WO2024029364A1 - 負極板及びそれを備えた亜鉛二次電池 - Google Patents

負極板及びそれを備えた亜鉛二次電池 Download PDF

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WO2024029364A1
WO2024029364A1 PCT/JP2023/026636 JP2023026636W WO2024029364A1 WO 2024029364 A1 WO2024029364 A1 WO 2024029364A1 JP 2023026636 W JP2023026636 W JP 2023026636W WO 2024029364 A1 WO2024029364 A1 WO 2024029364A1
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negative electrode
electrode plate
ldh
zinc
secondary battery
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English (en)
French (fr)
Japanese (ja)
Inventor
貴士 鈴木
洋志 林
稔久 平岩
雄樹 藤田
壮太 清水
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NGK Insulators Ltd
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NGK Insulators Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/474—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by their position inside the 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/477—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by their shape
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/48—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by the material
    • H01M50/486—Organic material

Definitions

  • the present invention relates to a negative electrode plate and a zinc secondary battery equipped with the same.
  • Patent Document 1 discloses providing an LDH separator between a positive electrode and a negative electrode in a nickel-zinc secondary battery.
  • Patent Document 2 discloses a separator structure including an LDH separator fitted or joined to a resin outer frame, and the LDH separator has gas impermeability and/or water impermeability. It is disclosed that the material has high density to the extent that it is transparent. This document also discloses that the LDH separator can be composited with a porous substrate.
  • Patent Document 3 discloses various methods for forming a dense LDH film on the surface of a porous base material to obtain a composite material.
  • a starting material that can provide a starting point for LDH crystal growth is uniformly adhered to a porous substrate, and the porous substrate is hydrothermally treated in an aqueous raw material solution to form a dense LDH film on the surface of the porous substrate.
  • An LDH separator has also been proposed in which further densification is achieved by roll pressing a composite material of LDH/porous base material produced through hydrothermal treatment.
  • Patent Document 4 (WO2019/124270) describes an LDH separator that includes a porous polymer base material and LDH filled in this porous base material, and has an in-line transmittance of 1% or more at a wavelength of 1000 nm. is disclosed.
  • LDH-like compounds are known as hydroxides and/or oxides with a layered crystal structure similar to LDH, although they cannot be called LDH. It exhibits ion conductive properties.
  • Patent Document 5 discloses a hydroxide ion conductive separator that includes a porous base material and a layered double hydroxide (LDH)-like compound that closes the pores of the porous base material.
  • the LDH-like compound is a hydroxide and/or oxide with a layered crystal structure containing Mg and at least one element containing at least Ti selected from the group consisting of Ti, Y, and Al. Disclosed.
  • This hydroxide ion conductive separator is said to have superior alkali resistance and to be able to more effectively suppress short circuits caused by zinc dendrites than conventional LDH separators.
  • Patent Document 6 discloses that the entire negative electrode active material layer is covered or wrapped with a liquid retaining member and an LDH separator, and the positive electrode active material layer is covered with a liquid retaining member.
  • Zinc secondary batteries have been proposed that are covered or wrapped in zinc.
  • a nonwoven fabric is used as the liquid retaining member. According to this configuration, a complicated sealing bond between the LDH separator and the battery container is not required, and a zinc secondary battery (especially a stacked battery thereof) that can prevent zinc dendrite expansion can be produced extremely easily and with high productivity. It is said that it can be done.
  • Patent Document 8 (WO2021/193436) describes a laminate including alternately positive electrode plates and negative electrode plates, a positive electrode current collector tab connected to a positive electrode current collector in the positive electrode plate, and a negative electrode current collector in the negative electrode plate.
  • a zinc secondary battery is disclosed in which a negative electrode current collecting tab connected to a body is vertically oriented, and a positive electrode current collecting tab and a negative electrode current collecting tab protrude upward from a laminate.
  • the problem of negative electrode shape change is known, in which the shape of the negative electrode changes to an undesirable shape and size with repeated charging and discharging.
  • the negative electrode plate which was initially square, is repeatedly charged and discharged, it shrinks unevenly from the edges toward the center, which means that the outer periphery of the negative electrode plate is unevenly eroded and lost.
  • ZnO negative electrode active material
  • the negative electrode plate gradually deforms toward the center due to the diffusion of zincate ions due to the dissolution of ZnO.
  • Such a shape change of the negative electrode plate leads to a decrease in the effective area of the negative electrode plate that faces the positive electrode plate, resulting in an increase in battery resistance, a decrease in battery capacity, and a shortened lifespan of the zinc secondary battery.
  • the present inventors have recently discovered that by providing partition walls on the surface of a negative electrode current collector plate to partition a plurality of individualized segments, and filling each of these segments with a negative electrode active material, zincate ions can be removed.
  • a negative electrode plate that can suppress in-plane diffusion and delay shape changes.
  • an object of the present invention is to provide a negative electrode plate that can suppress in-plane diffusion of zincate ions and delay shape change.
  • a negative electrode current collector plate a negative electrode current collector plate; a partition wall provided on at least one surface of the negative electrode current collector plate and partitioning a plurality of mutually individualized segments; a negative electrode active material containing at least one selected from the group consisting of zinc, zinc oxide, zinc alloy, and zinc compound, which is filled in each of the segments; A negative electrode plate.
