WO2023188490A1 - 亜鉛二次電池 - Google Patents

亜鉛二次電池 Download PDF

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Publication number
WO2023188490A1
WO2023188490A1 PCT/JP2022/039699 JP2022039699W WO2023188490A1 WO 2023188490 A1 WO2023188490 A1 WO 2023188490A1 JP 2022039699 W JP2022039699 W JP 2022039699W WO 2023188490 A1 WO2023188490 A1 WO 2023188490A1
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Prior art keywords
positive electrode
negative electrode
electrode plate
insulating tape
secondary battery
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/JP2022/039699
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English (en)
French (fr)
Japanese (ja)
Inventor
淳宣 松矢
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NGK Insulators Ltd
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NGK Insulators Ltd
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Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to DE112022006545.1T priority Critical patent/DE112022006545T5/de
Priority to JP2024511184A priority patent/JP7717961B2/ja
Priority to CN202280086659.6A priority patent/CN118476118A/zh
Publication of WO2023188490A1 publication Critical patent/WO2023188490A1/ja
Priority to US18/890,945 priority patent/US20250015339A1/en
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
    • H01M12/08—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M12/04—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/244—Zinc electrodes
    • 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
    • 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
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/466—U-shaped, bag-shaped or folded
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
    • 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
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • 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
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • 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
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • H01M50/595—Tapes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a zinc secondary battery.
  • 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. 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 zinc secondary battery 110 includes an electrode stack 111 including a positive electrode plate 112 including a positive electrode active material layer 112a and a positive electrode current collector 112b, and a negative electrode plate 114 including a negative electrode active material layer 114a and a negative electrode current collector 114b. As shown in FIG.
  • the upper part of the positive electrode plate 112 (or negative electrode plate 114) is not covered with the positive electrode active material layer 112a (or negative electrode active material layer 114a), but has a positive electrode current collector 112b (or negative electrode current collector 112b).
  • a positive electrode current collector 112b (or negative electrode current collector 112b).
  • the positive electrode plate 112 (or the negative electrode plate 114) is covered or wrapped with a hydroxide ion conductive separator 116 and/or a liquid retaining member 117, as shown in FIG. As shown in FIGS.
  • the positive electrode tab leads 113 extending from the plurality of positive electrode plates 112 are collectively joined to the positive electrode terminal 126 at the positive electrode tab joint 130, while the positive electrode tab leads 113 extending from the plurality of negative electrode plates 114
  • the negative electrode tab leads 115 are collectively joined to the negative electrode terminal 128 at the negative electrode tab joint portion 132.
  • the tab lead 113 or 115 will peel off from the current collector 112b or 114b due to the load generated when a plurality of tab leads 113 or 115 are combined. (or partially come off).
  • peeling can also be caused by a load caused by expansion and contraction of the positive electrode plate 112 and/or the negative electrode plate 114 during charging and discharging.
  • an object of the present invention is to provide a top-tab type zinc secondary battery that is less prone to short circuits.
  • a positive electrode plate including a positive electrode active material layer and a positive electrode current collector; a positive electrode tab lead extending from the end of the positive electrode plate; a negative electrode active material layer containing at least one selected from the group consisting of zinc, zinc oxide, zinc alloy, and zinc compound; and a negative electrode plate containing a negative electrode current collector; a negative tab lead extending from an end of the negative plate at a position that does not overlap with the positive tab lead; a hydroxide ion conductive separator that isolates the positive electrode plate and the negative electrode plate in a hydroxide ion conductive manner; electrolyte and A zinc secondary battery comprising: Each of the positive electrode plate, the positive tab lead, the negative plate, the negative tab lead, and the hydroxide ion conductive separator are arranged vertically, and the positive tab lead and the negative tab lead extend upward, The positive electrode plate has an uncoated area along the upper edge of the positive electrode plate where the positive electrode active material
  • an insulating tape is pasted on the uncoated area so that the welded part is covered with the insulating tape, and/or
  • the negative electrode plate has an uncoated area along the upper edge of the negative electrode plate where the negative electrode active material layer does not exist, and the negative electrode tab lead is welded to the negative electrode current collector in the uncoated area.
  • a zinc secondary battery wherein an insulating tape is attached to the uncoated area so that the welded portion is covered with the insulating tape.
