WO2023193399A1 - Core-shell resin material and preparation method therefor, water-based polymer coating, battery separator, and secondary battery - Google Patents

Core-shell resin material and preparation method therefor, water-based polymer coating, battery separator, and secondary battery Download PDF

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Publication number
WO2023193399A1
WO2023193399A1 PCT/CN2022/116296 CN2022116296W WO2023193399A1 WO 2023193399 A1 WO2023193399 A1 WO 2023193399A1 CN 2022116296 W CN2022116296 W CN 2022116296W WO 2023193399 A1 WO2023193399 A1 WO 2023193399A1
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Prior art keywords
core
resin material
shell resin
separator
shell
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PCT/CN2022/116296
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French (fr)
Chinese (zh)
Inventor
曹江
朱克均
余磊
汤皎宁
夏悦
卢智聪
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深圳市德立新材料科技有限公司
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Publication of WO2023193399A1 publication Critical patent/WO2023193399A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/18—Homopolymers or copolymers of nitriles
    • C08J2433/20—Homopolymers or copolymers of acrylonitrile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application belongs to the field of battery technology, and in particular relates to a core-shell resin material and its preparation method, aqueous polymer coating, battery separator, and secondary battery.
  • the service life, cost, and cruising range of the battery are very critical. This requires that the cycle life of the battery must reach more than 3,000 times, the battery cost must be less than 0.8 yuan/Wh, and the cruising range must be more than 600km. That is, the car can run more than 600km every time it is fully charged.
  • battery safety performance and battery power performance are also core indicators for the development of battery technology.
  • lithium-ion secondary batteries have been widely used in the global electric vehicle market. High-performance, high-safety lithium-ion secondary batteries have put forward new requirements for battery materials and battery structure design. For example, BYD's lithium iron phosphate blade batteries have effectively improved the safety and energy density of the battery through structural design.
  • High-safety, high-performance lithium-ion secondary batteries have gradually transformed from traditional liquid batteries to solid or semi-solid (dry or gel) batteries.
  • domestic and foreign battery manufacturers usually use the process to produce dry or gel batteries.
  • the surface of the separator is coated with absorbable electrolyte resin, such as PVDF-HFP, acrylic copolymer, and the functional separator coated with the resin is used to assemble the battery core to obtain a semi-solid battery.
  • the separator resin coating process is divided into oil-based process and water-based process.
  • the oil-based coating process usually uses N,N-dimethylpyrrolidone or acetone as the solvent.
  • solvent loss and recycling cause the cost of coating separators to remain high, and the production process is still There are safety and environmental risks.
  • the water-based polymer coating materials used in commercially coated separators mainly include water-based PVDF-HFP and water-based acrylic copolymers. Such materials usually The emulsion or suspension material is applied to the surface of the separator. After drying, the material adheres to the surface of the separator in the form of sub-micron particles.
  • the French Arkma model LBG PVDF-HFP currently used in the industry has a primary particle size of 200nm.
  • Type particles, acrylate copolymer (AFL) coating material provided by Japan Zeon Company emulsion particle size is about 400nm.
  • the coating separator In order for a water-based polymer coating to meet the requirements of battery applications, on the one hand, it must achieve excellent interfacial recombination force at the interface between the coating and the electrode. On the other hand, the coating separator must maintain good ion conductivity during long-term use of the battery to avoid coating The material blocks the pores of the separator, causing the internal resistance of the battery to increase and the cycle performance to decrease. In order to meet the requirements of battery applications, the swelling of the coated polymer particles needs to be controlled to prevent the particles from swelling too much in the electrolyte and blocking the pores of the separator.
  • PVDF-HFP the molecular chain contains PVDF with a crystalline structure and HFP with a non-crystalline structure, HFP content
  • the crystallinity of the material becomes lower and the swelling of the material increases.
  • the swollen particles block the pores of the separator and cause the battery cycle to deteriorate.
  • the HFP content is too low or even does not contain HFP, the crystallinity of the material increases, the electrolyte resistance becomes stronger, the swelling is low, and the separator pores are not blocked, but the electrode interface recombination force is poor and cannot meet the application requirements. Therefore, the water-based PVDF-HFP used in the battery industry achieves a balance between material swelling and electrode interface adhesion properties by controlling the appropriate HFP content.
  • amorphous polyester water-based polymers cannot meet battery application requirements by controlling the crystallization balance.
  • the AFL coating material of Japan's Zeon Company shows good interfacial adhesion between the coating and the electrode. Adhesive force, but the mass swelling at room temperature in the electrolyte reaches 300%, which can easily block the pores of the separator and increase the internal resistance of the battery.
  • the technical problem to be solved by this application is to provide a core-shell resin material and preparation method, aqueous polymer coating, battery separator, and secondary battery, aiming to solve the problem that the existing coating separator has a high swelling rate and is easy to block the pores of the separator. .
  • a core-shell resin material includes a resin core and a resin outer layer wrapped around the surface of the core.
  • the resin core includes a three-dimensional cross-linked network structure
  • the resin outer layer includes a plasticized linear semi-reciprocal network structure.
  • a method for preparing a core-shell resin material includes at least the following steps:
  • Preparing resin particles forming a resin coating layer containing a plasticizer on the surface of the resin particles to obtain core-shell resin particles;
  • the resin core and the resin coating layer are cross-linked to obtain a core-shell resin material.
  • a water-based polymer coating includes a mixture of core-shell resin material and other auxiliaries, wherein the core-shell resin material is the core-shell resin material provided by the present application or the core-shell resin material prepared by the preparation method.
  • a battery separator includes a separator body and a functional coating formed on the surface of the separator body by the water-based polymer coating in the embodiment of the present application.
  • a secondary battery includes a positive electrode and a negative electrode and a separator for isolating the positive electrode and the negative electrode.
  • the separator is the battery separator in the above embodiment of the present application.
  • the core-shell resin material provided by this application includes a resin core and a resin outer layer wrapped on the surface of the core.
  • the three-dimensional cross-linked network of the core has a very low swelling degree, and then the inner layer structure is covered by the outer layer structure.
  • the plasticizer is inserted into the layer structure to form a plasticized linear semi-reciprocal network structure, thereby increasing the electrode interface adhesion of the core-shell resin material. Therefore, the core-shell resin material can be used in battery separator materials, and its coating function The separator has good electrode interface bonding performance and ion transport performance.
  • the preparation method of the core-shell resin material provided by this application first prepares a resin core, and forms a resin coating layer containing a plasticizer on the surface of the resin core to obtain resin particles with a core-shell structure.
  • the resin core and the resin outer layer are The resin particles undergo a cross-linking reaction, which can increase the cross-linking degree of the core-shell resin material and reduce its swelling rate.
  • This application uses the above-mentioned core-shell resin material provided by this application and other additives to form a water-based polymer coating so as to form a film layer on the substrate.
  • the core-shell resin material provided by the above-mentioned embodiments of the present application has a low swelling rate and will be dispersed in other additives in a stable particle state.
  • due to the good interfacial connection performance of the core-shell resin material provided by the above-mentioned embodiments of the present application it has It is beneficial for the water-based polymer coating provided by the present application to form a film layer on the substrate.
  • the secondary battery provided by this application includes the above-mentioned battery separator in this application.
  • the battery separator maintains good ion conductivity and improves the internal resistance of the battery caused by the blocking of the separator pores by the coating material and the decrease in battery cycle performance. The problem.
  • Figure 1 is a schematic diagram of the spherical particle structure of the star-shaped intertransmission network provided by the embodiment of the present application;
  • Figure 2 is a TEM image of the primary particles of the functional coating material provided by the embodiment of the present application.
  • Figure 3 is an SEM image of the secondary particles of the functional coating material provided by the embodiment of the present application.
  • Figure 4 is an SEM image of the separator functional coating material provided by the embodiment of the present application after being air-pulverized
  • Figure 5 is a partially enlarged SEM image of Figure 4 provided by the embodiment of the present application.
  • Figure 6 is an SEM image of a functional coating separator with a coating amount of 0.6 g/ m2 provided by the embodiment of the present application.
  • the first aspect of the embodiment of the present application provides a core-shell resin material, which includes a resin core and a resin outer layer wrapped on the surface of the core.
  • the resin core includes a three-dimensional cross-linked network structure
  • the resin outer layer includes a plasticized linear semi-reciprocal network. structure.
  • the core-shell resin material provided in the embodiment of the present application has a resin core and a resin outer layer wrapped around the surface of the core.
  • the molecules in the inner layer are aggregated and solidly distributed in the center of the spherical particles, forming a three-dimensional cross-link. Network structure, the swelling degree of the core three-dimensional cross-linked network is extremely low, and then the inner layer structure is covered by the outer layer structure, and a plasticizer is inserted into the outer layer structure to form a plasticized linear semi-reciprocal network structure, thereby increasing the core-shell resin material
  • the core-shell resin material can be used in battery separator materials because of its excellent electrode interface adhesion.
  • the coated functional separator has good electrode interface adhesion and ion transport performance.
  • the core-shell resin material includes star-shaped mutual transmission network spherical particles, and the secondary particle size of the material may be a spherical particle structure.
  • the primary particle size of the core-shell resin material is 200 to 400 nm, and the secondary particle size is 5 to 40 ⁇ m, so that the slurry can be subsequently prepared for the coating process.
  • the material forming the resin core includes a first main monomer, a first functional monomer, an emulsifier and a first initiator, wherein the first main monomer and the first A functional monomer can be polymerized into a resin core under the action of an emulsifier.
  • the first main monomer includes methyl methacrylate, 2-ethyl methacrylate, methyl acrylate, styrene, acrylonitrile, ethyl acrylate, isooctyl acrylate, dodecyl acrylate, In stearyl acrylate, 1,3-butadiene, butyl acrylate, a-cyanoacrylate, butyl methacrylate, ethyl methacrylate, hydroxypropyl acrylate, phosphate acrylate, vinyl acetate At least one.
  • the first main monomer provided in the embodiments of the present application can form a matrix in the spherical core of the three-dimensional cross-linked network after polymerization, and can reduce the swelling degree of the spherical core of the three-dimensional cross-linked network.
  • the first functional monomer includes acrylic acid, hydroxyethyl acrylate, divinylbenzene, N-hydroxymethylacrylamide, N,N methylenebisacrylamide, 1,4-butanediol bisacrylamide Acrylate, methacrylic acid, hydroxyethyl methacrylate, diacetone acrylamide, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol Diacrylates with different polyethylene glycol molecular weights such as alcohol diacrylate, polyethylene glycol diacrylate, silane coupling agent KH570, ethylene glycol dimethacrylate, polypropylene glycol glycidyl ether, diacetone acrylamide, At least one kind of divinylbenzene.
  • the first functional monomer provided by the embodiment of the present application can modify the matrix of the spherical core of the three-dimensional cross-linked network, further reducing the swelling degree of the three-
  • the emulsifier includes sodium stearate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene ether OP series, stearic acid polyoxyethylene ether series, etc. At least one of Wen series, Triton 100, allyl ether sulfonates, acrylamide sulfonates, maleic acid derivatives, and sodium allyl alkyl succinate sulfonate.
  • the emulsifier provided in the embodiments of the present application can emulsify the first main monomer, the first functional monomer and the first initiator to form a core structure.
  • the alkylphenol polyoxyethylene ether OP series includes at least one of OP-4, OP-7, OP-9, OP-10, OP-13, OP-15 and OP-20.
  • the Twain series includes at least one of 20, 40, 60, and 80.
  • the emulsifier provided in the embodiments of the present application can further improve the reaction rate and is low in cost.
  • the first initiator includes benzoyl oxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanitrile, diisopropylperoxide At least one of dicyclohexyl carbonate, cumene hydroperoxide, potassium persulfate, and ammonium persulfate.
  • the first initiator provided in the embodiments of the present application can initiate the polymerization of the first main monomer and the first functional monomer, and can control the reaction rate.
  • the material forming the resin outer layer includes a second main monomer, a second functional monomer, a second initiator, an organic solvent and a plasticizer.
  • the second main monomer, the second functional monomer, the second initiator, the organic solvent and the plasticizer provided in the embodiments of the present application can be polymerized under certain conditions to form the material of the outer layer.
  • the second primary monomer includes methyl methacrylate, 2-ethyl methacrylate, methyl acrylate, styrene, acrylonitrile, ethyl acrylate, isooctyl acrylate, dodecyl acrylate, In stearyl acrylate, 1,3-butadiene, butyl acrylate, a-cyanoacrylate, butyl methacrylate, ethyl methacrylate, hydroxypropyl acrylate, phosphate acrylate, vinyl acetate At least one.
  • the second main monomer provided in the embodiments of the present application can form a matrix in the outer layer of a linear semi-reciprocal network structure after polymerization, and can reduce the electrode interface adhesion of the spherical outer layer of the three-dimensional cross-linked network.
  • the second functional monomer includes acrylic acid, hydroxyethyl acrylate, divinylbenzene, N-hydroxymethylacrylamide, N,N methylene bisacrylamide, 1,4-butanediol bisacrylamide Acrylate, methacrylic acid, hydroxyethyl methacrylate, diacetone acrylamide, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol Diacrylates with different polyethylene glycol molecular weights such as alcohol diacrylate, polyethylene glycol diacrylate, silane coupling agent KH570, ethylene glycol dimethacrylate, polypropylene glycol glycidyl ether, diacetone acrylamide, At least one kind of divinylbenzene.
  • the first functional monomer provided by the embodiment of the present application can modify the outer layer of the linear semi-reciprocal network structure to further reduce the swelling degree of the core three-dimensional cross-linked network.
  • the second initiator includes benzoyl oxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanitrile, diisopropyl peroxide At least one of dicyclohexyl carbonate and cumene hydroperoxide, potassium persulfate and ammonium persulfate.
