WO2023013248A1 - 電池 - Google Patents

電池 Download PDF

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Publication number
WO2023013248A1
WO2023013248A1 PCT/JP2022/023652 JP2022023652W WO2023013248A1 WO 2023013248 A1 WO2023013248 A1 WO 2023013248A1 JP 2022023652 W JP2022023652 W JP 2022023652W WO 2023013248 A1 WO2023013248 A1 WO 2023013248A1
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WO
WIPO (PCT)
Prior art keywords
metal
battery
negative electrode
lead terminal
electrode lead
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/JP2022/023652
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English (en)
French (fr)
Japanese (ja)
Inventor
宏隆 水畑
知 北川
俊輔 佐多
章人 吉田
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Sharp Corp
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Sharp Corp
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Publication date
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Priority to JP2023539681A priority Critical patent/JPWO2023013248A1/ja
Publication of WO2023013248A1 publication Critical patent/WO2023013248A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
    • H01M50/557—Plate-shaped terminals
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/562—Terminals characterised by the material
    • 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 disclosure relates to a battery in which a positive electrode, a metal negative electrode, and an alkaline aqueous solution are arranged inside an envelope.
  • Laminate batteries which are batteries configured by arranging a positive electrode, a metal negative electrode, and an electrolytic solution inside an outer envelope, have been put to practical use.
  • a heat-sealable resin container is often used for the outer casing of the laminated battery, and an alkaline aqueous solution such as a strongly alkaline potassium hydroxide aqueous solution is commonly used as the electrolytic solution.
  • the positive electrode and the metal negative electrode are provided with lead terminals extending from the inside of the outer casing to the outside, and the outer casing is welded and sealed with these lead terminals sandwiched therebetween.
  • Patent Document 1 discloses an air battery in which a positive electrode having a catalyst layer, a negative electrode containing a metal material, a separator, and an electrolytic solution are housed in an outer envelope, and the sealability of the welded portion of the outer envelope is improved. For this reason, it is disclosed that heat welding is performed after the polypropylene tape is attached to the lead terminal.
  • the envelope has a PET film on the outer surface of an aluminum foil, and an aluminum laminate film having a polypropylene film as a heat-sealable resin layer on the inner surface.
  • the present disclosure has been made in view of the above-mentioned problems, and its object is to increase the bonding strength between the lead portion extending from the inside of the outer package to the outside and the outer package.
  • An object of the present invention is to provide a battery capable of preventing leakage of an electrolytic solution from an outer package and determining whether or not the electrolyte is leaking.
  • the present disclosure provides a battery in which a positive electrode, a metal negative electrode, and an alkaline aqueous solution are arranged in an outer envelope, wherein the positive electrode and the metal negative electrode extend from the inside of the outer envelope to the outside.
  • a foil-like lead portion which is partly adhered to the outer package, and the outer package has a welded portion that is welded with the lead portion sandwiched therebetween, and the lead portion is
  • An uneven shape is provided on the outer surface at least in the region provided in the welded portion, and the outer envelope body is made of a transparent material that allows visual observation of the color inside the welded portion from the outside at least in the region provided with the welded portion. It is characterized by
  • the transparent material of the outer envelope is a transparent resin laminate having a multi-layer structure, and that the inner surface has a heat-fusible resin film material.
  • the uneven portions are made of nickel or copper.
  • the concave-convex shaped portion may have a metal particle layer coated with metal particles or metal oxide particles.
  • the metal negative electrode includes, as a negative electrode active material, a first metal material containing at least one metal element selected from among magnesium, aluminum, iron, and zinc, and the concave-convex portion is , and the second metal material containing at least one metal element selected from the group consisting of Groups 11 to 15 of the periodic table.
  • the second metal material preferably contains any one of copper, zinc, tin, or bismuth.
  • the positive electrode may be an air electrode
  • the metal negative electrode may be a zinc negative electrode
  • the battery according to the present disclosure it is possible to increase the adhesive strength between the lead portion extending from the inside of the outer shell to the outside and the outer shell, and prevent the electrolyte from leaking out of the outer shell. It is possible to easily determine the presence or absence of leakage.