  • a negative electrode plate A negative electrode plate.
  • Aspect 2 The negative electrode plate according to aspect 1, wherein the negative electrode active materials filled in adjacent segments are spaced apart from each other.
  • Aspect 3 The negative electrode plate according to aspect 1 or 2, wherein the partition wall and the negative electrode active material are provided on both sides of the negative electrode current collector plate.
  • Aspect 4 The negative electrode plate according to any one of aspects 1 to 3, wherein the partition wall has a gas venting structure that allows gas to pass between adjacent segments.
  • the gas venting structure includes at least one selected from the group consisting of a groove, a notch, and a hole.
  • Aspect 6 Aspect 4 or 4, wherein the negative electrode plate is assumed to be used vertically, and the gas venting structure is provided at a position that should be the top of each of the segments when the negative electrode plate is arranged vertically. 5.
  • Aspect 7 The negative electrode plate according to any one of aspects 1 to 6, wherein the partition walls are provided in a grid pattern.
  • the negative electrode plate has a rectangular shape, and the lattice-like partition wall is provided so as to be parallel or perpendicular to sides forming an outer periphery of the rectangular shape when the negative electrode plate is viewed from above.
  • negative electrode plate has a rectangular shape, and when the negative electrode plate is viewed from above, the lattice-like partition walls form an angle of 30 to 60 degrees with respect to one of the sides forming the outer periphery of the rectangular shape.
  • a positive electrode The negative electrode plate according to any one of aspects 1 to 10, a separator that isolates the positive electrode and the negative electrode plate in a manner that allows conduction of hydroxide ions; electrolyte and including zinc secondary batteries.
  • a separator that isolates the positive electrode and the negative electrode plate in a manner that allows conduction of hydroxide ions; electrolyte and including zinc secondary batteries.
  • the separator is an LDH separator containing layered double hydroxide (LDH) and/or an LDH-like compound.
  • the LDH separator further includes a porous base material, and the LDH and/or LDH-like compound is composited with the porous base material in a form filled in the pores of the porous base material.
  • LDH separator further includes a porous base material, and the LDH and/or LDH-like compound is composited with the porous base material in a form filled in the pores of the porous base material.
  • FIG. 1 is a schematic plan view showing an example of a negative electrode according to the present invention.
  • FIG. 2 is a diagram schematically showing a cross section along the line A-A' of the negative electrode shown in FIG. 1.
  • FIG. 3 is a diagram schematically showing states before and after shape change in the negative electrode according to the present invention.
  • FIG. 2 is a schematic top view showing an example of lattice-shaped partition walls in the negative electrode according to the present invention.
  • FIG. 7 is a schematic top view showing another example of lattice-shaped partition walls in the negative electrode according to the present invention.
  • FIG. 5 is a schematic top view showing an example of a configuration in which the lattice-shaped partition walls shown in FIG. 4 are provided with a gas venting structure.
  • FIG. 1 is a schematic plan view showing an example of a negative electrode according to the present invention.
  • FIG. 2 is a diagram schematically showing a cross section along the line A-A' of the negative electrode shown in FIG. 1.
  • FIG. 6 is a schematic top view showing an example of a configuration in which the lattice-shaped partition walls shown in FIG. 5 are provided with a gas venting structure.
  • FIG. 3 is a schematic cross-sectional view showing another example of the negative electrode according to the present invention.
  • 1 is a schematic cross-sectional view showing an example of the internal structure of a secondary battery according to the present invention.
  • 10 is a diagram schematically showing a cross section taken along the line B-B' of the secondary battery shown in FIG. 9.
  • FIG. 10 is a perspective view schematically showing battery elements of the secondary battery shown in FIG. 9.
  • FIG. 10 is a cross-sectional view schematically showing battery elements of the secondary battery shown in FIG. 9.
  • FIG. 9 is a cross-sectional view schematically showing battery elements of the secondary battery shown in FIG. 9. FIG.
  • Negative Plate Figures 1 and 2 show a negative plate 14 according to one embodiment of the present invention.
  • the negative electrode plate 14 includes a negative electrode current collector plate 16, a partition wall 18, and a negative electrode active material 20.
  • the partition wall 18 is provided on at least one surface of the negative electrode current collector plate 16 and partitions a plurality of segments S that are separated from each other.
  • the negative electrode active material 20 includes at least one selected from the group consisting of zinc, zinc oxide, zinc alloy, and zinc compound. Each of the segments S is filled with the negative electrode active material 20 . In this way, by providing the partition wall 18 on the surface of the negative electrode current collector plate 16 to divide a plurality of individualized segments S, and filling each of these segments S with the negative electrode active material 20, zincate ions can be removed. It is possible to provide a negative electrode plate 14 that can suppress in-plane diffusion and delay shape change.
  • the problem of negative electrode shape change is known in zinc secondary batteries. Specifically, as the negative electrode plate, which was initially square, is repeatedly charged and discharged, it shrinks unevenly from the edges toward the center, which means that the outer periphery of the negative electrode plate is unevenly eroded and lost. A phenomenon can be seen. This is because the negative electrode active material (ZnO) constituting the negative electrode plate moves from the end toward the center through repeated dissolution and precipitation during charging and discharging. In other words, the negative electrode plate gradually deforms toward the center due to the diffusion of zincate ions due to the dissolution of ZnO. According to the structure of the present invention, this diffusion of zincate ions is effectively suppressed.