  • the first initiator provided in the embodiments of the present application can initiate the polymerization of the second main monomer and the second functional monomer, and can control the reaction rate.
  • the organic solvent includes at least one of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
  • the solvent can dissolve the second main monomer and the second functional monomer. Reaction provides a good environment.
  • the plasticizer includes dimethyl phthalate, diethyl phthalate, dioctyl phthalate, butyl benzyl phthalate, dodecanol ester, dipentaerythritol ester , at least one of glyceryl triacetate and citrate.
  • the plasticizer provided in the embodiments of the present application can form a layer of molecules on the surface of the polymer generated by the second main monomer and the second functional monomer, thereby increasing the interface connectivity of the core-shell resin material.
  • the second aspect of the embodiments of the present application provides a method for preparing a core-shell resin material, which includes the following steps:
  • Step S10 Prepare resin particles, form a resin coating layer containing plasticizer on the surface of the resin particles, and obtain core-shell resin particles;
  • Step S20 Perform a cross-linking reaction on the resin core and the resin coating layer to obtain a core-shell resin material.
  • the core-shell resin material preparation method first prepares resin particles, forms a resin coating layer containing plasticizer on the surface of the resin particles, improves the interface connection performance of the core-shell resin particles, and obtains a core-shell structure.
  • the resin particles are used to cross-link the resin core and the resin particles in the outer layer of the resin, which can increase the cross-linking degree of the core-shell resin material and reduce its swelling rate, thereby obtaining the core-shell resin material.
  • the method of preparing resin particles and forming a resin coating layer on the surface of the resin particles includes the following steps:
  • a plasticizer is added to the third reaction liquid to obtain a fourth reaction liquid containing the core-shell resin particles.
  • the preparation method of the core-shell resin material provided by the embodiment of the present application first emulsifies and polymerizes the first main monomer, the first functional monomer, the emulsifier and water, so as to polymerize to form the resin core of the core-shell resin material. Then, a second reaction liquid and a second initiator are added to the first reaction liquid to perform a second polymerization reaction so as to polymerize to form the resin outer layer of the core-shell resin material. Finally, a plasticizer is added to the third reaction liquid. The plasticizer Through the interaction between molecules, it is inserted into the outer molecules to form a resin outer layer containing a plasticized linear semi-reciprocal network structure.
  • the mass ratio of the first main monomer and the first functional monomer is (80 ⁇ 95): (5 ⁇ 20); the sum of the total mass of the first main monomer and the first functional monomer and the emulsification
  • the mass ratio of the agent and the first initiator is 100: (0.1 ⁇ 5): (0.05 ⁇ 0.5).
  • the mass ratio of the second main monomer to the first functional monomer is (50 ⁇ 80): (20 ⁇ 50), and the sum of the total mass of the second main monomer and the second functional monomer is The mass ratio of the second initiator and organic solvent is 100: (0.1 ⁇ 1): (10 ⁇ 50).
  • the method for cross-linking the resin core and the resin coating layer includes the following steps:
  • a cross-linking agent is added to the fourth reaction liquid to perform cross-linking treatment and drying treatment to obtain a core-shell resin material.
  • a cross-linking agent is added to the fourth reaction solution to perform a cross-linking reaction on the outer molecules, which can further fix the plasticizer molecules and increase the overall cross-linking degree of the resin outer layer and the resin core, thereby obtaining a good Plasticized linear semi-reciprocal network structure of electrode interface adhesiveness.
  • the cross-linking agent includes propylene diamine, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, N-hydroxybenzotriazole, N- At least one of hydroxysuccinimide, ethyl orthosilicate, methyl orthosilicate, and trimethylolpropane.
  • the second cross-linking agent can promote the cross-linking of outer molecules and reduce the swelling of the core-shell resin material. rate, and the plasticizer is transferred to the outer molecules.
  • the mass ratio of the cross-linking agent to the cross-linking agent is 100: (0.5 ⁇ 5 ): (0.5 ⁇ 3) is added to the fourth reaction solution by controlling the proportions of the first main monomer, the second main monomer, the first functional monomer, the second functional monomer, the cross-linking agent and the plasticizer. The mass ratio can further improve the electrode interface bonding performance of the material.
  • the fourth reaction solution is also heat-insulated at 25° C. for 2 to 4 hours to prevent denaturation of the first emulsion and improve the formation rate of the outer layer.
  • the temperature of the cross-linking reaction is 100 ⁇ 180°C, which can increase the reaction rate.
  • spray drying is used to perform the drying process.
  • Spray drying can produce a core-shell resin material with a star-shaped mutual transmission network spherical particle structure. Further, please refer to Figures 2 to 3.
  • the core-shell resin material has a particle structure. Please refer to Figures 4 to 5. After the core-shell resin material is pulverized by airflow, the internal structure and secondary particles can be clearly observed. diameter and primary particle size.
  • the primary particle size of the core-shell resin material is 200 ⁇ 400nm, and the secondary particle size is 5 ⁇ 40 ⁇ m for subsequent coating processes.
  • the third aspect of the embodiment of the present application provides a water-based polymer coating, including a mixture of core-shell resin material and other additives, wherein the core-shell resin material is prepared by the core-shell resin material or the preparation method provided in the embodiment of the present application. Core-shell resin material.
  • the core-shell resin material provided in the embodiments of the present application and other additives are mixed to form a water-based polymer coating so as to form a film layer on the substrate.
  • the core-shell resin material provided by the above-mentioned embodiments of the present application has a low swelling rate and will be dispersed in other additives in a stable particle state.
  • the water-based polymer coating provided in the embodiment of the present application it is beneficial for the water-based polymer coating provided in the embodiment of the present application to form a film layer on the substrate.
  • additives in order to give the core-shell resin material some other properties, it is necessary to add some other additives to the core-shell resin material, where other additives also include dispersants, binders, wetting agents, thickeners, at least one defoaming agent.
  • the mass ratio of the core-shell resin material, dispersant, binder, wetting agent, thickener, defoaming agent and water is (5 ⁇ 30): (0.1 ⁇ 1): (0.4 ⁇ 4.5): (0.1 ⁇ 0.5): (0.1 ⁇ 0.5): (0.01 ⁇ 0.1): 100.
  • the dispersing agent includes sodium stearate, vinyl bis stearamide, sodium polyacrylate, sodium polymethacrylate, sodium dodecyl benzene sulfonate, polyethylene glycol, carboxymethyl cellulose At least one kind of sodium is mixed with the core-shell resin material and the dispersant to prevent the core-shell resin material from agglomerating and facilitate the formation of a film layer with uniform performance of the core-shell resin material.
  • the binder includes styrene-acrylic latex binder, styrene-butadiene latex binder, sodium polyacrylate, polyvinylpyrrolidone, polyoxyethylene, polyvinyl alcohol PVA, acrylonitrile and acrylate copolymer, propylene At least one of the copolymers of nitrile and lithium acrylate, the core-shell resin material and the binder are mixed, which can increase the connection performance between the core-shell resin material particles, and cooperate with the dispersant to facilitate the core-shell resin material in A film layer with uniform performance is formed on the surface of the substrate.
  • the wetting agent includes Tween 80, alkyl sulfate, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer, polyether modified At least one of the organic silicones, the core-shell resin material and the wetting agent are mixed, which can reduce the interfacial energy of the core-shell resin material, increase its adhesion on the substrate surface, and cooperate with the dispersant to benefit the core-shell
  • the resin material forms a film layer with uniform performance on the surface of the substrate.
  • the thickening agent includes at least one of carbomer gum, polyacrylamide, sodium hydroxymethylpropylcellulose, polyvinyl methyl ether/methyl acrylate and a cross-linked polymer of decadiene. kind.
  • the defoaming agent includes at least one of a silicone-based defoaming agent and a polyether-based defoaming agent.
  • the silicone-type defoaming agent includes modified polydimethylsiloxane
  • the polyether-type defoaming agent includes polyoxyethylene polyoxypropylene glyceryl ether. Since the core-shell resin material contains polymer materials, curing Fish eyes or bubbles may easily appear locally, so adding a defoamer can improve the overall performance of the core-shell resin material.
  • the fourth aspect of the embodiment of the present application provides a battery separator, which includes a separator body and a functional coating formed on the surface of the separator body by the water-based polymer coating in the embodiment of the present application.
  • the water-based polymer coating can be used in battery separator materials to prevent the battery separator from being blocked.
  • the batteries provided by the embodiments of the present application include lithium-ion batteries, hydrogen energy batteries and solid-state batteries, but are not limited thereto.
  • the core-shell resin material provided by the embodiments of the present application has good connectivity with most base films, where the base film includes PP separator, PE separator, PP/PE/PE film, and PP/PP multi-layer membrane and at least one of its single-sided or double-sided ceramic-coated separators, but is not limited thereto. Furthermore, the thickness of the base film is 5 ⁇ 40 ⁇ m, which can improve the overall performance of the separator.
  • a functional coating with a star-shaped intertransmission network spherical particle structure with an area density of 0.2 ⁇ 1.2 g/m 2 is coated on the base film.
  • a functional coating of 0.6 g/m 2 Can be evenly distributed on the base film.
  • a functional separator with a roll coating amount of 0.3g/ m2 has a recombination force at the interface with the electrode of more than 15 N/m.
  • the functional separator with a spray coating amount of 0.3g/ m2 has a composite force of more than 5 N/m at the interface with the electrode.
  • the coating methods include micro-concave roller coating, printing dot coating, and rotary spray coating, but are not limited to these.
  • the fifth aspect of the embodiment of the present application provides a secondary battery, including a positive electrode and a negative electrode and a separator for isolating the positive electrode and the negative electrode.
  • the separator is the battery separator in the above-mentioned embodiment of the present application.
  • the secondary battery provided by the embodiment of the present application includes the battery separator in the above embodiment of the present application, because the battery separator of the present application can maintain good ion conductivity during long-term use of the battery, thereby improving the blocking of the separator pores by the coating material. This causes the internal resistance of the battery to increase and the cycle performance of the battery to decrease.
  • the first aspect of this embodiment provides a core-shell resin material, which includes a resin core and a resin outer layer wrapped on the surface of the core.
  • the resin core includes a three-dimensional cross-linked network sphere, and the resin outer layer is a plasticized linear semi-reciprocal network structure. .
  • the second aspect of the embodiment provides a core-shell resin material preparation method, including the following steps:
  • Step S10 Take methyl methacrylate, acrylonitrile, butyl acrylate, and isooctyl acrylate as the first main monomers, and their mass ratio is 4:4:1:1.
  • the total amount of emulsifier is 5wt of the total monomer mass. %, configured as reaction solution A, monomer concentration 30%. Take the initiator potassium persulfate with a mass of 0.3wt% of the total monomer mass to prepare a solution with a concentration of 1mol/L for later use.
  • Step S20 Take acrylonitrile, styrene, stearyl acrylate, butyl acrylate, and ethyl acrylate as the second main monomer, and the mass ratio is 3:3:1:2.5:0.5.
  • the second initiator benzoyl peroxide accounts for 0.3% of the total monomer mass, and the monomer concentration is 30%.
  • Step S30 Add reaction solution A into the reaction kettle, raise the temperature to 70°C, and begin to drip the first initiator potassium persulfate solution.
  • the dripping time of the first initiator is 2 hours. After the dripping is completed, keep the temperature for 2 hours and start dripping.
  • Reaction liquid B an appropriate amount of the second initiator benzoyl peroxide is dissolved in reaction liquid B
  • the dripping time is 1 hour, and the temperature is maintained at 70°C for 1 hour.
  • the pressure is raised to 4 atmospheres, and the temperature is maintained for 2 hours. Return to normal pressure to obtain Synthetic lotion, ready to use.
  • Step S40 Add a cross-linking agent propylenediamine with a total solid content of 0.5% to the synthetic emulsion, and pass it through a 160°C spray drying tower to obtain a synthetic membrane functional coating powder for later use.
  • the average primary particle size of the powder is 250nm, and the secondary particle size is 5 ⁇ 40 ⁇ m.
  • the thickener sodium carboxymethyl cellulose CMC is configured into a 10 wt% homogeneous slurry, in which the dispersant accounts for 0.5wt% of the coating material, the wetting agent accounts for 3wt% of the functional powder material, and the adhesive styrene-butadiene latex Accounting for 10wt% of the functional powder material, CMC accounts for 0.5% of the functional powder material, and the defoaming agent accounts for 0.1wt% of the functional powder material.
  • the slurry is used for separator coating.
  • D 90 10.1 ⁇ m, viscosity 19cps.
  • the third aspect of this embodiment provides a lithium-ion battery coating separator, which includes a base film and a functional coating formed on the surface of the base film by a star-shaped mutual transmission network spherical particle structure. Specifically, the core-shell resin material is coated on both sides of the separator.
  • the base film is 9 ⁇ 1 ⁇ m, the porosity is 40 ⁇ 2% wet film, and the micro-gravure roller coating process is used.
  • the coating density is 0.5 ⁇ 0.1g/m 2 and is breathable. The increment is less than 30s, and the diaphragm performance index is tested.
  • This embodiment provides a lithium-ion battery coated separator.
  • the difference from Example 1 is that the core-shell resin material prepared in Example 1 is coated on both sides of the separator using a spraying process, with a coating coverage rate of 15%.
  • the coating surface density is 0.5 ⁇ 0.1 g/m 2 .
  • the base film adopts 9 ⁇ m + single-sided 3 ⁇ m wet ceramic coating separator.
  • the prepared functional coating separator has an air permeability increment of less than 20 seconds. The separator performance indicators are tested.
  • the first aspect of this embodiment provides a core-shell resin material, which includes a core and a spherical particle structure of a star-shaped mutual transmission network wrapped in an outer layer of the core.
