WO2025035596A1 - 粘合物质、粘合剂组合物、正极极片、二次电池和用电装置 - Google Patents

粘合物质、粘合剂组合物、正极极片、二次电池和用电装置 Download PDF

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Publication number
WO2025035596A1
WO2025035596A1 PCT/CN2023/127666 CN2023127666W WO2025035596A1 WO 2025035596 A1 WO2025035596 A1 WO 2025035596A1 CN 2023127666 W CN2023127666 W CN 2023127666W WO 2025035596 A1 WO2025035596 A1 WO 2025035596A1
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Prior art keywords
adhesive
structural unit
optionally
positive electrode
insulating
Prior art date
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PCT/CN2023/127666
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English (en)
French (fr)
Inventor
程丛
王星会
牛文全
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Application filed by Contemporary Amperex Technology Co Ltd filed Critical Contemporary Amperex Technology Co Ltd
Priority to KR1020257019979A priority Critical patent/KR20250114337A/ko
Priority to JP2025536045A priority patent/JP2026501212A/ja
Priority to EP23949016.2A priority patent/EP4671337A1/en
Publication of WO2025035596A1 publication Critical patent/WO2025035596A1/zh
Priority to US19/296,947 priority patent/US20250372655A1/en
Anticipated expiration legal-status Critical
Pending 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
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    • 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
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M50/593—Spacers; Insulating plates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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

Definitions

  • the present application relates to the field of battery technology, and in particular to an adhesive material, an adhesive composition, a positive electrode sheet, a secondary battery and an electrical device.
  • secondary ion batteries such as lithium ion secondary batteries or sodium ion secondary batteries
  • secondary ion batteries have the advantages of high operating voltage, high specific capacity, long charge and discharge life, and no memory effect.
  • the safety of secondary ion batteries has become more and more the focus of people's attention.
  • abnormal cells such as 0 resistance value in assembly short circuit test, low formation voltage, large self-discharge, and large module pressure difference.
  • the present application provides an adhesive material, an adhesive composition, a positive electrode plate, a secondary battery and an electrical device to solve the problem of poor wear resistance of insulating glue at the edge of the positive electrode plate.
  • the first aspect of the present application provides an adhesive material, including an adhesive, wherein the adhesive includes a structural unit A, a structural unit B, a structural unit C and a structural unit D, at least part of the structural unit A is cross-linked with at least part of the structural unit D, wherein the structural unit A is
  • the structural units B are each independently Any one or more of, optionally, structural unit B is
  • the structural units C are each independently Any one of, each m1 and each m2 are independently any integer from 1 to 20, optionally, m1 are independently any integer from 2 to 12, m2 are independently any integer from 8 to 12;
  • the structural unit D is independently Any one or more of, n1 is independently any integer from 1 to 20, optionally, n1 is any integer from 1 to 12, further optionally n1 is any integer from 1 to 6.
  • the structural unit B is provided by acrylonitrile monomer, which is a hard monomer and can enhance the strength of the insulating adhesive layer;
  • the structural unit C is provided by acrylate monomers, which are soft monomers and can improve the flexibility of the insulating adhesive layer and enhance the adhesion between the insulating adhesive layer and the current collector.
  • the structural unit A and the structural unit D form a three-dimensional cross-linked network through hydrogen bond interaction, so that the formed insulating rubber layer has better wear resistance, can isolate the effective contact and friction between the root of the pole ear and the edge of the positive electrode sheet caused by the bending of the pole ear when the battery cell is put into the shell, and effectively control the problem of short circuit between the pole ear and the positive electrode film layer.
  • the above-mentioned structural units A, C and D are polymers of acrylic monomers, in which the acrylic substances are resistant to high temperature and not easy to decompose.
  • the formed insulating rubber layer can prevent the collector of the positive electrode sheet from being directly cut by laser, effectively resisting the splash of metal particles, and the laser cutting in the insulating rubber layer is not easy to produce metal molten beads, which effectively alleviates the problem of metal particles splashing and penetrating the diaphragm caused by direct laser cutting of the collector; at the same time, the above-mentioned three-dimensional cross-linked network also further enhances the resistance to laser cutting, and better realizes the protection of the diaphragm.
  • At least part of the structural unit A, at least part of the structural unit B, at least part of the structural unit C and at least part of the structural unit D are connected in a chain to form a first chain structure, at least part of the structural unit A, at least part of the structural unit C and at least part of the structural unit D are connected in a chain to form a second chain structure; at least part of the structural unit A in the first chain structure is cross-linked with at least part of the structural unit D in the second chain structure; at least part of the structural unit D in the first chain structure is cross-linked with at least part of the structural unit A in the second chain structure.
  • the first chain structure and the second chain structure contain structural units A and D at the same time, providing more sites for the cross-linking of structural units A and D, thereby further improving the density of the formed three-dimensional network and better improving the wear resistance of the adhesive material;
  • the first chain structure contains structural units A, structural units B, structural units C and structural units D at the same time, which is more conducive to adjusting and controlling the strength provided by the chain structure by utilizing the content of structural units B and structural units C;
  • the second chain structure contains structural units A, structural units C and structural units D at the same time, and has better flexibility, which can be used to more flexibly adjust the content of structural units C, thereby more flexibly adjusting the bonding force of the adhesive material.
  • the adhesive material satisfies any one or more of the following conditions: 1) the wear resistance of the insulating adhesive layer with a thickness of 3 ⁇ m-7 ⁇ m formed by the adhesive material meets the following requirements: tested by an RCA paper tape wear tester, using a 55g weight and a flat tape for 300mm and 2 turns to form an experimental area, taking n test points in the experimental area and the spacing between the test points is not less than 2cm, the number of non-leaking points in the experimental area accounts for more than 30%, where 5 ⁇ n ⁇ 100, or the area of non-leaking points in the experimental area is more than 60% of the total area of the experimental area; 2) the cohesive force of the insulating adhesive layer formed by the adhesive material is 620N/m-750N/m, which can be 660N/m-725N/m; 3) the Shore hardness of the insulating adhesive layer formed by the adhesive material is 45HA-80HA, which can be 50HA-65HA; 4) the bonding force of the insulating adhesive
  • the molar ratio of the structural unit D to the structural unit A is 0.5:1-5:1, optionally 0.5:1-3:1, and further optionally 1:1-3:1; optionally, the molar content of the structural unit A is 4%-50%, optionally 4%-10%, and the molar content of the structural unit D is 1%-50%, optionally 5%-30%, and further optionally 5%-15%.
  • the cross-linking of the structural unit A and the structural unit D is utilized as much as possible to improve the wear resistance of the insulating adhesive layer formed by the adhesive substance.
  • the molar ratio of the structural unit C to the structural unit B is 1:1-300:1, and can be 5:1-50:1; optionally, the molar content of the structural unit B is 0.2%-20%, and can be 1%-5%; optionally, the molar content of the structural unit C is 1%-90%, and can be 55%-90%, and can be further 75%-80%.
  • the bonding force of the adhesive material can be improved as much as possible.
  • the adhesive substance further comprises an insulating filler and/or a dispersant.
  • the carboxyl group in the adhesive substance can form a hydrogen bond with the insulating filler to improve the adhesion of the formed insulating adhesive layer.
  • the weight ratio of the insulating filler, the adhesive and the dispersant is (70-90):(10-25):0.4.
  • the insulating filler can be used to reduce costs, and the dispersant can improve the dispersion effect of the insulating filler in the adhesive and avoid the subsequent cross-linking of the adhesive, and there is enough adhesive to provide good bonding force.
  • the insulating filler includes any one or more of alumina, magnesium oxide, silicon dioxide, titanium dioxide, barium titanate, aluminum nitride, silicon nitride, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, mica, talc, boehmite, zeolite, apatite, kaolin or glass powder.
  • the hardness of the above insulating fillers is different, and the hardness of boehmite is more moderate, which can improve the stability of the insulating rubber layer and will not cause the hardness to have a negative impact on the battery diaphragm.
  • the volume average particle size D V 50 of the insulating filler is ⁇ 1 ⁇ m.
  • the insulating filler within this particle size range can be completely embedded in an insulating layer of conventional thickness, thereby effectively controlling the friction of the insulating filler on the diaphragm.
  • the adhesive substance also includes a solvent; optionally, the solid content of the adhesive substance is 20%-40%; optionally, the solvent of the adhesive substance includes water; optionally, the viscosity of the adhesive substance measured at 25°C and 12rpm is 350mPa ⁇ s-900mPa ⁇ s.
  • the second aspect of the present application provides an adhesive composition, including an adhesive, wherein the adhesive includes a first adhesive and a second adhesive, wherein the first adhesive is a polymer, including a structural unit A, a structural unit B, a structural unit C and a structural unit D, and the second adhesive is a polymer, including a structural unit A, a structural unit C and a structural unit D, wherein the structural unit A is
  • the structural units B are each independently Any one or more of, optionally, structural unit B is
  • the structural unit C of the first binder and the structural unit C of the second binder are each independently Each m1 and each m2 is independently any integer from 1 to 20, for example, m1 is 1, 2, 3, 4, 5, 6, 8, 10, 12, 13, 14, 15, 16, 18 or 20, m1 is 1, 2, 3, 4, 5, 6, 8, 10, 12, 13, 14, 15, 16, 18 or 20; optionally, m1 is each independently any integer from 2 to 12, and m2 is each independently any integer from 8 to 12; the structural unit D of the first adhesive and the structural unit D of the
  • the structural unit B in the first adhesive is provided by an acrylonitrile monomer, which is a hard monomer and can enhance the strength of the insulating adhesive layer;
  • the structural unit C in the first adhesive and the second adhesive is provided by an acrylate monomer, which is a soft monomer and can improve the flexibility of the insulating adhesive layer and enhance the bonding force between the insulating adhesive layer and the current collector.
  • the structural unit A in the first adhesive and the structural unit D in the second adhesive, and the structural unit D in the first adhesive and the structural unit A in the second adhesive interact through hydrogen bonds to form a three-dimensional cross-linked network, so that the formed insulating adhesive layer has better wear resistance, can isolate the effective contact and friction between the root of the pole ear and the edge of the positive electrode sheet caused by the bending of the pole ear when the battery core is put into the shell, and effectively control the problem of short circuit between the pole ear and the positive electrode film layer.
  • the first adhesive and the second adhesive of the adhesive composition are polymers of acrylic monomers, and the acrylic substances therein have the properties of high temperature resistance and not easy to decompose.
  • the formed insulating adhesive layer can prevent the collector of the positive electrode sheet from being directly cut by laser, effectively resist the splash of metal particles, and the laser cutting in the insulating adhesive layer is not easy to produce metal molten beads, which effectively alleviates the problem of metal particles splashing and penetrating the diaphragm caused by direct laser cutting of the collector; at the same time, the above-mentioned three-dimensional cross-linked network also further enhances the resistance to laser cutting, and better realizes the protection of the diaphragm.
  • the weight ratio of the first adhesive to the second adhesive is 1:2.5-1:20, and can be 1:5-1:17.5.
  • the second adhesive is used to provide good adhesion and flexibility for the insulating adhesive layer, and an appropriate amount of the first adhesive is used to improve the strength of the insulating adhesive layer, so as to better adapt to the strength of the insulating filler in the adhesive composition and the strength of the positive electrode collector, so that the adhesion is fully exerted; and the above weight ratio is used to regulate the cross-linking network density of the insulating adhesive layer, providing sufficient network support for wear resistance and protection of the current collector.
  • the first adhesive satisfies any one or more of the following conditions: 1) the molar content of structural unit A in the first adhesive is 5%-30%; 2) the molar content of structural unit B in the first adhesive is 5%-85%; 3) the molar content of structural unit C in the first adhesive is 5%-85%; 4) the molar content of structural unit D in the first adhesive is 5%-15%.
  • the hardness of the first adhesive is adjusted by using the content of structural unit B and structural unit C to meet the hardness requirements of the insulating adhesive layer for different designs and different processing methods; the content of the above structural unit A and structural unit D is relatively small in all structural units, mainly used to form a cross-linked network with the second adhesive, and also well controls the self-crosslinking of the two in the first adhesive.
  • the second adhesive satisfies any one or more of the following conditions: 1) the molar content of structural unit A in the second adhesive is 5%-10%; 2) the molar content of structural unit C in the second adhesive is 70%-85%; 3) the molar content of structural unit D in the second adhesive is 5%-20%.
  • Structural unit C accounts for a major proportion in the second adhesive, thereby providing the second adhesive with more sufficient flexibility and adhesion, thereby improving the adhesion of the insulating adhesive layer formed by the adhesive composition to the insulating filler and the positive electrode current collector.
  • the weight average molecular weight of the first adhesive is 500,000-1.5 million; further, optionally, the difference between the weight average molecular weights of the first adhesive and the second adhesive is 100,000-1.5 million. This has a good suspension effect on the insulating filler, effectively preventing the insulating filler from settling, and improving the bonding force of the insulating adhesive layer.
  • the adhesive material further comprises an insulating filler and/or a dispersant.
  • the carboxyl groups of the first adhesive and the second adhesive can form hydrogen bonds with the insulating filler to improve the adhesive force of the formed insulating adhesive layer.
  • the weight ratio of the insulating filler, the adhesive and the dispersant is (70-90):(10-25):0.4.
  • the insulating filler can be used to reduce costs, and the dispersant can improve the dispersion effect of the insulating filler in the adhesive and avoid the subsequent cross-linking of the adhesive, and there is enough adhesive to provide good bonding force.
  • the insulating filler includes any one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, barium titanate, aluminum nitride, silicon nitride, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, mica, talc, boehmite, zeolite, apatite, kaolin or glass powder; optionally, the volume average particle size D V 50 of the insulating filler is ⁇ 1 ⁇ m.
  • the insulating filler within this particle size range can be completely embedded in an insulating layer of conventional thickness, thereby effectively controlling the friction of the insulating filler on the diaphragm.
  • the dispersant includes one or more of polyacrylate compounds, fatty alcohol polyether compounds or polyether-modified siloxane compounds.
  • the adhesive composition further comprises a solvent; optionally, the solid content of the adhesive composition is 20%-40%; further optionally, the solvent of the adhesive composition comprises water.
  • a positive electrode plate comprising: a positive electrode collector, at least one side of the positive electrode collector having a positive electrode film layer area and a hollow foil area; a positive electrode film layer, arranged in the positive electrode film layer area of the positive electrode collector; an insulating adhesive layer, arranged in the hollow foil area of the positive electrode collector, wherein the insulating adhesive layer is formed by using any one of the adhesive materials of the first aspect above, or is formed by curing any one of the adhesive compositions of the second aspect above.
  • the insulating rubber layer has good anti-wear performance, which can isolate the effective contact and friction between the root of the pole ear and the edge of the positive electrode sheet caused by the bending of the pole ear when the battery cell is put into the shell, and effectively control the problem of short circuit between the pole ear and the positive electrode film layer.
  • the insulating rubber layer can prevent the current collector of the positive electrode sheet from being directly cut by the laser, effectively resisting the splash of metal particles, and the laser cutting in the insulating rubber layer is not easy to produce metal molten beads, effectively alleviating the problem of metal particles splashing and penetrating the diaphragm caused by direct laser cutting of the current collector; at the same time, the above-mentioned three-dimensional cross-linked network also further enhances the resistance to laser cutting, and better realizes the protection of the diaphragm.
  • the thickness of the insulating adhesive layer is less than or equal to the thickness of the positive electrode film layer.
  • the thickness of the insulating adhesive layer is 3 ⁇ m-7 ⁇ m.
  • the fourth aspect of the present application provides a method for preparing a positive electrode plate, including a process of setting a positive electrode film layer and an insulating adhesive layer on at least one side or both sides of a positive electrode current collector, wherein the process of setting the insulating adhesive layer includes: mixing the components of any one of the adhesive compositions of the first aspect to form an adhesive solution; coating the adhesive solution on the empty foil area of the positive electrode current collector to obtain a preform with the adhesive solution; heating the preform with the adhesive solution to obtain an insulating adhesive layer, and the heating temperature is optionally 90°C-120°C to accelerate the removal rate of the solvent therein.
  • the process of mixing the components of the adhesive composition to form a slurry comprises: mixing the dispersant in the adhesive composition with water to form a first dispersion, optionally, mixing as a first stirring, the first stirring time is 5min-30min, and the stirring speed is 200rpm-400rpm; mixing the first dispersion with the insulating filler in the adhesive composition to form a second dispersion, optionally, mixing as a second stirring, the second stirring time is 30min-120min, and the stirring speed is 1200rpm-1800rpm; mixing the second dispersion with the first adhesive in the adhesive composition to form a third dispersion, optionally, mixing as a third stirring, the third stirring time is 15min-60min, and the stirring speed is 400rpm-700rpm; mixing the third dispersion with the second adhesive in the adhesive composition to form a glue, optionally, mixing as a fourth stirring, the fourth stirring time is 5min-30min, and the stirring speed is 200rpm-400rpm.
  • the fifth aspect of the present application provides a secondary battery, comprising a positive electrode plate, wherein the positive electrode plate comprises any one of the positive electrode plates provided in the third aspect or a positive electrode plate prepared by any one of the preparation methods provided in the fourth aspect.
  • a sixth aspect of the present application provides an electrical device, including a secondary battery, wherein the secondary battery includes any one of the secondary batteries provided in the fifth aspect.