  • FIG. 1 is a perspective view schematically showing a metal-air battery, which is a battery according to an embodiment of the present disclosure.
  • FIG. 2 is a front view showing an enlarged upper portion of the metal-air battery.
  • FIG. 3 is a cross-sectional view showing a configuration example of the metal-air battery.
  • FIG. 4 is a cross-sectional view corresponding to AA in FIG. 2 showing an enlarged internal structure of the upper portion of the metal-air battery.
  • FIG. 5 is a partially enlarged sectional view schematically showing a negative electrode lead terminal in the metal-air battery.
  • FIG. 6 is a partially enlarged sectional view schematically showing another example of the negative electrode lead terminal in the metal-air battery.
  • FIG. 1 is a perspective view schematically showing a metal-air battery, which is a battery according to an embodiment of the present disclosure.
  • FIG. 2 is a front view showing an enlarged upper portion of the metal-air battery.
  • FIG. 3 is a cross-sectional view showing a
  • the battery according to the present disclosure is the metal-air battery 1
  • the metal-air battery 1 will be shown as an example, and will be described with reference to the drawings.
  • the metal-air battery 1 is configured by accommodating a positive electrode 3 and a metal negative electrode 4 in an outer envelope 2, which is a bag-like outer case.
  • the positive electrode 3 is provided with a positive electrode lead terminal (lead portion) 7 extending from the inside of the envelope 2 to the outside.
  • the metal negative electrode 4 is also provided with a negative electrode lead terminal (lead portion) 5 extending from the inside of the envelope 2 to the outside.
  • an alkali metal hydroxide aqueous solution alkaline aqueous solution
  • alkaline aqueous solution which is a liquid having ionic conductivity
  • an aqueous lithium hydroxide solution As the alkaline aqueous solution, an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or the like can be used. Among them, it is particularly preferable to use an aqueous potassium hydroxide solution, which is excellent in ion conductivity.
  • a gelling agent or a metal oxide may be added as an additive to the electrolytic solution.
  • the envelope 2 is a bag-like container with a bottom, and is prepared in advance with an open top for containing the positive electrode 3, the metal negative electrode 4, and the electrolytic solution. After accommodating the positive electrode 3 and the metal negative electrode 4, the upper portion of the outer package 2 is welded and sealed with the positive electrode lead terminal 7 and the negative electrode lead terminal 5 extending to the outside of the outer package 2.
  • the outer envelope 2 is made of a thermoplastic resin film material with excellent alkali resistance.
  • the resin film material constituting the envelope 2 has a single-layer structure consisting only of a heat-fusible resin film material, or has a multilayer structure in which a heat-fusible resin film material and a heat-resistant substrate are laminated. can be
  • polyolefin-based resin film materials such as polypropylene (PP) and polyethylene (PE), and polyvinyl alcohol (PVA) can be used as heat-fusible resin film materials.
  • the heat-resistant substrate preferably contains a heat-resistant synthetic resin material.
  • resin substrates such as nylon, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT) can be suitably used. can.
  • a heat-fusible resin film material is arranged on the inner surface facing the positive electrode lead terminal 7 and the negative electrode lead terminal 5 . be done.
  • a welding method such as heat welding, vibration welding, or ultrasonic welding. can.
  • the upper portion of the outer envelope 2 is welded and sealed to form a welded portion 21 .
  • the envelope 2 is adhered to the lead terminals 7 and 5 while sandwiching the positive lead terminal 7 and the negative lead terminal 5 .
  • the positive electrode lead terminal 7 and the negative electrode lead terminal 5 are metal foil conductors, are provided on the positive electrode 3 and the metal negative electrode 4 respectively, and extend outside the envelope 2 .
  • FIG. 3 is a cross-sectional view schematically showing a configuration example of the metal-air battery 1.
  • the metal-air battery 1 can be constructed as shown in FIG.
  • the metal-air battery 1 includes a positive electrode 3 , a metal negative electrode 4 , a separator 11 and a water-repellent film 12 inside the envelope 2 .
