in the first resin film.
  • a water-repellent film made of a polytetrafluoroethylene film having a size of 70 mm ⁇ 70 mm and a thickness of 200 ⁇ m was placed so as to cover the air intake port of the resin film, and was heat-welded to the resin film.
  • the welding width was 2 mm.
  • the catalyst layer is a porous body (thickness: 500 ⁇ m) containing MnO 2 as an oxygen reduction catalyst, acetylene black as an oxygen reduction catalyst and a conductive agent, and polytetrafluoroethylene as a binder.
  • the positive electrode current collector is a Ni expand having a thickness of 180 ⁇ m.
  • a Ni foil having a thickness of 50 ⁇ 10 mm and a thickness of 100 ⁇ m to which a tab film was attached was used.
  • the separator is a polyolefin non-woven fabric having a size of 92 mm ⁇ 80 mm and a thickness of 200 ⁇ m.
  • the welding width between the separator and the first resin film and the separator and the tab film was 2 mm.
  • the negative electrode current collector is a Cu expand with a thickness of 280 ⁇ m.
  • the negative electrode current collector has a lead to which a tab film made of Ni foil having a thickness of 50 mm ⁇ 10 mm and a thickness of 100 ⁇ m is attached.
  • a 110 mm ⁇ 110 mm square resin film similar to the first resin film was laminated as the second resin film on the negative electrode current collector. Then, the first resin film and the second resin film were welded to each other so that the welding width was 2 mm on three sides excluding one side. Heat welded.
  • the electrolytic solution and the negative electrode active material were inserted between the separator and the second resin film from one side where the first resin film and the second resin film were not welded.
  • the electrolytic solution is a 7M aqueous solution of KOH.
  • the negative electrode active material particles are zinc powder.
  • the manufactured metal-air battery had a thickness of 8 mm.
  • a metal-air battery was manufactured in the same manner.
  • a member having a thickness of 2 mm and having a shape shown in FIG. 5 was prepared as the regulating member of each embodiment.
  • the thickness W1 and the distance (width of the ring-shaped portion) L1 between the rod-shaped portions at the initial stage of the metal-air battery in each embodiment are as shown in Table 1 below. L1 is the same in the three ring-shaped portions.
  • the three metal-air batteries produced above were mounted on each of the regulatory members of each embodiment at the positions shown in FIG. 6 and installed in the housing. By connecting the positive electrode and the negative electrode of the adjacent metal-air battery, the metal-air battery device according to each embodiment was manufactured. ABS resin was used as the material for the regulatory member and the housing according to each embodiment. In Comparative Example 1, a metal-air battery device in which three metal-air batteries were simply connected was manufactured without using a regulating member.
  • the discharge capacity was tested for the metal-air battery devices of Examples and Comparative Examples.
  • the metal-air battery device was connected to the load device, and the discharge test was performed in a room temperature environment until the voltage fell below 2.4 V at the discharge rate shown in Table 1.
  • the results are shown in Table 1.
  • the discharge capacity is shown as a relative value with reference to Example 2 as a reference (100).
  • Example 5 although L1 was larger than W1 in the initial stage, the metal-air battery expanded during discharge and was regulated by the regulating member to form a curved portion.
  • the present invention is not limited to the above-described embodiment, and is substantially the same as the configuration shown in the above-described embodiment, has the same effect and effect, or can achieve the same object. May be replaced with.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)
  • Battery Mounting, Suspending (AREA)
PCT/JP2021/011427 2020-04-07 2021-03-19 金属空気電池装置 Ceased WO2021205847A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023114169A (ja) * 2022-02-04 2023-08-17 シャープ株式会社 電池モジュール

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004288571A (ja) * 2003-03-25 2004-10-14 Toshiba Battery Co Ltd 水系金属空気電池およびこれを用いた電子機器
JP3183369U (ja) * 2013-02-25 2013-05-16 一般社団法人 Ｓｕｗｅｉ 空気電池のための収容体
JP2016012468A (ja) * 2014-06-29 2016-01-21 和之 豊郷 押圧型電池ケース
JP2016081643A (ja) * 2014-10-14 2016-05-16 古河電池株式会社 カートリッジ式空気電池、及びカートリッジ式空気電池システム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004288571A (ja) * 2003-03-25 2004-10-14 Toshiba Battery Co Ltd 水系金属空気電池およびこれを用いた電子機器
JP3183369U (ja) * 2013-02-25 2013-05-16 一般社団法人 Ｓｕｗｅｉ 空気電池のための収容体
JP2016012468A (ja) * 2014-06-29 2016-01-21 和之 豊郷 押圧型電池ケース
JP2016081643A (ja) * 2014-10-14 2016-05-16 古河電池株式会社 カートリッジ式空気電池、及びカートリッジ式空気電池システム

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023114169A (ja) * 2022-02-04 2023-08-17 シャープ株式会社 電池モジュール
JP7810567B2 (ja) 2022-02-04 2026-02-03 シャープ株式会社 電池モジュール

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