  • FIG. 1 is a side view of a positive electrode plate provided in one embodiment of the present application.
  • FIG. 2 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 3 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 2 .
  • FIG. 4 is a schematic diagram of a battery module according to an embodiment of the present application.
  • FIG. 5 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 6 is an exploded view of the battery pack shown in FIG. 5 according to an embodiment of the present application.
  • FIG. 7 is a schematic diagram of an electric device using a secondary battery as a power source according to an embodiment of the present application.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can form a scope with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "a-b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • any of the following conditions satisfies the condition "A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
  • an adhesive material including an adhesive, the adhesive including a structural unit A, a structural unit B, a structural unit C and a structural unit D, at least part of the structural unit A is cross-linked with at least part of the structural unit D, wherein the structural unit A is
  • the structural units B are each independently Any one or more of, optionally, structural unit B is
  • the structural units C are each independently Any one of, each m1 and each m2 are independently any integer from 1 to 20, optionally, m1 are independently any integer from 2 to 12, m2 are independently any integer from 8 to 12;
  • the structural unit D is independently Any one or more of, n1 is independently any integer from 1 to 20, optionally, n1 is any integer from 1 to 12, further optionally n1 is any integer from 1 to 6.
  • the structural unit A and the structural unit D form a three-dimensional cross-linked network through hydrogen bond interaction, so that the formed insulating rubber layer has better wear resistance, can isolate the effective contact and friction between the root of the pole ear and the edge of the positive electrode sheet caused by the bending of the pole ear when the battery cell enters the shell, and effectively control the problem of short circuit between the pole ear and the positive electrode film layer.
  • the above-mentioned structural units A, C and D are polymers of acrylic monomers, in which the acrylic substances have the properties of high temperature resistance and non-decomposition, so the formed insulating rubber layer can prevent the collector of the positive electrode sheet from being directly cut by laser, effectively resist the splash of metal particles, and the laser cutting in the insulating rubber layer is not easy to produce metal molten beads, which effectively alleviates the problem of metal particles splashing and penetrating the diaphragm caused by direct laser cutting of the collector; at the same time, the above-mentioned three-dimensional cross-linked network also further enhances the resistance to laser cutting, and better realizes the protection of the diaphragm.
  • At least part of the structural unit A, at least part of the structural unit B, at least part of the structural unit C and at least part of the structural unit D are connected in a chain to form a first chain structure, and at least part of the structural unit A, at least part of the structural unit C and at least part of the structural unit D are connected in a chain to form a second chain structure; the structural unit A in at least part of the first chain structure is cross-linked with the structural unit D in at least part of the second chain structure; and the structural unit D in at least part of the first chain structure is cross-linked with the structural unit A in at least part of the second chain structure.
  • the first chain structure and the second chain structure contain structural units A and D at the same time, providing more sites for the cross-linking of structural units A and D, thereby further improving the density of the formed three-dimensional network and better improving the wear resistance of the adhesive material;
  • the first chain structure contains structural units A, structural units B, structural units C and structural units D at the same time, which is more conducive to adjusting and controlling the strength provided by the chain structure by utilizing the content of structural units B and structural units C;
  • the second chain structure contains structural units A, structural units C and structural units D at the same time, and has better flexibility, which can be used to more flexibly adjust the content of structural units C, thereby more flexibly adjusting the bonding force of the adhesive material.
  • the adhesive material satisfies any one or more of the following conditions: 1) The wear resistance of the insulating adhesive layer with a thickness of 5 ⁇ m formed by the adhesive material meets the following requirements: tested by an RCA paper tape wear tester, using a 55g weight and a flat tape for 300mm and 2 turns to form an experimental area, taking n test points in the experimental area and the spacing between the test points is not less than 2cm, the number of non-leaking points in the experimental area accounts for more than 30%, where 5 ⁇ n ⁇ 100, or the area of non-leaking points in the experimental area is more than 60% of the total area of the experimental area; 2) The cohesive force of the insulating adhesive layer formed by the adhesive material is 620N/m-750N/m, which can be optionally 660N/m-725N/m; 3) The insulating adhesive layer formed by the adhesive material The Shore hardness is 45HA-80HA, and can be selected as 50HA-65HA; 4) The bonding force of the insulating adhesive layer formed
  • test method for the above cohesion is as follows:
  • the adhesive substance is prepared into a slurry and then applied to the carbon-coated layer of the carbon-coated copper foil. After drying, a sample sheet is obtained, one side of the sample sheet is a copper foil surface, and the other side is a glue layer formed by the adhesive substance; the sample sheet is then cut into a sample strip with a size of 2 cm wide and 6 cm long; the copper foil surface of the sample strip is bonded to the surface of the hard substrate (steel plate) with 3M-55230H double-sided adhesive (note that there are no bubbles during the bonding process).
  • the adhesive layer of the fixed sample strip is bonded with 3M-55230H double-sided adhesive, and the copper foil of the same size as the double-sided adhesive is covered on the surface of the double-sided adhesive (note that there are no bubbles during the bonding process).
  • the double-sided adhesive used twice is of the same size to obtain a test sample.
  • the tensile tester was set to a tensile speed of 50 mm/min and a tensile length of 100 mm for testing.
  • the peeling force data obtained in the test is the cohesive force of the coating material.
  • the test method of the above hardness is as follows: the hardness of the surface of the insulating rubber layer is tested using a Shaw A hardness tester.
  • the molar ratio of the structural unit D to the structural unit A is 0.5:1-5:1, such as: 0.5:1, 1:1, 1.1:1, 2:1, 2.1:1, 2.2:1, 2.5:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.5:1 or 5:1, which can be 0.5:1-3:1, and further 1:1-3:1;
  • the molar ratio of the structural unit A is 0.5:1-3:1, and the molar ratio of the structural unit D to the structural unit A is 0.5:1-5:1, such as 0.5:1, 1:1, 1.1:1, 2:1, 2.1:1, 2.2:1, 2.5:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.5:1 or 5:1, which can be 0.5:1-3:1, and further 1:1-3:1;
  • the molar ratio of the structural unit A is
  • the molar content of structural unit D is 4%-50%, such as 4%, 4.5%, 4.8%, 5%, 5.3%, 5.5%, 6%, 6.2%, 6.4%, 6.8%, 7%, 10%, 15%, 20%, 30%, 40% or 50%, and can be optionally 4%-10%.
  • the molar content of structural unit D is 1%-50%, such as 1%, 4%, 5%, 6%, 8%, 10%, 13%, 14%, 15%, 20%, 30%, 40% or 50%, and can be optionally 5%-30%, and can be further optionally 5%-15%.
  • the cross-linking of the structural unit A and the structural unit D is utilized as much as possible to improve the wear resistance of the insulating adhesive layer formed by the adhesive substance.
  • the molar ratio of structural unit C to structural unit B is 1:1-300:1, such as: 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 60:1, 100:1, 150:1, 200:1, 250:1, 280:1, 290:1 or 300:1; it can be optionally 5:1-50:1;
  • the molar content of the structural unit B is 0.2%-20%, such as 0.2%, 0.25%, 0.5%, 1%, 1.5%, 2%, 2.1%, 2.5%, 3%, 3.5%, 5%, 10%, 11%, 13%, 15% or 20%, optionally 1%-5%; optionally, the molar content of structural unit C is 1%-90%, such as 5%, 10%, 20%, 30%, 40%, 45%, 50%, 55%, 58%, 60%, 68%, 70%, 75%, 77%, 78%, 80%, 85% or 90%, optionally 55%-9
  • the above-mentioned adhesive material also includes an insulating filler and/or a dispersant.
  • the use of the insulating filler reduces the cost, and the dispersant promotes the dispersion effect of the insulating filler in the adhesive; and the carboxyl group of the above-mentioned structural unit A can form hydrogen bonds with the insulating filler to improve the adhesion of the formed insulating adhesive layer.
  • the ratio of insulating filler, adhesive and dispersant can refer to the composition of conventional adhesive materials.
  • the weight ratio of insulating filler, adhesive and dispersant is (70-90):(10-25):0.4.
  • Insulating filler can be used to reduce costs, dispersant can improve the dispersion effect of insulating filler in adhesive, avoid the subsequent cross-linking of adhesive, and there is enough adhesive to provide good bonding force.
  • the insulating filler can be the insulating filler commonly used in the adhesive. Considering that the adhesive composition is used in the positive electrode plate and needs to withstand laser radiation later, the insulating filler can be selected from a heat-resistant and electrochemically stable inorganic material that does not soften or melt at a temperature above 600°C, typically above 700°C, for example, above 900°C, and can insulate the positive electrode from the negative electrode.
  • the insulating filler includes any one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, barium titanate, aluminum nitride, silicon nitride, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, mica, talc, boehmite, zeolite, apatite, kaolin, or glass powder.
  • the hardness of the above insulating fillers is different, and the hardness of boehmite is more moderate, which can improve the stability of the insulating glue layer and will not cause the hardness to have a negative impact on the battery separator.
  • the D V 50 particle size of the insulating filler is ⁇ 1 ⁇ m.
  • the insulating filler within this particle size range can be completely embedded in the insulating layer of conventional thickness, thereby effectively controlling the friction of the insulating filler on the diaphragm.
  • the above Dv50 represents the volume average particle size, which refers to the particle size corresponding to when the cumulative volume distribution percentage of the material reaches 50%.
  • the test method can refer to the standard GB/T 19077-2016 and be measured using a laser particle size analyzer (e.g., Malvern Master Size 3000).
  • the dispersant used for the adhesive material of the present application can be selected from conventional dispersants that are beneficial to the dispersion of insulating fillers.
  • the above-mentioned dispersant includes one or more of polyacrylate compounds, fatty alcohol polyether compounds, and polyether-modified siloxane compounds, such as Chemadd-6004 of Yueyang Kaimen Water-based Additive Co., Ltd. and Elaecpure LW-10 of Dow Chemical; when no solvent is included, the packaging and transportation of the adhesive material is more convenient; when a solvent is included, the use of the adhesive material is more convenient.
  • the viscosity of adhesives with different solid contents is different, the coating properties of the construction are different, and the curing conditions are also different.
  • the solid content of the adhesive material is optionally 20%-40% to improve the construction and curing efficiency.
  • the viscosity of the adhesive material measured at 25°C and 12rpm is 550mPa ⁇ s.
  • the solvent of the adhesive material further optionally includes water, that is, a water-based adhesive is provided.
  • an adhesive composition comprising an adhesive, wherein the adhesive comprises a first adhesive and a second adhesive, the first adhesive is a polymer, comprising a structural unit A, a structural unit B, a structural unit C and a structural unit D, the second adhesive is a polymer, comprising a structural unit A, a structural unit C and a structural unit D,
  • the structural unit A is
  • the structural units B are each independently Any one or more of, optionally, structural unit B is Structural unit C of the first binder and structural unit C of the second binder Each independently Each m1 and each m2 are each independently an integer of 1-20, for example, m1 is 1, 2, 3, 4, 5, 6, 8, 10, 12, 13, 14, 15, 16, 18 or 20, and m1 is 1, 2, 3, 4, 5, 6, 8, 10, 12, 13, 14, 15, 16, 18 or 20; optionally, m1 is each independently any integer of 2 to 12, and m2 is each independently any integer of 8 to 12; the structural unit D of the first adhesive and the structural unit D of the second adhesive are each independently n1 is each independently any integer from 1 to 20, for example, n1 is 1, 2, 3, 4, 5, 6, 8, 10, 12, 13, 14, 15, 16, 18 or 20, and optionally, n1 is each independently any integer from 1 to 12; further optionally, n1 is each independently any integer from 1 to 6.
  • the structural unit B in the first adhesive is provided by an acrylonitrile monomer, which is a hard monomer and can enhance the strength of the insulating adhesive layer;
  • the structural unit C in the first adhesive and the second adhesive is provided by an acrylate monomer, which is a soft monomer and can improve the flexibility of the insulating adhesive layer and enhance the bonding force between the insulating adhesive layer and the current collector.
  • the structural unit A in the first adhesive and the structural unit D in the second adhesive, and the structural unit D in the first adhesive and the structural unit A in the second adhesive interact through hydrogen bonds to form a three-dimensional cross-linked network, so that the formed insulating adhesive layer has better wear resistance, can isolate the effective contact and friction between the root of the pole ear and the edge of the positive electrode sheet caused by the bending of the pole ear when the battery core is put into the shell, and effectively control the problem of short circuit between the pole ear and the positive electrode film layer.
  • the first adhesive and the second adhesive of the adhesive composition are polymers of acrylic monomers, and the acrylic substances therein have the properties of high temperature resistance and not easy to decompose.
  • the formed insulating adhesive layer can prevent the collector of the positive electrode sheet from being directly cut by laser, effectively resist the splash of metal particles, and the laser cutting in the insulating adhesive layer is not easy to produce metal molten beads, which effectively alleviates the problem of metal particles splashing and penetrating the diaphragm caused by direct laser cutting of the collector; at the same time, the above-mentioned three-dimensional cross-linked network also further enhances the resistance to laser cutting, and better realizes the protection of the diaphragm.
  • the weight ratio of the first adhesive to the second adhesive can be selected to be 1:2.5-1:20, such as 1:17.5, 2:17.5, 4:17.5, 1:5, 2:12.5, 2:15 or 1:10; 1:5-1:17.5 can be selected.
  • the amount of the second adhesive is relatively large relative to the amount of the first adhesive, and the first adhesive is used to provide the insulating adhesive layer with better adhesion and flexibility.
  • an appropriate amount of the second adhesive is used to improve the strength of the insulating adhesive layer, so as to better adapt to the strength of the insulating filler in the adhesive composition and the strength of the positive electrode collector, so that the bonding force can be fully exerted; and the above-mentioned weight ratio is used to regulate the density of the cross-linked network of the insulating adhesive layer to provide sufficient network support for wear resistance and protection of the current collector.
  • the first adhesive and the second adhesive in the adhesive composition of the present application can be polymerized by acrylic monomers and acrylic acid derivative monomers corresponding to the above structural units.
  • the properties of the adhesives will be different if the contents of each structural unit are different. In order to adjust the properties of each adhesive and make the two adhesives work together to achieve better synergy.
  • the first adhesive is a copolymer, and the first adhesive optionally meets any one or more of the following conditions: 1) the molar content of the structural unit A in the first adhesive is 5%-30%; 2) the molar content of the structural unit B in the first adhesive is 5%-85%, which can be 5%-55%; 3) the molar content of the structural unit C in the first adhesive is 5%-85%, which can be 35%-85%; 4) the molar content of the structural unit D in the first adhesive is 5%-15%.
  • the hardness of the first adhesive is adjusted by the content of the structural unit B and the structural unit C to meet the hardness requirements of the insulating adhesive layer for different designs and different processing methods; the content of the above structural unit A and the structural unit D is relatively small in all structural units, mainly used to form a cross-linked network with the second adhesive, and also well controls the self-crosslinking of the two in the first adhesive.
  • the second adhesive is a copolymer, and the second adhesive optionally satisfies any one or more of the following conditions: 1) the molar content of structural unit A in the second adhesive is 5%-10%; 2) the molar content of structural unit C in the second adhesive is 70%-85%; 3) the molar content of structural unit D in the second adhesive is 5%-20%.
  • Structural unit C accounts for the majority of the second adhesive, thereby providing the second adhesive with more sufficient flexibility and adhesion, thereby improving the adhesion of the insulating adhesive layer formed by the adhesive composition to the insulating filler and the positive electrode current collector.
  • the first adhesive and the second adhesive in the adhesive composition of the present application are used to bond the insulating filler and the substrate. Due to the effect of gravity, the insulating filler will settle in the adhesive solution formed by the adhesive composition. When the settling phenomenon is particularly serious, it will affect the bonding force of the insulating adhesive layer on the substrate.
  • the weight average molecular weight of the first adhesive is 500,000-1.5 million; the first adhesive with the above weight average molecular weight has a high viscosity, so it has a good suspension effect on the insulating filler, effectively preventing the settling of the insulating filler and improving the bonding force of the insulating adhesive layer.
  • the second adhesive has better flexibility and fluidity, and its suspension effect on insulating fillers is not as good as the first adhesive.
  • the second adhesive also has the characteristics of conventional polymers, that is, its viscosity increases with the increase of molecular weight.
  • the glue formed by the adhesive composition still using the second adhesive provides sufficient fluidity for easy construction.
  • the difference in weight average molecular weight between the first adhesive and the second adhesive is 0-1.5 million. The above difference can be the difference when the weight average molecular weight of the first adhesive is greater than the weight average molecular weight of the second adhesive, or it can be the difference when the weight average molecular weight of the first adhesive is less than the weight average molecular weight of the second adhesive.
  • the adhesive material further includes an insulating filler and/or a dispersant.
  • an insulating filler in the adhesive composition of the present application reduces the cost of the composition, and the dispersant promotes the dispersion effect of the insulating filler in the adhesive; in addition, the carboxyl group can form a hydrogen bond with the insulating filler to improve the adhesion of the formed insulating adhesive layer.
  • the ratio of insulating filler, adhesive and dispersant can refer to the composition of conventional adhesive composition.
  • the weight ratio of insulating filler, adhesive and dispersant is (70-90): (10-25): 0.4.
  • Insulating filler can be used to reduce costs, dispersant can improve the dispersion effect of insulating filler in adhesive, avoid the subsequent cross-linking of adhesive, and there is enough adhesive to provide good bonding force.