  • the lower end of the insulating tape on the positive electrode plate is located between the upper end of the positive electrode active material layer and the lower end of the positive electrode tab lead, and/or The zinc secondary battery according to aspect 1 or 2, wherein the lower end of the insulating tape on the negative electrode plate is located between the upper end of the negative electrode active material layer and the lower end of the negative electrode tab lead.
  • the insulating tape is pasted on both sides of the uncoated area of the positive electrode plate such that the upper end of the insulating tape is located above the upper end of the positive electrode current collector, so that the positive electrode current collector
  • the upper end portions of the insulating tape protruding from the upper end are attached to each other, and/or
  • the insulating tape is pasted on both sides of the uncoated area of the negative electrode plate such that the upper end of the insulating tape is located above the upper end of the negative electrode current collector, so that the negative electrode current collector
  • the zinc secondary battery according to any one of aspects 1 to 3, wherein upper end portions of the insulating tape protruding from the upper end are bonded to each other.
  • the insulating tape is attached to both sides of the uncoated area of the positive electrode plate such that the left and right ends of the insulating tape are located outside the left and right ends of the positive electrode current collector, and The left and right end portions of the insulating tape protruding from the left and right ends are attached to each other, and/or The insulating tape is attached to both sides of the uncoated area of the negative electrode plate so that the left and right ends of the insulating tape are located outside the left and right ends of the negative electrode current collector, and The zinc secondary battery according to aspect 4, wherein left and right end portions of the insulating tape protruding from the left and right ends are bonded to each other.
  • the hydroxide ion-conducting 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.
  • Zinc secondary battery described.
  • 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. battery.
  • Aspect 12 The zinc secondary battery according to any one of aspects 1 to 10, wherein the positive electrode active material layer is an air electrode layer, thereby making the zinc secondary battery a zinc-air secondary battery.
  • Aspect 13 Aspects 1 to 12, including a plurality of unit cells having a pair of the positive electrode plate and the negative electrode plate together with the hydroxide ion conductive separator, whereby the plurality of unit cells as a whole form a multilayer cell.
  • FIG. 1 is a schematic cross-sectional view showing an example of a zinc secondary battery according to the present invention.
  • 2 is a diagram schematically showing a cross section along the line A-A' of the zinc secondary battery shown in FIG. 1.
  • FIG. FIG. 2 is a perspective view schematically showing an electrode laminate of the zinc secondary battery shown in FIG. 1.
  • FIG. FIG. 2 is a cross-sectional view schematically showing an electrode laminate of the zinc secondary battery shown in FIG. 1.
  • FIG. FIG. 4B is a cross-sectional view schematically showing a state in which the tab lead is peeled off in the electrode stack shown in FIG. 4A.
  • 2 is a perspective view showing an example of a positive electrode plate or a negative electrode plate to which an insulating tape is attached in the zinc secondary battery shown in FIG. 1.
  • FIG. 6 is a perspective view showing a positive electrode plate or a negative electrode plate shown in FIG. 5 covered with a hydroxide ion conductive separator or a liquid retaining member.
  • FIG. 2 is a diagram for explaining an example of an attachment position of an insulating tape in the zinc secondary battery shown in FIG. 1.
  • FIG. FIG. 2 is a diagram for explaining another example of the attachment position of an insulating tape in the zinc secondary battery shown in FIG. 1.
  • FIG. FIG. 2 is a cross-sectional view schematically showing an electrode laminate of a conventional zinc secondary battery.
  • 9A is a cross-sectional view schematically showing a state in which the tab lead is peeled off in the electrode stack shown in FIG. 9A.
  • FIG. 9 is a perspective view showing a positive electrode plate or a negative electrode plate in the conventional zinc secondary battery shown in FIGS. 9A and 9B.
  • FIG. 11 is a perspective view showing a positive electrode plate or a negative electrode plate shown in FIG. 10 covered with a hydroxide ion conductive separator or a liquid retaining member.
  • the zinc secondary battery of the present invention is not particularly limited as long as it uses zinc as a negative electrode 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. 1 to 6 show a zinc secondary battery 10 and its components according to one embodiment of the present invention.
  • the zinc secondary battery 10 includes an electrode laminate 11 and an electrolyte (not shown) in a battery case 20, and the electrode laminate 11 includes a positive electrode plate 12, a positive tab lead 13, and a negative electrode plate 14. , a negative electrode tab lead 15 , and a hydroxide ion conductive separator 16 .