  • ZnO negative electrode active material
  • each segment S is partitioned by the partition wall 18, the movement of zincate ions Z between the segments S is blocked by the partition wall 18, as shown by arrows and x in FIG. be done.
  • in-plane diffusion of zincate ions can be suppressed and shape change can be delayed. That is, as shown in FIG. 3, although the shape change itself occurs, each segment S distributed within the plane of the negative electrode plate 14 is eroded from its outer periphery, so that the effective area of the negative electrode plate 14 facing the positive electrode plate is can significantly delay the decrease in As a result, the timing at which battery resistance increases and battery capacity decreases can be significantly delayed, making it possible to extend the life of the zinc secondary battery.
  • the negative electrode current collector plate 16 may be a non-porous metal plate, it is preferable to use a metal plate having multiple (or many) openings from the viewpoint of fixing the negative electrode active material to the current collector.
  • Preferred examples of such negative electrode current collector plate 16 include expanded metal, punched metal, metal mesh, and combinations thereof, more preferably copper expanded metal, copper punched metal, and combinations thereof, especially Preferably, copper expanded metal is used.
  • a mixture containing zinc oxide powder and/or zinc powder, and optionally a binder (for example, polytetrafluoroethylene particles) is applied onto copper expanded metal to form a negative electrode/negative electrode current collector.
  • a plate can be preferably produced.
  • expanded metal is a mesh-like metal plate that is made by expanding a metal plate while cutting it in a staggered manner using an expander, and forming the cuts into a rhombus or tortoiseshell shape.
  • Punched metal also called perforated metal, is a metal plate with holes formed by punching.
  • Metal mesh is a metal product with a wire mesh structure, and is different from expanded metal and punched metal.
  • the partition wall 18 is provided on at least one surface of the negative electrode current collector plate 16 and partitions a plurality of segments S that are individualized from each other.
  • the partition wall 18 is preferably made of at least one member selected from the group consisting of metal, insulating resin, and ceramic, from the viewpoint of blocking the passage of zincate ions.
  • the metal, insulating resin, or ceramic constituting the partition wall 18 is not particularly limited as long as it can prevent the passage of zincate ions, but is preferably an insulating resin.
  • Preferred examples of metals constituting the partition wall 18 include alkali-resistant metals such as nickel, titanium, zirconium, and tantalum, and metals coated with alkali-resistant resin.
  • Preferred examples of the ceramic forming the partition wall 18 include alkali-resistant ceramics such as aluminum oxide, silicon carbide, zirconia, and silicon nitride.
  • Preferred examples of the insulating resin constituting the partition wall 18 include alkali-resistant materials such as polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), polyvinylidene fluoride (PVDF), polypropylene (PP), and polyethylene (PE). Examples include resin.
  • the height of the partition wall 18 is not particularly limited, but the difference between the height of the partition wall 18 and the height of the active material (specifically, the value obtained by subtracting the height of the partition wall from the height of the active material) is -0.3 to +0. It is preferably .2 mm, more preferably -0.1 to 0 mm.
  • the thickness of the partition wall 18 is not particularly limited, but is preferably 0.1 to 5.0 mm, more preferably 0.2 to 3.0 mm, and still more preferably 0.5 to 2.0 mm.
  • the partition walls 18 are provided in a grid pattern.
  • the grating pitch is preferably 0.05 to 50 mm, more preferably 0.1 to 20 mm, and still more preferably 0.2 to 5 mm. If the partition wall 18 is in a lattice shape, it can be eroded in a uniform lattice pattern in the plane of the negative electrode plate 14, as shown in FIG. This can be delayed even more effectively.
  • the negative electrode plate 14 has a rectangular shape, and when the negative electrode plate 14 is viewed from above, as shown in FIG. Preferably, they are arranged parallel or perpendicular.
  • the lattice-like partition wall 18 is located at one side of the outer periphery of the rectangular shape of the negative electrode plate 14, as shown in FIG. It is preferable that the angle is 30 to 60 degrees (preferably 40 to 50 degrees, for example 45 degrees) with respect to each other.
  • the partition wall 18 has a gas vent structure 18a that allows the gas G to pass between adjacent segments S. It is known that hydrogen gas is generated from zinc in the negative electrode of a zinc secondary battery, but the gas venting structure 18a promotes the escape of hydrogen gas G from each segment S, thereby increasing the charging and discharging efficiency. I can do it. It is preferable that the gas venting structure 18a includes at least one selected from the group consisting of a groove, a notch, and a hole, and more preferably a groove or a notch. It is preferable that the negative electrode plate 14 is intended to be used vertically.
  • Each of the segments S is filled with a negative electrode active material 20. It is preferable that the negative electrode active materials 20 filled in adjacent segments S are spaced apart from each other. This ensures that the partition wall 18 prevents the movement of zincate ions between the segments S (as indicated by arrows and x in FIG. 2). However, as long as the desired shape change delay effect is obtained, the negative electrode active materials 20 filled in adjacent segments S above the partition wall 18 may be connected to each other to some extent.
  • the partition wall 18 and the negative electrode active material 20 may be provided only on one side of the negative electrode current collector plate 16, but it is preferable from the viewpoint of increasing energy density that the partition wall 18 and the negative electrode active material 20 are provided on both sides of the negative electrode current collector plate 16. .