  • the insulating filler can be the insulating filler commonly used in the adhesive. Considering that the adhesive composition is used in the positive electrode plate and needs to withstand laser radiation later, the insulating filler can be selected from a heat-resistant and electrochemically stable inorganic material that does not soften or melt at a temperature above 600°C, typically above 700°C, for example, above 900°C, and can insulate the positive electrode from the negative electrode.
  • the insulating filler includes any one or more of aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, barium titanate, aluminum nitride, silicon nitride, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, mica, talc, boehmite, zeolite, apatite, kaolin, or glass powder.
  • the hardness of the insulating fillers is different, and the hardness of boehmite is more moderate, which can improve the stability of the insulating rubber layer and will not cause the hardness to have a negative impact on the battery separator.
  • the D V 50 particle size of the insulating filler is ⁇ 1 ⁇ m.
  • the insulating filler within this particle size range can be completely embedded in the insulating layer of conventional thickness, thereby effectively controlling the friction of the insulating filler on the diaphragm.
  • the dispersant used in the adhesive composition of the present application can be selected from conventional dispersants that are conducive to the dispersion of insulating fillers.
  • the above-mentioned dispersant includes one or more of polyacrylate compounds, fatty alcohol polyether compounds, and polyether-modified siloxane compounds, such as Chemadd-6004 of Yueyang Kaimen Water-based Additive Co., Ltd. and Elaecpure LW-10 of Dow Chemical.
  • the above-mentioned adhesive composition also includes a solvent; when no solvent is included, the packaging and transportation of the adhesive composition is more convenient; when a solvent is included, the use of the adhesive composition is more convenient.
  • the viscosity of adhesive compositions with different solid contents is different, the coating properties of the construction are different, and the curing conditions are also different.
  • the solid content of the adhesive composition is optionally 20%-40% to improve the construction and curing efficiency.
  • the solvent of the adhesive composition further optionally includes water, that is, a water-based adhesive is provided.
  • the wear resistance, cohesion, hardness and adhesion of the adhesive composition also meet the requirements of the above-mentioned adhesive material, which will not be repeated here.
  • the first adhesive and the second adhesive used in the adhesive composition of the present application can be prepared by referring to the preparation method of the prior art or using known materials. In order to facilitate those skilled in the art to implement the present application, the following preparation method is provided for reference.
  • a chain transfer agent such as n-dodecyl mercaptan
  • a surfactant such as dialkyl sulfosuccinate salt M-30S
  • a surfactant such as dialkyl sulfosuccinate salt M-30S
  • nitrogen is used for deoxygenation protection, and the temperature is raised to 80°C-90°C to obtain a reactive surfactant solution.
  • An ammonium persulfate solution is prepared with deionized water as the first initiator solution, and the pre-emulsion and the first initiator solution are simultaneously and continuously added dropwise to the reactive surfactant solution in the reactor, and the addition is completed, and the acrylic acid (ester) copolymer seed solution is obtained.
  • An ammonium persulfate solution is prepared with deionized water as the second initiator solution, and the concentration of the second initiator solution is greater than that of the first initiator solution.
  • the second initiator solution is added dropwise to the acrylic acid (ester) copolymer seed solution, and the addition is continued for 100min-150min, and the addition is completed, and the temperature is kept for 1h-3h to obtain an acrylic acid (ester) copolymer solution.
  • the acrylic acid (ester) copolymer solution in the reaction kettle is cooled to 60-70°C, cooled naturally to room temperature, and decompressed to evacuate the air. The vacuum degree in the reaction kettle is lower than 0.09 MPa, and maintained for 10-50 minutes. Then the air is released to atmospheric pressure and filtered to obtain a water-based binder emulsion.
  • the pH is then adjusted to 7-8.
  • chain transfer agent such as n-dodecyl mercaptan
  • Dissolve the surfactant such as dialkyl sulfosuccinate salt M-30S
  • the surfactant such as dialkyl sulfosuccinate salt M-30S
  • the second initiator solution is added dropwise to the acrylic acid (ester) copolymer seed solution for 100-150 minutes. After the addition is complete, keep warm for 1-3 hours to obtain an acrylic acid (ester) copolymer solution. Cool the acrylic acid (ester) copolymer solution in the reactor to 60-70°C, cool it naturally to room temperature, and decompress and evacuate the air. The vacuum degree in the reactor is lower than 0.09 MPa, and it is maintained for 10-50 minutes. Then, the air is released to atmospheric pressure and filtered to obtain an aqueous binder emulsion. The pH is then adjusted to 7-8.
  • Secondary batteries also known as rechargeable batteries or storage batteries, refer to batteries that can continue to be used by recharging the active materials after the battery is discharged.
  • a secondary battery includes a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte.
  • active ions such as lithium ions
  • the separator is arranged between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing active ions to pass through.
  • the electrolyte is between the positive electrode sheet and the negative electrode sheet, mainly to conduct active ions.
  • the above-mentioned adhesive composition can be considered to be applied to the position where the adhesive is needed in the secondary battery, or to be used as a raw material for a separator. In some embodiments, it is applied to the positive electrode sheet.
  • the positive electrode sheet 10 generally includes a positive electrode current collector 11 and a positive electrode film layer 12 disposed on at least one side of the positive electrode current collector 11 , and the positive electrode film layer 12 includes a positive electrode active material.
  • the positive electrode current collector 11 has two surfaces opposite to each other in its thickness direction, and the positive electrode film layer 12 is disposed on any one or both of the two opposite surfaces of the positive electrode current collector 11 .
  • the positive electrode current collector 11 also has an empty foil area around the positive electrode film layer 12.
  • the positive electrode plate 10 also includes an insulating adhesive layer 13, which is arranged in the empty foil area of the positive current collector 11, wherein the insulating adhesive layer 13 is cured by the adhesive composition provided in any of the above embodiments.
  • the specific location of the insulating adhesive layer 13 in the empty foil area can be based on the prior art, such as avoiding the root of the open tab.
  • the insulating adhesive layer 13 in the positive electrode sheet 10 is solidified by the adhesive composition mentioned above in the present application.
  • the structural unit A in the first adhesive and the structural unit D in the second adhesive, and the structural unit D in the first adhesive and the structural unit A in the second adhesive interact through hydrogen bonds to form a three-dimensional cross-linked network, so that the insulating adhesive layer has better wear resistance, can isolate the effective contact and friction between the root of the pole ear and the edge of the positive electrode sheet caused by the bending of the pole ear when the battery core is put into the shell, and effectively control the problem of short circuit between the pole ear and the positive electrode film layer.
  • the first adhesive and the second adhesive of the adhesive composition are polymers of acrylic monomers, and the acrylic substances therein have the properties of high temperature resistance and not easy to decompose. Therefore, the insulating adhesive layer can prevent the current collector of the positive electrode sheet from being directly cut by laser, effectively resist the splash of metal particles, and the laser cutting in the insulating adhesive layer is not easy to produce metal molten beads, which effectively alleviates the problem of metal particles splashing and penetrating the diaphragm caused by direct laser cutting of the current collector; at the same time, the above-mentioned three-dimensional cross-linked network also further enhances the resistance to laser cutting, and better realizes the protection of the diaphragm.
  • the carboxyl groups of the first adhesive and the second adhesive can form hydrogen bonds with the insulating filler to improve the adhesion of the insulating adhesive layer.
  • the structural unit B in the first adhesive is provided by acrylonitrile monomer, which is a hard monomer and can enhance the strength of the insulating adhesive layer;
  • the structural unit C in the first adhesive and the second adhesive is provided by acrylate monomers, which are soft monomers and can improve the flexibility of the insulating adhesive layer and enhance the adhesion between the insulating adhesive layer and the current collector.
  • the thickness of the insulating glue layer 13 of the positive electrode sheet 10 can be based on the conventional thickness of the insulating glue layer, or the thickness can be set according to the design requirements of the battery. In some embodiments, the thickness of the insulating glue layer 13 is less than or equal to the thickness of the positive electrode film layer 12. Optionally, the thickness of the insulating glue layer 13 is 3 ⁇ m-7 ⁇ m. This can protect the positive current collector 11 and avoid increasing the volume of the battery cell due to the excessive thickness of the insulating glue layer 12.
  • the formation process of the above insulating adhesive layer can refer to conventional techniques, such as by coating.
  • the process of forming the insulating adhesive layer includes: mixing the adhesive composition to form an adhesive solution; coating the adhesive solution on the empty foil area of the positive electrode current collector to obtain a preform with the adhesive solution; heating the preform with the adhesive solution to obtain the insulating adhesive layer, and the heating temperature is optionally 90°C-120°C to accelerate the removal of the solvent therein.
  • the process of mixing the adhesive composition to form a slurry includes:
  • the dispersant in the adhesive composition is mixed with water to form a first dispersion, and optionally, mixed into a first Stirring, the first stirring time is 5min-30min, and the stirring speed is 200rpm-400rpm;
  • the first dispersion is mixed with the insulating filler in the adhesive composition to form a second dispersion.
  • the mixing is a second stirring, the second stirring time is 30 min-120 min, and the stirring speed is 1200 rpm-1800 rpm;
  • the second dispersion is mixed with the first adhesive in the adhesive composition to form a third dispersion.
  • the mixing is a third stirring, the third stirring time is 15 min-60 min, and the stirring speed is 400 rpm-700 rpm;
  • the third dispersion is mixed with the second adhesive in the adhesive composition to form an adhesive solution.
  • the mixing is performed as a fourth stirring process, wherein the fourth stirring process has a time of 5 min to 30 min and a stirring speed of 200 rpm to 400 rpm.
  • the stirring time and speed do not need to be adjusted according to the objects to be mixed, and stirring is used to improve the mixing effect of each component.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • aluminum foil may be used as the metal foil.
  • the composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base.
  • the composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the positive electrode active material may be a positive electrode active material for a battery known in the art.
  • the positive electrode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used.
  • These positive electrode active materials may be used alone or in combination of two or more.
  • lithium transition metal oxides include, but are not limited to, lithium cobalt oxide (such as LiCoO 2 ), lithium nickel oxide (such as LiNiO 2 ), lithium manganese oxide (such as LiMnO 2 , LiMn 2 O 4 ), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), and LiNi 0.8 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 811 ), lithium
  • lithium-containing phosphates with an olivine structure may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate and carbon
  • the positive electrode active material of the sodium ion secondary battery may include at least one of the following materials: at least one of a sodium transition metal oxide, a polyanionic compound, and a Prussian blue compound.
  • the present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for sodium ion batteries may also be used.
  • the transition metal in the sodium transition metal oxide, may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce.
  • the sodium transition metal oxide is Na x MO 2 , wherein M is one or more of Ti, V, Mn, Co, Ni, Fe, Cr and Cu, and 0 ⁇ x ⁇ 1.
  • the polyanionic compound can be a class of compounds having sodium ions, transition metal ions and tetrahedral (YO 4 ) n- anion units.
  • the transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce;
  • Y can be at least one of P, S and Si;
  • n represents the valence state of (YO 4 ) n- .
  • the polyanionic compound may also be a compound having sodium ions, transition metal ions, tetrahedral (YO 4 ) n- anion units and halogen anions.
  • the transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce;
  • Y may be at least one of P, S and Si, and n represents the valence state of (YO 4 ) n- ;
  • the halogen may be at least one of F, Cl and Br.
  • the polyanionic compound may also be a compound having sodium ions, tetrahedral (YO 4 ) n- anion units, polyhedral units (ZO y ) m+ and optional halogen anions.
  • Y may be at least one of P, S and Si
  • n represents the valence of (YO 4 ) n-
  • Z represents a transition metal, which may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce
  • m represents the valence of (ZO y ) m+
  • the halogen may be at least one of F, Cl and Br.
  • the polyanionic compound is, for example, at least one of NaFePO 4 , Na 3 V 2 (PO 4 ) (sodium trivanadium phosphate, abbreviated as NVP), Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ), NaM'PO 4 F (M' is one or more of V, Fe, Mn and Ni) and Na 3 (VO y ) 2 (PO 4 ) 2 F 3-2y (0 ⁇ y ⁇ 1).
  • the Prussian blue compound may be a compound having sodium ions, transition metal ions and cyanide ions (CN-).
  • the transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr and Ce.
  • the Prussian blue compound is, for example, Na a Me b Me' c (CN) 6 , wherein Me and Me' are each independently at least one of Ni, Cu, Fe, Mn, Co and Zn, 0 ⁇ a ⁇ 2, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1.
  • the positive electrode film layer may also optionally include a binder.
  • the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • vinylidene fluoride-tetrafluoroethylene-propylene terpolymer vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer
  • the positive electrode film layer may further include a conductive agent, for example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode collector, and after drying, cold pressing and other processes, the positive electrode sheet can be obtained.
  • a solvent such as N-methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • a metal foil a copper foil may be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative electrode active material may adopt the negative electrode active material for the battery known in the art.
  • the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, etc.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further include a binder.
  • the binder may be selected from at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer may further include a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the negative electrode film layer may optionally include other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
  • a thickener eg, sodium carboxymethyl cellulose (CMC-Na)
  • the negative electrode sheet can be prepared in the following manner: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays the role of conducting ions between the positive electrode and the negative electrode.
  • the present application has no specific restrictions on the type of electrolyte, which can be selected according to needs.
  • the electrolyte can be liquid, gel or all-solid.
  • the electrolyte is liquid and includes an electrolyte salt and a solvent.
  • the electrolyte salt for lithium ion secondary battery may include lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonyl imide, lithium bistrifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate or lithium tetrafluorooxalate phosphate.
  • the electrolyte salt for sodium ion secondary battery may include sodium hexafluorophosphate ( NaPF6 ), sodium tetrafluoroborate ( NaBF4 ), sodium hexafluoroarsenate ( NaAsF6 ), sodium trifluoroacetate ( CF3COONa ), sodium trifluoromethanesulfonate ( CF3NaO3S , NaOTf) or sodium tetraphenylborate ( NaBPh4 ) One or more.
  • NaPF6 sodium hexafluorophosphate
  • NaBF4 sodium tetrafluoroborate
  • NaAsF6 sodium hexafluoroarsenate
  • CF3COONa sodium trifluoroacetate
  • CF3NaO3S , NaOTf sodium trifluoromethanesulfonate
  • NaBPh4 sodium tetraphenylborate
  • the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, cyclopentane sulfone, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte may further include additives.
  • the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the secondary battery further includes a separator.
  • the present application has no particular limitation on the type of separator, and any known porous separator with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • the positive electrode sheet, the negative electrode sheet, and the separator may be formed into an electrode assembly by a winding process or a lamination process.
  • the secondary battery includes a secondary battery cell, or includes a battery module and a battery pack.
  • the secondary battery may include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
  • FIG2 is a secondary battery cell 5 of a square structure as an example.
  • the outer package may include a shell 51 and a cover plate 53 .
  • 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 can be covered on the opening to close the receiving cavity.
  • the positive electrode sheet, the negative electrode sheet and the isolation film can form an electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the electrolyte is infiltrated in the electrode assembly 52.
  • the number of electrode assemblies 52 contained in the secondary battery cell 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary battery cells may be assembled into a battery module.
  • the number of secondary battery cells contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
  • FIG4 is a battery module 4 as an example.
  • a plurality of secondary battery cells 5 may be arranged in sequence along the length direction of the battery module 4. Of course, they may also be arranged in any other manner. Further, the plurality of secondary battery cells 5 may be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space, and the plurality of secondary battery cells 5 are received in the receiving space.
  • the battery modules described above may also be assembled into a battery pack.
  • the battery pack may contain one or more battery modules, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
  • FIG5 and FIG6 are battery packs 1 as an example.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 to form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electric device, which includes a secondary battery provided in the present application.
  • the secondary battery can be used as a power source for the electric device, or as an energy storage unit for the electric device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
  • a secondary battery cell, a battery module or a battery pack may be selected according to its usage requirements.
  • Fig. 7 is an example of an electric device.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • the first binder (structural unit B is ) is prepared as follows:
  • ammonium persulfate solution 3.5g was prepared with deionized water as the first initiator solution, and the pre-emulsion and the first initiator solution were simultaneously and continuously added dropwise to the reactive surfactant solution in the reactor, and the addition was completed for 160min, and the temperature was kept warm for 0.5h to obtain a seed solution.
  • 1.0g of ammonium persulfate initiator solution was prepared with deionized water as the second initiator solution, and the second initiator solution was added dropwise to the seed solution, and the addition was continued for 120min, and the addition was completed, and the acrylic acid (ester) copolymer solution was obtained by keeping warm for 2h.
  • the acrylic acid (ester) copolymer in the reaction kettle is cooled to 65°C at a rate of 2°C/min, kept at this temperature for 30 minutes, cooled naturally to room temperature, and decompressed to evacuate the air, with the vacuum degree in the reaction kettle being lower than 0.09 MPa, and kept for 30 minutes, and then vented to atmospheric pressure, and filtered through a 300-mesh filter cloth to obtain a second adhesive emulsion with a solid content of 50%.
  • the pH value is then adjusted to 7-8.
  • the solid content of the first adhesive is 15%.
  • composition of the first adhesive was adjusted by adjusting the composition or amount of each monomer, and the compositions of the first adhesive 1 to the first adhesive 21 obtained are recorded in Table 1-1.