  • the resin core includes a three-dimensional cross-linked network sphere, and the resin outer layer is plasticized. Linear semi-mutual transmission network structure.
  • the second aspect of this embodiment provides a core-shell resin material preparation method, including the following steps:
  • Step S10 Take styrene, butyl methacrylate, and isooctyl acrylate as the first main monomer, with a mass ratio of 8:1:1, and take methylhydroxymethacrylate, acrylic acid, and divinylbenzene as the third main monomer.
  • a functional monomer, and the initiator ammonium persulfate The mass ratio of the total mass of the first main monomer to the first functional monomer is 100:5:2:10. Mix them thoroughly and add them to the water.
  • add the emulsifier OP- The mass ratio of 10 to Tween 80 is 1:1.
  • the total amount of emulsifier is 4 wt% of the total monomer mass. It is configured as reaction solution A with a monomer concentration of 35%. Take 0.3 wt% of the initiator ammonium persulfate based on the total monomer mass to prepare a solution with a concentration of 1 mol/L for later use.
  • Step S20 Take acrylonitrile, stearyl acrylate, isooctyl acrylate, and ethyl acrylate as the main monomers, with a mass ratio of 5:1:2:2, take methacrylic acid, and N-methylol acrylamide, a-cyanoacrylate, polyethylene glycol (200) diacrylate as the second functional monomer, benzoyl peroxide as the second initiator, mix with the organic solvent dimethyl carbonate, and prepare reaction solution B, Among them, the mass ratio of the total mass of the second main monomer to the second functional monomer is 100:2:5:2:2.
  • the second initiator azobisisobutyronitrile accounts for 0.3% of the total monomer mass, and the monomer concentration is 35%.
  • Step S20 Add reaction solution A into the reaction kettle, raise the temperature to 85°C, and start to dropwise add the initiator ammonium persulfate solution.
  • the initiator dropwise addition time is 2 hours. After the dropwise addition, keep the temperature for 2 hours, and start dropping reaction solution B ( An appropriate amount of initiator benzoyl peroxide is dissolved in reaction solution B.
  • the total mass of monomers in reaction solution A and the total mass of monomers in reaction solution B are 8:2.
  • the dropping time is 1 hour, and the temperature is maintained at 85°C for 1 hour. Add The plasticizer diethyl phthalate accounting for 1% of the total monomer mass was raised to 4.5 atmospheres at the same time, kept incubated for 2 hours, and returned to normal pressure to obtain a synthetic emulsion, which is ready for use.
  • Step S40 In the synthetic emulsion, add the cross-linking agent propylenediamine and N-hydroxybenzotriazole with a total solid content of 0.6%, the mass ratio of propylenediamine to N-hydroxybenzotriazole is 1:1, pass In the spray drying tower at 150°C, the synthesized membrane functional coating powder is obtained and is ready for use.
  • the average primary particle size of the powder is 300nm, and the secondary particle size is 5 ⁇ 40 ⁇ m.
  • the defoaming agent polyoxyethylene polyoxypropylene glyceryl ether disperse at high speed for 60 minutes, then pass through the homogenizer, adjust the homogenizer pressure to 1000bar, and add the SBR emulsion specifically for lithium batteries after the homogenizer, and the thickener carboxymethyl fiber Sodium, configured into a homogeneous slurry of 7wt%, in which the dispersant accounts for 1wt% of the coating material, the wetting agent accounts for 2wt% of the functional powder material, and the adhesive styrene-butadiene latex accounts for 8wt% of the functional powder material, CMC Accounting for 0.6wt% of the functional powder material, polyoxyethylene polyoxypropylene glyceryl ether accounts for 0.01wt% of the slurry mass.
  • the slurry is used for separator coating.
  • the third aspect of this embodiment provides a lithium-ion battery coating separator, which includes a base film and a functional coating formed on the surface of the base film by a star-shaped mutual transmission network spherical particle structure. Specifically, the core-shell resin material is coated on both sides of the separator.
  • the base film is 12 ⁇ 1 ⁇ m
  • the porosity is 42 ⁇ 2% wet film
  • the micro-gravure roller coating process is used.
  • the coating density is 0.4 ⁇ 0.1g/m 2 and is breathable.
  • the increment is less than 35s, and the diaphragm performance index is tested.
  • This embodiment provides a lithium-ion battery coated separator.
  • the difference from Example 3 is that the separator coating slurry prepared in Example 1 is coated on both sides of the separator using a spraying process, and the coating coverage is 15 %, the coating surface density is 0.5 ⁇ 0.1 g/m 2 , the base film adopts 12 ⁇ m + single-sided 4 ⁇ m wet ceramic coating separator, the prepared functional coating separator has an air permeability increment of less than 30s, and the separator performance indicators are tested.
  • the first aspect of this embodiment provides a core-shell resin material, which includes a core and a spherical particle structure of a star-shaped mutual transmission network wrapped in an outer layer of the core.
  • the resin core includes a three-dimensional cross-linked network sphere, and the resin outer layer is plasticized. Linear semi-mutual transmission network structure.
  • the second aspect of this embodiment provides a core-shell resin material preparation method, including the following steps:
  • Step S10 Take styrene, methyl methacrylate, and butyl methacrylate as the first main monomer, with a mass ratio of 4:4.5:1.5, take hydroxymethyl methacrylate, methacrylic acid, N, and N Methylene bisacrylamide, 1,4-butanediol diacrylate as the first functional monomer, and potassium persulfate as the initiator, wherein the mass ratio of the total mass of the first main monomer to the first functional monomer is 100 : 5:2:2:5, mix thoroughly and add to water.
  • emulsifiers sodium allyl alkyl succinate sulfonate and Tween 80 with a mass ratio of 1:1.
  • the total amount of emulsifier is the total mass of monomers. 3wt%, configured as reaction solution A, monomer concentration 20%. Take the first initiator potassium persulfate with a mass of 0.3 wt% of the total monomer mass to prepare a solution with a concentration of 1 mol/L for later use.
  • Step S20 Take acrylonitrile, methyl methacrylate, butyl acrylate, and ethyl acrylate as the second main monomer, with a mass ratio of 5:1:2:2, take methacrylic acid, and N-hydroxymethylpropylene Amide, a-cyanoacrylate, silane coupling agent KH570 as the second functional monomer, benzoyl peroxide as the second initiator, mix with the organic solvent diethyl carbonate, and configure B reaction liquid, in which the The mass ratio of the total mass of the two main monomers to the second functional monomer is 100:2:5:2:0.5.
  • the second initiator azobisisoheptanitrile accounts for 0.4% of the total monomer mass, and the monomer concentration is 20%.
  • Step S30 Add reaction solution A into the reaction kettle, raise the temperature to 65°C, and start dropping the initiator potassium persulfate solution for 2 hours. After the dropwise addition, keep the temperature for 2 hours, and start adding reaction solution B dropwise ( An appropriate amount of the second initiator azobisisoheptanitrile is dissolved in reaction solution B. The total mass of monomers in reaction solution A and the total mass of monomers in reaction solution B are 7:3. The dropping time is 2 hours, and the temperature is maintained at 65°C for 2 hours.
  • Step S40 In the synthetic emulsion, add cross-linking agents ethyl orthosilicate and N-hydroxybenzotriazole with a total solid content of 0.6%.
  • the mass ratio of ethyl silicate to N-hydroxybenzotriazole is 1: 1.
  • the average primary particle size of the powder is 350nm, and the secondary particle size is 5 ⁇ 40 ⁇ m.
  • the thickener polyacrylamide is configured into a homogeneous slurry of 8 wt%, in which the dispersant accounts for 1wt% of the functional coating powder mass, the wetting agent accounts for 0.2wt% of the overall mass of the slurry, and the adhesive acrylonitrile and acrylic acid
  • the lithium copolymer accounts for 8wt% of the functional powder material
  • the thickener polyacrylamide accounts for 0.1wt% of the slurry mass
  • the defoaming agent polyoxyethylene polyoxypropylene glyceryl ether accounts for 0.01% of the overall slurry mass.
  • the material is used for separator coating.
  • the third aspect of this embodiment provides a lithium-ion battery coating separator, which includes a base film and a functional coating formed on the surface of the base film by a star-shaped mutual transmission network spherical particle structure. Specifically, the core-shell resin material is coated on both sides of the separator.
  • the base film uses a 12 ⁇ m + single-sided 4 ⁇ m dry ceramic coating separator with a porosity of 45 ⁇ 2%. A micro-gravure roller coating process is used, and the coating density is 0.5 ⁇ 0.1g/ m 2 , the air permeability increment is less than 30s, and the membrane performance index is tested.
  • This embodiment provides a lithium-ion battery coated separator.
  • the difference from Example 5 is that the separator functional coating slurry prepared in Example 5 is coated on both sides of the separator using a spraying process, and the coating coverage is 15 %, the coating surface density is 0.5 ⁇ 0.1 g/m 2 , the base film adopts 12 ⁇ m + single-sided 4 ⁇ m dry ceramic coating separator, the prepared functional coating separator has an air permeability increment of less than 30s, and the separator performance indicators are tested.
  • the base film is 9 ⁇ m wet + double-sided roller coated with PVDF-HFP@LBG, and the coating amount is 0.5 ⁇ 0.1g/m 2 .
  • the base film is 9 ⁇ m wet + 3 ⁇ m ceramic on one side + PVDF-HFP@LBG sprayed on both sides, coating amount 0.5 ⁇ 0.1g/m 2 .
  • the base film is 9 ⁇ m wet + 3 ⁇ m ceramic on one side + AFL sprayed on both sides, coating amount 0.2 ⁇ 0.1g/m 2 .
  • Dry pressure bonding test Cut the tested pole pieces and diaphragms into standard samples with a width of 25 ⁇ mm and a length of 200mm, hot press them at 80°C and a pressure of 1MPa for 60 seconds, and then use the 180° peel strength test method.
  • Separator ion conductivity test Use two steel sheets to assemble a simulated battery, use the AC impedance method to measure the DC impedance of the separator, and then calculate its ion conductivity.

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Abstract

The present application belongs to the technical field of batteries, and particularly relates to a core-shell resin material and a preparation method therefor, a water-based polymer coating, a battery separator, and a secondary battery. Provided in the present application is a core-shell resin material, which comprises a resin inner core and a resin outer layer wrapping the surface of the inner core, wherein the resin inner core comprises a three-dimensional cross-linked network structure, and the resin outer layer comprises a plasticized linear semi-interpenetrating network structure. The core-shell resin material provided in the present application comprises a resin inner core and a resin outer layer wrapping the surface of the inner core; the swelling degree of the three-dimensional cross-linked network of the inner core is extremely low, then, the inner layer structure is wrapped by the outer layer structure, and a plasticizer is intercalated into the outer layer structure to form a plasticized linear semi-interpenetrating network structure, thereby improving the electrode interface cohesiveness of the core-shell resin material; therefore, the core-shell resin material can be used in a battery separator material, and a functional separator coated with the core-shell resin material has good electrode interface cohesiveness and ion transmission performance.

Description

核壳树脂材料以及制备方法、水性聚合物涂料、电池隔膜、二次电池Core-shell resin material and preparation method, water-based polymer coating, battery separator, secondary battery
本申请要求于2022年04月06日在中国专利局提交的、申请号为202210355830.0、申请名称为“核壳树脂材料以及制备方法、水性聚合物涂料、电池隔膜、二次电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires a Chinese patent application submitted with the China Patent Office on April 6, 2022, with the application number 202210355830.0 and the application name "core-shell resin material and preparation method, water-based polymer coating, battery separator, secondary battery" priority, the entire contents of which are incorporated herein by reference.
技术领域Technical field
本申请属于电池技术领域，尤其涉及一种核壳树脂材料以及制备方法、水性聚合物涂料、电池隔膜、二次电池。The present application belongs to the field of battery technology, and in particular relates to a core-shell resin material and its preparation method, aqueous polymer coating, battery separator, and secondary battery.
背景技术Background technique
新能源汽车要取代传统的燃油车，电池的使用寿命、成本、续航里程都非常关键。这就要求电池的循环寿命必须达到3000次以上，电池成本做到0.8元/Wh以下，续航里程达到600km以上，即：每充满一次电，汽车可以跑600km以上。此外，电池的安全性能以及电池功率性能也是电池技术发展的核心指标。锂离子二次电池作为新能源汽车发展重要方向，已经在全球电动车市场得到广泛应用。高性能，高安全的锂离子二次电池对电池材料以及电池结构设计提出了新的要求，比如，比亚迪的磷酸铁锂刀片电池，通过结构设计在电池的安全性和能量密度均得到有效提升。For new energy vehicles to replace traditional fuel vehicles, the service life, cost, and cruising range of the battery are very critical. This requires that the cycle life of the battery must reach more than 3,000 times, the battery cost must be less than 0.8 yuan/Wh, and the cruising range must be more than 600km. That is, the car can run more than 600km every time it is fully charged. In addition, battery safety performance and battery power performance are also core indicators for the development of battery technology. As an important direction for the development of new energy vehicles, lithium-ion secondary batteries have been widely used in the global electric vehicle market. High-performance, high-safety lithium-ion secondary batteries have put forward new requirements for battery materials and battery structure design. For example, BYD's lithium iron phosphate blade batteries have effectively improved the safety and energy density of the battery through structural design.