  • the separator 11 is arranged so as to face the resin film material forming the outer package 2, and its peripheral edge is adhered to the peripheral edge of the resin film material.
  • the positive electrode 3 is accommodated together with the water-repellent film 12 between one of the resin film materials provided with the openings 22 and the separator 11 to form an air electrode. This opening 22 is used as an air intake.
  • the positive electrode 3 as an air electrode includes a current collector 31 and a catalyst layer 32 in contact with the current collector 31, and has oxygen reduction ability and oxygen generation ability.
  • a positive electrode lead terminal 7 is provided on the current collector 31 and extends outward.
  • the catalyst layer 32 contains at least an air electrode catalyst.
  • the air electrode catalyst is a catalyst having at least oxidation-reduction ability. Examples of the air electrode catalyst include Ketjenblack, acetylene black, Denka black, carbon nanotubes, conductive carbon such as fullerene, metals, metal oxides, metal hydroxides and metal sulfides.
  • the metal negative electrode 4 constitutes the envelope 2 by laminating a current collector 41 having a negative electrode lead terminal 5 and an active material layer 42 containing a negative electrode active material electrically connected to the current collector 41 . It is housed between the other resin film material and the separator 11 .
  • the negative lead terminal 5 is provided on the current collector 41 .
  • the current collector 41 and the particulate negative electrode active material eg, zinc or zinc oxide
  • the metal negative electrode 4 may include a current collector 41 and a colloidal slurry in which negative electrode active material particles and an electrolytic solution are mixed.
  • the metal negative electrode 4 contains, as a negative electrode active material, a first metal material containing at least one metal element of magnesium, aluminum, iron, or zinc. When these metal elements are used as the negative electrode active material, an aqueous solution with no risk of ignition can be used as the electrolyte. As described above, the metal negative electrode 4 is a foil-shaped negative electrode that extends from the inside of the envelope 2 to the outside, is partly adhered to the envelope 2, and is exposed to the outside of the envelope 2. It has a lead terminal 5 .
  • the current collector 41 of the metal negative electrode 4 constitutes a current conducting path from the negative electrode material.
  • the current collector 41 has, for example, a plate shape, a sheet shape, or the like.
  • the current collector 41 may be a current collector having a three-dimensional mesh structure made of foam metal, expanded metal, punching metal, metal fiber felt, or the like.
  • FIG. 4 is an enlarged cross-sectional view showing the internal structure of the upper portion of the metal-air battery 1, corresponding to the AA cross-section in FIG. FIG. 4 shows the metal-air battery 1 and the negative electrode lead terminal 5 arranged sideways.
  • FIG. 5 is a partially enlarged sectional view schematically showing part of the negative lead terminal 5. As shown in FIG.
  • the negative lead terminal 5 is arranged between the outer wrappers 2 and extends out from the outer wrapper 2 (to the right in FIG. 4).
  • the negative lead terminal 5 has an uneven portion 51 provided on the outer surface facing the inner surface of the outer envelope 2 and a main body layer 52 inside the uneven portion 51 .
  • the main body layer 52 constitutes the central portion of the negative electrode lead terminal 5 in the thickness direction (vertical direction in FIG. 4).
  • the outer surface of the positive electrode lead terminal 7 provided on the positive electrode 3 is provided with an uneven portion (not shown).
  • the concave-convex portion 51 is provided on the outer surface of the negative electrode lead terminal 5 in a concave-convex shape, and is configured to increase the bonding strength between the welding portion 21 and the outer package 2 .
  • the outer surface of the main body layer 52 may be provided with an uneven portion 51 having an uneven shape by attaching particles 514 of metal particles or metal oxide particles. The details of the concave-convex shape portion 51 will be described later.
  • a metal foil having a width of 5 to 20 mm and a thickness of 20 to 200 ⁇ m can be used for the negative electrode lead terminal 5 . More preferably, the width is 10-15 mm and the thickness is 35-100 ⁇ m. If the width and thickness are small, there is a problem that the resistance of the negative electrode lead terminal 5 increases. On the other hand, if the width and thickness are too large, liquid leakage may occur even when the negative electrode lead terminal 5 is provided with the uneven portion 51 on its outer surface.