  • the positive electrode plate 12 includes a positive electrode active material layer 12a and a positive electrode current collector 12b, and a positive electrode tab lead 13 extends from the end of the positive electrode plate 12.
  • the negative electrode plate 14 includes a negative electrode active material layer 14a and a negative electrode current collector 14b, and the negative electrode tab lead 15 extends from the end of the negative electrode plate 14 at a position where it does not overlap with the positive electrode tab lead 13.
  • the negative electrode active material layer 14a contains at least one selected from the group consisting of zinc, zinc oxide, zinc alloy, and zinc compound.
  • the hydroxide ion conductive separator 16 isolates the positive electrode plate 12 and the negative electrode plate 14 so that hydroxide ions can be conducted thereto.
  • Each of the positive electrode plate 12, positive electrode tab lead 13, negative electrode plate 14, negative electrode tab lead 15, and hydroxide ion conductive separator 16 is arranged vertically, and the positive electrode tab lead 13 and the negative electrode tab lead 15 extend upward.
  • the positive electrode plate 12 has an uncoated area U along the upper end of the positive electrode plate 12 where the positive electrode active material layer 12a does not exist, and in this uncoated area U, the positive electrode tab lead 13 is welded and joined to the positive electrode current collector 12b.
  • An insulating tape 18 is attached to the uncoated area U so that the welded portion W is covered with the insulating tape 18.
  • the negative electrode plate 14 has an uncoated area U along the upper end of the negative electrode plate 14 where the negative electrode active material layer 14a does not exist, and in this uncoated area U, the negative electrode tab lead 15 is connected to the negative electrode current collector 14b.
  • the insulating tape 18 is attached to the uncoated area U so that the welded part W is covered with the insulating tape 18.
  • the tab lead 113 or 115 is connected to the current collector 112b or 114b by welding. 115 will be connected to electrode terminal 126 or 128.
  • the tab lead 113 or 115 may peel off from the current collector 112b or 114b due to the load generated when a plurality of tab leads 113 or 115 are combined. (or partially come off).
  • peeling can also be caused by a load caused by expansion and contraction of the positive electrode plate 112 and/or the negative electrode plate 114 during charging and discharging.
  • the insulating tape 18 be applied to both the positive electrode plate 12 and the negative electrode plate 14 as shown in the illustrated example, it may be applied only to one of the positive electrode plate 12 and the negative electrode plate 14. Even in this case, short circuits due to peeling of either the positive electrode tab lead 13 or the negative electrode tab lead 15 can be made less likely to occur.
  • the insulating tape 18 is not particularly limited, and any commercially available insulating tape may be used. Insulating tape 18 typically includes a base material made of insulating resin and an adhesive layer or pressure-sensitive adhesive layer provided on the base material. An example of the insulating resin is polypropylene.
  • the thickness of the insulating tape 19 is preferably 30 to 70 ⁇ m, more preferably 40 to 60 ⁇ m.
  • the difference in level between the positive electrode active material layer 12a and the positive electrode current collector 12b and the difference in level between the negative electrode active material layer 14a and the negative electrode current collector 14b can be conveniently filled, and the positive electrode active material layer
  • the upper end of the negative electrode active material layer 12a or the negative electrode active material layer 14a is less likely to be damaged. Therefore, it is preferable to use the insulating tape 19 with a thickness that does not exceed the level difference between the positive electrode active material layer 12a and the positive electrode current collector 12b or the level difference between the negative electrode active material layer 14a and the negative electrode current collector 14b.
  • 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.
  • a positive electrode containing nickel hydroxide and/or nickel oxyhydroxide may be used.
  • the positive electrode active material layer 12a may contain at least one additive selected from the group consisting of a silver compound, a manganese compound, and a titanium compound, thereby causing hydrogen gas generated by a self-discharge reaction. can promote the positive electrode reaction.
  • the positive electrode active material layer 12a may further contain cobalt.
  • Cobalt is preferably included in the positive electrode plate 12 in the form of cobalt oxyhydroxide.
  • cobalt functions as a conductive additive and contributes to improving the charge/discharge capacity.
  • the air electrode may be used as the positive electrode.
  • the positive electrode plate 12 further includes a positive electrode current collector 12b.