高安全，高性能的锂离子二次电池已经从传统的液态电池逐步向固态或者半固体（干态或者凝胶态）电池转变，国内外电池厂家生产干态或者凝胶态电池通常采用的工艺是在隔膜表面涂布可吸收电解液树脂，如PVDF-HFP、丙烯酯共聚物，涂布树脂的功能隔膜用于组装电芯得到半固体电池。隔膜树脂涂布工艺分为油性工艺和水性工艺，油性涂布工艺通常采用N,N-二甲基吡咯烷酮或者丙酮作为溶剂，而溶剂损耗与回收造成涂布隔膜成本居高不下，且生产过程仍然存在安全和环境风险。相比之下，水性涂布工艺相对要经济和环保得多，商品化的涂布隔膜所使用的水性聚合物涂布材料主要包括水性PVDF-HFP和水性丙烯酸酯类共聚物，这类材料通常以乳液或者悬浮液物料方式涂布于隔膜表面，干燥后，材料以亚微米级颗粒形态黏附在隔膜表面，如目前行业大量使用的法国Arkma型号为LBG的PVDF-HFP，一次粒径为200nm球型颗粒，日本Zeon公司提供的丙烯酸酯共聚物（AFL）涂层材料，乳液颗粒粒径在400nm左右。水性聚合物涂层要达到电池应用的要求，一方面需实现涂层与电极界面优良的界面复合力，另一方面涂层隔膜在电池长期使用过程中必须保持良好的离子传导性能，避免涂层材料阻塞隔膜孔隙造成电池内阻增大，循环性能下降。为了达到电池应用要求，涂层聚合物颗粒需控制溶胀，避免颗粒在电解液中溶胀过大阻塞隔膜孔隙，如PVDF-HFP，分子链中含有结晶结构的PVDF和非结晶结构的HFP，HFP含量增大，材料结晶度变低，材料溶胀增大，溶胀的颗粒堵塞隔膜孔隙造成电池循环恶化。与之相反，当HFP含量过低甚至不含HFP，材料结晶度增加，耐电解液变强，溶胀低，不阻塞隔膜孔隙，但电极界面复合力差，达不到应用要求。因此，电池行业使用的水性PVDF-HFP通过控制合适的HFP含量，以达到材料溶胀和电极界面粘附性能的平衡。High-safety, high-performance lithium-ion secondary batteries have gradually transformed from traditional liquid batteries to solid or semi-solid (dry or gel) batteries. Domestic and foreign battery manufacturers usually use the process to produce dry or gel batteries. The surface of the separator is coated with absorbable electrolyte resin, such as PVDF-HFP, acrylic copolymer, and the functional separator coated with the resin is used to assemble the battery core to obtain a semi-solid battery. The separator resin coating process is divided into oil-based process and water-based process. The oil-based coating process usually uses N,N-dimethylpyrrolidone or acetone as the solvent. However, solvent loss and recycling cause the cost of coating separators to remain high, and the production process is still There are safety and environmental risks. In contrast, the water-based coating process is relatively more economical and environmentally friendly. The water-based polymer coating materials used in commercially coated separators mainly include water-based PVDF-HFP and water-based acrylic copolymers. Such materials usually The emulsion or suspension material is applied to the surface of the separator. After drying, the material adheres to the surface of the separator in the form of sub-micron particles. For example, the French Arkma model LBG PVDF-HFP currently used in the industry has a primary particle size of 200nm. Type particles, acrylate copolymer (AFL) coating material provided by Japan Zeon Company, emulsion particle size is about 400nm. In order for a water-based polymer coating to meet the requirements of battery applications, on the one hand, it must achieve excellent interfacial recombination force at the interface between the coating and the electrode. On the other hand, the coating separator must maintain good ion conductivity during long-term use of the battery to avoid coating The material blocks the pores of the separator, causing the internal resistance of the battery to increase and the cycle performance to decrease. In order to meet the requirements of battery applications, the swelling of the coated polymer particles needs to be controlled to prevent the particles from swelling too much in the electrolyte and blocking the pores of the separator. For example, PVDF-HFP, the molecular chain contains PVDF with a crystalline structure and HFP with a non-crystalline structure, HFP content When the particle size increases, the crystallinity of the material becomes lower and the swelling of the material increases. The swollen particles block the pores of the separator and cause the battery cycle to deteriorate. On the contrary, when the HFP content is too low or even does not contain HFP, the crystallinity of the material increases, the electrolyte resistance becomes stronger, the swelling is low, and the separator pores are not blocked, but the electrode interface recombination force is poor and cannot meet the application requirements. Therefore, the water-based PVDF-HFP used in the battery industry achieves a balance between material swelling and electrode interface adhesion properties by controlling the appropriate HFP content.
相比半结晶的PVDF-HFP，无定形结构的聚酯类水性聚合物无法通过控制结晶平衡达到电池应用要求，如日本Zeon公司AFL涂层材料，该涂层与电极界面粘接表现出良好的粘结力，但在电解液中的常温质量溶胀达到了300%，很容易堵塞隔膜孔隙，造成电池内阻增大。Compared with semi-crystalline PVDF-HFP, amorphous polyester water-based polymers cannot meet battery application requirements by controlling the crystallization balance. For example, the AFL coating material of Japan's Zeon Company shows good interfacial adhesion between the coating and the electrode. Adhesive force, but the mass swelling at room temperature in the electrolyte reaches 300%, which can easily block the pores of the separator and increase the internal resistance of the battery.
技术问题technical problem
本申请所要解决的技术问题是：提供一种核壳树脂材料以及制备方法、水性聚合物涂料、电池隔膜、二次电池，旨在解决现有涂布隔膜溶胀率高，容易堵塞隔膜孔隙的问题。The technical problem to be solved by this application is to provide a core-shell resin material and preparation method, aqueous polymer coating, battery separator, and secondary battery, aiming to solve the problem that the existing coating separator has a high swelling rate and is easy to block the pores of the separator. .
技术解决方案Technical solutions
为了实现上述申请目的，本申请采用的技术方案如下：In order to achieve the above application purpose, the technical solutions adopted in this application are as follows:
一种核壳树脂材料，包括树脂内核和包裹在内核表面的树脂外层，树脂内核包括三维交联网络结构，树脂外层含有增塑的线性半互传网络结构。A core-shell resin material includes a resin core and a resin outer layer wrapped around the surface of the core. The resin core includes a three-dimensional cross-linked network structure, and the resin outer layer includes a plasticized linear semi-reciprocal network structure.
相应地，一种核壳树脂材料的制备方法，至少包括以下步骤：Correspondingly, a method for preparing a core-shell resin material includes at least the following steps:
制备树脂颗粒，在树脂颗粒的表面形成含增塑剂的树脂包覆层，得到核壳树脂颗粒；Preparing resin particles, forming a resin coating layer containing a plasticizer on the surface of the resin particles to obtain core-shell resin particles;
对树脂内核和树脂包覆层进行交联反应，得到核壳树脂材料。The resin core and the resin coating layer are cross-linked to obtain a core-shell resin material.
相应地，一种水性聚合物涂料，包括核壳树脂材料和其他助剂的混合物，其中，核壳树脂材料为上述本申请提供的核壳树脂材料或制备方法制备的核壳树脂材料。Correspondingly, a water-based polymer coating includes a mixture of core-shell resin material and other auxiliaries, wherein the core-shell resin material is the core-shell resin material provided by the present application or the core-shell resin material prepared by the preparation method.
相应地，一种电池隔膜，包括隔膜本体和上述本申请实施例水性聚合物涂料在隔膜本体表面形成的功能涂层。Correspondingly, a battery separator includes a separator body and a functional coating formed on the surface of the separator body by the water-based polymer coating in the embodiment of the present application.
以及，一种二次电池，包括正极和负极以及用于隔绝正极与负极的隔膜，隔膜为上述本申请实施例中的电池隔膜。And, a secondary battery includes a positive electrode and a negative electrode and a separator for isolating the positive electrode and the negative electrode. The separator is the battery separator in the above embodiment of the present application.
有益效果beneficial effects
相对于现有技术，本申请提供的核壳树脂材料包括树脂内核和包裹在内核表面的树脂外层，内核三维交联网络的溶胀度极低，然后内层结构被外层结构包覆，外层结构中***增塑剂形成增塑的线性半互传网络结构，进而增加核壳树脂材料的电极界面粘结性，因而该核壳树脂材料可应用于电池隔膜材料中，其涂布的功能隔膜具备良好的电极界面粘结性能和离子送性能。Compared with the existing technology, the core-shell resin material provided by this application includes a resin core and a resin outer layer wrapped on the surface of the core. The three-dimensional cross-linked network of the core has a very low swelling degree, and then the inner layer structure is covered by the outer layer structure. The plasticizer is inserted into the layer structure to form a plasticized linear semi-reciprocal network structure, thereby increasing the electrode interface adhesion of the core-shell resin material. Therefore, the core-shell resin material can be used in battery separator materials, and its coating function The separator has good electrode interface bonding performance and ion transport performance.
本申请提供的核壳树脂材料的制备方法的通过先制备树脂内核，在树脂内核的表面形成含增塑剂的树脂包覆层，得到核壳结构的树脂颗粒，对树脂内核和树脂外层的树脂颗粒进行交联反应，可以提高核壳树脂材料的交联度，降低其溶胀率。The preparation method of the core-shell resin material provided by this application first prepares a resin core, and forms a resin coating layer containing a plasticizer on the surface of the resin core to obtain resin particles with a core-shell structure. The resin core and the resin outer layer are The resin particles undergo a cross-linking reaction, which can increase the cross-linking degree of the core-shell resin material and reduce its swelling rate.
本申请以包括上述本申请提供的核壳树脂材料和其他助剂的混合形成水性聚合物涂料以便在基体形成膜层物质。具体的，上述本申请实施例提供的核壳树脂材料溶胀率低，会以稳定的颗粒状态分散于其他助剂中，且由于上述本申请实施例提供的核壳树脂材料界面连接性能好，有利于本申请提供的水性聚合物涂料在基体上形成膜层物质。This application uses the above-mentioned core-shell resin material provided by this application and other additives to form a water-based polymer coating so as to form a film layer on the substrate. Specifically, the core-shell resin material provided by the above-mentioned embodiments of the present application has a low swelling rate and will be dispersed in other additives in a stable particle state. Moreover, due to the good interfacial connection performance of the core-shell resin material provided by the above-mentioned embodiments of the present application, it has It is beneficial for the water-based polymer coating provided by the present application to form a film layer on the substrate.
正是由于上述本申请中的核壳树脂材料溶胀度低，电极界面粘结性优异，因而水性聚合物涂料可应用于电池隔膜材料中，以防止电池隔膜被堵塞。It is precisely because of the low swelling degree of the core-shell resin material in this application and the excellent electrode interface adhesion that the water-based polymer coating can be used in battery separator materials to prevent the battery separator from being blocked.
本申请提供的二次电池包括上述本申请中的电池隔膜，在电池长期使用过程中电池隔膜保持良好的离子传导性能，改善了涂层材料阻塞隔膜孔隙造成电池内阻增大，电池循环性能下降的问题。The secondary battery provided by this application includes the above-mentioned battery separator in this application. During the long-term use of the battery, the battery separator maintains good ion conductivity and improves the internal resistance of the battery caused by the blocking of the separator pores by the coating material and the decrease in battery cycle performance. The problem.
附图说明Description of the drawings
图1为本申请实施例提供的星型互传网络的球状颗粒结构示意图；Figure 1 is a schematic diagram of the spherical particle structure of the star-shaped intertransmission network provided by the embodiment of the present application;
图2为本申请实施例提供的功能涂层材料一次颗粒的TEM图；Figure 2 is a TEM image of the primary particles of the functional coating material provided by the embodiment of the present application;
图3为本申请实施例提供的功能涂层材料二次颗粒的SEM图；Figure 3 is an SEM image of the secondary particles of the functional coating material provided by the embodiment of the present application;
图4 为本申请实施例提供的隔膜功能涂层材料经过气流粉碎后SEM图；Figure 4 is an SEM image of the separator functional coating material provided by the embodiment of the present application after being air-pulverized;
图5 为本申请实施例提供的图4的局部放大SEM图；Figure 5 is a partially enlarged SEM image of Figure 4 provided by the embodiment of the present application;
图6为本申请实施例提供的涂布量为0.6 g/m 2的功能涂布隔膜SEM图。 Figure 6 is an SEM image of a functional coating separator with a coating amount of 0.6 g/ m2 provided by the embodiment of the present application.
本发明的实施方式Embodiments of the invention
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例和附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clear, the present invention will be further described in detail below in conjunction with the embodiments and drawings. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention.
本申请实施例第一方面提供了一种核壳树脂材料，包括树脂内核和包裹在内核表面的树脂外层，树脂内核包括三维交联网络结构，树脂外层含有增塑的线性半互传网络结构。The first aspect of the embodiment of the present application provides a core-shell resin material, which includes a resin core and a resin outer layer wrapped on the surface of the core. The resin core includes a three-dimensional cross-linked network structure, and the resin outer layer includes a plasticized linear semi-reciprocal network. structure.
本申请实施例提供的核壳树脂材料，树脂内核和包裹在内核表面的树脂外层，具体的，请参考图1所示，内层分子聚集实心分布于球状颗粒的中心部分，形成三维交联网络结构，内核三维交联网络的溶胀度极低，然后内层结构被外层结构包覆，外层结构中***增塑剂形成增塑的线性半互传网络结构，进而增加核壳树脂材料的电极界面粘结性，因而该核壳树脂材料可应用于电池隔膜材料中，其涂布的功能隔膜具备良好的电极界面粘结性能和离子送性能。The core-shell resin material provided in the embodiment of the present application has a resin core and a resin outer layer wrapped around the surface of the core. For details, please refer to Figure 1. The molecules in the inner layer are aggregated and solidly distributed in the center of the spherical particles, forming a three-dimensional cross-link. Network structure, the swelling degree of the core three-dimensional cross-linked network is extremely low, and then the inner layer structure is covered by the outer layer structure, and a plasticizer is inserted into the outer layer structure to form a plasticized linear semi-reciprocal network structure, thereby increasing the core-shell resin material The core-shell resin material can be used in battery separator materials because of its excellent electrode interface adhesion. The coated functional separator has good electrode interface adhesion and ion transport performance.