  • the partition wall 18 on one side of the negative electrode current collector plate 16 and the partition wall 18 on the other side of the negative electrode current collector plate 16 are provided symmetrically to each other. This is preferable from the viewpoint of uniform reaction during lamination.
  • the partition wall 18 on one side of the negative electrode current collector plate 16 and the partition wall 18 on the other side of the negative electrode current collector plate 16 may be provided so as to be offset from each other. It has the advantage of absorbing the expansion and contraction of the battery and preventing expansion of the battery.
  • the negative electrode active material 20 includes at least one selected from the group consisting of zinc, zinc oxide, zinc alloy, and zinc compound.
  • Zinc may be contained in any form of zinc metal, zinc compound, or zinc alloy as long as it has electrochemical activity suitable for the negative electrode.
  • Preferred examples of the negative electrode material include zinc oxide, zinc metal, calcium zincate, etc., and a mixture of zinc metal and zinc oxide is more preferred.
  • the negative electrode active material may be configured in a gel state, or may be mixed with the electrolytic solution 28 to form a negative electrode composite material.
  • a gelled negative electrode can be easily obtained by adding an electrolyte and a thickener to the negative electrode active material.
  • the thickener include polyvinyl alcohol, polyacrylate, CMC, alginic acid, etc., and polyacrylic acid is preferred because it has excellent chemical resistance to strong alkalis.
  • the zinc alloy a zinc alloy that does not contain mercury and lead and is known as a non-toxic zinc alloy can be used.
  • a zinc alloy containing 0.01 to 0.1% by mass of indium, 0.005 to 0.02% by mass of bismuth, and 0.0035 to 0.015% by mass of aluminum has the effect of suppressing hydrogen gas generation. Therefore, it is preferable.
  • indium and bismuth are advantageous in improving discharge performance.
  • the use of zinc alloys in negative electrodes can improve safety by slowing down the rate of self-dissolution in alkaline electrolytes, suppressing hydrogen gas generation.
  • the shape of the negative electrode material is not particularly limited, but it is preferably in the form of powder, which increases the surface area and makes it possible to handle large current discharge.
  • the preferred average particle size of the negative electrode material is in the range of 3 to 100 ⁇ m in terms of short diameter; within this range, the surface area is large, making it suitable for large current discharge, and also suitable for electrolyte and gel. It is easy to mix uniformly with the chemical agent and is easy to handle when assembling the battery.
  • the method for manufacturing the negative electrode plate 14 is not particularly limited.
  • a frame as a partition wall 18 is installed on the surface of the negative electrode current collector plate 16 (for example, a copper plate such as a Sn-plated copper plate), and each segment S partitioned by the partition wall 18 is filled with the negative electrode active material 20.
  • a plate 14 can be produced.
  • methods for installing the partition wall 18 include a method of bonding the partition wall 18 onto the negative electrode current collector plate 16, a method of forming the partition wall 18 by screen printing resin on the negative electrode current collector plate 16, and a method of forming the partition wall 18 on the negative electrode current collector plate 16.
  • Examples include a method of applying resin onto the plate 16 with a dispenser to form the partition wall 18.
  • the zinc secondary battery according to this embodiment is not particularly limited as long as it uses the negative electrode plate of the present invention and an alkaline electrolyte (typically an aqueous alkali metal hydroxide solution). . Therefore, it can be a nickel-zinc secondary battery, a silver-zinc oxide secondary battery, a manganese-zinc oxide secondary battery, a zinc-air secondary battery, and various other alkaline zinc secondary batteries.
  • the positive electrode active material layer contains nickel hydroxide and/or nickel oxyhydroxide, so that the zinc secondary battery forms a nickel-zinc secondary battery.
  • the positive electrode active material layer may be an air electrode layer, so that the zinc secondary battery may form a zinc-air secondary battery.
  • FIGS. 9 to 12 show a zinc secondary battery 10 according to one embodiment of the present invention.
  • the zinc secondary battery 10 includes a battery element 11 in a battery case 30, and the battery element 11 includes a positive electrode plate 12, the above-mentioned negative electrode plate 14, and a positive electrode plate 12 and negative electrode plate 14 that are hydrated. It includes a separator 26 that conducts and isolates ions, and an electrolyte 28.
  • the positive electrode plate 12 includes a positive electrode active material layer 12a.
  • the positive electrode active material constituting the positive electrode active material layer 12a may be appropriately selected from known positive electrode materials depending on the type of zinc secondary battery, and is not particularly limited. For example, in the case of a nickel-zinc secondary battery, a positive electrode containing nickel hydroxide and/or nickel oxyhydroxide may be used. Alternatively, in the case of a zinc-air secondary battery, the air electrode may be used as the positive electrode.
  • the positive electrode plate 12 further includes a positive electrode current collector (not shown), and the positive electrode current collector preferably has a positive electrode current collector tab 12b extending from an end (for example, an upper end) of the positive electrode plate 12.
  • a preferred example of the positive electrode current collector is a porous nickel substrate such as a foamed nickel plate.
  • a positive electrode plate consisting of a positive electrode/positive electrode current collector can be preferably produced by uniformly applying a paste containing an electrode active material such as nickel hydroxide onto a porous nickel substrate and drying the paste. . At that time, it is also preferable to perform a press treatment on the dried positive electrode plate (ie, positive electrode/positive electrode current collector) to prevent the electrode active material from falling off and to improve the electrode density.