  • the first adhesive 22 (structural unit B is ) is prepared as follows:
  • nitrogen protection was introduced at a flow rate of 110 mL/min to form a pre-emulsion.
  • the pre-emulsion was heated to 85°C at a heating rate of 2°C/min and kept warm for 30 min to obtain a pre-emulsion.
  • 3.8 g of a reactive surfactant containing a double bond group of dialkyl sulfosuccinate salt M- 30S was dissolved in 61.3g of deionized water and added to the reactor at a speed of 300rpm. Nitrogen was used for deoxygenation protection at a flow rate of 100mL/min. The temperature was raised to 88°C at a heating rate of 2°C/min and kept warm for 30min to obtain a reactive surfactant solution.
  • ammonium persulfate solution 3.5g was prepared with deionized water as the first initiator solution.
  • the pre-emulsion and the first initiator solution were simultaneously and continuously added dropwise to the reactive surfactant solution in the reactor.
  • the addition was completed over 160min and kept warm for 0.5h to obtain a seed solution.
  • 1.0g of ammonium persulfate initiator solution was prepared with deionized water as the second initiator solution.
  • the second initiator solution was added dropwise to the seed solution and continued to be added dropwise for 120min. After the addition was completed, the acrylic acid (ester) copolymer solution was obtained by keeping warm for 2h.
  • the acrylic acid (ester) copolymer in the reaction kettle is cooled to 65°C at a rate of 2°C/min, kept at this temperature for 30 minutes, cooled naturally to room temperature, and decompressed to evacuate the air, with the vacuum degree in the reaction kettle being lower than 0.09 MPa, and kept for 30 minutes, and then vented to atmospheric pressure, and filtered through a 300-mesh filter cloth to obtain a second adhesive emulsion with a solid content of 50%.
  • the pH value is then adjusted to 7-8.
  • the solid content of the first adhesive is 15%.
  • the first adhesive 23 (structural unit B is ) is prepared as follows:
  • the mixture was uniformly blended at a rotation speed of 350 rpm for 25 min, during which nitrogen protection was introduced at a flow rate of 110 mL/min to form a pre-emulsion.
  • the pre-emulsion was heated to 85°C at a heating rate of 2°C/min and kept warm for 30 min to obtain a pre-emulsion.
  • ammonium persulfate solution 3.5g was prepared with deionized water as the first initiator solution, and the pre-emulsion and the first initiator solution were simultaneously and continuously added dropwise to the reactive surfactant solution in the reactor, and the addition was completed for 160min, and the temperature was kept warm for 0.5h to obtain a seed solution.
  • 1.0g of ammonium persulfate initiator solution was prepared with deionized water as the second initiator solution, and the second initiator solution was added dropwise to the seed solution, and the addition was continued for 120min, and the addition was completed, and the acrylic acid (ester) copolymer solution was obtained by keeping warm for 2h.
  • the acrylic acid (ester) copolymer in the reaction kettle is cooled to 65°C at a rate of 2°C/min, kept at this temperature for 30 minutes, cooled naturally to room temperature, and decompressed to evacuate the air, with the vacuum degree in the reaction kettle being lower than 0.09 MPa, and kept for 30 minutes, and then vented to atmospheric pressure, and filtered through a 300-mesh filter cloth to obtain a second adhesive emulsion with a solid content of 50%.
  • the pH value is then adjusted to 7-8.
  • the solid content of the first adhesive is 15%.
  • the pre-emulsion was formed at a rate of 110 mL/min, and the pre-emulsion was heated to 85°C at a rate of 2°C/min, and kept warm for 30 minutes to obtain a pre-emulsion.
  • 3.8 g of the reactive surfactant M-30S containing a double bond group was dissolved in 61.3 g of deionized water and added to the reactor at a speed of 300 rpm. Nitrogen was used for deoxygenation protection, and the flow rate was 100 mL/min. The temperature was raised to 88°C at a rate of 2°C/min, and kept warm for 30 minutes to obtain a reactive surfactant solution.
  • ammonium persulfate solution 3.5 g was prepared with deionized water as the first initiator solution.
  • the pre-emulsion and the first initiator solution were continuously added dropwise to the reactive surfactant solution in the reactor at the same time.
  • the addition was completed in 160 minutes, and the mixture was kept warm for 0.5 hours to obtain a seed solution.
  • 1.0g ammonium persulfate initiator solution was prepared with deionized water as the second initiator solution, and the second initiator solution was added dropwise to the seed solution for 120 minutes. After the addition was completed, the solution was kept warm for 2 hours to obtain an acrylic acid (ester) copolymer solution.
  • the acrylic acid (ester) copolymer in the reactor was cooled to 65°C at a rate of 2°C/min, kept warm for 30 minutes, cooled naturally to room temperature, and decompressed to evacuate the air.
  • the vacuum degree in the reactor was lower than 0.09 MPa, and maintained for 30 minutes.
  • the air was vented to atmospheric pressure and filtered through a 300-mesh filter cloth to obtain a second adhesive emulsion with a solid content of 50%.
  • the pH value was then adjusted to 7-8.
  • the solid content of the first adhesive was 15%.
  • the molecular weights in Table 1-1 are weight average molecular weights rounded to the nearest ten thousand.
  • the test method can refer to the standard GB/T 21863-2008, measured using ultra-high performance polymer chromatography.
  • the preparation process of the second adhesive is as follows:
  • the mixture was uniformly mixed at a rotation speed of 300 rpm for 30 minutes, during which nitrogen was introduced for deoxygenation protection at a flow rate of 100 mL/min to form a pre-emulsion.
  • the pre-emulsion was heated to 85°C at a heating rate of 2°C/min and kept warm for 30 minutes to obtain a pre-emulsion.
  • ammonium persulfate solution 3g (0.15wt%) was prepared with deionized water as the first initiator solution, and the pre-emulsion and the first initiator solution were continuously added dropwise to the reactive surfactant solution in the reactor at the same time, and the addition was completed over 150min, and the temperature was kept for 0.5h to obtain an acrylic acid (ester) copolymer seed solution.
  • 1.0g (0.1wt%) ammonium persulfate initiator solution was prepared with deionized water as the second initiator solution, and the second initiator solution was added dropwise to the acrylic acid (ester) copolymer seed solution, and the addition was continued for 120min.
  • the acrylic acid (ester) copolymer solution was obtained by heat preservation for 2h.
  • the acrylic acid (ester) copolymer in the reactor was cooled to 65°C at a rate of 2°C/min, and the temperature was kept for 30min.
  • the temperature was naturally cooled to room temperature, and the vacuum degree in the reactor was reduced to less than 0.09mpa, and the vacuum was maintained for 30min, and then the air was released to atmospheric pressure, and the solution was filtered through a 300-mesh filter cloth to obtain a second adhesive emulsion with a solid content of 50%.
  • the pH value was then adjusted to 7-8.
  • composition of the second adhesive was adjusted by adjusting the composition and amount of each monomer, and the compositions of the obtained second adhesives 1 to 12 are recorded in Table 1-2.
  • the molecular weights in Table 1-2 are weight average molecular weights rounded to the nearest ten thousand.
  • the test method can refer to the standard GB/T21863-2008 and be measured using an ultra-high performance polymer chromatograph.
  • the dispersant was added into deionized water, and the mixture was dispersed and stirred at 300 rpm for 15 min to obtain a first dispersion;
  • the first adhesive emulsion was added into the second dispersion, and the mixture was dispersed and stirred at 1500 rpm for 60 min to obtain a third dispersion;
  • the second adhesive latex was added to the third dispersion liquid, and dispersed at 500 rpm for 60 min to obtain an adhesive solution.
  • the specific materials and amounts of the dispersant, insulating filler, first adhesive and second adhesive used are recorded in Table 2.
  • Embodiments 2 to 47 are identical to Embodiments 2 to 47:
  • the corresponding glue solution was prepared by referring to the process of Example 1.
  • the specific substances and amounts of the dispersant, insulating filler, first adhesive (dry matter) and second adhesive (dry matter) used in each example are recorded in Table 2.
  • the dispersant was added into deionized water, and the mixture was dispersed and stirred at 300 rpm for 15 min to obtain a first dispersion;
  • the first adhesive emulsion was added to the above dispersion, and the mixture was dispersed and stirred at 1500 rpm for 60 min to obtain an adhesive solution.
  • the specific materials and amounts of the dispersant, insulating filler and the first adhesive used are recorded in Table 2.
  • the dispersant was added into deionized water, and the mixture was dispersed and stirred at 300 rpm for 15 min to obtain a first dispersion;