  • the width of the positive electrode lead terminal 7 is preferably 5-20 mm and the thickness is 20-200 ⁇ m, and more preferably the width is 10-15 mm and the thickness is 35-100 ⁇ m. If the width and thickness are small, there is a problem that the resistance of the positive electrode lead terminal 7 increases. On the other hand, if the width and thickness are too large, liquid leakage may occur even when the positive electrode lead terminal 7 is provided on both sides.
  • the metal negative electrode 4 and the positive electrode 3 have uneven portions 51 on the outer surfaces of the lead terminals 5 and 7, respectively, so that it is possible to increase the adhesive strength with the heat-fusible resin film material that constitutes the outer package 2. It is That is, the heat-fusible resin film material of the outer package 2 is melted so as to conform to the uneven shape, and is closely adhered to the negative electrode lead terminal 5 and the positive electrode lead terminal 7 . Thereby, the adhesive strength between the negative lead terminal 5 and the positive lead terminal 7 and the outer package 2 can be increased at the welded portion 21 of the outer package 2 .
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 7 are provided with unevenness on the outer surface, light is scattered and absorbed by the uneven surface.
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 7, whose reflectance is lowered due to the concave and convex shape, are visually recognized as a low-brightness color in which the outer surfaces have lost metallic luster, and are matte black in color from brown (dark brown) to near black. It exhibits a refined appearance.
  • the outer surface which was silvery white in a smooth state, loses its metallic luster due to the uneven shape. It becomes a thing exhibiting a color close to black.
  • the main body layer 52 is formed of copper (Cu)
  • the outer surface which was glossy brown in a smooth state, loses its metallic luster and becomes matte by providing the uneven shape.
  • the color becomes dark brown or close to dark brown, and when a metal plating layer of tin (Sn) is further formed thereon, as described later, the color changes from matte black gray to black.
  • the outer package 2 is formed of a single-layer structure of a heat-fusible resin film material or a multi-layer structure in which a heat-fusible resin film material and a heat-resistant substrate are laminated. Moreover, the outer envelope 2 is made of a transparent material at least in the region where the welded portion 21 is provided.
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 7 are visually observed from the outside of the outer package 2 made of a transparent material at least in the region where the welded portion 21 is provided. can do.
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 7 have a matte black appearance due to the concave-convex shape, they can be clearly visually recognized. Needless to say, the entire envelope 2 may be made of such a transparent material.
  • the region where the welded portion 21 is provided has the property of transmitting light from near-infrared to near-ultraviolet, it is also possible to observe it using a camera or the like capable of detecting near-infrared or near-ultraviolet instead of visual observation. Become.
  • the carbon dioxide in the atmosphere reacts with the alkaline aqueous solution at the air-liquid interface between the alkaline aqueous solution, which is the electrolytic solution, and the outside air, causing precipitation.
  • White crystals of carbonate formed. Therefore, when the welded portion 21 is viewed from the outside of the outer package 2 made of a transparent material, it is possible to visually recognize white crystals adhering to the blackened negative electrode lead terminal 5 or the positive electrode lead terminal 7 .
  • both the negative electrode lead terminal 5 and the positive electrode lead terminal 7 are blackened due to a decrease in reflectance due to the uneven shape, so that the presence or absence of white crystals can be clearly visually recognized by comparing the brightness thereof.
  • FIG. 6 and 7 are cross-sectional views schematically showing enlarged portions of the negative electrode lead terminal 5.
  • FIG. The negative lead terminal 5 has an uneven portion 51 on the outer surface of the body layer 52 .
  • the negative electrode lead terminal 5 is provided with a concave-convex portion 51 particularly in a region arranged inside the envelope 2 .
  • the uneven portions 51 are provided on both surfaces of the body layer 52 .
  • the uneven portion 51 includes an uneven portion 511 having a mountain-valley shape (uneven shape) formed on the outer surface of the main body layer 52, and a surface layer provided to cover the uneven portion 511. It has a metal particle layer 512 or a metal plated layer 513 .