  • a preferred example of the positive electrode current collector 12b 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 current collector 12b is a nickel porous substrate such as a foamed nickel plate, the uncoated area of the positive electrode current collector 12b may be pressed into a tab shape.
  • the positive electrode tab lead 13 is provided so as to extend from the end of the positive electrode plate 12.
  • the positive electrode tab lead 13 is not particularly limited as long as a commercially available thin metal piece may be used. It is preferable that a plurality of positive electrode tab leads 13 are joined to one positive electrode terminal 26 or a member electrically connected thereto to form a positive electrode tab joint portion 30. By doing so, current can be collected with a simple configuration in a space-efficient manner, and connection to the positive electrode terminal 26 is also facilitated.
  • the positive electrode tab lead 13 and members such as the positive electrode current collector 12b and the positive electrode terminal 26 may be joined using a known joining method such as ultrasonic welding (ultrasonic bonding), laser welding, TIG welding, resistance welding, etc. .
  • the positive electrode plate 12 has an uncoated area U along the upper end of the positive electrode plate 12 where the positive electrode active material layer 12a does not exist, and in the uncoated area U, the positive electrode tab lead 13 is It is welded and joined to the electric body 12b.
  • An insulating tape 18 is attached to the uncoated area U so that the welded portion W is covered with the insulating tape 18.
  • the insulating tape 18 is attached to both sides of the positive electrode plate 12.
  • the insulating tape 18 may be applied to one side and the other side of the positive electrode plate 12 separately, or one piece of insulating tape 18 may be folded back and applied to both sides of the positive electrode plate 12. In the latter case, a single insulating tape 18 may be wound at least once around both sides of the positive electrode plate 12, and in this case, the insulating tape 18 and the positive tab lead 13 are more difficult to peel off. It is preferable that 60% or more of the area of the uncoated area U on both sides of the positive electrode plate 12 (including the area of the hole if there is a hole) is covered with the insulating tape, more preferably 70% or more, More preferably it is 80% or more, ideally 100%. This increases the bonding area between the positive electrode current collector 12b and the insulating tape 18, making it difficult for the insulating tape 18 to peel off.
  • the lower end of the insulating tape 18 on the positive electrode plate 12 is preferably located between the upper end P 3 of the positive electrode active material layer and the lower end P 2 of the positive electrode tab lead 13 .
  • the tip of the positive electrode tab lead 13 is protected by the insulating tape 18, and the positive electrode tab lead 13 is more easily peeled off. This makes it difficult for short circuits to occur even if the positive electrode tab lead 13 is peeled off.
  • the lower end of the insulating tape 18 is located above the upper end P3 of the positive electrode active material layer 12a, capacity loss can be prevented.
  • the positive electrode active material layer 12a is covered with the insulating tape 18, a region that does not contribute to the reaction is created and the battery capacity is reduced, but with the above configuration, the positive electrode active material layer 12a is not covered with the insulating tape 18. Such problems can be avoided.
  • An insulating tape 18 is pasted on both sides of the uncoated area U of the positive electrode plate 12 so that the upper end of the insulating tape 18 is located above the upper end P1 of the positive electrode current collector 12b, thereby making the positive electrode current collector It is preferable that the upper end portions of the insulating tape 18 protruding from the upper end P1 of the insulating tape 12b are attached to each other. By doing so, the end portion of the positive electrode current collector 12b can be protected, so that short circuits caused by the end portion of the positive electrode current collector 12b can be prevented. More preferably, as shown in FIG.
  • the insulating tape 18 is placed on both sides of the uncoated area U of the positive electrode plate 12, and the left and right ends of the insulating tape 18 are located outside the left and right ends of the positive electrode current collector 12b.
  • the left and right end portions of the insulating tape 18 protruding from the left and right ends of the positive electrode current collector 12b are pasted together. By doing this, even if the adhesion between the positive electrode current collector 12b and the insulating tape 18 is low, the protruding portions of the insulating tape 18 over three sides that protrude from the top and left and right ends of the positive electrode current collector 12b will not touch the insulating tapes 18.
  • the adhesive area between the positive electrode tab lead 13 and the insulating tape 18 has a high adhesion area ratio (because the positive electrode tab lead 13 is typically made of a non-porous material), so inherently high adhesion can be ensured. .
  • the negative electrode plate 14 includes a negative electrode active material layer 14a.
  • the negative electrode active material constituting the negative electrode active material layer 14a 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 an electrolytic solution 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 negative electrode plate 14 further includes a negative electrode current collector 14b.