  • the positive electrode plate 12 shown in FIG. 12 includes a positive electrode current collector (for example, foamed nickel), which is not shown.
  • the positive electrode current collector tab 12b may be made of the same material as the positive electrode current collector, or may be made of a different material.
  • the positive electrode current collector is a nickel porous substrate such as a foamed nickel plate, it can be pressed into a tab shape. In any case, the positive electrode current collecting tab 12b may be extended by adding another current collecting member such as a tab lead to such a tab.
  • a plurality of positive electrode current collecting tabs 12b be joined to one positive electrode terminal 36 or a member electrically connected thereto to form a positive electrode tab joint (not shown).
  • the positive electrode current collector tab 12b and members such as terminals may be bonded using a known bonding method such as ultrasonic welding (ultrasonic bonding), laser welding, TIG welding, resistance welding, or the like.
  • the positive electrode plate 12 may contain at least one additive selected from the group consisting of a silver compound, a manganese compound, and a titanium compound, thereby promoting a positive electrode reaction that absorbs hydrogen gas generated by a self-discharge reaction. can be promoted.
  • the positive electrode plate 12 may further contain cobalt. Cobalt is preferably included in the positive electrode plate 12 in the form of cobalt oxyhydroxide. In the positive electrode plate 12, cobalt functions as a conductive additive and contributes to improving charge/discharge capacity.
  • the negative electrode plate 14 has the configuration as described above.
  • a negative electrode current collector tab 22 extending from an end (for example, an upper end) of the negative electrode plate 14 is connected to the negative electrode current collector plate 16. It is preferable that the negative electrode current collector tab 22 extends in a predetermined direction (for example, upwardly) from the end (for example, the upper end) of the negative electrode plate 14 at a position that does not overlap with the positive electrode current collector tab 12b.
  • the negative electrode current collector tab 22 may be made of the same material as the negative electrode current collector plate 16, or may be made of a different material. In any case, the negative electrode current collecting tab 22 may be extended by adding another current collecting member such as a tab lead to such a tab.
  • a plurality of negative electrode current collecting tabs 22 be joined to one negative electrode terminal 38 or a member electrically connected thereto to form the negative electrode tab joint 40.
  • the negative electrode current collector tab 22 and members such as terminals may be bonded using a known bonding method such as ultrasonic welding (ultrasonic bonding), laser welding, TIG welding, resistance welding, or the like.
  • the separator 26 is provided to isolate the positive electrode plate 12 and the negative electrode plate 14 so that hydroxide ions can be conducted thereto. Therefore, separator 26 is preferably a hydroxide ion conducting separator.
  • the hydroxide ion conductive separator 26 may have a configuration in which the negative electrode plate 14 is covered or wrapped in the hydroxide ion conductive separator 26, for example, as shown in FIG. This eliminates the need for a complicated sealing bond between the hydroxide ion-conducting separator 26 and the battery container, and makes it possible to produce a nickel-zinc secondary battery (particularly its laminated battery) that can prevent zinc dendrite expansion in an extremely simple manner. It becomes possible to manufacture with high productivity. However, a simple configuration in which the hydroxide ion conductive separator 26 is arranged on one side of the positive electrode plate 12 or the negative electrode plate 14 may be used.
  • the hydroxide ion conductive separator 26 is not particularly limited as long as it is a separator that can isolate the positive electrode plate 12 and the negative electrode plate 14 in a hydroxide ion conductive manner, but typically includes a hydroxide ion conductive solid electrolyte. , is a separator that selectively passes hydroxide ions by exclusively utilizing hydroxide ion conductivity.
  • Preferred hydroxide ion-conducting solid electrolytes are layered double hydroxides (LDH) and/or LDH-like compounds. Therefore, hydroxide ion conductive separator 26 is preferably an LDH separator.
  • LDH separator refers to a separator containing LDH and/or an LDH-like compound, which selectively removes hydroxide ions by exclusively utilizing the hydroxide ion conductivity of LDH and/or the LDH-like compound. Defined as something that passes through.
  • an "LDH-like compound” may not be called LDH, but is a hydroxide and/or oxide with a layered crystal structure similar to LDH, and can be said to be an equivalent of LDH.
  • LDH can be interpreted to include not only LDH but also LDH-like compounds.
  • the LDH separator is composited with a porous base material.
  • the LDH separator further includes a porous base material, and is composited with the porous base material in such a manner that LDH and/or an LDH-like compound is filled in the pores of the porous base material.
  • a preferred LDH separator is one in which the LDH and/or LDH-like compound is porous so as to exhibit hydroxide ion conductivity and gas impermeability (and thus function as a hydroxide ion conductive LDH separator).
  • the pores of the solid base material are blocked.
  • the porous substrate is made of a polymeric material, and it is particularly preferred that the LDH is incorporated throughout the thickness of the porous substrate made of a polymeric material.
  • LDH separators such as those disclosed in Patent Documents 1 to 7 can be used.
  • the thickness of the LDH separator is preferably 5 to 100 ⁇ m, more preferably 5 to 80 ⁇ m, even more preferably 5 to 60 ⁇ m, particularly preferably 5 to 40 ⁇ m.