  • the second adhesive emulsion was added into the second dispersion liquid, and the mixture was dispersed and stirred at 1500 rpm for 60 min to obtain a glue solution.
  • the dispersant used in each embodiment and comparative example is Chemadd-6004 produced by Yueyang Kaimen Water-Based Additive Co., Ltd., with a mass fraction of 0.4 parts.
  • Viscosity test The rotational viscosity of the glue was tested at 25°C and 12 rpm. The results are recorded in Table 3.
  • Abrasion resistance test Use a 5 ⁇ m scraper to scrape each of the above adhesives onto a 13 ⁇ m aluminum foil, transfer to a 100°C oven for drying, and prepare the insulating adhesive layer to be tested.
  • RCA paper tape wear tester (BGD 530 from BGD Precision Instruments (Guangzhou) Co., Ltd.); Test principle: The motor drives the paper tape to pass through an area on the surface of the test sample at a uniform speed and applies a certain pressure to wear the test surface; Test method: After the insulating rubber layer to be tested is 5 ⁇ m thick and the flat tape is walked for 300mm (2 turns) with a 55g weight, the number of points that are not leaked in the test area (a total of 10 points are tested) is recorded in Table 3, and the area of the leaking points is recorded at the same time to calculate the proportion of the area of the non-leaking points in the total area of the test area.
  • the adhesive substance is prepared into a slurry and then applied to the carbon-coated layer of the carbon-coated copper foil. After drying, a sample sheet is obtained, one side of the sample sheet is a copper foil surface, and the other side is a glue layer formed by the adhesive substance; the sample sheet is then cut into a sample strip with a size of 2 cm wide and 6 cm long; the copper foil surface of the sample strip is bonded to the surface of the hard substrate (steel plate) with 3M-55230H double-sided adhesive (note that there are no bubbles during the bonding process).
  • the adhesive layer of the fixed sample strip is bonded with 3M-55230H double-sided adhesive, and the copper foil of the same size as the double-sided adhesive is covered on the surface of the double-sided adhesive (note that there are no bubbles during the bonding process).
  • the double-sided adhesive used twice is of the same size to obtain a test sample.
  • the tensile tester was set to a tensile speed of 50 mm/min and a tensile length of 100 mm for testing.
  • the peel force data obtained in the test is the cohesive force of the coating material. The results are recorded in Table 3.
  • Hardness test The hardness of the surface of the insulating rubber layer was tested using a Shore A hardness tester. The results are recorded in Table 3.
  • the above adhesive solutions were respectively scraped onto 13 ⁇ m aluminum foil using a 5 ⁇ m scraper, and then transferred to a 100° C. oven for drying to prepare the insulating adhesive layer to be tested.
  • the test sample on the testing machine fix the end of the steel plate without the electrode with the lower clamp, fold the paper tape upwards and fix it with the upper clamp, keep the axial direction of the sample consistent with the direction of force, and load the testing machine at a peeling speed of 10mm/min until the sample breaks, stop the test, and record.
  • the maximum load force is F (unit N)
  • the sample width L 20 mm
  • the peel strength is the adhesive force.
  • the wear resistance of the insulating adhesive layer formed by the adhesive composition of the present application is significantly better than the wear resistance of the first adhesive 1 or the second adhesive 1 when used alone; and the viscosity of the first adhesive 1 is too large, which is not conducive to construction when used alone and the bonding force is too low; the viscosity of the second adhesive 1 is too small, which affects the construction performance and thus affects the film-forming effect.

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Abstract

本申请提供了一种粘合物质、粘合剂组合物、正极极片、二次电池和用电装置。粘合物质，包括粘合剂，粘合剂包括结构单元A、结构单元B、结构单元C和结构单元D，至少部分结构单元A与至少部分结构单元D交联；结构单元A为式（1）；其中，结构单元B各自独立地为式（2），式（3），式（4），式（5）或式（6）中的任意一种或多种，可选地，结构单元B为式（1）或式（2）；结构单元C各自独立地为式（7）或式（8）中的任意一种，各m1和各m2各自独立地为1-20的整数，可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；结构单元D各自独立地为式（9）中的任意一种或多种，n1各自独立地为1-20的任意整数，可选地，n1为1至12的任意整数，进一步可选地n1为1至6的任意整数。

Description

粘合物质、粘合剂组合物、正极极片、二次电池和用电装置
相关申请的交叉引用
本申请要求享有于2023年08月15日提交的名称为“粘合物质、粘合剂组合物、正极极片、二次电池和用电装置”的中国专利申请202311027156.4的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请涉及电池技术领域，特别是涉及一种粘合物质、粘合剂组合物、正极极片、二次电池和用电装置。
背景技术
二次离子电池(比如锂离子二次电池或钠离子二次电池)作为一种新能源电池，具有工作电压高、比容量高、充放电寿命长、无记忆效应等优点。同时二次离子电池使用的安全性也越来越成为人们关注的焦点，在日常二次离子电池制造过程会出现组装短路测试0阻值、化成电压低、自放电大、模组压差大等异常电芯，其中拆解成品电池会发现电芯正极极片边缘留白对应的隔膜有被击穿的点，分析原因为激光切过程中产生金属颗粒溅射在留白位置，从而造成异物击穿留白对应隔膜，轻则导致电芯压差大，严重的可能导致短路，造成严重事故；且电芯入壳时极耳弯折会导致极耳根部与正极极片边缘留白处接触，也会产生短路的问题。
为解决以上问题，在电芯正极极片边缘设置绝缘胶层十分有助于避免上述短路问题的发生。
发明内容
本申请提供一种粘合物质、粘合剂组合物、正极极片、二次电池和用电装置，以解决正极极片边缘绝缘胶耐磨性差的问题。
本申请的第一方面提供了一种粘合物质，包括粘合剂，粘合剂包括结构单元A、结构单元B、结构单元C和结构单元D，至少部分结构单元A与至少部分结构单元D交联，其中，结构单元A为结构单元B各自独立地为 中的任意一种或多种，可选地，结构单元B为结构单元C各自独立地为中的任意一种，各m1和各m2各自独立地为1-20的任意整数，可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；结构单元D各自独立地为中的任意一种或多种，n1各自独立地为1-20的任意整数，可选地，n1为1至12的任意整数，进一步可选地n1为1至6的任意整数。
结构单元B经丙烯腈单体提供，该单体为硬单体可增强绝缘胶层的强度；结构单元C由丙烯酸酯类单体提供，丙烯酸酯类为软单体，可提高绝缘胶层的柔韧性，同时可增强绝缘胶层与集流体的粘结力。
结构单元A和结构单元D通过氢键相互作用形成三维交联网络，使得所形成的绝缘胶层具有较佳的抗磨性能，能隔离电芯入壳时极耳弯折导致的极耳根部与正极极片边缘有效接触与摩擦，有效控制产生极耳与正极膜层短接问题。另一方面，上述各结构单元A、C和D均为丙烯酸类单体的聚合物，其中的丙烯酸类物质具有耐高温、不易分解的性能，因此所形成的绝缘胶层可避免正极极片的集流体直接受激光切割，有效抵御金属颗粒飞溅，而且激光在绝缘胶层中切割不易产生金属熔珠颗粒，有效地缓解了激光直接切割集流体导致的金属颗粒飞溅击穿隔膜问题；同时，上述三维交联网路也进一步增强了对激光切割的抵抗能力，更好地实现了对隔膜的保护作用。
在本申请第一方面的任意实施方式中，至少部分结构单元A、至少部分结构单元 B、至少部分结构单元C和至少部分结构单元D呈链状连接形成第一链结构，至少部分结构单元A、至少部分结构单元C和至少部分结构单元D呈链状连接形成第二链结构；至少部分第一链结构中的结构单元A与至少部分第二链结构中的结构单元D交联；至少部分第一链结构中的结构单元D与至少部分第二链结构中的结构单元A交联。
第一链结构和第二链结构同时含有结构单元A和结构单元D，为结构单元A和结构单元D的交联提供更多的位点，从而进一步改善所形成的三维网络的致密性，更好地改善粘合物质的耐磨性；第一链结构同时含有结构单元A、结构单元B、结构单元C和结构单元D，一方面更有利于利用结构单元B和结构单元C的含量调整控制该链结构所提供的强度；第二链结构同时含有结构单元A、结构单元C和结构单元D，其柔韧性更好，可以利用其更灵活地调整结构单元C的含量，进而更灵活地调整粘合物质的粘结力。
在本申请第一方面的任意实施方式中，粘合物质满足以下条件中的任意一种或多种：1)粘合物质形成厚度为3μm-7μm的绝缘胶层的耐磨性满足以下要求：采用RCA纸带耐磨测试机测试，利用55g砝码与平面走带300mm、2圈后形成实验区，在实验区取n个测试点且测试点的间距不小于2cm，实验区中未漏点数占比在30％以上，其中5≤n≤100，或者实验区中未漏点的面积为实验区总面积的60％以上；2)粘合物质形成的绝缘胶层的内聚力为620N/m-750N/m，可选为660N/m-725N/m；3)粘合物质形成的绝缘胶层的邵氏硬度为45HA-80HA，可选为50HA-65HA；4)粘合物质形成的绝缘胶层的粘结力为30N/m-90N/m，可选为40N/m-80N/m。
在本申请第一方面的任意实施方式中，粘合剂中，结构单元D和结构单元A的摩尔比为0.5:1-5:1，可选为0.5:1-3:1，进一步可选为1:1-3:1；可选地，结构单元A的摩尔含量为4％-50％，可选为4％-10％，结构单元D的摩尔含量为1％-50％，可选为5％-30％，进一步可选为5％-15％。从而尽可能利用结构单元A和结构单元D的交联提高粘合物质形成的绝缘胶层的耐磨性。
在本申请第一方面的任意实施方式中，粘合剂中，结构单元C和结构单元B的摩尔比为1:1-300:1，可选为5:1-50:1；可选地，结构单元B的含量的摩尔含量为0.2％-20％，可选为1％-5％；可选地，结构单元C的摩尔含量为1％-90％，可选为55％-90％，进一步可选为75％-80％。利用上述结构单元B和结构单元C的比例控制，尽可能改善粘合物质的粘结力。
在本申请第一方面的任意实施方式中，粘合物质还包括绝缘填料和/或分散剂。粘合物质中的羧基可与绝缘填料形成氢键从而提高所形成的绝缘胶层的粘合力。
在本申请第一方面的任意实施方式中，绝缘填料、粘合剂和分散剂的重量比为(70-90):(10-25):0.4。既可以利用绝缘填料降低成本，分散剂既可以实现改善绝缘填料在粘合剂中的分散效果，又避免了对粘合剂后续交联的发挥，而且有充分多的粘合剂提供较好的粘结力。
在本申请第一方面的任意实施方式中，绝缘填料包括氧化铝、氧化镁、二氧化硅、二氧化钛、钛酸钡、氮化铝、氮化硅、氢氧化钙、氢氧化镁、氢氧化铝、云母、滑石、勃姆石、沸石、磷灰石、高岭土或玻璃粉中的任意一种或多种。上述各绝缘填料的硬度有所不同，其的勃姆石硬度更为适中，既可以改善绝缘胶层的稳定性而且不会引硬度对电池的隔膜产生负面影响。
在本申请第一方面的任意实施方式中，绝缘填料的体积平均粒径DV50≤1μm。该粒径范围内的绝缘填料能够完全包埋在常规厚度的绝缘层中，从而有效地控制了绝缘填料对隔膜的摩擦。
在本申请第一方面的任意实施方式中，粘合物质还包括溶剂；可选地粘合物质的固含量为20％-40％；可选地粘合物质的溶剂包括水；可选地粘合物质在25℃、12rpm下测得的粘度在350mPa·s-900mPa·s。
本申请的第二方面提供了一种粘合剂组合物，包括粘合剂，粘合剂包括第一粘合剂和第二粘合剂，第一粘合剂为聚合物，包括结构单元A、结构单元B、结构单元C和结构单元D，第二粘合剂为聚合物，包括结构单元A、结构单元C和结构单元D，其中，结构单元A为结构单元B各自独立地为 中的任意一种或多种，可选地，结构单元B为第一粘合剂的结构单元C和第二粘合剂的结构单元C各自独立地为各m1和各m2各自独立地为1-20的任意整数，比如m1为1、2、3、4、5、6、8、10、12、13、 14、15、16、18或20，m1为1、2、3、4、5、6、8、10、12、13、14、15、16、18或20；可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；第一粘合剂的结构单元D和第二粘合剂的结构单元D各自独立地为n1各自独立地为1-20的任意整数，可选地n1各自独立地为1-12的任意整数；进一步可选地n1各自独立地为1-6的任意整数。
当将该粘合剂组合物应用于正极极片制备绝缘胶层时，第一粘合剂中结构单元B经丙烯腈单体提供，该单体为硬单体可增强绝缘胶层的强度；第一粘合剂和第二粘合剂中的结构单元C由丙烯酸酯类单体提供，丙烯酸酯类为软单体，可提高绝缘胶层的柔韧性，同时可增强绝缘胶层与集流体的粘结力。
同时，一方面第一粘合剂中的结构单元A和第二粘合剂中的结构单元D、第一粘合剂中的结构单元D和第二粘合剂中的结构单元A通过氢键相互作用形成三维交联网络，使得所形成的绝缘胶层具有较佳的抗磨性能，能隔离电芯入壳时极耳弯折导致的极耳根部与正极极片边缘有效接触与摩擦，有效控制产生极耳与正极膜层短接问题。另一方面，该粘合剂组合物的第一粘合剂和第二粘合剂均为丙烯酸类单体的聚合物，其中的丙烯酸类物质具有耐高温、不易分解的性能，因此所形成的绝缘胶层可避免正极极片的集流体直接受激光切割，有效抵御金属颗粒飞溅，而且激光在绝缘胶层中切割不易产生金属熔珠颗粒，有效地缓解了激光直接切割集流体导致的金属颗粒飞溅击穿隔膜问题；同时，上述三维交联网路也进一步增强了对激光切割的抵抗能力，更好地实现了对隔膜的保护作用。
在第二方面的任意实施方式中，第一粘合剂和第二粘合剂的重量比为1:2.5-1:20，可选为1:5-1:17.5。利用第二粘合剂为绝缘胶层提供较好的粘结力和柔韧性，同时利用适量的第一粘合剂提高绝缘胶层的强度，从而更好地与粘合剂组合物中的绝缘填料的强度以及正极集流体强度相适应，使得粘结力得到充分发挥；而且利用上述重量比，调控绝缘胶层的交联网络密实程度，为耐磨性和对集流体的保护提供充分的网络支撑。
在第二方面的任意实施方式中，第一粘合剂满足以下条件中的任意一个或多个：1)结构单元A在第一粘合剂中的摩尔含量为5％-30％；2)结构单元B在第一粘合剂中的摩尔含量为5％-85％；3)结构单元C在第一粘合剂中的摩尔含量为5％-85％；4)结构单元D在第一粘合剂中的摩尔含量为5％-15％。利用结构单元B和结构单元C的含量调整第一粘合剂的硬度，以满足不同设计、不同加工方法对绝缘胶层的硬度要求；上述结构单元A和结构单元D的含量在所有结构单元中的含量相对较少，主要用于与第二粘合剂形成交联网络，同时也很好地控制了二者在第一粘合剂中的自交联。
在第二方面的任意实施方式中，第二粘合剂满足以下条件中的任意一个或多个：1)结构单元A在第二粘合剂中的摩尔含量为5％-10％；2)结构单元C在第二粘合剂中的摩尔含量为70％-85％；3)结构单元D在第二粘合剂中的摩尔含量为5％-20％。第二粘合剂中结构单元C占主要比例，从而为第二粘合剂提供更加充分的柔韧性和粘结力，从而提高了粘合剂组合物所形成的绝缘胶层对绝缘填料和正极集流体的粘合力。
在第二方面的任意实施方式中，第一粘合剂的重均分子量为50万-150万；进一步可选地第一粘合剂和第二粘合剂的重均分子量的差值为10万-150万。对绝缘填料起到较好的悬浮作用，有效地阻止了绝缘填料的沉降，提高了绝缘胶层的粘结力。
在第二方面的任意实施方式中，粘合物质还包括绝缘填料和/或分散剂。第一粘合剂、第二粘合剂的羧基可与绝缘填料形成氢键从而提高所形成的绝缘胶层的粘合力。
在本申请第二方面的任意实施方式中，绝缘填料、粘合剂和分散剂的重量比为(70-90):(10-25):0.4。既可以利用绝缘填料降低成本，分散剂既可以实现改善绝缘填料在粘合剂中的分散效果，又避免了对粘合剂后续交联的发挥，而且有充分多的粘合剂提供较好的粘结力。