在一些实施例中，核壳树脂材料包括星型互传网络球状颗粒，该材料的二次粒径的可为球状颗粒结构。在一些实施例中，核壳树脂材料的一次粒径为200~400nm，二次粒径为5~40μm，以便后续配成浆料，进行涂布工艺。In some embodiments, the core-shell resin material includes star-shaped mutual transmission network spherical particles, and the secondary particle size of the material may be a spherical particle structure. In some embodiments, the primary particle size of the core-shell resin material is 200 to 400 nm, and the secondary particle size is 5 to 40 μm, so that the slurry can be subsequently prepared for the coating process.
在一些实施例中，作为核壳树脂材料的树脂内核，形成树脂内核的材料包括第一主单体、第一功能单体、乳化剂和第一引发剂，其中，第一主单体和第一功能单体在乳化剂的作用下，可聚合成树脂内核。In some embodiments, as the resin core of the core-shell resin material, the material forming the resin core includes a first main monomer, a first functional monomer, an emulsifier and a first initiator, wherein the first main monomer and the first A functional monomer can be polymerized into a resin core under the action of an emulsifier.
在一些实施例中，第一主单体包括甲基丙烯酸甲酯、2-甲基丙烯酸乙酯、丙烯酸甲酯、苯乙烯、丙烯腈、丙烯酸乙酯、丙烯酸异辛酯、丙烯酸十二酯、丙烯酸十八酯、1，3-丁二烯、丙烯酸丁酯、a-氰基丙烯酸酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯、丙烯酸羟丙酯、丙烯酸磷酸酯、醋酸乙烯酯中的至少一种。本申请实施例提供的第一主单体聚合反应后可形成三维交联网络球状的内核中的基体，可降低三维交联网络球状的内核的溶胀度。In some embodiments, the first main monomer includes methyl methacrylate, 2-ethyl methacrylate, methyl acrylate, styrene, acrylonitrile, ethyl acrylate, isooctyl acrylate, dodecyl acrylate, In stearyl acrylate, 1,3-butadiene, butyl acrylate, a-cyanoacrylate, butyl methacrylate, ethyl methacrylate, hydroxypropyl acrylate, phosphate acrylate, vinyl acetate At least one. The first main monomer provided in the embodiments of the present application can form a matrix in the spherical core of the three-dimensional cross-linked network after polymerization, and can reduce the swelling degree of the spherical core of the three-dimensional cross-linked network.
在一些实施例中，第一功能单体包括丙烯酸、丙烯酸羟乙酯、二乙烯基苯、N-羟甲基丙烯酰胺、N、N亚甲基双丙烯酰胺、1，4-丁二醇双丙烯酸酯、甲基丙烯酸、甲基丙烯酸羟乙酯、双丙酮丙烯酰胺、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯等不同聚乙二醇分子量的二丙烯酸酯、硅烷偶联剂KH570、二甲基丙烯酸乙二醇酯、聚丙二醇缩水甘油醚、双丙酮丙烯酰胺、二乙烯基苯中的至少一种。本申请实施例提供的第一功能单体可对三维交联网络球状的内核的基体进行改性，进一步降低内核三维交联网络的溶胀度。In some embodiments, the first functional monomer includes acrylic acid, hydroxyethyl acrylate, divinylbenzene, N-hydroxymethylacrylamide, N,N methylenebisacrylamide, 1,4-butanediol bisacrylamide Acrylate, methacrylic acid, hydroxyethyl methacrylate, diacetone acrylamide, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol Diacrylates with different polyethylene glycol molecular weights such as alcohol diacrylate, polyethylene glycol diacrylate, silane coupling agent KH570, ethylene glycol dimethacrylate, polypropylene glycol glycidyl ether, diacetone acrylamide, At least one kind of divinylbenzene. The first functional monomer provided by the embodiment of the present application can modify the matrix of the spherical core of the three-dimensional cross-linked network, further reducing the swelling degree of the three-dimensional cross-linked network of the core.
在一些实施例中，乳化剂包括硬脂酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、烷基酚聚氧乙烯醚OP系列，硬脂酸聚氧乙烯醚系列、吐温系列、曲拉通100、烯丙基醚类磺酸盐、丙烯酰胺基磺酸盐、马来酸衍生物、烯丙基琥珀酸烷基酯磺酸钠中的至少一种。本申请实施例提供的乳化剂可对第一主单体、第一功能单体和第一引发剂进行乳化处理形成核结构。其中，烷基酚聚氧乙烯醚OP系列包括OP-4、OP-7、OP-9、OP-10、OP-13、OP-15、OP-20中的至少一种。另外，吐温系列包括20、40、60、80中的至少一种。本申请实施例提供的乳化剂可进一步提高反应率，且成本低。In some embodiments, the emulsifier includes sodium stearate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene ether OP series, stearic acid polyoxyethylene ether series, etc. At least one of Wen series, Triton 100, allyl ether sulfonates, acrylamide sulfonates, maleic acid derivatives, and sodium allyl alkyl succinate sulfonate. The emulsifier provided in the embodiments of the present application can emulsify the first main monomer, the first functional monomer and the first initiator to form a core structure. Among them, the alkylphenol polyoxyethylene ether OP series includes at least one of OP-4, OP-7, OP-9, OP-10, OP-13, OP-15 and OP-20. In addition, the Twain series includes at least one of 20, 40, 60, and 80. The emulsifier provided in the embodiments of the present application can further improve the reaction rate and is low in cost.
在一些实施例中，第一引发剂包括氧化苯甲酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙酯、偶氮二异丁腈、偶氮二异庚腈、过氧化二碳酸二环己酯、异丙苯过氧化氢中、过硫酸钾、过硫酸铵中的至少一种。本申请实施例提供的第一引发剂可引发第一主单体和第一功能单体聚合，且可控制反应速率。In some embodiments, the first initiator includes benzoyl oxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanitrile, diisopropylperoxide At least one of dicyclohexyl carbonate, cumene hydroperoxide, potassium persulfate, and ammonium persulfate. The first initiator provided in the embodiments of the present application can initiate the polymerization of the first main monomer and the first functional monomer, and can control the reaction rate.
在一些实施例中，作为核壳树脂材料的树脂外层，形成树脂外层的材料包括第二主单体、第二功能单体、第二引发剂、有机溶剂和增塑剂。本申请实施例提供的第二主单体、第二功能单体、第二引发剂、有机溶剂和增塑剂在一定的条件下可聚合形成外层的材料。In some embodiments, as the resin outer layer of the core-shell resin material, the material forming the resin outer layer includes a second main monomer, a second functional monomer, a second initiator, an organic solvent and a plasticizer. The second main monomer, the second functional monomer, the second initiator, the organic solvent and the plasticizer provided in the embodiments of the present application can be polymerized under certain conditions to form the material of the outer layer.
在一些实施例中，第二主单体包括甲基丙烯酸甲酯、2-甲基丙烯酸乙酯、丙烯酸甲酯、苯乙烯、丙烯腈、丙烯酸乙酯、丙烯酸异辛酯、丙烯酸十二酯、丙烯酸十八酯、1，3-丁二烯、丙烯酸丁酯、a-氰基丙烯酸酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯、丙烯酸羟丙酯、丙烯酸磷酸酯、醋酸乙烯酯中的至少一种。本申请实施例提供的第二主单体聚合反应后可形成线性半互传网络结构的外层中的基体，可降低三维交联网络球状的外层的电极界面粘结性。In some embodiments, the second primary monomer includes methyl methacrylate, 2-ethyl methacrylate, methyl acrylate, styrene, acrylonitrile, ethyl acrylate, isooctyl acrylate, dodecyl acrylate, In stearyl acrylate, 1,3-butadiene, butyl acrylate, a-cyanoacrylate, butyl methacrylate, ethyl methacrylate, hydroxypropyl acrylate, phosphate acrylate, vinyl acetate At least one. The second main monomer provided in the embodiments of the present application can form a matrix in the outer layer of a linear semi-reciprocal network structure after polymerization, and can reduce the electrode interface adhesion of the spherical outer layer of the three-dimensional cross-linked network.
在一些实施例中，第二功能单体包括丙烯酸、丙烯酸羟乙酯、二乙烯基苯、N-羟甲基丙烯酰胺、N、N亚甲基双丙烯酰胺、1，4-丁二醇双丙烯酸酯、甲基丙烯酸、甲基丙烯酸羟乙酯、双丙酮丙烯酰胺、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯等不同聚乙二醇分子量的二丙烯酸酯、硅烷偶联剂KH570、二甲基丙烯酸乙二醇酯、聚丙二醇缩水甘油醚、双丙酮丙烯酰胺、二乙烯基苯中的至少一种。本申请实施例提供的第一功能单体可对线性半互传网络结构的外层中进行改性，进一步降低内核三维交联网络的溶胀度。In some embodiments, the second functional monomer includes acrylic acid, hydroxyethyl acrylate, divinylbenzene, N-hydroxymethylacrylamide, N,N methylene bisacrylamide, 1,4-butanediol bisacrylamide Acrylate, methacrylic acid, hydroxyethyl methacrylate, diacetone acrylamide, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol Diacrylates with different polyethylene glycol molecular weights such as alcohol diacrylate, polyethylene glycol diacrylate, silane coupling agent KH570, ethylene glycol dimethacrylate, polypropylene glycol glycidyl ether, diacetone acrylamide, At least one kind of divinylbenzene. The first functional monomer provided by the embodiment of the present application can modify the outer layer of the linear semi-reciprocal network structure to further reduce the swelling degree of the core three-dimensional cross-linked network.
在一些实施例中，第二引发剂包括氧化苯甲酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙酯、偶氮二异丁腈、偶氮二异庚腈、过氧化二碳酸二环己酯、异丙苯过氧化氢中，过硫酸钾、过硫酸铵中的至少一种。本申请实施例提供的第一引发剂可引发第二主单体和第二功能单体聚合，且可控制反应速率。In some embodiments, the second initiator includes benzoyl oxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptanitrile, diisopropyl peroxide At least one of dicyclohexyl carbonate and cumene hydroperoxide, potassium persulfate and ammonium persulfate. The first initiator provided in the embodiments of the present application can initiate the polymerization of the second main monomer and the second functional monomer, and can control the reaction rate.
在一些实施例中，有机溶剂包括碳酸二甲酯、碳酸二乙酯、乙基甲基碳酸酯中的至少一种，该溶剂可以溶解第二主单体和第二功能单体，为两者反应提供一个良好的环境。In some embodiments, the organic solvent includes at least one of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The solvent can dissolve the second main monomer and the second functional monomer. Reaction provides a good environment.
在一些实施例中，增塑剂包括邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛酯、邻苯二甲酸丁苄酯、十二醇酯、双季戊四醇酯、甘油三乙酸酯、柠檬酸酯中的至少一种。本申请实施例提供的增塑剂可以在第二主单体和第二功能单体生成的聚合物表面形成一层分子，进而增加核壳树脂材料的界面连接性。In some embodiments, the plasticizer includes dimethyl phthalate, diethyl phthalate, dioctyl phthalate, butyl benzyl phthalate, dodecanol ester, dipentaerythritol ester , at least one of glyceryl triacetate and citrate. The plasticizer provided in the embodiments of the present application can form a layer of molecules on the surface of the polymer generated by the second main monomer and the second functional monomer, thereby increasing the interface connectivity of the core-shell resin material.
本申请实施例第二方面提供了一种核壳树脂材料的制备方法，包括如下步骤：The second aspect of the embodiments of the present application provides a method for preparing a core-shell resin material, which includes the following steps:
步骤S10:制备树脂颗粒，在树脂颗粒的表面形成含增塑剂的树脂包覆层，得到核壳树脂颗粒；Step S10: Prepare resin particles, form a resin coating layer containing plasticizer on the surface of the resin particles, and obtain core-shell resin particles;
步骤S20:对树脂内核和树脂包覆层进行交联反应，得到核壳树脂材料。Step S20: Perform a cross-linking reaction on the resin core and the resin coating layer to obtain a core-shell resin material.
本申请实施例提供的核壳树脂材料的制备方法的通过先制备树脂颗粒，在树脂颗粒的表面形成含增塑剂的树脂包覆层，提高核壳树脂颗粒的界面连接性能，得到核壳结构的树脂颗粒，对树脂内核和树脂外层的树脂颗粒进行交联反应，可以提高核壳树脂材料的交联度，降低其溶胀率，进而得到核壳树脂材料。The core-shell resin material preparation method provided by the embodiments of the present application first prepares resin particles, forms a resin coating layer containing plasticizer on the surface of the resin particles, improves the interface connection performance of the core-shell resin particles, and obtains a core-shell structure. The resin particles are used to cross-link the resin core and the resin particles in the outer layer of the resin, which can increase the cross-linking degree of the core-shell resin material and reduce its swelling rate, thereby obtaining the core-shell resin material.
上述步骤S10中，制备树脂颗粒，在树脂颗粒的表面形成树脂包覆层的方法包括如下步骤：In the above step S10, the method of preparing resin particles and forming a resin coating layer on the surface of the resin particles includes the following steps:
将第一主单体、第一功能单体、乳化剂与水进行乳化处理，得到第一乳液；emulsify the first main monomer, the first functional monomer, the emulsifier and water to obtain a first emulsion;
将第二主单体、第二功能单体与有机溶剂进行混合处理，得到第一反应液；Mix the second main monomer, the second functional monomer and the organic solvent to obtain the first reaction liquid;
向第一乳液中加入第一引发剂进行第一聚合反应，得到第二反应液；Adding a first initiator to the first emulsion to perform a first polymerization reaction to obtain a second reaction liquid;
向第二反应液中加入第一反应液和第二引发剂进行第二聚合反应，得到第三反应液；Add the first reaction liquid and the second initiator to the second reaction liquid to perform a second polymerization reaction to obtain a third reaction liquid;
向第三反应液中加入增塑剂，得到含所述核壳树脂颗粒第四反应液。A plasticizer is added to the third reaction liquid to obtain a fourth reaction liquid containing the core-shell resin particles.