  • the uneven portion 511 promotes the growth of metal crystals in an uneven shape on the outer surface by adjusting the electrodeposition conditions for the metal foil constituting the main body layer 52 when manufacturing the negative electrode lead terminal 5, or It can be formed by various chemical or physical treatments such as etching or blasting the surface.
  • metal particles or metal oxide particles are adhered to the outer surface of the main body layer 52 of the negative lead terminal 5 to form an uneven portion 511, and the metal particles cover the uneven portion 511.
  • a layer 512 or metal plated layer 513 may be provided.
  • the main body layer 52 secures the mechanical strength of the negative electrode lead terminal 5 and is responsible for electronic conductivity.
  • the metal particle layer 512 or the metal plated layer 513 of the concave-convex portion 51 suppresses hydrogen generation due to contact with the alkaline aqueous solution, which is the electrolytic solution.
  • both the concave-convex portion 51 and the main body layer 52 of the negative electrode lead terminal 5 are preferably made of a metal material having alkali resistance.
  • the metal particle layer 512 or the metal plating layer 513 of the uneven portion 51 of the negative electrode lead terminal 5 contains at least one metal element selected from the group consisting of Groups 11 to 15 of the periodic table. and a second metal material comprising:
  • the metal negative electrode 4 contains a first metal material containing at least one metal element selected from among magnesium, aluminum, iron, and zinc as the negative electrode active material, and an aqueous solution is used as the electrolyte, an electrolytic solution is produced as a side reaction.
  • the elements of Groups 11 to 15 of the periodic table have relatively high hydrogen overvoltages. Therefore, by including the second metal material in the metal particle layer 512 or the metal plating layer 513 of the concave-convex shaped portion 51, the progress of such a side reaction can be suppressed.
  • the metal particle layer 512 or the metal plating layer 513 may include copper (Cu), zinc (Zn), indium (In), tin ( Sn), antimony (Sb), thallium (Tl), lead (Pb), and bismuth (Bi), and at least one of these metal elements is preferably used as the second metal material.
  • antimony, thallium, and lead are toxic, and indium is costly. Therefore, copper, zinc, tin, or bismuth, which is inexpensive, has low toxicity, and can be used safely, should be used as the second metal material. is preferred, and it is particularly preferred to use zinc or tin, which have particularly high hydrogen overvoltages.
  • the main body layer 52 of the negative electrode lead terminal 5 contains one metal element selected from copper (Cu), zinc (Zn), brass (Cu/Zn alloy), nickel (Ni), and gold (Au). is preferably formed as a material. Of these, nickel is likely to generate hydrogen, gold is expensive, and zinc cannot be expected to have mechanical strength. 52 is more preferred.
  • the main body layer 52 may be made of the same second metal material as the metal particle layer 512 or the metal plating layer 513 of the concave-convex shaped portion 51 .
  • the body layer 52 is formed of a metal element different from the second metal material of the metal particle layer 512 or the metal plating layer 513. is more preferable.
  • the main body layer 52 is a foil-shaped body made of copper, A copper metal layer or copper particles are deposited on the outer surface to form the uneven portion 511, and the metal particle layer 512 or the metal plating layer 513 covering the uneven portion 511 contains tin.
  • the concave-convex shape portion 51 is a groove along a direction intersecting the length direction of the negative electrode lead terminal 5 (horizontal direction in the drawing). is preferably formed, and liquid leakage can be prevented more effectively.
  • the uneven portion 511 when the uneven portion 511 is provided by attaching metal particles, the uneven portion 511 has an uneven shape having a constricted portion, so that the uneven portion 51 is more firmly attached to the outer envelope 2. It is possible to adhere to
  • the concave-convex shaped portion 51 has a surface roughness (arithmetic mean roughness) Ra of 0.4 ⁇ m to 3.0 ⁇ m (more preferably 1.5 ⁇ m to 3.0 ⁇ m) for both the negative electrode lead terminal 5 and the positive electrode lead terminal 7 . range.