  • the negative electrode active material layer 14a may be arranged on both sides of the negative electrode current collector 14b, or the negative electrode active material layer 14a may be arranged only on one side of the negative electrode current collector 14b. It is preferable to use a metal plate having a plurality of (or a large number of) openings for the negative electrode current collector 14b from the viewpoint of fixing the negative electrode active material to the current collector.
  • Preferred examples of such negative electrode current collector 14b 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
  • 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 negative electrode tab lead 15 is provided so as to extend from the end of the negative electrode plate 14 at a position that does not overlap with the positive electrode tab lead 13 (see FIG. 3).
  • the negative electrode tab lead 15 is not particularly limited as long as a commercially available thin metal piece may be used. It is preferable that a plurality of negative electrode tab leads 15 are joined to one negative electrode terminal 28 or a member electrically connected thereto to form the negative electrode tab joint portion 32. By doing so, it is possible to collect current with a simple configuration with good space efficiency, and it is also easy to connect to the negative electrode terminal 28.
  • the negative electrode tab lead 15 and members such as the negative electrode current collector 14b and the negative electrode terminal 28 may be joined using a known joining method such as ultrasonic welding (ultrasonic bonding), laser welding, TIG welding, resistance welding, etc. .
  • the negative electrode plate 14 has an uncoated area U along the upper end of the negative electrode plate 14 where the negative electrode active material layer 14a does not exist, and in the uncoated area U, the negative electrode tab lead 15 is It is welded and joined to the electric body 14b.
  • An insulating tape 18 is attached to the uncoated area U so that the welded portion W is covered with the insulating tape 18. With this configuration, as described above, short circuits due to peeling of the negative electrode tab lead 15 can be made less likely to occur.
  • the insulating tape 18 is preferably attached to both sides of the negative electrode plate 14.
  • the insulating tape 18 may be applied to one side and the other side of the negative electrode plate 14 separately, or one piece of insulating tape 18 may be folded back and applied to both sides of the negative electrode plate 14. In the latter case, a single insulating tape 18 may be wound at least once around both sides of the negative electrode plate 14. In this case, the insulating tape 18 and the negative tab lead 15 are more difficult to peel off. It is preferable that 60% or more of the area of the uncoated area U on both sides of the negative electrode plate 14 (including the area of the hole if there is a hole) is covered with the insulating tape, more preferably 70% or more, More preferably it is 80% or more, ideally 100%. This increases the bonding area between the negative electrode current collector 14b and the insulating tape 18, making it difficult for the insulating tape 18 to peel off.
  • the lower end of the insulating tape 18 on the negative electrode plate 14 is preferably located between the upper end P 3 of the negative electrode active material layer 14 a and the lower end P 2 of the negative electrode tab lead 15 .
  • the lower end of the insulating tape 18 is located below the lower end P2 of the negative tab lead 15, so the tip of the negative tab lead 15 is protected by the insulating tape 18, and the negative tab lead 15 is more easily peeled off. Even if the negative electrode tab lead 15 were to peel off, short circuits would be less likely to occur.
  • the lower end of the insulating tape 18 is located above the upper end P3 of the positive electrode active material layer, capacity loss can be prevented.
  • the insulating tape 18 covers the negative electrode active material layer 14a, a region that does not contribute to the reaction is created and the battery capacity decreases, but with the above configuration, the insulating tape 18 does not cover the negative electrode active material layer 14a, so that Such problems can be avoided.
  • An insulating tape 18 is pasted on both sides of the uncoated area U of the negative electrode plate 14 so that the upper end of the insulating tape 18 is located above the upper end P 1 of the negative electrode current collector 14b, so that the negative electrode current collector It is preferable that the upper end portions of the insulating tape 18 protruding from the upper end P1 of the insulating tape 14b are attached to each other. By doing so, the ends of the negative electrode current collector 14b can be protected, so that short circuits caused by the ends of the negative electrode current collector 14b can be prevented. More preferably, as shown in FIG.
  • the insulating tape 18 is placed on both sides of the uncoated area U of the negative electrode plate 14, and the left and right ends of the insulating tape 18 are located outside the left and right ends of the negative electrode current collector 14b.