本申请实施例提供的核壳树脂材料的制备方法，首先将第一主单体、第一功能单体、乳化剂与水进行乳化处理和聚合处理，以便聚合形成核壳树脂材料的树脂内核，然后向第一反应液中加入第二反应液和第二引发剂进行第二聚合反应，以便聚合形成核壳树脂材料的树脂外层，最后向第三反应液中加入增塑剂，增塑剂通过分子之间的相互作用进而***到外层分子中，形成含有增塑的线性半互传网络结构的树脂外层。The preparation method of the core-shell resin material provided by the embodiment of the present application first emulsifies and polymerizes the first main monomer, the first functional monomer, the emulsifier and water, so as to polymerize to form the resin core of the core-shell resin material. Then, a second reaction liquid and a second initiator are added to the first reaction liquid to perform a second polymerization reaction so as to polymerize to form the resin outer layer of the core-shell resin material. Finally, a plasticizer is added to the third reaction liquid. The plasticizer Through the interaction between molecules, it is inserted into the outer molecules to form a resin outer layer containing a plasticized linear semi-reciprocal network structure.
上述步骤S10中，第一主单体与第一功能单体的质量比为（80~95）：（5~20）；第一主单体和第一功能单体的总质量之和与乳化剂、第一引发剂的质量比为100：（0.1~5）：（0.05~0.5），通过控制第一主单体、第一功能单体和第一引发剂的质量比，可进一步减少该材料的溶胀率。在一些实施例中，还包括对第一乳液进行保温处理，且在25℃条件下，保温1~4小时，以防止第一乳液的变性，提高内核的形成率。In the above step S10, the mass ratio of the first main monomer and the first functional monomer is (80~95): (5~20); the sum of the total mass of the first main monomer and the first functional monomer and the emulsification The mass ratio of the agent and the first initiator is 100: (0.1~5): (0.05~0.5). By controlling the mass ratio of the first main monomer, the first functional monomer and the first initiator, this can be further reduced. The swelling rate of the material. In some embodiments, the method further includes insulating the first emulsion at 25° C. for 1 to 4 hours to prevent denaturation of the first emulsion and improve the formation rate of the core.
在一些实施例中，第二主单体与第一功能单体的质量比为（50~80）：（20~50），第二主单体和第二功能单体的总质量之和与第二引发剂、有机溶剂的质量比为100：（0.1~1）：（10~50），通过控制第二主单体、第二功能单体、第二引发剂、有机溶剂的质量比，可进一步减少该材料的溶胀率。In some embodiments, the mass ratio of the second main monomer to the first functional monomer is (50~80): (20~50), and the sum of the total mass of the second main monomer and the second functional monomer is The mass ratio of the second initiator and organic solvent is 100: (0.1~1): (10~50). By controlling the mass ratio of the second main monomer, the second functional monomer, the second initiator and the organic solvent, The swelling rate of the material can be further reduced.
上述步骤S20中，对树脂内核和树脂包覆层进行交联反应的方法包括如下步骤：In the above step S20, the method for cross-linking the resin core and the resin coating layer includes the following steps:
向第四反应液中加入交联剂进行交联处理、干燥处理，得到核壳树脂材料。本申请实施例向第四反应液中加入交联剂，对外层分子进行交联反应，可以进一步固定增塑剂分子，且提高树脂外层和树脂内核的整体的交联度，可得到具有良好电极界面粘结性的增塑的线性半互传网络结构。A cross-linking agent is added to the fourth reaction liquid to perform cross-linking treatment and drying treatment to obtain a core-shell resin material. In the embodiment of the present application, a cross-linking agent is added to the fourth reaction solution to perform a cross-linking reaction on the outer molecules, which can further fix the plasticizer molecules and increase the overall cross-linking degree of the resin outer layer and the resin core, thereby obtaining a good Plasticized linear semi-reciprocal network structure of electrode interface adhesiveness.
在一些实施例中，交联剂包括丙二胺、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、N-羟基苯并三氮唑、N-羟基琥珀酰亚胺、正硅酸乙酯、正硅酸甲酯、三羟甲基丙烷中的至少一种，第二交联剂可促使外层分子进行交联，降低核壳树脂材料的溶胀率，且使增塑剂互传于外层分子中。In some embodiments, the cross-linking agent includes propylene diamine, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, N-hydroxybenzotriazole, N- At least one of hydroxysuccinimide, ethyl orthosilicate, methyl orthosilicate, and trimethylolpropane. The second cross-linking agent can promote the cross-linking of outer molecules and reduce the swelling of the core-shell resin material. rate, and the plasticizer is transferred to the outer molecules.
在一些实施例中，交联剂按照第一主单体、第二主单体、第一功能单体、第二功能单体总质量之和与交联剂质量比为100：（0.5~5）：（0.5~3）的比例添加第四反应液中，通过控制第一主单体、第二主单体、第一功能单体、第二功能单体、交联剂和增塑剂的质量比，可进一步提高该材料的电极界面粘结性能。在一些实施例中，还包括对第四反应液进行保温处理，且在25℃条件下，保温2~4小时，以防止第一乳液的变性，提高外层的形成率。In some embodiments, the mass ratio of the cross-linking agent to the cross-linking agent is 100: (0.5~5 ): (0.5~3) is added to the fourth reaction solution by controlling the proportions of the first main monomer, the second main monomer, the first functional monomer, the second functional monomer, the cross-linking agent and the plasticizer. The mass ratio can further improve the electrode interface bonding performance of the material. In some embodiments, the fourth reaction solution is also heat-insulated at 25° C. for 2 to 4 hours to prevent denaturation of the first emulsion and improve the formation rate of the outer layer.
在一些实施例中，交联反应的温度为100~180℃，可提高反应速率。In some embodiments, the temperature of the cross-linking reaction is 100~180°C, which can increase the reaction rate.
在一些实施例中，用喷雾干燥的方法进行干燥处理，采用喷雾干燥可造出星型互传网络球状颗粒结构的核壳树脂材料。进一步的，请参考图2至图3所示，核壳树脂材料为颗粒结构，请参考图4至图5所示，核壳树脂材料的经过气流粉碎后，可清晰观察内部结构、二次粒径和一次粒径。核壳树脂材料的一次粒径为200~400nm，二次粒径为5~40μm，以便后续进行涂布工艺。In some embodiments, spray drying is used to perform the drying process. Spray drying can produce a core-shell resin material with a star-shaped mutual transmission network spherical particle structure. Further, please refer to Figures 2 to 3. The core-shell resin material has a particle structure. Please refer to Figures 4 to 5. After the core-shell resin material is pulverized by airflow, the internal structure and secondary particles can be clearly observed. diameter and primary particle size. The primary particle size of the core-shell resin material is 200~400nm, and the secondary particle size is 5~40μm for subsequent coating processes.
本申请实施例第三方面提供了一种水性聚合物涂料，包括核壳树脂材料和其他助剂的混合物，其中，核壳树脂材料为上述本申请实施例提供的核壳树脂材料或制备方法制备的核壳树脂材料。The third aspect of the embodiment of the present application provides a water-based polymer coating, including a mixture of core-shell resin material and other additives, wherein the core-shell resin material is prepared by the core-shell resin material or the preparation method provided in the embodiment of the present application. Core-shell resin material.
本申请实施例以包括上述本申请实施例提供的核壳树脂材料和其他助剂的混合形成水性聚合物涂料以便在基体形成膜层物质。第一方面，上述本申请实施例提供的核壳树脂材料溶胀率低，会以稳定的颗粒状态分散于其他助剂中，另一方面由于上述本申请实施例提供的核壳树脂材料界面连接性能好，有利于本申请实施例提供的水性聚合物涂料在基体上形成膜层物质。In the embodiments of the present application, the core-shell resin material provided in the embodiments of the present application and other additives are mixed to form a water-based polymer coating so as to form a film layer on the substrate. Firstly, the core-shell resin material provided by the above-mentioned embodiments of the present application has a low swelling rate and will be dispersed in other additives in a stable particle state. On the other hand, due to the interfacial connection properties of the core-shell resin material provided by the above-mentioned embodiments of the present application Well, it is beneficial for the water-based polymer coating provided in the embodiment of the present application to form a film layer on the substrate.
在一些实施例中，为了赋予核壳树脂材料一些其他性能，需要核壳树脂材料中加入一些其他助剂，其中，其他助剂还包括分散剂、粘结剂、润湿剂、增稠剂、消泡剂中的至少一种。In some embodiments, in order to give the core-shell resin material some other properties, it is necessary to add some other additives to the core-shell resin material, where other additives also include dispersants, binders, wetting agents, thickeners, at least one defoaming agent.
在一些实施例中，核壳树脂材料、分散剂、粘结剂、润湿剂、增稠剂、消泡剂和水的质量比为（5~30）：（0.1~1）：（0.4~4.5）：（0.1~0.5）：（0.1~0.5）：（0.01~0.1）：100，通过控制核壳树脂材料和添加剂的质量比，可进一步提高该材料的整体性能。In some embodiments, the mass ratio of the core-shell resin material, dispersant, binder, wetting agent, thickener, defoaming agent and water is (5~30): (0.1~1): (0.4~ 4.5): (0.1~0.5): (0.1~0.5): (0.01~0.1): 100. By controlling the mass ratio of the core-shell resin material and additives, the overall performance of the material can be further improved.
在一些实施例中，分散剂包括硬脂酸钠、乙烯基双硬脂酰胺，聚丙烯酸钠、聚甲基丙烯酸钠、十二烷基苯磺酸钠、聚乙二醇、羧甲基纤维素钠中的至少一种，核壳树脂材料和分散剂混合，以防止核壳树脂材料团聚，有利于核壳树脂材料的形成性能均一的膜层。In some embodiments, the dispersing agent includes sodium stearate, vinyl bis stearamide, sodium polyacrylate, sodium polymethacrylate, sodium dodecyl benzene sulfonate, polyethylene glycol, carboxymethyl cellulose At least one kind of sodium is mixed with the core-shell resin material and the dispersant to prevent the core-shell resin material from agglomerating and facilitate the formation of a film layer with uniform performance of the core-shell resin material.
在一些实施例中，粘结剂包括苯丙乳胶粘结剂、丁苯乳胶粘结剂、聚丙烯酸钠、聚乙烯吡咯烷酮、聚氧乙烯、聚乙烯醇PVA、丙烯腈与丙烯酸酯共聚物、丙烯腈与丙烯酸锂的共聚物中的至少一种，核壳树脂材料和粘结剂混合，可增加核壳树脂材料颗粒之间的连接性能，且与分散剂协同合作，有利于核壳树脂材料在基材表面形成性能均一的膜层。In some embodiments, the binder includes styrene-acrylic latex binder, styrene-butadiene latex binder, sodium polyacrylate, polyvinylpyrrolidone, polyoxyethylene, polyvinyl alcohol PVA, acrylonitrile and acrylate copolymer, propylene At least one of the copolymers of nitrile and lithium acrylate, the core-shell resin material and the binder are mixed, which can increase the connection performance between the core-shell resin material particles, and cooperate with the dispersant to facilitate the core-shell resin material in A film layer with uniform performance is formed on the surface of the substrate.
在一些实施例中，润湿剂包括吐温80、烷基硫酸盐、聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚、聚氧乙烯聚氧丙烯嵌段共聚物、聚醚改性的有机硅中的至少一种，核壳树脂材料和润湿剂混合，可降低核壳树脂材料的界面能，增加其在基材表面的粘附性，且与分散剂协同合作，有利于核壳树脂材料在基材表面形成性能均一膜层。In some embodiments, the wetting agent includes Tween 80, alkyl sulfate, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer, polyether modified At least one of the organic silicones, the core-shell resin material and the wetting agent are mixed, which can reduce the interfacial energy of the core-shell resin material, increase its adhesion on the substrate surface, and cooperate with the dispersant to benefit the core-shell The resin material forms a film layer with uniform performance on the surface of the substrate.
在一些实施例中，增稠剂包括卡波姆胶、聚丙烯酰胺、羟甲基丙基纤维素钠、聚乙烯甲基醚/丙烯酸甲酯与癸二烯的交联聚合物中的至少一种。In some embodiments, the thickening agent includes at least one of carbomer gum, polyacrylamide, sodium hydroxymethylpropylcellulose, polyvinyl methyl ether/methyl acrylate and a cross-linked polymer of decadiene. kind.
在一些实施例中，消泡剂包括有机硅型消泡剂和聚醚型消泡剂中的至少一种。在一些实施例中，机硅型消泡剂包括改性聚二甲基硅氧烷，聚醚型消泡剂包括聚氧乙烯聚氧丙烯甘油醚，由于核壳树脂材料含有高分子材料，固化后容易局部出现鱼眼或者气泡，因此加入消泡剂后可以提高核壳树脂材料的整体性能。In some embodiments, the defoaming agent includes at least one of a silicone-based defoaming agent and a polyether-based defoaming agent. In some embodiments, the silicone-type defoaming agent includes modified polydimethylsiloxane, and the polyether-type defoaming agent includes polyoxyethylene polyoxypropylene glyceryl ether. Since the core-shell resin material contains polymer materials, curing Fish eyes or bubbles may easily appear locally, so adding a defoamer can improve the overall performance of the core-shell resin material.
本申请实施例第四方面提供了一种电池隔膜，包括隔膜本体和上述本申请实施例水性聚合物涂料在隔膜本体表面形成的功能涂层。The fourth aspect of the embodiment of the present application provides a battery separator, which includes a separator body and a functional coating formed on the surface of the separator body by the water-based polymer coating in the embodiment of the present application.