  • the ten-point average surface roughness Rz is preferably in the range of 2.0 ⁇ m to 15.0 ⁇ m (more preferably 7.0 ⁇ m to 15.0 ⁇ m).
  • the surface roughness is within such a numerical range, light is sufficiently diffusely reflected by the concave-convex shape portion 51. As a result, the difference in brightness between the white crystals caused by leakage of the electrolytic solution becomes large, and the leakage of the electrolytic solution increases. The presence or absence can be easily determined.
  • the surface roughness of the uneven shape portion 51 is measured using a stylus type surface roughness measuring instrument (JIS B0651:2001), and the arithmetic average roughness and the maximum height roughness (JIS B0601:2001) are measured. It is measured by asking.
  • a stylus type surface roughness measuring instrument for example, a stylus type surface roughness measuring instrument SE-3500 manufactured by Kosaka Laboratory Ltd. can be used.
  • FIG. 8A and 8B are partially enlarged cross-sectional views schematically showing configuration examples of the concave-convex shaped portion 51 of the negative electrode lead terminal 5.
  • FIG. 8A and 8B are partially enlarged cross-sectional views schematically showing configuration examples of the concave-convex shaped portion 51 of the negative electrode lead terminal 5.
  • the metal particle layer 512 can be formed by applying metal particles or metal oxide particles containing the second metal element. From the viewpoint of electron conductivity in the negative electrode lead terminal 5, the metal particle layer 512 made of metal particles is more preferable than metal oxide particles.
  • a metal plating layer 513 containing the second metal element may be provided as the surface layer of the uneven portion 51.
  • the negative electrode lead terminal 5 is provided with uneven portions 511 on both front and back surfaces of a main body layer 52 made of copper as uneven portions 51 , and a metal plating layer 513 is provided so as to cover the uneven portions 511 . It is
  • the metal particles form an uneven shape having a constricted portion on the surface of the uneven portion 511 .
  • the brightness of the negative electrode lead terminal 5 is lowered, and the visibility at the time of leakage of the electrolyte is improved, compared to the case of the concave-convex portion 51 having the metal plating layer 513 shown in FIG. 8B.
  • the uneven portion 51 formed by adhering the particles 514
  • the surface roughness can be made larger than in the case of . Therefore, the sealability of the adhesive interface with the outer package 2 can be enhanced.
  • both the metal particle layer 512 and the metal plating layer 513 may be provided on the uneven portion 51 .
  • the negative electrode lead terminal 5 can increase the bonding strength with the outer package 2 by the uneven shape portion 51, and the hydrogen generation that is easy to accelerate can be performed by the metal particle layer 512 or the metal plating layer. It is possible to suppress it by the action of 513 . Therefore, in the metal-air battery 1, leakage of the alkaline aqueous solution from the welding portion 21 extending from the negative electrode lead terminal 5 is prevented, and the envelope 2 can be stably sealed.
  • the negative electrode lead terminal 5 may be provided with a zinc layer, which is a metal particle layer containing zinc as the second metal material or a metal plating layer, on the outer surface of the region inside the welded portion 21 .
  • a zinc layer which is a metal particle layer containing zinc as the second metal material or a metal plating layer
  • the region inside the welded portion 21 is a region that comes into contact with the alkaline aqueous solution, which is the electrolytic solution.
  • the negative electrode lead terminal 5 is a region where the decomposition reaction of the alkaline aqueous solution proceeds and hydrogen gas is generated.
  • the zinc layer on the outer surface of the negative electrode lead terminal 5 in this region it is possible to effectively suppress hydrogen generation. Since the zinc layer can contribute as an active material during discharge, the discharge capacity can be increased.
  • the concave-convex shaped portion 51 is provided for bonding strength with the outer package 2, the negative lead terminal 5 disposed inside the welded portion 21 of the outer package 2 is not limited to the above configuration. . Further, the configuration of the concave-convex shaped portion 51 of the negative electrode lead terminal 5 is not limited to the same configuration on both the front and back surfaces of the main body layer 52. One surface is configured as shown in FIG. 8A, and the other surface is configured as shown in FIG. 8B. It can be configured by various combinations such as configured as follows.