  • the hydroxide ion conductive separator 26 but also a liquid retaining member 27 be interposed between the positive electrode plate 12 and the negative electrode plate 14.
  • the positive electrode plate 12 and/or the negative electrode plate 14 are covered or wrapped in the liquid retaining member 27.
  • a simple configuration in which the liquid retaining member 27 is arranged on one side of the positive electrode plate 12 or the negative electrode plate 14 may be used.
  • the electrolytic solution 28 can be evenly present between the positive electrode plate 12 and/or negative electrode plate 14 and the hydroxide ion conductive separator 26, and the positive electrode plate And/Hydroxide ions can be efficiently exchanged between the negative electrode plate 14 and the hydroxide ion conductive separator 26.
  • the liquid retaining member 27 is not particularly limited as long as it is a member capable of retaining the electrolytic solution 28, but is preferably a sheet-like member.
  • Preferred examples of the liquid retaining member 27 include non-woven fabrics, water-absorbing resins, liquid-retaining resins, porous sheets, and various spacers. Particularly preferred are non-woven fabrics because they can produce a negative electrode structure with good performance at low cost. be.
  • the liquid retaining member 27 or nonwoven fabric preferably has a thickness of 10 to 200 ⁇ m, more preferably 20 to 200 ⁇ m, even more preferably 20 to 150 ⁇ m, particularly preferably 20 to 100 ⁇ m, and most preferably 20 to 200 ⁇ m. ⁇ 60 ⁇ m. When the thickness is within the above range, a sufficient amount of electrolyte 28 can be held in the liquid retaining member 27 while keeping the overall size of the positive electrode structure and/or negative electrode structure compact without waste.
  • the positive electrode plate 12 and/or the negative electrode plate 14 are covered or wrapped with the liquid retaining member 27 and/or the separator 26, their outer edges (the side from which the positive electrode current collecting tab 12b and the negative electrode current collecting tab 22 are extended) are ) is preferably closed.
  • the closed side of the outer edge of the liquid retaining member 27 and/or the separator 26 is realized by bending the liquid retaining member 27 and/or the separator 26 or sealing the liquid retaining members 27 and/or the separators 26 together.
  • the Preferred examples of sealing techniques include adhesives, heat welding, ultrasonic welding, adhesive tapes, sealing tapes, and combinations thereof.
  • an LDH separator containing a porous base material made of a polymeric material has the advantage of being easy to bend due to its flexibility. It is preferable to form a state in which the sides are closed. Thermal welding and ultrasonic welding may be performed using a commercially available heat sealer, etc., but in the case of sealing LDH separators, the outer circumferential portion of the liquid retaining member 27 should be sandwiched between the LDH separators forming the outer circumferential portion. It is preferable to carry out thermal welding and ultrasonic welding in order to achieve more effective sealing.
  • adhesives such as acrylic, acrylic, and silicone resins, among which epoxy resin adhesives have the highest resistance. It is more preferred in that it is particularly excellent in alkalinity.
  • An example of a product of an epoxy resin adhesive is the epoxy adhesive Hysol (registered trademark) (manufactured by Henkel).
  • This top open type configuration makes it possible to deal with the problem of overcharging in nickel-zinc batteries and the like. That is, when a nickel-zinc battery or the like is overcharged, oxygen (O 2 ) may be generated in the positive electrode plate 12, but since the LDH separator has a high degree of density that substantially only hydroxide ions can pass therethrough, Does not pass O2 .
  • O 2 can escape above the positive electrode plate 12 in the battery case 30 and be sent to the negative electrode plate 14 side through the upper open part, thereby O 2 Zn in the negative electrode active material can be oxidized and returned to ZnO.
  • the overcharge resistance can be improved by using the top-open type battery element 11 in a sealed zinc secondary battery.
  • a ventilation hole can be provided in a part of the closed outer edge to achieve the same structure as the open type described above. You can expect good results. For example, a vent hole may be opened after sealing the outer edge of one side, which is the upper end of the LDH separator, or a part of the outer edge may be left unsealed so that a vent hole is formed during sealing. good.
  • the electrolytic solution 28 preferably contains an aqueous alkali metal hydroxide solution. Although the electrolytic solution 28 is only shown locally in FIG. 12, this is because it is distributed throughout the positive electrode plate 12 and the negative electrode plate 14. Examples of alkali metal hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, and the like, with potassium hydroxide being more preferred. In order to suppress self-dissolution of zinc and/or zinc oxide, a zinc compound such as zinc oxide or zinc hydroxide may be added to the electrolytic solution. As described above, the electrolytic solution may be mixed with a positive electrode active material and/or a negative electrode active material to exist in the form of a positive electrode composite material and/or a negative electrode composite material.
  • the electrolyte may be gelled to prevent leakage of the electrolyte.
  • the gelling agent it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells, such as polymers such as polyethylene oxide, polyvinyl alcohol, polyacrylamide, or starch.
  • the battery element 11 includes a plurality of positive electrode plates 12, a plurality of negative electrode plates 14, and a plurality of separators 26, and has a unit of positive electrode plate 12/separator 26/negative electrode plate 14. It is preferable that the positive and negative electrodes are laminated in such a manner that the positive and negative electrodes are stacked repeatedly. That is, it is preferable that the zinc secondary battery 10 includes a plurality of unit cells 10a, so that the plurality of unit cells 10a as a whole form a multilayer cell. This is a so-called assembled battery or laminated battery configuration, and is advantageous in that high voltage and large current can be obtained.