在第二方面的任意实施方式中，绝缘填料包括氧化铝、氧化镁、二氧化硅、二氧化钛、钛酸钡、氮化铝、氮化硅、氢氧化钙、氢氧化镁、氢氧化铝、云母、滑石、勃姆石、沸石、磷灰石、高岭土或玻璃粉中的任意一种或多种；可选地，绝缘填料的体积平均粒径DV50≤1μm。该粒径范围内的绝缘填料能够完全包埋在常规厚度的绝缘层中，从而有效地控制了绝缘填料对隔膜的摩擦。
在第二方面的任意实施方式中，分散剂包括聚丙烯酸酯类化合物、脂肪醇聚醚类化合物或聚醚改性硅氧烷类化合物中的一种或多种。
在第二方面的任意实施方式中，粘合剂组合物还包括溶剂；可选地粘合剂组合物的固含量为20％-40％；进一步可选地粘合剂组合物的溶剂包括水。
在本申请的第三方面，提供了一种正极极片，包括：正极集流体，正极集流体的至少一侧具有正极膜层区和空箔区；正极膜层，设置在正极集流体的正极膜层区；绝缘胶层，设置在正极集流体的空箔区，其中，绝缘胶层采用上述第一方面的任一种的粘合物质形成，或者通过上述第二方面的任一种的粘合剂组合物固化而成。
绝缘胶层具有较佳的抗磨性能，能隔离电芯入壳时极耳弯折导致的极耳根部与正极极片边缘有效接触与摩擦，有效控制产生极耳与正极膜层短接问题。同时绝缘胶层可避免正极极片的集流体直接受激光切割，有效抵御金属颗粒飞溅，而且激光在绝缘胶层中切割不易产生金属熔珠颗粒，有效地缓解了激光直接切割集流体导致的金属颗粒飞溅击穿隔膜问题；同时，上述三维交联网路也进一步增强了对激光切割的抵抗能力，更好地实现了对隔膜的保护作用。
在第三方面的任意实施方式中，绝缘胶层的厚度小于或等于正极膜层的厚度，可选地，绝缘胶层的厚度为3μm-7μm。
本申请的第四方面，提供了一种正极极片的制备方法，包括在正极集流体的至少一侧或两侧设置正极膜层和绝缘胶层的过程，其中，设置绝缘胶层的过程包括：将第一方面的任意一种粘合剂组合物的组分混合形成胶液；将胶液涂覆在正极集流体的空箔区，得到具有胶液的预制件；对具有胶液的预制件加热，得到绝缘胶层，可选地加热的温度为90℃-120℃，以加快其中的溶剂脱除速度。
在第四方面的任意实施方式中，将粘合剂组合物的组分混合形成浆液的过程包括:将粘合剂组合物中的分散剂与水混合，形成第一分散液，可选地，混合为第一搅拌，第一搅拌的时间为5min-30min、搅拌速度为200rpm-400rpm；将第一分散液与粘合剂组合物中的绝缘填料混合，形成第二分散液，可选地，混合为第二搅拌，第二搅拌的时间为30min-120min、搅拌速度为1200rpm-1800rpm；将第二分散液与粘合剂组合物中的第一粘合剂混合，形成第三分散液，可选地，混合为第三搅拌，第三搅拌的时间为15min-60min、搅拌速度为400rpm-700rpm；将第三分散液与粘合剂组合物中的第二粘合剂混合，形成胶液，可选地，混合为第四搅拌，第四搅拌的时间为5min-30min、搅拌速度为200rpm-400rpm。
本申请的第五方面提供了一种二次电池，包括正极极片，其中，正极极片包括上述第三方面提供的任意一种的正极极片或上述第四方面提供的任意一种制备方法制备的正极极片。
本申请的第六方面提供了一种用电装置，包括二次电池，其中，二次电池包括上述第五方面提供的任意一种二次电池。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1为本申请一实施方式提供的正极极片的侧视图。
图2是本申请一实施方式的二次电池的示意图。
图3是图2所示的本申请一实施方式的二次电池的分解图。
图4是本申请一实施方式的电池模块的示意图。
图5是本申请一实施方式的电池包的示意图。
图6是图5所示的本申请一实施方式的电池包的分解图。
图7是本申请一实施方式的二次电池用作电源的用电装置的示意图。
在附图中，附图并未按照实际的比例绘制。
附图标记说明：
10正极极片；11正极集流体；12正极膜层；13绝缘胶层；
1电池包；2上箱体；3下箱体；4电池模块；5二次电池；51壳体；52电极组件；53顶盖组件。
具体实施方式
下面结合附图和实施例对本申请的实施方式作进一步详细描述。以下实施例的详细描述和附图用于示例性地说明本申请的原理，但不能用来限制本申请的范围，即本申请不限于所描述的实施例。
以下，适当地参照附图详细说明具体公开了本申请的粘合物质、粘合剂组合物、正极极片、二次电池和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式。例如，所述“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
[粘合物质]
二次离子电池工作中总是避免不了震动，随着震动的发生，电芯中极耳也会存在相对的运动，从而形成内部摩擦。但是，常规的绝缘胶层的耐磨性不够，极耳的相对运动将造成涂层磨损、极片漏箔，从而造成电芯内部短路。
为了解决上述问题，在本申请第一种实施方式中，提供了一种粘合物质，包括粘合剂，粘合剂包括结构单元A、结构单元B、结构单元C和结构单元D，至少部分结构单元A与至少部分结构单元D交联，其中，结构单元A为结构单元B各自独立地为 中的任意一种或多种，可选地，结构单元B为 结构单元C各自独立地为中的任意一种，各m1和各m2各自独立地为1-20的任意整数，可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；结构单元D各自独立地为 中的任意一种或多种，n1各自独立地为1-20的任意整数，可选地，n1为1至12的任意整数，进一步可选地n1为1至6的任意整数。
上述粘合物质的粘合剂中，结构单元B经丙烯腈单体提供，该单体为硬单体可增强绝缘胶层的强度；结构单元C由丙烯酸酯类单体提供，丙烯酸酯类为软单体，可提高绝缘胶层的柔韧性，同时可增强绝缘胶层与集流体的粘结力。
同时，结构单元A和结构单元D通过氢键相互作用形成三维交联网络，使得所形成的绝缘胶层具有较佳的抗磨性能，能隔离电芯入壳时极耳弯折导致的极耳根部与正极极片边缘有效接触与摩擦，有效控制产生极耳与正极膜层短接问题。另一方面，上述各结构单元A、C和D均为丙烯酸类单体的聚合物，其中的丙烯酸类物质具有耐高温、不易分解的性能，因此所形成的绝缘胶层可避免正极极片的集流体直接受激光切割，有效抵御金属颗粒飞溅，而且激光在绝缘胶层中切割不易产生金属熔珠颗粒，有效地缓解了激光直接切割集流体导致的金属颗粒飞溅击穿隔膜问题；同时，上述三维交联网路也进一步增强了对激光切割的抵抗能力，更好地实现了对隔膜的保护作用。
在一些实施方式中，至少部分结构单元A、至少部分结构单元B、至少部分结构单元C和至少部分结构单元D呈链状连接形成第一链结构，至少部分结构单元A、至少部分结构单元C和至少部分结构单元D呈链状连接形成第二链结构；至少部分第一链结构中的结构单元A与至少部分第二链结构中的结构单元D交联；至少部分第一链结构中的结构单元D与至少部分第二链结构中的结构单元A交联。
第一链结构和第二链结构同时含有结构单元A和结构单元D，为结构单元A和结构单元D的交联提供更多的位点，从而进一步改善所形成的三维网络的致密性，更好地改善粘合物质的耐磨性；第一链结构同时含有结构单元A、结构单元B、结构单元C和结构单元D，一方面更有利于利用结构单元B和结构单元C的含量调整控制该链结构所提供的强度；第二链结构同时含有结构单元A、结构单元C和结构单元D，其柔韧性更好，可以利用其更灵活地调整结构单元C的含量，进而更灵活地调整粘合物质的粘结力。
在本申请一些实施方式中，粘合物质满足以下条件中的任意一种或多种：1)粘合物质形成厚度为5μm的绝缘胶层的耐磨性满足以下要求：采用RCA纸带耐磨测试机测试，利用55g砝码与平面走带300mm、2圈后形成实验区，在实验区取n个测试点且测试点的间距不小于2cm，实验区中未漏点数占比在30％以上，其中5≤n≤100，或者实验区中未漏点的面积为实验区总面积的60％以上；2)粘合物质形成的绝缘胶层的内聚力为620N/m-750N/m，可选为660N/m-725N/m；3)粘合物质形成的绝缘胶层 的邵氏硬度为45HA-80HA，可选为50HA-65HA；4)粘合物质形成的绝缘胶层的粘结力为30N/m-90N/m，可选为40N/m-80N/m。
上述内聚力的测试方法如下：
将粘合物质制备成浆料后涂覆于涂炭铜箔的涂炭层，经过烘干，得到样品片，样品片的一面为铜箔面，另一面为粘合物质形成的胶层；后将样品片裁切为尺寸大小为宽2cm，长为6cm长的样条；将该样条的铜箔面用3M-55230H双面胶粘结于硬基底(钢板)表面(注意粘贴过程中无气泡)。将固定好的样条的胶层面粘结3M-55230H双面胶，并在双面胶表面覆盖与双面胶相同尺寸的铜箔(注意粘贴过程无气泡)，两次所用双面胶尺寸相同，得到测试样品。
将测试样品第一端的铜箔与双面胶整体向其180°方向手动剥离一段距离，使其向后超出整个测试样品的第一端对向(即第二端)1cm。应用拉力测试机一端夹具固定第一端(硬基底、涂炭铜箔、胶层)；拉力测试机另一端夹具固定第二端。
设置拉力试验机拉伸速度为50mm/min，测试拉伸长度为100mm进行测试。测试中的所获取的剥离力数据即为涂层材料的内聚力。
上述硬度的测试方法如下：采用邵氏A型硬度测试仪对绝缘胶层表面的硬度进行测试。
上述粘结力的测试方法如下：
具体为：
取待测试正极极片，正极极片外观良好，不允许外观坏品。用刀片截取宽20mm、长度为100-160mm的正极极片的具有绝缘胶层的试样。将专用双面胶NITTO.NO5000NS贴于钢板上，胶带宽度10mm、长度90-150mm；将宽度与试样等宽，长度大于试样长度80-200mm的纸带固定在双面胶上，且纸带上面设置皱纹胶；将上述截取的固定尺寸试样贴在皱纹胶上，绝缘胶层面朝下，后用3kg压辊在试样表面同一个方向滚压三次，得到测试样品。将测试样品固定在试验机上，钢板未贴极片的一端用下夹具固定，将纸带向上翻折，用上夹具固定，试样轴线方向与施力方向保持一致，试验机以10mm/min剥离速度加载，直至试样断裂，停止测试，记录最大负载力为F(单位N)，试样宽度L＝20mm，根据f1＝F/L，计算剥离强度f1(单位N/m)。剥离强度即为粘结力。
在本申请一些实施方式中，上述粘合剂中，结构单元D和结构单元A的摩尔比为0.5:1-5:1，比如：0.5:1、1:1、1.1:1、2:1、2.1:1、2.2:1、2.5:1、2.7:1、2.8:1、2.9:1、3:1、3.2:1、3.5:1、3.8:1、4:1、4.5:1或5:1，可选为0.5:1-3:1，进一步可选为1:1-3:1；可选地，结构单元A的摩尔含量为4％-50％，比如为4％、4.5％、4.8％、5％、5.3％、5.5％、6％、6.2％、6.4％、6.8％、7％、10％、15％、20％、30％、40％或50％，可选为4％-10％，结构单元D的摩尔含量为1％-50％，比如为1％、4％、5％、6％、8％、10％、13％、14％、15％、20％、30％、40％或50％，可选为5％-30％，进一步可选为 5％-15％。从而尽可能利用结构单元A和结构单元D的交联提高粘合物质形成的绝缘胶层的耐磨性。
在本申请一些实施方式中，上述粘合剂中，结构单元C和结构单元B的摩尔比为1:1-300:1，比如为：1:1、5:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1、50:1、60:1、100:1、150:1、200:1、250:1、280:1、290:1或300:1；可选为5:1-50:1；结构单元B的含量的摩尔含量为0.2％-20％，比如为0.2％、0.25％、0.5％、1％、1.5％、2％、2.1％、2.5％、3％、3.5％、5％、10％、11％、13％、15％或20％，可选为1％-5％；可选地，结构单元C的摩尔含量为1％-90％，比如5％、10％、20％、30％、40％、45％、50％、55％、58％、60％、68％、70％、75％、77％、78％、80％、85％或90％，可选为55％-90％，进一步可选为75％-80％。利用上述结构单元B和结构单元C的比例控制，尽可能改善粘合物质的粘结力。
本申请的一些实施方式中，上述粘合物质还包括绝缘填料和/或分散剂，绝缘填料的使用降低了成本，分散剂促进了绝缘填料在粘合剂中的分散效果；而且上述结构单元A的羧基可与绝缘填料形成氢键从而提高所形成的绝缘胶层的粘合力。
本申请的一些实施方式中，绝缘填料、粘合剂和分散剂的比例可以参考常规粘合物质的组成，在一些实施方式中，绝缘填料、粘合剂和分散剂的重量比为(70-90):(10-25):0.4。既可以利用绝缘填料降低成本，分散剂既可以实现改善绝缘填料在粘合剂中的分散效果，又避免了对粘合剂后续交联的发挥，而且有充分多的粘合剂提供较好的粘结力。
绝缘填料可以采用粘合剂中常用的绝缘填料，考虑到粘合剂组合物应用于正极极片中，且后续需要耐受激光辐射，绝缘填料可选择600℃以上、典型的是700℃以上、例如900℃以上的温度下不软化、不熔融、能够使正极与负极绝缘的具有耐热性且电化学稳定的无机材料。
在一些实施方式中，绝缘填料包括氧化铝、氧化镁、二氧化硅、二氧化钛、钛酸钡、氮化铝、氮化硅、氢氧化钙、氢氧化镁、氢氧化铝、云母、滑石、勃姆石、沸石、磷灰石、高岭土或玻璃粉中的任意一种或多种。上述各绝缘填料的硬度有所不同，其的勃姆石硬度更为适中，既可以改善绝缘胶层的稳定性而且不会引硬度对电池的隔膜产生负面影响。
在一些实施方式中，为了进一步改善绝缘填料在粘合剂中的分散效果同时避免填料粒径过大对隔膜的影响，可选地，绝缘填料的DV50粒径≤1μm。该粒径范围内的绝缘填料能够完全包埋在常规厚度的绝缘层中，从而有效地控制了绝缘填料对隔膜的摩擦。上述Dv50表示体积平均粒径，是指材料累计体积分布百分数达到50％时所对应的粒径，其测试方法可以参照标准GB/T 19077-2016，使用激光粒度分析仪(例如Malvern Master Size 3000)进行测定。
用于本申请粘合物质的分散剂可以从常规的有利于绝缘填料分散的分散剂中进行 选择，在一些实施方式中，上述分散剂包括聚丙烯酸酯类化合物、脂肪醇聚醚类化合物、聚醚改性硅氧烷类化合物中的一种或多种，比如岳阳凯门水性助剂有限公司的Chemadd-6004、陶氏化学的Elaecpure LW-10；当不包含溶剂时，粘合物质的包装和运输更为方便；包含溶剂时粘合物质的使用更为方便。固含量不同粘合物质的粘度不同，施工的可涂覆性不同，固化条件也存在差异，本领域技术人员可以根据施工要求选择固含量在一些实施方式中，可选地粘合物质的固含量为20％-40％，以提高施工和固化效率。可选地粘合物质在25℃、12rpm下测得的粘度为550mPa·s。
在一些实施方式中，为了节约成本、提高操作环境的安全性，进一步可选地粘合物质的溶剂包括水，即提供水系的粘合剂。
[粘合剂组合物]
在本申请的第二实施方式中，提供了一种粘合剂组合物，包括粘合剂，其中，粘合剂包括第一粘合剂和第二粘合剂，第一粘合剂为聚合物，包括结构单元A、结构单元B、结构单元C和结构单元D，第二粘合剂为聚合物，包括结构单元A、结构单元C和结构单元D，
其中，结构单元A为
结构单元B各自独立地为 中的任意一种或多种，可选地，结构单元B为第一粘合剂的结构单元C和第二粘合剂的结构单元C 各自独立地为各m1和各m2各自独立地为1-20的整数，比如m1为1、2、3、4、5、6、8、10、12、13、14、15、16、18或20，m1为1、2、3、4、5、6、8、10、12、13、14、15、16、18或20；可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；第一粘合剂的结构单元D和第二粘合剂的结构单元D各自独立地为n1各自独立地为1-20的任意整数，比如n1为1、2、3、4、5、6、8、10、12、13、14、15、16、18或20，可选地n1各自独立地为1-12的任意整数；进一步可选地n1各自独立地为1-6的任意整数。
当将该粘合剂组合物应用于正极极片制备绝缘胶层时，第一粘合剂中结构单元B经丙烯腈单体提供，该单体为硬单体可增强绝缘胶层的强度；第一粘合剂和第二粘合剂中的结构单元C由丙烯酸酯类单体提供，丙烯酸酯类为软单体，可提高绝缘胶层的柔韧性，同时可增强绝缘胶层与集流体的粘结力。
同时，一方面第一粘合剂中的结构单元A和第二粘合剂中的结构单元D、第一粘合剂中的结构单元D和第二粘合剂中的结构单元A通过氢键相互作用形成三维交联网络，使得所形成的绝缘胶层具有较佳的抗磨性能，能隔离电芯入壳时极耳弯折导致的极耳根部与正极极片边缘有效接触与摩擦，有效控制产生极耳与正极膜层短接问题。另一方面，该粘合剂组合物的第一粘合剂和第二粘合剂均为丙烯酸类单体的聚合物，其中的丙烯酸类物质具有耐高温、不易分解的性能，因此所形成的绝缘胶层可避免正极极片的集流体直接受激光切割，有效抵御金属颗粒飞溅，而且激光在绝缘胶层中切割不易产生金属熔珠颗粒，有效地缓解了激光直接切割集流体导致的金属颗粒飞溅击穿隔膜问题；同时，上述三维交联网路也进一步增强了对激光切割的抵抗能力，更好地实现了对隔膜的保护作用。
在本申请一些实施方式中，为了进一步改善粘合剂组合物所形成的绝缘胶层的综合性能，可选择第一粘合剂和第二粘合剂的重量比为1:2.5-1:20，比如可以为1:17.5、2:17.5、4:17.5、1:5、2:12.5、2:15或1:10；可选为1:5-1:17.5。第二粘合剂的用量相对于第一粘合剂的用量较多，利用第一粘合剂为绝缘胶层提供较好的粘结力和柔韧性， 同时利用适量的第二粘合剂提高绝缘胶层的强度，从而更好地与粘合剂组合物中的绝缘填料的强度以及正极集流体强度相适应，使得粘结力得到充分发挥；而且利用上述重量比，调控绝缘胶层的交联网络密实程度，为耐磨性和对集流体的保护提供充分的网络支撑。
本申请的粘合剂组合物中的第一粘合剂和第二粘合剂均可通过丙烯酸类单体以及对应上述结构单元的丙烯酸衍生物单体聚合而成，各结构单元含量不同，粘合剂的性质也会有所不同，为了调节各粘合剂的性质，并使两种粘合剂配合起到更好地协同作用。在本申请的一些实施方式中，第一粘合剂为共聚物，可选地第一粘合剂满足以下条件中的任意一个或多个：1)结构单元A在第一粘合剂中的摩尔含量为5％-30％；2)结构单元B在第一粘合剂中的摩尔含量为5％-85％，可选为5％-55％；3)结构单元C在第一粘合剂中的摩尔含量为5％-85％，可选为35％-85％；4)结构单元D在第一粘合剂中的摩尔含量为5％-15％。利用结构单元B和结构单元C的含量调整第一粘合剂的硬度，以满足不同设计、不同加工方法对绝缘胶层的硬度要求；上述结构单元A和结构单元D的含量在所有结构单元中的含量相对较少，主要用于与第二粘合剂形成交联网络，同时也很好地控制了二者在第一粘合剂中的自交联。
在本申请的一些实施方式中，第二粘合剂为共聚物，可选地第二粘合剂满足以下条件中的任意一个或多个：1)结构单元A在第二粘合剂中的摩尔含量为5％-10％；2)结构单元C在第二粘合剂中的摩尔含量为70％-85％；3)结构单元D在第二粘合剂中的摩尔含量为5％-20％。第二粘合剂中结构单元C占主要比例，从而为第二粘合剂提供更加充分的柔韧性和粘结力，从而提高了粘合剂组合物所形成的绝缘胶层对绝缘填料和正极集流体的粘合力。
本申请的粘合剂组合物中的第一粘合剂和第二粘合剂的粘结对象是绝缘填料和基材，由于重力作用绝缘填料在粘合剂组合物形成的胶液中存在沉降现象，沉降现象特别严重时会对绝缘胶层在基材上的粘结力产生影响。在本申请一些实施方式中，第一粘合剂的重均分子量为50万-150万；具有上述重均分子量的第一粘合剂的粘度较高，因此对绝缘填料起到较好的悬浮作用，有效地阻止了绝缘填料的沉降，提高了绝缘胶层的粘结力。
第二粘合剂的柔韧性和流动性较好，对绝缘填料的悬浮作用不如第一粘合剂。但是第二粘合剂也具有常规聚合物的特点，即随着分子量的增加其粘度增加，在一些实施方式中，仍然以第二粘合剂为粘合剂组合物形成的胶液提供充分的流动性，便于施工。进一步可选地第一粘合剂和第二粘合剂的重均分子量的差值为0-150万。上述差值可以为第一粘合剂的重均分子量大于第二粘合剂的重均分子量时的差值，也可以为第一粘合剂的重均分子量小于第二粘合剂的重均分子量的差值。
在一些实施方式中，粘合物质还包括绝缘填料和/或分散剂。本申请的粘合剂组合物中绝缘填料的使用降低了组合物成本，分散剂促进了绝缘填料在粘合剂中的分散效果；另外羧基可与绝缘填料形成氢键从而提高所形成的绝缘胶层的粘合力。
绝缘填料、粘合剂和分散剂的比例可以参考常规粘合剂组合物的组成，在一些实施方式中，绝缘填料、粘合剂和分散剂的重量比为(70-90):(10-25):0.4。既可以利用绝缘填料降低成本，分散剂既可以实现改善绝缘填料在粘合剂中的分散效果，又避免了对粘合剂后续交联的发挥，而且有充分多的粘合剂提供较好的粘结力。
绝缘填料可以采用粘合剂中常用的绝缘填料，考虑到粘合剂组合物应用于正极极片中，且后续需要耐受激光辐射，绝缘填料可选择600℃以上、典型的是700℃以上、例如900℃以上的温度下不软化、不熔融、能够使正极与负极绝缘的具有耐热性且电化学稳定的无机材料。
在一些实施方式中，上述绝缘填料包括氧化铝、氧化镁、二氧化硅、二氧化钛、钛酸钡、氮化铝、氮化硅、氢氧化钙、氢氧化镁、氢氧化铝、云母、滑石、勃姆石、沸石、磷灰石、高岭土或玻璃粉中的任意一种或多种。上述各绝缘填料的硬度有所不同，其的勃姆石硬度更为适中，既可以改善绝缘胶层的稳定性而且不会引硬度对电池的隔膜产生负面影响。
在一些实施方式中，为了进一步改善绝缘填料在粘合剂中的分散效果同时避免填料粒径过大对隔膜的影响，可选地，绝缘填料的DV50粒径≤1μm。该粒径范围内的绝缘填料能够完全包埋在常规厚度的绝缘层中，从而有效地控制了绝缘填料对隔膜的摩擦。
用于本申请粘合剂组合物的分散剂可以从常规的有利于绝缘填料分散的分散剂中进行选择，在一些实施方式中，上述分散剂包括聚丙烯酸酯类化合物、脂肪醇聚醚类化合物、聚醚改性硅氧烷类化合物中的一种或多种，比如岳阳凯门水性助剂有限公司的Chemadd-6004、陶氏化学的Elaecpure LW-10。