  • the negative electrode lead terminal 5 may be provided with the concave-convex shaped portion 51 not only on the front and back surfaces (or one surface) but also on the side surface as long as it is the outer surface of the main body layer 52 .
  • the adhesion between the side surface of the negative lead terminal 5 and the outer envelope 2 can be further enhanced.
  • the uneven portion 51 may be provided on the negative electrode lead terminal 5 in the region corresponding to the welding portion 21 .
  • the concave-convex portion 51 does not necessarily have to be provided on the negative electrode lead terminal 5 in the region extending outside the envelope 2 . Since the portion extending to the outside is electrically connected to the negative electrode lead terminal 5, in the absence of the uneven shape portion 51, it is possible to suppress dust generation due to scraping of the uneven shape portion 51 due to connection.
  • the negative electrode lead terminal 5 disposed inside the welded portion 21 of the outer package 2 does not necessarily have to be provided with the concave-convex shaped portion 51 . Since the portion disposed inside is a region that contacts the alkaline electrolyte, the contact area can be reduced without the concave-convex shape portion 51, so that the decomposition reaction of the alkaline aqueous solution can be suppressed. On the other hand, on the front and back of the metal foil constituting the body layer 52 of the negative electrode lead terminal 5, providing the uneven shape portions 51 on the entire front and back surfaces was more productive than providing the uneven shape portions 51 only on a partial region. can be
  • the positive electrode lead terminal 7 may also be provided with a similar concave-convex shape portion.
  • the requirements that the concave-convex portion of the positive lead terminal 7 should have are the same as those of the negative lead terminal 5 except for the surface layer such as the metal particle layer or the metal plating layer.
  • the negative electrode lead terminal 5 has a problem that hydrogen is generated when it comes into contact with the alkaline aqueous solution, which is the electrolytic solution, but the positive electrode lead terminal 7 does not have such a problem. Therefore, the positive electrode lead terminal 7 may or may not have a metal particle layer or a metal plating layer.
  • the metal-air battery 1 can be implemented in various forms other than the above embodiments.
  • the metal-air battery 1 may be provided with a sealing member 6 made of a transparent material.
  • FIG. 9 is a perspective view schematically showing a metal-air battery 1 provided with a sealing member 6,
  • FIG. 10 is a front view showing an enlarged upper portion of the metal-air battery 1 of FIG. 9, and
  • FIG. 10 is a cross-sectional view showing an enlarged internal structure of the upper portion of the metal-air battery 1, corresponding to the cross-sectional view taken along line BB in FIG.
  • FIG. 11 shows the metal-air battery 1 and the negative lead terminal 5 arranged sideways.
  • 12 is a sectional view taken along the line CC in FIG. 11.
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 7 are provided with sealing members 6 made of a transparent material so as to correspond to the welded portions with the outer package 2 .
  • the sealing member 6 is arranged so as to overlap the welded portion 21 .
  • the sealing member 6 is made of a transparent polyolefin-based resin film material such as polypropylene (PP), polyvinyl alcohol (PVA), polyethylene (PE), etc., which is a thermally adhesive resin film material.
  • PP polypropylene
  • PVA polyvinyl alcohol
  • PE polyethylene
  • the sealing member 6 is provided so as to extend above the welded portion 21 outside the outer envelope 2 , and also extend below the welded portion 21 inside the outer envelope 2 . is provided.
  • the sealing member 6 may be interposed between the outer package 2 and the negative lead terminal 5 and the positive lead terminal 7 at the welded portion 21 . Therefore, the sealing member 6 may be provided so as to be exposed to the outside from the upper end portion of the outer envelope 2 or may be provided so as not to be exposed to the outside of the outer envelope 2 .
  • the sealing member 6 is preferably adhered to the negative lead terminal 5 in advance. As shown in FIG. 10 , at the welded portion 21 , the outer envelope 2 and the negative lead terminal 5 are adhered and sealed via the sealing member 6 .