  • the battery case 30 is made of resin.
  • the resin constituting the battery case 30 is preferably a resin that has resistance to alkali metal hydroxides such as potassium hydroxide, more preferably polyolefin resin, ABS resin, or modified polyphenylene ether, and even more preferably ABS resin. Or modified polyphenylene ether.
  • Battery case 30 has an upper lid 30a.
  • the battery case 30 (for example, the top lid 30a) may have a pressure relief valve for releasing gas.
  • a case group in which two or more battery cases 30 are arranged may be housed in an outer frame to form a battery module.
  • the LDH separator can include an LDH-like compound.
  • LDH-like compound is as described above.
  • Preferred LDH-like compounds are: (a) is a hydroxide and/or oxide with a layered crystal structure containing Mg and one or more elements containing at least Ti selected from the group consisting of Ti, Y, and Al; or (b) (i ) Ti, Y, and optionally Al and/or Mg, and (ii) an additive element M that is at least one selected from the group consisting of In, Bi, Ca, Sr, and Ba.
  • (c) is a hydroxide and/or oxide with a layered crystal structure containing Mg, Ti, Y, and optionally Al and/or In;
  • the LDH-like compound is present in the form of a mixture with In(OH) 3 .
  • the LDH-like compound is a hydroxide with a layered crystal structure containing Mg and at least one element containing at least Ti selected from the group consisting of Ti, Y, and Al. and/or oxides. Therefore, typical LDH-like compounds are complex hydroxides and/or complex oxides of Mg, Ti, optionally Y, and optionally Al. Although the above elements may be replaced with other elements or ions to the extent that the basic properties of the LDH-like compound are not impaired, it is preferable that the LDH-like compound does not contain Ni.
  • the LDH-like compound may further contain Zn and/or K. By doing so, the ionic conductivity of the LDH separator can be further improved.
  • LDH-like compounds can be identified by X-ray diffraction. Specifically, when an A peak derived from an LDH-like compound is detected in this range.
  • LDH is a material having an alternating layer structure in which exchangeable anions and H 2 O exist as intermediate layers between stacked hydroxide basic layers.
  • a peak due to the crystal structure of LDH ie, the (003) peak of LDH
  • a peak is typically detected in the above range shifted to a lower angle than the peak position of LDH.
  • the interlayer distance of the layered crystal structure can be determined by Bragg's equation using 2 ⁇ corresponding to the peak derived from the LDH-like compound in X-ray diffraction.
  • the interlayer distance of the layered crystal structure constituting the LDH-like compound thus determined is typically 0.883 to 1.8 nm, more typically 0.883 to 1.3 nm.
  • the atomic ratio of Mg/(Mg+Ti+Y+Al) in the LDH-like compound is 0.03 to 0.25, as determined by energy dispersive X-ray analysis (EDS). More preferably it is 0.05 to 0.2. Further, the atomic ratio of Ti/(Mg+Ti+Y+Al) in the LDH-like compound is preferably 0.40 to 0.97, more preferably 0.47 to 0.94. Further, the atomic ratio of Y/(Mg+Ti+Y+Al) in the LDH-like compound is preferably 0 to 0.45, more preferably 0 to 0.37.
  • EDS energy dispersive X-ray analysis
  • the atomic ratio of Al/(Mg+Ti+Y+Al) in the LDH-like compound is preferably 0 to 0.05, more preferably 0 to 0.03. Within the above range, the alkali resistance is even better, and the effect of suppressing short circuits caused by zinc dendrites (that is, dendrite resistance) can be more effectively realized.
  • LDH which is conventionally known regarding LDH separators, has the general formula: M 2+ 1-x M 3+ x (OH) 2 A n- x/n ⁇ mH 2 O (wherein, M 2+ is a divalent cation, M 3+ is a trivalent cation, A n- is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is 0 or more). It can be expressed.
  • the above atomic ratios in LDH-like compounds generally deviate from the above general formula for LDH. Therefore, it can be said that the LDH-like compound in this embodiment generally has a different composition ratio (atomic ratio) from that of conventional LDH.
  • an EDS analyzer for example, X-act, manufactured by Oxford Instruments
  • X-act for example, X-act, manufactured by Oxford Instruments
  • the LDH-like compound has a layered crystal structure containing (i) Ti, Y, and optionally Al and/or Mg, and (ii) an additive element M.
  • It can be a hydroxide and/or an oxide. Therefore, a typical LDH-like compound is a composite hydroxide and/or composite oxide of Ti, Y, the additive element M, optionally Al, and optionally Mg.
  • the additive element M is In, Bi, Ca, Sr, Ba, or a combination thereof.
  • the above elements may be replaced with other elements or ions to the extent that the basic properties of the LDH-like compound are not impaired, it is preferable that the LDH-like compound does not contain Ni.
  • the atomic ratio of Ti/(Mg+Al+Ti+Y+M) in the LDH-like compound is 0.50 to 0.85, as determined by energy dispersive X-ray analysis (EDS). More preferably, it is 0.56 to 0.81.
  • the atomic ratio of Y/(Mg+Al+Ti+Y+M) in the LDH-like compound is preferably 0.03 to 0.20, more preferably 0.07 to 0.15.