在一些实施方式中，上述粘合剂组合物还包括溶剂；当不包含溶剂时，粘合剂组合物的包装和运输更为方便；包含溶剂时粘合剂组合物的使用更为方便。固含量不同粘合剂组合物的粘度不同，施工的可涂覆性不同，固化条件也存在差异，本领域技术人员可以根据施工要求选择固含量在一些实施方式中，可选地粘合剂组合物的固含量为20％-40％，以提高施工和固化效率。在一些实施方式中，为了节约成本、提高操作环境的安全性，进一步可选地粘合剂组合物的溶剂包括水，即提供水系的粘合剂。
在一些实施方式中，粘合剂组合物也的耐磨性、内聚力、硬度和粘结力也满足上述粘合物质的要求，在此不再赘述。
本申请粘合剂组合物中所用的第一粘合剂和第二粘合剂均可参考现有技术的制备方法制备而成或者采用已知材料。为了便于本领域技术人员实施本申请，提供以下制备方法供参考。
第一粘结剂：在10℃-30℃下，将表面活性剂溶于水中，依次加入单体A CH2＝CHCOOH、单体B CH2＝CHCN、单体C CH2＝CHCOO(CH2)m1CH3和单体D CH2＝CHCOO(CH2)n1OH、链转移剂(比如正十二基硫醇)，共混均匀，期间通入氮气 进行除氧保护，形成预乳液，将预乳液升温至80℃-90℃，得到预乳液。将表面活性剂(比如双烷基磺基琥珀酸酯盐M-30S)溶于去离子水中，加入到反应釜中搅拌，使用氮气除氧保护，升温至80℃-90℃，得到反应型表面活性剂溶液。用去离子水配制过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，滴加完毕，保温得到丙烯酸(酯)共聚物种子溶液。用去离子水配制过硫酸铵溶液，作为第二引发剂溶液，第二引发剂溶液的浓度大于第一引发剂溶液的浓度，将第二引发剂溶液滴加加入到丙烯酸(酯)共聚物种子溶液中，持续滴加100min-150min，滴加完毕，保温1h-3h，得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物溶液降温至60℃-70℃，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持10min-50min，然后放气至大气压，过滤，得到水性粘结剂乳液。后调pH至7-8。
第二粘结剂：在10℃-30℃下，将表面活性剂溶于水中，依次加入单体A CH2＝CHCOOH、单体C CH2＝CHCOO(CH2)m1CH3、单体D CH2＝CHCOO(CH2)n1OH、链转移剂(比如正十二基硫醇)，共混均匀，期间通入氮气进行除氧保护，形成预乳液，将预乳液升温至80℃-90℃，得到预乳液。将表面活性剂(比如双烷基磺基琥珀酸酯盐M-30S)溶于去离子水中，加入到反应釜中搅拌，使用氮气除氧保护，升温至80℃-90℃，得到反应型表面活性剂溶液。用去离子水配制过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，滴加完毕，保温得到丙烯酸(酯)共聚物种子溶液。用去离子水配制过硫酸铵溶液，作为第二引发剂溶液，第二引发剂溶液的浓度大于第一引发剂溶液的浓度，将第二引发剂溶液滴加加入到丙烯酸(酯)共聚物种子溶液中，持续滴加100min-150min，滴加完毕，保温1h-3h，得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物溶液降温至60℃-70℃，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持10min-50min，然后放气至大气压，过滤，得到水性粘结剂乳液。后调pH至7-8。
[二次电池]
二次电池又称为充电电池或蓄电池，是指在电池放电后可通过充电的方式使活性材料激活而继续使用的电池。
通常情况下，二次电池包括正极极片、负极极片、隔离膜及电解质。在电池充放电过程中，活性离子(例如锂离子)在正极极片和负极极片之间往返嵌入和脱出。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使活性离子通过。电解质在正极极片和负极极片之间，主要起到传导活性离子的作用。
上述粘合剂组合物可以考虑应用于二次电池中需要粘合剂的位置，或者是考虑作为隔离膜的原料使用。在一些实施方式中，将其应用于正极极片中。
[正极极片]
如图1所示，正极极片10通常包括正极集流体11以及设置在正极集流体11至少一侧的正极膜层12，正极膜层12包括正极活性材料。
作为示例，正极集流体11具有在其自身厚度方向相对的两个表面，正极膜层12设置在正极集流体11相对的两个表面的其中任意一者或两者上。
如图1所示，正极集流体11除了设置正极膜层12外，在正极膜层12外周还存在空箔区，在本申请一些实施方式中，正极极片10还包括绝缘胶层13，设置在正集流体11的空箔区，其中，绝缘胶层13采用上述任意实施方式提供的粘合剂组合物固化而成。绝缘胶层13在空箔区的具体设置位置可以以现有技术为参考，比如避让开极耳根部。
正极极片10中的绝缘胶层13由本申请上述的粘合剂组合物固化而成，一方面第一粘合剂中的结构单元A和第二粘合剂中的结构单元D、第一粘合剂中的结构单元D和第二粘合剂中的结构单元A通过氢键相互作用形成三维交联网络，使得绝缘胶层具有较佳的抗磨性能，能隔离电芯入壳时极耳弯折导致的极耳根部与正极极片边缘有效接触与摩擦，有效控制产生极耳与正极膜层短接问题。另一方面，该粘合剂组合物的第一粘合剂和第二粘合剂均为丙烯酸类单体的聚合物，其中的丙烯酸类物质具有耐高温、不易分解的性能，因此绝缘胶层可避免正极极片的集流体直接受激光切割，有效抵御金属颗粒飞溅，而且激光在绝缘胶层中切割不易产生金属熔珠颗粒，有效地缓解了激光直接切割集流体导致的金属颗粒飞溅击穿隔膜问题；同时，上述三维交联网路也进一步增强了对激光切割的抵抗能力，更好地实现了对隔膜的保护作用。
此外，第一粘合剂、第二粘合剂的羧基可与绝缘填料形成氢键从而提高绝缘胶层的粘合力。第一粘合剂中结构单元B经丙烯腈单体提供，该单体为硬单体可增强绝缘胶层的强度；第一粘合剂和第二粘合剂中的结构单元C由丙烯酸酯类单体提供，丙烯酸酯类为软单体，可提高绝缘胶层的柔韧性，同时可增强绝缘胶层与集流体的粘结力。
上述正极极片10的绝缘胶层13的厚度可以以绝缘胶层的常规厚度作为参考，或者根据电池的设计要求设置厚度，在一些实施方式中，上述绝缘胶层13的厚度小于或等于正极膜层12的厚度，可选地，绝缘胶层13的厚度为3μm-7μm。既可以实现对正极集流体11的保护作用，又避免因绝缘胶层12厚度过大导致电芯体积增加。
上述绝缘胶层的形成过程可以参考常规技术，比如通过涂覆的方式。在一些实施方式中，形成绝缘胶层的过程包括：将粘合剂组合物混合形成胶液；将胶液涂覆在正极集流体的空箔区，得到具有胶液的预制件；对具有胶液的预制件加热，得到绝缘胶层，可选地加热的温度为90℃-120℃，以加快其中的溶剂脱除速度。
在一些实施方式中，为了提高粘合剂组合物中各组分混合的均匀性，将粘合剂组合物混合形成浆液的过程包括:
将粘合剂组合物中的分散剂与水混合，形成第一分散液，可选地，混合为第一 搅拌，第一搅拌的时间为5min-30min、搅拌速度为200rpm-400rpm；
将第一分散液与粘合剂组合物中的绝缘填料混合，形成第二分散液，可选地，混合为第二搅拌，第二搅拌的时间为30min-120min、搅拌速度为1200rpm-1800rpm；
将第二分散液与粘合剂组合物中的第一粘合剂混合，形成第三分散液，可选地，混合为第三搅拌，第三搅拌的时间为15min-60min、搅拌速度为400rpm-700rpm；
将第三分散液与粘合剂组合物中的第二粘合剂混合，形成胶液，可选地，混合为第四搅拌，第四搅拌的时间为5min-30min、搅拌速度为200rpm-400rpm。
上述过程中，根据所混合对象不用调整搅拌的时间和速度，利用搅拌改善各组分的混合效果。
在一些实施方式中，正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，当二次电池为锂离子二次电池时，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO2)、锂镍氧化物(如LiNiO2)、锂锰氧化物(如LiMnO2、LiMn2O4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333)、LiNi0.5Co0.2Mn0.3O2(也可以简称为NCM523)、LiNi0.5Co0.25Mn0.25O2(也可以简称为NCM211)、LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622)、LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811)、锂镍钴铝氧化物(如LiNi0.85Co0.15Al0.05O2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
当二次电池为钠离子二次电池时，作为示例，钠离子二次电池的正极活性材料可包括以下材料中的至少一种：钠过渡金属氧化物、聚阴离子型化合物和普鲁士蓝类化合物中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作钠离子电池正极活性材料的传统公知的材料。
作为本申请可选的技术方案，钠过渡金属氧化物中，过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种。钠过渡金属氧化物例如为 NaxMO2，其中M为Ti、V、Mn、Co、Ni、Fe、Cr及Cu中的一种或几种，0＜x≤1。
作为本申请可选的技术方案，聚阴离子型化合物可以是具有钠离子、过渡金属离子及四面体型(YO4)n‐阴离子单元的一类化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种；Y可以是P、S及Si中的至少一种；n表示(YO4)n‐的价态。
聚阴离子型化合物还可以是具有钠离子、过渡金属离子、四面体型(YO4)n‐阴离子单元及卤素阴离子的一类化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种；Y可以是P、S及Si中的至少一种，n表示(YO4)n‐的价态；卤素可以是F、Cl及Br中的至少一种。
聚阴离子型化合物还可以是具有钠离子、四面体型(YO4)n‐阴离子单元、多面体单元(ZOy)m+及可选的卤素阴离子的一类化合物。Y可以是P、S及Si中的至少一种，n表示(YO4)n‐的价态；Z表示过渡金属，可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种，m表示(ZOy)m+的价态；卤素可以是F、Cl及Br中的至少一种。
聚阴离子型化合物例如是NaFePO4、Na3V2(PO4)(3磷酸钒钠，简称NVP)、Na4Fe3(PO4)2(P2O7)、NaM’PO4F(M’为V、Fe、Mn及Ni中的一种或几种)及Na3(VOy)2(PO4)2F3‐2y(0≤y≤1)中的至少一种。
普鲁士蓝类化合物可以是具有钠离子、过渡金属离子及氰根离子(CN‐)的一类化合物。过渡金属可以是Mn、Fe、Ni、Co、Cr、Cu、Ti、Zn、V、Zr及Ce中的至少一种。普鲁士蓝类化合物例如为NaaMebMe’c(CN)6，其中Me及Me’各自独立地为Ni、Cu、Fe、Mn、Co及Zn中的至少一种，0＜a≤2，0＜b＜1，0＜c＜1。
在一些实施方式中，正极膜层还可选地包括粘合剂。作为示例，粘合剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施方式中，正极膜层还可选地包括导电剂。作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘合剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层， 所述负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施方式中，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施方式中，负极活性材料可采用本领域公知的用于电池的负极活性材料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料和钛酸锂等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施方式中，负极膜层还可选地包括粘合剂。作为示例，粘合剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施方式中，负极膜层还可选地包括导电剂。作为示例，导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施方式中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施方式中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘合剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[电解质]
电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可以是液态的、凝胶态的或全固态的。
在一些实施方式中，电解质为液态的，且包括电解质盐和溶剂。
在一些实施方式中，用于锂离子二次电池的电解质盐可包括六氟磷酸锂、四氟硼酸锂、高氯酸锂、六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂或四氟草酸磷酸锂中的一种或多种。用于钠离子二次电池的电解质盐可包括六氟磷酸钠(NaPF6)、四氟硼酸钠(NaBF4)、六氟砷酸钠(NaAsF6)、三氟乙酸钠(CF3COONa)、三氟甲磺酸钠(CF3NaO3S，NaOTf)或四苯硼钠(NaBPh4)中的一种或多种。
在一些实施方式中，溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸甲乙酯、碳酸二乙酯、碳酸二甲酯、碳酸二丙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸亚丁酯、氟代碳酸亚乙酯、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丁酸甲酯、丁酸乙酯、1,4-丁内酯、环丁砜、二甲砜、甲乙砜及二乙砜中的至少一种。
在一些实施方式中，电解液还可选地包括添加剂。作为示例，添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
[隔离膜]
在一些实施方式中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施方式中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制成电极组件。
在一些实施方式中，二次电池包括二次电池单体，或者包括电池模组和电池包。
在一些实施方式中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施方式中，二次电池的外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。
本申请对二次电池单体的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图2是作为一个示例的方形结构的二次电池单体5。
在一些实施方式中，参照图3，外包装可包括壳体51和盖板53。其中，壳体 51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件52。电极组件52封装于所述容纳腔内。电解液浸润于电极组件52中。二次电池单体5所含电极组件52的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施方式中，二次电池单体可以组装成电池模块，电池模块所含二次电池单体的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图4是作为一个示例的电池模块4。参照图4，在电池模块4中，多个二次电池单体5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池单体5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池单体5容纳于该容纳空间。
在一些实施方式中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。
图5和图6是作为一个示例的电池包1。参照图5和图6，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，所述用电装置包括本申请提供的二次电池。所述二次电池可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。
作为所述用电装置，可以根据其使用需求来选择二次电池单体、电池模块或电池包。
图7是作为一个示例的用电装置。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
[实施例]
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域 内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
第一粘合剂(结构单元B为)的制备过程如下：
在20℃工作温度下，将5.4g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于62g去离子水中，依次加入单体A CH2＝CHCOOH、单体B CH2＝CHCN、单体C CH2＝CHCOO(CH2)m1CH3和单体D CH2＝CHCOO(CH2)n1OH，链转移剂正十二基硫醇0.058g，转速为350rpm，25min共混均匀，期间通入氮气保护，流量为110mL/min，形成预乳液，将预乳液以2℃/min的升温速度，升温至85℃，保温30min，得到预乳液。将3.8g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于61.3g去离子水中，加入到反应釜中，转速为300rpm，使用氮气除氧保护，流量为100mL/min，以2℃/min的升温速度，升温至88℃，保温30min，得到反应型表面活性剂溶液。用去离子水配制3.5g过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，160min滴加完毕，保温0.5h，得到种子溶液。用去离子水配制1.0g过硫酸铵引发剂溶液，作为第二引发剂溶液，将第二引发剂溶液滴加入到种子溶液中，持续滴加120min，滴加完毕，保温2h得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物以2℃/min的降低速度，降温至65℃，保温30min，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持30min，然后放气至大气压，过300目滤布，得到固含量为50％第二粘合剂乳液。后调pH值至7-8。该第一粘合剂的固含量为15％。
通过调整各单体的组成或用量调整第一粘合剂的组成，得到的第一粘合剂1至第一粘合剂21的组成记录在表1-1中。
第一粘合剂22(结构单元B为)的制备过程如下：
在20℃工作温度下，将5.4g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于62g去离子水中，依次加入单体A CH2＝CHCOOH、单体B苯乙烯、单体C CH2＝CHCOO(CH2)m1CH3和单体D CH2＝CHCOO(CH2)n1OH，链转移剂正十二基硫醇0.058g，转速为350rpm，25min共混均匀，期间通入氮气保护，流量为110mL/min，形成预乳液，将预乳液以2℃/min的升温速度，升温至85℃，保温30min，得到预乳液。将3.8g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M- 30S溶于61.3g去离子水中，加入到反应釜中，转速为300rpm，使用氮气除氧保护，流量为100mL/min，以2℃/min的升温速度，升温至88℃，保温30min，得到反应型表面活性剂溶液。用去离子水配制3.5g过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，160min滴加完毕，保温0.5h，得到种子溶液。用去离子水配制1.0g过硫酸铵引发剂溶液，作为第二引发剂溶液，将第二引发剂溶液滴加入到种子溶液中，持续滴加120min，滴加完毕，保温2h得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物以2℃/min的降低速度，降温至65℃，保温30min，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持30min，然后放气至大气压，过300目滤布，得到固含量为50％第二粘合剂乳液。后调pH值至7-8。该第一粘合剂的固含量为15％。