  • welding between the outer wrappers 2 and bonding between the outer wrapper 2 and the negative electrode lead terminal 5 (and the positive electrode lead terminal 7) have welding conditions and bonding conditions such as suitable temperature and time, respectively. Even if the welding conditions between the outer package 2 and the bonding conditions between the outer package 2 and the lead terminals 5 and 7 are different, the sealing member 6 should be sufficiently bonded to the lead terminals 5 and 7 . For example, by welding the sealing member 6 and the outer package 2 together, the outer package 2 and the lead terminals 5 and 7 can be reliably adhered to each other. Since the encapsulant 2 and the sealing member 6 are welded together by resin film materials, the possibility of defective welding is low, and the bonding strength between the lead terminals 5 and 7 can be increased. In addition, the sealing member 6 is adhered to the concave-convex portions (51) of the lead terminals 5 and 7, so that the adhesion interfaces between the outer package 2 and the lead terminals 5 and 7 are well formed without gaps. can be done.
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 5 inside the sealing member 6 made of a transparent material are at least in the region where the welding portion 21 is provided.
  • the lead terminal 7 can be visually observed.
  • the negative electrode lead terminal 5 and the positive electrode lead terminal 7 have a blackened appearance due to the uneven shape of the outer surface, and can be clearly visually recognized.
  • the present disclosure can be embodied in various other forms without departing from its spirit or essential characteristics.
  • Application of the battery according to the present disclosure is not limited to metal-air batteries in which the positive electrode is the air electrode.
  • the positive electrode 3 is not limited to the air electrode.
  • the configurations of the concave-convex portion 51 and the sealing member 6 in the metal-air battery 1 are not limited to the above-described embodiments, and may be configured in any shape.
  • the metal-air battery 1 is suitable for, for example, a zinc-air battery, a magnesium-air battery, an aluminum-air battery, an iron-air battery, etc., and can be applied to both primary batteries and secondary batteries. In particular, it is effective when applied to a zinc-air battery that uses a highly permeable alkaline aqueous solution as an electrolyte.

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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)
  • Sealing Battery Cases Or Jackets (AREA)
  • Connection Of Batteries Or Terminals (AREA)
PCT/JP2022/023652 2021-08-02 2022-06-13 電池 Ceased WO2023013248A1 (ja)

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JP2011243490A (ja) * 2010-05-20 2011-12-01 Sharp Corp ２次電池、２次電池モジュール、２次電池の製造方法、および２次電池モジュールの製造方法
JP2011249071A (ja) * 2010-05-25 2011-12-08 Toyota Motor Corp 水系電解液電池及び水系電解液電池の製造方法
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JP2014186914A (ja) * 2013-03-25 2014-10-02 Showa Denko Packaging Co Ltd タブリード
TWI515342B (zh) * 2013-09-05 2016-01-01 三井金屬鑛業股份有限公司 表面處理銅箔、使用該表面處理銅箔所得之貼銅積層板以及印刷配線板
JP6232302B2 (ja) * 2014-01-29 2017-11-15 Ｊｘ金属株式会社 リチウムイオン電池用電極タブの製造方法
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WO1988006645A1 (en) * 1987-03-02 1988-09-07 Gould Inc. Hydrogel loaded active layer in pressure tolerant gas diffusion electrodes
JP2004095401A (ja) * 2002-08-30 2004-03-25 Nissan Motor Co Ltd ラミネート二次電池、組電池モジュール、組電池ならびにこの電池を搭載した電気自動車
JP2004362935A (ja) * 2003-06-04 2004-12-24 Sumitomo Electric Ind Ltd リード導体、リード、電力貯蔵デバイス、リード導体の製造方法、及び、リードの製造方法
JP2011243490A (ja) * 2010-05-20 2011-12-01 Sharp Corp ２次電池、２次電池モジュール、２次電池の製造方法、および２次電池モジュールの製造方法
JP2011249071A (ja) * 2010-05-25 2011-12-08 Toyota Motor Corp 水系電解液電池及び水系電解液電池の製造方法
WO2020235389A1 (ja) * 2019-05-21 2020-11-26 シャープ株式会社 金属空気電池

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