正是由于上述本申请实施例中的核壳树脂材料溶胀度低，电极界面粘结性优异，因而水性聚合物涂料可应用于电池隔膜材料中，以防止电池隔膜被堵塞。另外，本申请实施例提供的电池包括锂离子电池、氢能源电池和固态电池，但并限于此。Precisely because the core-shell resin material in the embodiments of the present application has low swelling degree and excellent electrode interface adhesion, the water-based polymer coating can be used in battery separator materials to prevent the battery separator from being blocked. In addition, the batteries provided by the embodiments of the present application include lithium-ion batteries, hydrogen energy batteries and solid-state batteries, but are not limited thereto.
在一些实施例中，本申请实施例提供的核壳树脂材料与大部分基膜具有良好的连接性，其中，基膜包括PP隔膜、PE隔膜、PP/PE/PE膜、PP/PP多层膜以及其单面或者双面陶瓷涂布隔膜中的至少一种，但不限于此。进一步的，基膜厚度5~40μm，可提高隔膜的整体性能。In some embodiments, the core-shell resin material provided by the embodiments of the present application has good connectivity with most base films, where the base film includes PP separator, PE separator, PP/PE/PE film, and PP/PP multi-layer membrane and at least one of its single-sided or double-sided ceramic-coated separators, but is not limited thereto. Furthermore, the thickness of the base film is 5~40 μm, which can improve the overall performance of the separator.
在一些实施例中，锂离子电池涂布隔膜在LiPF 6 1mol/L EC:DMC:EMC=1:1:1的电解液中70℃浸泡24小时，其质量溶胀度小于50%，体积溶胀小于20%，因此其涂布隔膜仍然能保持良好的离子传导性能。 In some embodiments, the lithium-ion battery coated separator is soaked in LiPF 6 1mol/L EC:DMC:EMC=1:1:1 electrolyte at 70°C for 24 hours, and its mass swelling is less than 50%, and its volume swelling is less than 20%, so its coated separator can still maintain good ion conductivity.
在一些实施例中，在基膜上涂布面密度0.2~1.2 g/m 2星型互传网络球状颗粒结构的功能涂层，请参考图6所示，0.6 g/m 2的功能涂布能够均与地分布于基膜上。示例性地，在80℃，1MPa，1mins热压条件下，辊涂涂布量达到0.3g/m 2的功能隔膜，与电极界面的复合力达到15 N/m以上。喷涂涂布量达到0.3g/m 2的功能隔膜，与电极界面的复合力达到5 N/m以上。需要说明的，涂布方式才有微凹辊涂，印刷点涂，旋转喷涂，但并不限于此。 In some embodiments, a functional coating with a star-shaped intertransmission network spherical particle structure with an area density of 0.2~1.2 g/m 2 is coated on the base film. Please refer to Figure 6 for a functional coating of 0.6 g/m 2 Can be evenly distributed on the base film. For example, under hot pressing conditions of 80°C, 1MPa, and 1mins, a functional separator with a roll coating amount of 0.3g/ m2 has a recombination force at the interface with the electrode of more than 15 N/m. The functional separator with a spray coating amount of 0.3g/ m2 has a composite force of more than 5 N/m at the interface with the electrode. It should be noted that the coating methods include micro-concave roller coating, printing dot coating, and rotary spray coating, but are not limited to these.
本申请实施例第五方面提供了一种二次电池，包括正极和负极以及用于隔绝正极与负极的隔膜，隔膜为上述本申请实施例中的电池隔膜。The fifth aspect of the embodiment of the present application provides a secondary battery, including a positive electrode and a negative electrode and a separator for isolating the positive electrode and the negative electrode. The separator is the battery separator in the above-mentioned embodiment of the present application.
本申请实施例提供的二次电池包括上述本申请实施例中的电池隔膜，因为本申请电池隔膜在电池长期使用过程中，能够保持良好的离子传导性能，进而改善了涂层材料阻塞隔膜孔隙，造成电池内阻增大，电池循环性能下降的问题。The secondary battery provided by the embodiment of the present application includes the battery separator in the above embodiment of the present application, because the battery separator of the present application can maintain good ion conductivity during long-term use of the battery, thereby improving the blocking of the separator pores by the coating material. This causes the internal resistance of the battery to increase and the cycle performance of the battery to decrease.
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例核壳树脂材料以及制备方法、水性聚合物涂料、电池隔膜、二次电池的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。In order that the above implementation details and operations of the present application can be clearly understood by those skilled in the art, and that the core-shell resin materials and preparation methods, water-based polymer coatings, battery separators, and secondary batteries in the embodiments of the present application can significantly reflect the progressive performance, The above technical solutions are illustrated below through multiple embodiments.
为了更好的说明本发明实施例提供的核壳树脂材料以及制备方法、水性聚合物涂料、电池隔膜、二次电池，下面通过多个实施例进一步解释说明。In order to better explain the core-shell resin material and preparation method, aqueous polymer coating, battery separator, and secondary battery provided by the embodiments of the present invention, multiple examples are further explained below.
实施例1Example 1
本实施例第一方面提供了一种核壳树脂材料，包括树脂内核和包裹在内核表面的树脂外层，树脂内核包括三维交联网络球状，树脂外层为增塑的线性半互传网络结构。The first aspect of this embodiment provides a core-shell resin material, which includes a resin core and a resin outer layer wrapped on the surface of the core. The resin core includes a three-dimensional cross-linked network sphere, and the resin outer layer is a plasticized linear semi-reciprocal network structure. .
实施例第二方面提供了一种核壳树脂材料制备方法，包括如下步骤：The second aspect of the embodiment provides a core-shell resin material preparation method, including the following steps:
步骤S10：取甲基丙烯酸甲酯、丙烯腈、丙烯酸丁酯、丙烯酸异辛酯为第一主单体，其质量比为4:4:1:1，取羟甲基丙烯酸甲酯、甲基丙烯酸、二乙烯基苯、聚乙二醇（200）二丙烯酸酯作为第一功能单体，以及第一引发剂过硫酸钾，其中，第一主单体总质量与第一功能单体的质量比为100：5：0.5：5：5，充分混合加入水中，同时加入乳化剂OP-10和十二烷基磺酸钠和质量比1：1，乳化剂总用量为单体总质量的5wt%，配置成A反应液，单体浓度30%。取质量为总单体质量的0.3wt%的引发剂过硫酸钾配成1mol/L浓度的溶液，备用。Step S10: Take methyl methacrylate, acrylonitrile, butyl acrylate, and isooctyl acrylate as the first main monomers, and their mass ratio is 4:4:1:1. Take hydroxymethyl methyl acrylate, methyl Acrylic acid, divinylbenzene, polyethylene glycol (200) diacrylate as the first functional monomer, and the first initiator potassium persulfate, where the total mass of the first main monomer and the mass of the first functional monomer The ratio is 100:5:0.5:5:5. Mix thoroughly and add to water. At the same time, add emulsifier OP-10 and sodium dodecyl sulfonate with a mass ratio of 1:1. The total amount of emulsifier is 5wt of the total monomer mass. %, configured as reaction solution A, monomer concentration 30%. Take the initiator potassium persulfate with a mass of 0.3wt% of the total monomer mass to prepare a solution with a concentration of 1mol/L for later use.
步骤S20：取丙烯腈，苯乙烯，丙烯酸十八酯，丙烯酸丁酯，丙烯酸乙酯为第二主单体，其质量比为3:3:1:2.5:0.5，取丙烯酸，N-羟甲基丙烯酰胺，a-氰基丙烯酸酯，聚乙二醇(400)二丙烯酸酯为第二功能单体，过氧化苯甲酰为第二引发剂，与有机溶剂碳酸二甲酯混合，配置成B反应液，其中，第二主单体总质量与第二能单体的质量比100：2：2：2：2。第二引发剂过氧化苯甲酰占总单体质量的0.3%，单体浓度30%。Step S20: Take acrylonitrile, styrene, stearyl acrylate, butyl acrylate, and ethyl acrylate as the second main monomer, and the mass ratio is 3:3:1:2.5:0.5. Take acrylic acid, N-hydroxymethyl Acrylamide, a-cyanoacrylate, polyethylene glycol (400) diacrylate as the second functional monomer, benzoyl peroxide as the second initiator, mixed with the organic solvent dimethyl carbonate, configured into B reaction liquid, in which the mass ratio of the total mass of the second main monomer to the second energy monomer is 100:2:2:2:2. The second initiator benzoyl peroxide accounts for 0.3% of the total monomer mass, and the monomer concentration is 30%.
步骤S30：将A反应液加入反应釜中，升温至70℃，开始滴加第一引发剂过硫酸钾溶液，第一引发剂滴加时间2小时，滴加完后保温2小时，开始滴加B反应液（B反应液中以及溶解了适量的第二引发剂过氧化苯甲酰），反应液A单体总质量与反应液B单体总质量9：1。滴加时间1小时，70℃保温1小时，加入总单体质量的1%的增塑剂邻苯二甲酸二乙酯，同时升压到4个大气压，继续保温2小时，恢复到常压得到合成乳液，待用。Step S30: Add reaction solution A into the reaction kettle, raise the temperature to 70°C, and begin to drip the first initiator potassium persulfate solution. The dripping time of the first initiator is 2 hours. After the dripping is completed, keep the temperature for 2 hours and start dripping. Reaction liquid B (an appropriate amount of the second initiator benzoyl peroxide is dissolved in reaction liquid B), the total mass of monomers in reaction liquid A and the total mass of monomers in reaction liquid B are 9:1. The dripping time is 1 hour, and the temperature is maintained at 70°C for 1 hour. Add 1% of the plasticizer diethyl phthalate based on the total monomer mass. At the same time, the pressure is raised to 4 atmospheres, and the temperature is maintained for 2 hours. Return to normal pressure to obtain Synthetic lotion, ready to use.
步骤S40：在合成乳液中，添加总固含量0.5%的交联剂丙二胺，通过160℃喷雾干燥塔中，得到合成的隔膜功能涂层粉体，备用。粉体一次平均粒径为250nm，二次粒径为5~40μm。Step S40: Add a cross-linking agent propylenediamine with a total solid content of 0.5% to the synthetic emulsion, and pass it through a 160°C spray drying tower to obtain a synthetic membrane functional coating powder for later use. The average primary particle size of the powder is 250nm, and the secondary particle size is 5~40μm.
步骤S50：通过气流粉碎机，粉碎得到D 50=5~μm，D 90＜20 μm粉体，将粉碎后的粉末加入水中，加入分散剂聚甲基丙烯酸钠，润湿剂聚氧乙烯烷基酚醚，消泡剂改性聚二甲基硅氧烷，高速分散30分钟，再通过均质机，调整均质机压力1500bar，过完均质机后加入锂电池专用苯丙乳胶SBR，增稠剂羧甲基纤维素钠CMC，配置成10 wt% 的均相浆料，其中，分散剂占涂层材料的0.5wt%，润湿剂占功能粉体材料的3wt%，胶粘剂丁苯乳胶占功能粉体材料10wt%，CMC占功能粉体材料的0.5%，消泡剂占功能粉体材料的0.1wt%，该浆料用于隔膜涂布，浆料粒径D 50=2.3μm，D 90=10.1μm，粘度19cps。 Step S50: Use a jet mill to pulverize to obtain D 50 =5~μm, D 90 <20 μm powder. Add the pulverized powder to water, add dispersant polysodium methacrylate, and wetting agent polyoxyethylene alkyl. Phenol ether, antifoaming agent modified polydimethylsiloxane, disperse at high speed for 30 minutes, then pass through the homogenizer, adjust the homogenizer pressure to 1500bar, add styrene acrylic latex SBR specifically for lithium batteries after passing through the homogenizer. The thickener sodium carboxymethyl cellulose CMC is configured into a 10 wt% homogeneous slurry, in which the dispersant accounts for 0.5wt% of the coating material, the wetting agent accounts for 3wt% of the functional powder material, and the adhesive styrene-butadiene latex Accounting for 10wt% of the functional powder material, CMC accounts for 0.5% of the functional powder material, and the defoaming agent accounts for 0.1wt% of the functional powder material. The slurry is used for separator coating. The particle size of the slurry is D 50 =2.3 μm. D 90 =10.1μm, viscosity 19cps.
本实施例第三方面提供了一种锂离子电池涂布隔膜，包括基膜和星型互传网络球状颗粒结构在基膜表面形成的功能涂层。具体将核壳树脂材料涂布在隔膜两面，基膜采用9±1μm，孔隙率40±2%湿法膜，采用微凹辊涂布工艺，涂布密度在0.5±0.1g /m 2，透气增量小于30s，测试隔膜性能指标。 The third aspect of this embodiment provides a lithium-ion battery coating separator, which includes a base film and a functional coating formed on the surface of the base film by a star-shaped mutual transmission network spherical particle structure. Specifically, the core-shell resin material is coated on both sides of the separator. The base film is 9±1μm, the porosity is 40±2% wet film, and the micro-gravure roller coating process is used. The coating density is 0.5±0.1g/m 2 and is breathable. The increment is less than 30s, and the diaphragm performance index is tested.
实施例2Example 2
本实施例提供了一种锂离子电池涂布隔膜，其与实施例1的区别在于，将实施例1制备的核壳树脂材料采用喷涂的工艺涂布在隔膜两面，涂层覆盖率15%，涂布面密度0.5±0.1 g /m 2，基膜采用9μm+单面3μm湿法陶瓷涂布隔膜，制备的功能涂布隔膜透气增量小于20s，测试隔膜性能指标。 This embodiment provides a lithium-ion battery coated separator. The difference from Example 1 is that the core-shell resin material prepared in Example 1 is coated on both sides of the separator using a spraying process, with a coating coverage rate of 15%. The coating surface density is 0.5±0.1 g/m 2 . The base film adopts 9 μm + single-sided 3 μm wet ceramic coating separator. The prepared functional coating separator has an air permeability increment of less than 20 seconds. The separator performance indicators are tested.