  • the atomic ratio of M/(Mg+Al+Ti+Y+M) in the LDH-like compound is preferably 0.03 to 0.35, more preferably 0.03 to 0.32.
  • the atomic ratio of Mg/(Mg+Al+Ti+Y+M) in the LDH-like compound is preferably 0 to 0.10, more preferably 0 to 0.02.
  • the atomic ratio of Al/(Mg+Al+Ti+Y+M) in the LDH-like compound is preferably 0 to 0.05, more preferably 0 to 0.04.
  • LDH which is conventionally known regarding LDH separators, has the general formula: M 2+ 1-x M 3+ x (OH) 2 A n- x/n ⁇ mH 2 O (wherein, M 2+ is a divalent cation, M 3+ is a trivalent cation, A n- is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is 0 or more). It can be expressed.
  • the above atomic ratios in LDH-like compounds generally deviate from the above general formula for LDH. Therefore, it can be said that the LDH-like compound in this embodiment generally has a different composition ratio (atomic ratio) from that of conventional LDH.
  • an EDS analyzer for example, X-act, manufactured by Oxford Instruments
  • X-act for example, X-act, manufactured by Oxford Instruments
  • the LDH-like compound is a hydroxide and/or oxide with a layered crystal structure containing Mg, Ti, Y, and optionally Al and/or In.
  • the LDH-like compound may be present in the form of a mixture with In(OH) 3 .
  • the LDH-like compound of this embodiment is a hydroxide and/or oxide with a layered crystal structure containing Mg, Ti, Y, and optionally Al and/or In.
  • typical LDH-like compounds are complex hydroxides and/or complex oxides of Mg, Ti, Y, optionally Al, and optionally In.
  • LDH-like compounds In addition, In that can be contained in LDH-like compounds is not only intentionally added to LDH-like compounds, but also In that is unavoidably mixed into LDH-like compounds due to the formation of In(OH) 3 , etc. It may be something. Although the above elements may be replaced with other elements or ions to the extent that the basic properties of the LDH-like compound are not impaired, it is preferable that the LDH-like compound does not contain Ni.
  • LDH which is conventionally known regarding LDH separators, has the general formula: M 2+ 1-x M 3+ x (OH) 2 A n- x/n ⁇ mH 2 O (wherein, M 2+ is a divalent cation, M 3+ is a trivalent cation, A n- is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is 0 or more). It can be expressed.
  • the atomic ratios in LDH-like compounds generally deviate from the above general formula for LDH. Therefore, it can be said that the LDH-like compound in this embodiment generally has a different composition ratio (atomic ratio) from that of conventional LDH.
  • the mixture according to embodiment (c) above contains not only LDH-like compounds but also In(OH) 3 (typically composed of LDH-like compounds and In(OH) 3 ).
  • In(OH) 3 typically composed of LDH-like compounds and In(OH) 3 ).
  • the content of In(OH) 3 in the mixture is preferably an amount that can improve the alkali resistance and dendrite resistance without substantially impairing the hydroxide ion conductivity of the LDH separator, and is not particularly limited.
  • In(OH) 3 may have a cubic crystal structure, or may have a structure in which a crystal of In(OH) 3 is surrounded by an LDH-like compound.
  • In(OH) 3 can be identified by X-ray diffraction.

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JPS4814519U (https=) * 1971-06-28 1973-02-17
JPS58186162A (ja) * 1982-04-06 1983-10-31 ル−カス・インダストリ−ズ・パブリツク・リミテツド・カンパニイ 二次電池用補助亜鉛電極及びその製造方法
JPH04206468A (ja) * 1990-11-30 1992-07-28 Yuasa Corp 密閉型アルカリ亜鉛蓄電池
JP2015060665A (ja) * 2013-09-17 2015-03-30 国能科技創新有限公司 空気電池、空気電池用負極及び空気電池ユニット
JP2019021518A (ja) * 2017-07-18 2019-02-07 日本碍子株式会社 亜鉛二次電池用負極及び亜鉛二次電池
JP2019106351A (ja) * 2017-10-03 2019-06-27 日本碍子株式会社 亜鉛二次電池
WO2021049609A1 (ja) * 2019-09-12 2021-03-18 学校法人同志社 金属負極及び該金属負極の作製方法並びに該金属負極を備える二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4814519U (https=) * 1971-06-28 1973-02-17
JPS58186162A (ja) * 1982-04-06 1983-10-31 ル−カス・インダストリ−ズ・パブリツク・リミテツド・カンパニイ 二次電池用補助亜鉛電極及びその製造方法
JPH04206468A (ja) * 1990-11-30 1992-07-28 Yuasa Corp 密閉型アルカリ亜鉛蓄電池
JP2015060665A (ja) * 2013-09-17 2015-03-30 国能科技創新有限公司 空気電池、空気電池用負極及び空気電池ユニット
JP2019021518A (ja) * 2017-07-18 2019-02-07 日本碍子株式会社 亜鉛二次電池用負極及び亜鉛二次電池
JP2019106351A (ja) * 2017-10-03 2019-06-27 日本碍子株式会社 亜鉛二次電池
WO2021049609A1 (ja) * 2019-09-12 2021-03-18 学校法人同志社 金属負極及び該金属負極の作製方法並びに該金属負極を備える二次電池

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