第一粘合剂23(结构单元B为)的制备过程如下：
在20℃工作温度下，将5.4g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于62g去离子水中，依次加入单体A CH2＝CHCOOH、单体B甲基丙烯酸甲酯、单体C CH2＝CHCOO(CH2)m1CH3和单体D CH2＝CHCOO(CH2)n1OH，链转移剂正十二基硫醇0.058g，转速为350rpm，25min共混均匀，期间通入氮气保护，流量为110mL/min，形成预乳液，将预乳液以2℃/min的升温速度，升温至85℃，保温30min，得到预乳液。将3.8g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于61.3g去离子水中，加入到反应釜中，转速为300rpm，使用氮气除氧保护，流量为100mL/min，以2℃/min的升温速度，升温至88℃，保温30min，得到反应型表面活性剂溶液。用去离子水配制3.5g过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，160min滴加完毕，保温0.5h，得到种子溶液。用去离子水配制1.0g过硫酸铵引发剂溶液，作为第二引发剂溶液，将第二引发剂溶液滴加入到种子溶液中，持续滴加120min，滴加完毕，保温2h得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物以2℃/min的降低速度，降温至65℃，保温30min，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持30min，然后放气至大气压，过300目滤布，得到固含量为50％第二粘合剂乳液。后调pH值至7-8。该第一粘合剂的固含量为15％。
第一粘合剂24(结构单元C为甲基丙烯酸月桂酯CH3CH2＝CHCOO(CH2)12CH3)的制备过程如下：
在20℃工作温度下，将5.4g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于62g去离子水中，依次加入单体A CH2＝CHCOOH、单体B CH2＝CHCN、单体C CH3CH2＝CHCOO(CH2)12CH3和单体D CH2＝CHCOO(CH2)n1OH，链转移剂正十二基硫醇0.058g，转速为350rpm，25min共混均匀，期间通入氮气保 护，流量为110mL/min，形成预乳液，将预乳液以2℃/min的升温速度，升温至85℃，保温30min，得到预乳液。将3.8g反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于61.3g去离子水中，加入到反应釜中，转速为300rpm，使用氮气除氧保护，流量为100mL/min，以2℃/min的升温速度，升温至88℃，保温30min，得到反应型表面活性剂溶液。用去离子水配制3.5g过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，160min滴加完毕，保温0.5h，得到种子溶液。用去离子水配制1.0g过硫酸铵引发剂溶液，作为第二引发剂溶液，将第二引发剂溶液滴加入到种子溶液中，持续滴加120min，滴加完毕，保温2h得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物以2℃/min的降低速度，降温至65℃，保温30min，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持30min，然后放气至大气压，过300目滤布，得到固含量为50％第二粘合剂乳液。后调pH值至7-8。该第一粘合剂的固含量为15％。
表1-1
表1-1中的分子量为取整万位后的重均分子量，测试方法可以参照标准GB/T 21863-2008，使用超高效聚合物色谱仪进行测定。
第二粘合剂的制备过程如下：
在20℃工作温度下，将4.2g(4.2％)反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于58g(116％)去离子水中，依次加入单体A CH2＝CHCOOH、单体C CH2＝CHCOO(CH2)m1CH3、单体D CH2＝CHCOO(CH2)n1OH，链转移剂正十二基硫醇0.048g(0.096％)，转速为300rpm，30min共混均匀，期间通入氮气进行除氧保护，流量为100mL/min，形成预乳液，将预乳液以2℃/min的升温速度，升温至85℃，保温30min，得到预乳液。将2.8g(2.8％)反应型表面活性剂含双键基的双烷基磺基琥珀酸酯盐M-30S溶于51.3g(102.6％)去离子水中，加入到反应釜中，转速为300rpm，使用氮气除氧保护，流量为100mL/min，以2℃/min的升温速度，升温至86℃，保温30min，得到反应型表面活性剂溶液。用去离子水配制3g(0.15wt％)过硫酸铵溶液，作为第一引发剂溶液，将预乳液和第一引发剂溶液同时连续滴加加入反应釜里的反应型表面活性剂溶液中，150min滴加完毕，保温0.5h，得到丙烯酸(酯)共聚物种子溶液。用去离子水配制1.0g(0.1wt％)过硫酸铵引发剂溶液，作为第二引发剂溶液，将第二引发剂溶液滴加加入到丙烯酸(酯)共聚物种子溶液中，持续滴加120min，滴加完毕，保温2h得到丙烯酸(酯)共聚物溶液。将反应釜内丙烯酸(酯)共聚物以2℃/min的降低速度，降温至65℃，保温30min，自然降温至室温，减压抽气，反应釜中真空度低于0.09mpa，保持30min，然后放气至大气压，过300目滤布，得到固含量为50％第二粘合剂乳液。后调pH值至7-8。
通过调整各单体的组成和用量调整第二粘合剂的组成，得到的第二粘合剂1至第二粘合剂12的组成记录在表1-2中。
表1-2
表1-2中的分子量为取整万位后的重均分子量，测试方法可以参照标准GB/T21863-2008，使用超高效聚合物色谱仪进行测定。
实施例1
将分散剂加入至去离子水中，300rpm分散搅拌15min，得第一分散液；
将绝缘填料加入上述第一分散液中，1500rpm分散搅拌75min，得第二分散液；
将第一粘合剂乳液加入上述第二分散液中，1500rpm分散搅拌60min，得第三分散液；
将第二粘合剂乳液加入上述第三分散液中，500rpm分散60min，得胶液。其中分散剂、绝缘填料、第一粘合剂和第二粘合剂所用的具体物质和用量均记录在表2中。
实施例2至47：
参照实施例1的过程制备对应的胶液，各实施例的分散剂、绝缘填料、第一粘合剂(干物质)和第二粘合剂(干物质)所用的具体物质和用量均记录在表2中。
对比例1
将分散剂加入至去离子水中，300rpm分散搅拌15min，得第一分散液；
将绝缘填料加入上述第一分散液中，1500rpm分散搅拌75min，得第二分散液；
将第一粘合剂乳液加入上述分散液中，1500rpm分散搅拌60min，得胶液。其中分散剂、绝缘填料、第一粘合剂所用的具体物质和用量均记录在表2中。
对比例2
将分散剂加入至去离子水中，300rpm分散搅拌15min，得第一分散液；
将绝缘填料加入上述第一分散液中，1500rpm分散搅拌75min，得第二分散液；
将第二粘合剂乳液加入上述第二分散液中，1500rpm分散搅拌60min，得胶液。
其中分散剂、绝缘填料、第二粘合剂所用的具体物质和用量均记录在表2中。
各实施例和对比例所用分散剂均为岳阳凯门水性助剂有限公司的Chemadd-6004，质量份为0.4份。
粘度测试：在25℃、12rpm下测试胶液的旋转粘度，结果记录在表3中。
耐磨性测试：采用5μm刮刀将上述各胶液分别刮涂于13μm的铝箔上，转移至100℃烘箱中烘干，制备待测试绝缘胶层。
RCA纸带耐磨测试机(标格达精密仪器(广州)有限公司BGD 530)；测试原理：电机驱动纸带匀速经过测试样品表面的一个区域，并施加一定的压力，对测试表面进行磨损；测试方法：5μm厚度待测试绝缘胶层，55g砝码与平面走带300mm(2圈)后，记录实验区未漏的点数(共测试10点)在表3中，同时记录漏点的面积，以此计算未漏点的面积在实验区的总面积的比例。
评价标准：相同压力下，未磨出光铝箔，纸带走过越长，越耐磨；或相同走带长度下测试多点未漏光箔点数量，数量越多越耐磨。
内聚力的测试：
将粘合物质制备成浆料后涂覆于涂炭铜箔的涂炭层，经过烘干，得到样品片，样品片的一面为铜箔面，另一面为粘合物质形成的胶层；后将样品片裁切为尺寸大小为宽2cm，长为6cm长的样条；将该样条的铜箔面用3M-55230H双面胶粘结于硬基底(钢板)表面(注意粘贴过程中无气泡)。将固定好的样条的胶层面粘结3M-55230H双面胶，并在双面胶表面覆盖与双面胶相同尺寸的铜箔(注意粘贴过程无气泡)，两次所用双面胶尺寸相同，得到测试样品。
将测试样品第一端的铜箔与双面胶整体向其180°方向手动剥离一段距离，使其向后超出整个测试样品的第一端对向(即第二端)1cm。应用拉力测试机一端夹具固定第一端(硬基底、涂炭铜箔、胶层)；拉力测试机另一端夹具固定第二端。
设置拉力试验机拉伸速度为50mm/min，测试拉伸长度为100mm进行测试。测试中的所获取的剥离力数据即为涂层材料的内聚力。结果记录在表3中。
硬度的测试：采用邵氏A型硬度测试仪对绝缘胶层表面的硬度进行测试。结果记录在表3中。
粘结力的测试：
采用5μm刮刀将上述各胶液分别刮涂于13μm的铝箔上，转移至100℃烘箱中烘干，制备待测试绝缘胶层。
用刀片截取宽20mm、长度为100-160mm的上述具有绝缘胶层的试样。将专用双面胶NITTO.NO5000NS贴于钢板上，胶带宽度20mm、长度90-150mm；将宽度与试样等宽，长度大于试样长度80-200mm的纸带固定在双面胶上，且纸带上面设置皱纹胶；将上述截取的固定尺寸试样贴在皱纹胶上，绝缘胶层面朝下，后用3kg压辊在试样表面同一个方向滚压三次，得到测试样品。将测试样品固定在试验机上，钢板未贴极片的一端用下夹具固定，将纸带向上翻折，用上夹具固定，试样轴线方向与施力方向保持一致，试验机以10mm/min剥离速度加载，直至试样断裂，停止测试，记录 最大负载力为F(单位N)，试样宽度L＝20mm，根据f1＝F/L，计算剥离强度f1(单位N/m)，剥离强度即为粘结力。结果记录在表3中。
耐热性测试：采用TG-DSC技术对测试涂层样品进行热重分析，记录热分解温度在表3中。
表3

根据各实施例和对比例的对比可以看出，本申请的粘合剂组合物形成的绝缘胶层的耐磨性明显优于第一粘合剂1或第二粘合剂1单独应用时的耐磨性；而且第一粘合剂1的粘度过大，单独使用时不利于施工且粘结力太低；第二粘合剂1的粘度过小，影响施工性能进而影响成膜效果。
实施例2、实施例4和5的对比、以及实施例1、实施例6至9的对比可以看出，当第一粘合剂中结构单元B的含量增加，结构单元C的含量减小时，即第一粘合剂的硬单体结构单元含量增加，导致对应的粘合剂组合物的粘结力有所减小。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件。尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (23)

  1. 一种粘合物质，包括粘合剂，其中，所述粘合剂包括结构单元A、结构单元B、结构单元C和结构单元D，至少部分所述结构单元A与至少部分所述结构单元D交联；
    其中，所述结构单元A为
    其中，所述结构单元B各自独立地为 中的任意一种或多种，可选地，所述结构单元B为
    所述结构单元C各自独立地为中的任意一种，各m1和各m2各自独立地为1-20的任意整数，可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；
    所述结构单元D各自独立地为中的任意一种或多种，
    n1各自独立地为1-20的任意整数，可选地，n1为1至12的任意整数，进一步可选地n1为1至6的任意整数。
  2. 根据权利要求1所述的粘合物质，其中，
    至少部分所述结构单元A、至少部分所述结构单元B、至少部分所述结构单元C和至少部分所述结构单元D呈链状连接形成第一链结构，
    至少部分所述结构单元A、至少部分所述结构单元C和至少部分所述结构单元D呈链状连接形成第二链结构；
    至少部分所述第一链结构中的结构单元A与至少部分所述第二链结构中的结构单元D交联；
    至少部分所述第一链结构中的结构单元D与至少部分所述第二链结构中的结构单元A交联。
  3. 根据权利要求1或2所述的粘合物质，其中，所述粘合物质满足以下条件中的任意一种或多种：
    1)所述粘合物质形成厚度为3μm-7μm的绝缘胶层的耐磨性满足以下要求：采用RCA纸带耐磨测试机测试，利用55g砝码与平面走带300mm、2圈后形成实验区，在所述实验区取n个测试点且测试点的间距不小于2cm，实验区中未漏点数占比在30％以上，其中5≤n≤100，或者所述实验区中未漏点的面积为所述实验区总面积的60％以上；
    2)所述粘合物质形成的绝缘胶层的内聚力为620N/m-750N/m，可选为660N/m-725N/m；
    3)所述粘合物质形成的绝缘胶层的邵氏硬度为45HA-80HA，可选为50HA-65HA；
    4)所述粘合物质形成的绝缘胶层的粘结力为30N/m-90N/m，可选为40N/m-80N/m。
  4. 根据权利要求1至3中任一项所述的粘合物质，其中，所述粘合剂中，所述结构单元D和所述结构单元A的摩尔比为0.5:1-5:1，可选为0.5:1-3:1，进一步可选为1:1-3:1；可选地，所述结构单元A的摩尔含量为4％-50％，可选为4％-10％，所述结构单元D的摩尔含量为1％-50％，可选为5％-30％，进一步可选为5％-15％。
  5. 根据权利要求1至4中任一项所述的粘合物质，其中，所述粘合剂中，所述结构单元C和所述结构单元B的摩尔比为1:1-300:1，可选为5:1-50:1；可选地，所述结构单元B的含量的摩尔含量为0.2％-20％，可选为1％-5％；可选地，所述结构单元C的摩尔含量为1％-90％，可选为55％-90％，进一步可选为75％-80％。
  6. 根据权利要1至5中任一项所述的粘合物质，其中，所述粘合物质还包括绝缘填料和/或分散剂；可选地，所述绝缘填料、所述粘合剂和所述分散剂的重量比为(70-90):(10-25):0.4。
  7. 根据权利要求6所述的粘合物质，其中，所述绝缘填料包括氧化铝、氧化镁、二氧化硅、二氧化钛、钛酸钡、氮化铝、氮化硅、氢氧化钙、氢氧化镁、氢氧化铝、云母、滑石、勃姆石、沸石、磷灰石、高岭土或玻璃粉中的任意一种或多种；可选地，所述绝缘填料的体积平均粒径DV50≤1μm。
  8. 根据权利要求1至7中任一项所述的粘合物质，其中，所述粘合物质还包括溶剂；可选地所述粘合物质的固含量为20％-40％；
    可选地所述粘合物质的溶剂包括水；
    可选地所述粘合物质在25℃、12rpm下测得的粘度在350mPa·s-900mPa·s。
  9. 一种粘合剂组合物，包括粘合剂，其中，所述粘合剂包括第一粘合剂和第二粘合剂，
    所述第一粘合剂为聚合物，包括结构单元A、结构单元B、结构单元C和结构单元D，
    所述第二粘合剂为聚合物，包括结构单元A、结构单元C和结构单元D，
    其中，所述结构单元A为
    所述结构单元B各自独立地为 中的任意一种或多种，可选地，所述结构单元B为
    所述第一粘合剂的结构单元C和所述第二粘合剂的结构单元C各自独立地为
    各m1和各m2各自独立地为1-20的任意整数；可选地，m1各自独立地为2至12的任意整数，m2各自独立地为8-12的任意整数；
    所述第一粘合剂的结构单元D和所述第二粘合剂的结构单元D各自独立地为
    n1各自独立地为1-20的任意整数，可选地n1各自独立地为1-12的任意整数；进一步可选地n1各自独立地为1-6的任意整数。
  10. 根据权利要求9所述的粘合剂组合物，其中，所述第一粘合剂和所述第二粘合剂的重量比为1:2.5-1:20，可选为1:5-1:17.5。
  11. 根据权利要求9或10所述的粘合剂组合物，其中，所述第一粘合剂满足以下条件中的任意一个或多个：
    1)所述结构单元A在所述第一粘合剂中的摩尔含量为5％-30％；
    2)所述结构单元B在所述第一粘合剂中的摩尔含量为5％-85％；
    3)所述结构单元C在所述第一粘合剂中的摩尔含量为5％-85％；
    4)所述结构单元D在所述第一粘合剂中的摩尔含量为5％-15％。
  12. 根据权利要求9至11中任一项所述的粘合剂组合物，其中，所述第二粘合剂满足以下条件中的任意一个或多个：
    1)所述结构单元A在所述第二粘合剂中的摩尔含量为5％-10％；
    2)所述结构单元C在所述第二粘合剂中的摩尔含量为70％-85％；
    3)所述结构单元D在所述第二粘合剂中的摩尔含量为5％-20％。
  13. 根据权利要求9至12中任一项所述的粘合剂组合物，其中，所述第一粘合剂的重均分子量为50万-150万；进一步可选地所述第一粘合剂和所述第二粘合剂的重均分子量的差值为10万-150万。
  14. 根据权利要求9至13中任一项所述的粘合剂组合物，其中，所述粘合剂组合物还包括绝缘填料和/或分散剂；可选地，所述绝缘填料、所述粘合剂和所述分散剂的重量比为(70-90):(10-25):0.4。
  15. 根据权利要求14所述的粘合剂组合物，其中，所述绝缘填料包括氧化铝、氧化镁、二氧化硅、二氧化钛、钛酸钡、氮化铝、氮化硅、氢氧化钙、氢氧化镁、氢氧化铝、云母、滑石、勃姆石、沸石、磷灰石、高岭土或玻璃粉中的任意一种或多种；可选地，所述绝缘填料的体积平均粒径DV50≤1μm。
  16. 根据权利要求14或15所述的粘合剂组合物，其中，所述分散剂包括聚丙烯酸酯类化合物、脂肪醇聚醚类化合物或聚醚改性硅氧烷类化合物中的一种或多种。
  17. 根据权利要求9至16中任一项所述的粘合剂组合物，其中，所述粘合剂组合物还包括溶剂；可选地所述粘合剂组合物的固含量为20％-40％；进一步可选地所述粘合剂组合物的溶剂包括水。
  18. 一种正极极片，包括：
    正极集流体(11)，所述正极集流体(11)的至少一侧具有正极膜层区和空箔区；
    正极膜层(12)，设置在所述正极集流体(11)的正极膜层区；
    绝缘胶层(13)，设置在所述正极集流体(11)的空箔区，其中，所述绝缘胶层(13)采用权利要求1至8中任一项所述的粘合物质形成，或者通过权利要求9至17中任一项所述的粘合剂组合物固化而成。
  19. 根据权利要求18所述的正极极片，其中，所述绝缘胶层(13)的厚度小于或等于所述正极膜层(12)的厚度，可选地，所述绝缘胶层(13)的厚度为3μm-7μm。
  20. 一种正极极片的制备方法，包括在正极集流体(11)的至少一侧或两侧设置正极膜层和绝缘胶层的过程，其中，设置所述绝缘胶层(13)的过程包括：
    将权利要求1至8中任一项所述的粘合物质或权利要求9至17中任一项所述的粘合剂组合物的组分混合形成胶液；
    将所述胶液涂覆在所述正极集流体的空箔区，得到具有胶液的预制件；
    对所述具有胶液的预制件加热，得到所述绝缘胶层，可选地所述加热的温度为90℃-120℃。
  21. 根据权利要求20所述的制备方法，其中，将所述粘合剂组合物的组分混合形成浆液的过程包括:
    将所述粘合剂组合物中的分散剂与水混合，形成第一分散液，可选地，所述混合为第一搅拌，所述第一搅拌的时间为5min-30min、搅拌速度为200rpm-400rpm；
    将所述第一分散液与所述粘合剂组合物中的绝缘填料混合，形成第二分散液，可选地，所述混合为第二搅拌，所述第二搅拌的时间为30min-120min、搅拌速度为1200rpm-1800rpm；
    将所述第二分散液与所述粘合剂组合物中的第一粘合剂混合，形成第三分散液，可选地，所述混合为第三搅拌，所述第三搅拌的时间为15min-60min、搅拌速度为400rpm-700rpm；
    将所述第三分散液与所述粘合剂组合物中的第二粘合剂混合，形成所述胶液，可选地，所述混合为第四搅拌，所述第四搅拌的时间为5min-30min、搅拌速度为200rpm-400rpm。
  22. 一种二次电池，包括正极极片，其中，所述正极极片包括权利要求18或19所述的正极极片、或权利要求20或21所述的制备方法得到的正极极片。
  23. 一种用电装置，包括二次电池，其中，所述二次电池包括权利要求22所述的二次电池。
PCT/CN2023/127666 2023-08-15 2023-10-30 粘合物质、粘合剂组合物、正极极片、二次电池和用电装置 Pending WO2025035596A1 (zh)

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JP2025536045A JP2026501212A (ja) 2023-08-15 2023-10-30 粘着物質、粘着剤組成物、正極極板、二次電池および電力消費装置
EP23949016.2A EP4671337A1 (en) 2023-08-15 2023-10-30 ADHESION SUBSTANCE, ADHESIVE COMPOSITION, POSITIVE ELECTRODE SHEET, SECONDARY BATTERY AND ELECTRICAL DEVICE
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