  • the left and right end portions of the insulating tape 18 protruding from the left and right ends of the negative electrode current collector 14b are pasted together. By doing this, even if the adhesion between the negative electrode current collector 14b and the insulating tape 18 is low, the protruding portions of the insulating tape 18 over three sides that protrude from the upper end and left and right ends of the negative electrode current collector 14b will not touch the insulating tapes 18.
  • the adhesion area ratio with the insulating tape 18 is low, and therefore the negative electrode current collector 14b and the insulating tape 18 are in close contact with each other. Although the force is low, even in such a case, peeling of the insulating tape 18 can be effectively prevented due to the high adhesion force in the protruding portion over the three sides.
  • the adhesive area ratio between the negative electrode tab lead 15 and the insulating tape 18 is high (because the negative electrode tab lead 15 is typically made of a non-porous material), so inherently high adhesive strength can be ensured. .
  • the hydroxide ion conductive separator 16 is provided to isolate the positive electrode plate 12 and the negative electrode plate 14 so that hydroxide ions can be conducted thereto.
  • the positive electrode plate 12 and/or the negative electrode plate 14 may be covered or wrapped with a hydroxide ion conductive separator 16.
  • a simple configuration in which the hydroxide ion conductive separator 16 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 16 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 conducting separator 16 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 16 it is preferable that not only the hydroxide ion conductive separator 16 but also a liquid retaining member 17 be interposed between the positive electrode plate 12 and the negative electrode plate 14. As shown in FIGS. 4A, 4B, and 6, it is preferable that the positive electrode plate 12 and/or the negative electrode plate 14 be covered or wrapped in the liquid retaining member 17. However, a simple configuration in which the liquid retaining member 17 is arranged on one side of the positive electrode plate 12 or the negative electrode plate 14 may be used. In any case, by interposing the liquid retaining member 17, the electrolyte can be evenly present between the positive electrode plate 12 and/or the negative electrode plate 14 and the hydroxide ion conductive separator 16.
  • the liquid retaining member 17 is not particularly limited as long as it is a member capable of retaining an electrolytic solution, but is preferably a sheet-like member.
  • Preferred examples of the liquid retaining member 17 include non-woven fabrics, water-absorbing resins, liquid-retaining resins, porous sheets, and various spacers. Particularly preferred are non-woven fabrics, since a negative electrode structure with good performance can be produced at low cost. be.
  • the liquid retaining member 17 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 can be held in the liquid retaining member 17 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 17 and/or the separator 16, their outer edges are closed (except for the sides from which the positive electrode tab lead 13 and the negative electrode tab lead 15 are extended). It is preferable that the closed side of the outer edge of the liquid retaining member 17 and/or the separator 16 is realized by bending the liquid retaining member 17 and/or the separator 16 or sealing the liquid retaining members 17 and/or the separators 16 together. It is preferable that 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 circumference of the liquid retaining member 17 should be sandwiched between the LDH separators forming the outer circumference. 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).
  • the outer edge of one side, which is the upper end of the separator 16 be open.
  • 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 and be sent to the negative electrode plate 14 side through the upper open part in the battery case 20, thereby allowing O 2 Zn in the negative electrode active material can be oxidized and returned to ZnO.
  • 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 preferably contains an aqueous alkali metal hydroxide solution.
  • alkali metal hydroxides include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, and the like, with potassium hydroxide being more preferred.
  • a zinc compound such as zinc oxide or zinc hydroxide may be added to the electrolytic solution.
  • 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 electrode laminate 11 is a laminate including a plurality of electrode layers. As shown in FIGS. 3, 4A, and 4B, the electrode stack 11 includes a plurality of positive electrode plates 12, a plurality of negative electrode plates 14, and a plurality of separators 16, and has a positive electrode plate 12/separator 16/negative electrode plate. It is preferable to take the form of a positive and negative electrode laminate in which 14 units are stacked repeatedly. That is, the zinc secondary battery 10 includes a plurality of unit cells 10a having a pair of positive electrode plates 12 and a negative electrode plate 14 together with a hydroxide ion conductive separator 16, so that the plurality of unit cells 10a as a whole form a multilayer cell. It is preferable that the 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 20 is made of resin.
  • the resin constituting the battery case 20 is preferably a resin that is resistant 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 20 has an upper lid 20a.
  • the battery case 20 (for example, the top lid 20a) may have a pressure relief valve for releasing gas.
  • a case group in which two or more battery cases 20 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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