实施例3Example 3
本实施例第一方面提供了一种核壳树脂材料，包括内核和包裹在内核的外层的星型互传网络的球状颗粒结构，树脂内核包括三维交联网络球状，树脂外层为增塑的线性半互传网络结构。The first aspect of this embodiment provides a core-shell resin material, which includes a core and a spherical particle structure of a star-shaped mutual transmission network wrapped in an outer layer of the core. The resin core includes a three-dimensional cross-linked network sphere, and the resin outer layer is plasticized. Linear semi-mutual transmission network structure.
本实施例第二方面提供了一种核壳树脂材料制备方法，包括如下步骤：The second aspect of this embodiment provides a core-shell resin material preparation method, including the following steps:
步骤S10：取苯乙烯、甲基丙烯酸丁酯、丙烯酸异辛酯为第一主单体，其质量比为8:1:1，取羟甲基丙烯酸甲酯、丙烯酸、二乙烯基苯作为第一功能单体，以及引发剂过硫酸铵，其中，第一主单体总质量与第一功能单体的质量比为100：5：2：10，充分混合加入水中，同时加入乳化剂OP-10和吐温80和质量比1：1，乳化剂总用量为单体总质量的4 wt%，配置成A反应液，单体浓度35%。取质量为总单体质量的0.3 wt%的引发剂过硫酸铵配成1mol/L浓度的溶液，备用。Step S10: Take styrene, butyl methacrylate, and isooctyl acrylate as the first main monomer, with a mass ratio of 8:1:1, and take methylhydroxymethacrylate, acrylic acid, and divinylbenzene as the third main monomer. A functional monomer, and the initiator ammonium persulfate. The mass ratio of the total mass of the first main monomer to the first functional monomer is 100:5:2:10. Mix them thoroughly and add them to the water. At the same time, add the emulsifier OP- The mass ratio of 10 to Tween 80 is 1:1. The total amount of emulsifier is 4 wt% of the total monomer mass. It is configured as reaction solution A with a monomer concentration of 35%. Take 0.3 wt% of the initiator ammonium persulfate based on the total monomer mass to prepare a solution with a concentration of 1 mol/L for later use.
步骤S20：取丙烯腈，丙烯酸十八酯，丙烯酸异辛酯，丙烯酸乙酯为主单体，其质量比为5:1:2:2，取甲基丙烯酸，N-羟甲基丙烯酰胺，a-氰基丙烯酸酯，聚乙二醇(200)二丙烯酸酯为第二功能单体，过氧化苯甲酰为第二引发剂，与有机溶剂碳酸二甲酯混合，配置成B反应液，其中，第二主单体总质量与第二功能单体的质量比100：2：5：2：2。第二引发剂偶氮二异丁腈占总单体质量的0.3%，单体浓度35%。Step S20: Take acrylonitrile, stearyl acrylate, isooctyl acrylate, and ethyl acrylate as the main monomers, with a mass ratio of 5:1:2:2, take methacrylic acid, and N-methylol acrylamide, a-cyanoacrylate, polyethylene glycol (200) diacrylate as the second functional monomer, benzoyl peroxide as the second initiator, mix with the organic solvent dimethyl carbonate, and prepare reaction solution B, Among them, the mass ratio of the total mass of the second main monomer to the second functional monomer is 100:2:5:2:2. The second initiator azobisisobutyronitrile accounts for 0.3% of the total monomer mass, and the monomer concentration is 35%.
步骤S20：将A反应液加入反应釜中，升温至85℃，开始滴加引发剂过硫酸铵溶液，引发剂滴加时间2小时，滴加完后保温2小时，开始滴加B反应液（B反应液中以及溶解了适量的引发剂过氧化苯甲酰），反应液A单体总质量与反应液B单体总质量8：2，滴加时间1小时，85℃保温1小时，加入总单体质量的1%的增塑剂邻苯二甲酸二乙酯，同时升压到4.5个大气压，继续保温2小时，恢复到常压得到合成乳液，待用。Step S20: Add reaction solution A into the reaction kettle, raise the temperature to 85°C, and start to dropwise add the initiator ammonium persulfate solution. The initiator dropwise addition time is 2 hours. After the dropwise addition, keep the temperature for 2 hours, and start dropping reaction solution B ( An appropriate amount of initiator benzoyl peroxide is dissolved in reaction solution B. The total mass of monomers in reaction solution A and the total mass of monomers in reaction solution B are 8:2. The dropping time is 1 hour, and the temperature is maintained at 85°C for 1 hour. Add The plasticizer diethyl phthalate accounting for 1% of the total monomer mass was raised to 4.5 atmospheres at the same time, kept incubated for 2 hours, and returned to normal pressure to obtain a synthetic emulsion, which is ready for use.
步骤S40：在合成乳液中，添加总固含量0.6%的交联剂丙二胺和N-羟基苯并三氮唑，丙二胺与N-羟基苯并三氮唑质量比1：1，通过150℃喷雾干燥塔中，得到合成的隔膜功能涂层粉体，备用。粉体一次平均粒径为300nm，二次粒径为5~40μm。Step S40: In the synthetic emulsion, add the cross-linking agent propylenediamine and N-hydroxybenzotriazole with a total solid content of 0.6%, the mass ratio of propylenediamine to N-hydroxybenzotriazole is 1:1, pass In the spray drying tower at 150°C, the synthesized membrane functional coating powder is obtained and is ready for use. The average primary particle size of the powder is 300nm, and the secondary particle size is 5~40μm.
步骤S50：通过气流粉碎机，粉碎得到D50=5~8μm，D90＜20μm粉体，将粉碎后的粉末加入水中，加入分散剂乙烯基双硬脂酰胺，润湿剂聚醚改性的有机硅，消泡剂聚氧乙烯聚氧丙烯甘油醚，高速分散60分钟，再通过均质机，调整均质机压力1000bar，过完均质机加入锂电池专用SBR乳液，增稠剂羧甲基纤维素钠，配置成7wt% 的均相浆料，其中，分散剂占涂层材料的1wt%，润湿剂占功能粉体材料的2wt%，胶粘剂丁苯乳胶占功能粉体材料8wt%，CMC占功能粉体材料的0.6wt%，聚氧乙烯聚氧丙烯甘油醚占浆料质量0.01wt%，该浆料用于隔膜涂布，浆料粒径D 50=4.5μm，D 90=13.1μm，粘度35cps。 Step S50: Crush the powder through a jet mill to obtain D50=5~8μm, D90<20μm powder. Add the pulverized powder to water, add the dispersant vinyl bisstearamide, and the wetting agent polyether-modified silicone. , the defoaming agent polyoxyethylene polyoxypropylene glyceryl ether, disperse at high speed for 60 minutes, then pass through the homogenizer, adjust the homogenizer pressure to 1000bar, and add the SBR emulsion specifically for lithium batteries after the homogenizer, and the thickener carboxymethyl fiber Sodium, configured into a homogeneous slurry of 7wt%, in which the dispersant accounts for 1wt% of the coating material, the wetting agent accounts for 2wt% of the functional powder material, and the adhesive styrene-butadiene latex accounts for 8wt% of the functional powder material, CMC Accounting for 0.6wt% of the functional powder material, polyoxyethylene polyoxypropylene glyceryl ether accounts for 0.01wt% of the slurry mass. The slurry is used for separator coating. The slurry particle size D 50 =4.5μm, D 90 =13.1μm , viscosity 35cps.
本实施例第三方面提供了一种锂离子电池涂布隔膜，包括基膜和星型互传网络球状颗粒结构在基膜表面形成的功能涂层。具体将核壳树脂材料涂布在隔膜两面，基膜采用12±1μm，孔隙率42±2%湿法膜，采用微凹辊涂布工艺，涂布密度在0.4±0.1g /m 2，透气增量小于35s，测试隔膜性能指标。 The third aspect of this embodiment provides a lithium-ion battery coating separator, which includes a base film and a functional coating formed on the surface of the base film by a star-shaped mutual transmission network spherical particle structure. Specifically, the core-shell resin material is coated on both sides of the separator. The base film is 12±1μm, the porosity is 42±2% wet film, and the micro-gravure roller coating process is used. The coating density is 0.4±0.1g/m 2 and is breathable. The increment is less than 35s, and the diaphragm performance index is tested.
实施例4Example 4
本实施例提供了一种锂离子电池涂布隔膜，其与实施例3的区别在于，将实施例1制备的隔膜能涂布浆料采用喷涂的工艺涂布在隔膜两面，涂层覆盖率15%，涂布面密度0.5±0.1 g /m 2，基膜采用12μm+单面4μm湿法陶瓷涂布隔膜，制备的功能涂布隔膜透气增量小于30s，测试隔膜性能指标。 This embodiment provides a lithium-ion battery coated separator. The difference from Example 3 is that the separator coating slurry prepared in Example 1 is coated on both sides of the separator using a spraying process, and the coating coverage is 15 %, the coating surface density is 0.5±0.1 g/m 2 , the base film adopts 12μm + single-sided 4μm wet ceramic coating separator, the prepared functional coating separator has an air permeability increment of less than 30s, and the separator performance indicators are tested.
实施例5Example 5
本实施例第一方面提供了一种核壳树脂材料，包括内核和包裹在内核的外层的星型互传网络的球状颗粒结构，树脂内核包括三维交联网络球状，树脂外层为增塑的线性半互传网络结构。The first aspect of this embodiment provides a core-shell resin material, which includes a core and a spherical particle structure of a star-shaped mutual transmission network wrapped in an outer layer of the core. The resin core includes a three-dimensional cross-linked network sphere, and the resin outer layer is plasticized. Linear semi-mutual transmission network structure.
本实施例第二方面提供了一种核壳树脂材料制备方法，包括如下步骤：The second aspect of this embodiment provides a core-shell resin material preparation method, including the following steps:
步骤S10：取苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸丁酯为第一主单体，其质量比为4:4.5:1.5，取羟甲基丙烯酸甲酯、甲基丙烯酸、N、N亚甲基双丙烯酰胺，1，4丁二醇双丙烯酸酯作为第一功能单体，以及引发剂过硫酸钾，其中，第一主单体总质量与第一功能单体的质量比为100：5：2：2:5，充分混合加入水中，同时加入乳化剂烯丙基琥珀酸烷基酯磺酸钠和吐温80和质量比1：1，乳化剂总用量为单体总质量的3wt%，配置成A反应液，单体浓度20%。取质量为总单体质量的0.3 wt%的第一引发剂过硫酸钾配成1mol/L浓度的溶液，备用。Step S10: Take styrene, methyl methacrylate, and butyl methacrylate as the first main monomer, with a mass ratio of 4:4.5:1.5, take hydroxymethyl methacrylate, methacrylic acid, N, and N Methylene bisacrylamide, 1,4-butanediol diacrylate as the first functional monomer, and potassium persulfate as the initiator, wherein the mass ratio of the total mass of the first main monomer to the first functional monomer is 100 : 5:2:2:5, mix thoroughly and add to water. At the same time, add emulsifiers sodium allyl alkyl succinate sulfonate and Tween 80 with a mass ratio of 1:1. The total amount of emulsifier is the total mass of monomers. 3wt%, configured as reaction solution A, monomer concentration 20%. Take the first initiator potassium persulfate with a mass of 0.3 wt% of the total monomer mass to prepare a solution with a concentration of 1 mol/L for later use.
步骤S20：取丙烯腈，甲基丙烯酸甲酯，丙烯酸丁酯，丙烯酸乙酯为第二主单体，其质量比为5:1:2:2，取甲基丙烯酸，N-羟甲基丙烯酰胺，a-氰基丙烯酸酯，硅烷偶联剂KH570为第二功能单体，过氧化苯甲酰为第二引发剂，与有机溶剂碳酸二乙酯混合，配置成B反应液，其中，第二主单体总质量与第二功能单体的质量比100：2：5：2：0.5。第二引发剂偶氮二异庚腈占总单体质量的0.4%，单体浓度20%。Step S20: Take acrylonitrile, methyl methacrylate, butyl acrylate, and ethyl acrylate as the second main monomer, with a mass ratio of 5:1:2:2, take methacrylic acid, and N-hydroxymethylpropylene Amide, a-cyanoacrylate, silane coupling agent KH570 as the second functional monomer, benzoyl peroxide as the second initiator, mix with the organic solvent diethyl carbonate, and configure B reaction liquid, in which the The mass ratio of the total mass of the two main monomers to the second functional monomer is 100:2:5:2:0.5. The second initiator azobisisoheptanitrile accounts for 0.4% of the total monomer mass, and the monomer concentration is 20%.
步骤S30：将A反应液加入反应釜中，升温至65℃，开始滴加引发剂过硫酸钾溶液，引发剂滴加时间2小时，滴加完后保温2小时，开始滴加B反应液（B反应液中以及溶解了适量的第二引发剂偶氮二异庚腈），反应液A单体总质量与反应液B单体总质量7：3，滴加时间2小时，65℃保温2小时，加入总单体质量的1%的增塑剂十二醇酯，同时升压到4个大气压，继续保温2小时，恢复到常压得到合成乳液，待用。Step S30: Add reaction solution A into the reaction kettle, raise the temperature to 65°C, and start dropping the initiator potassium persulfate solution for 2 hours. After the dropwise addition, keep the temperature for 2 hours, and start adding reaction solution B dropwise ( An appropriate amount of the second initiator azobisisoheptanitrile is dissolved in reaction solution B. The total mass of monomers in reaction solution A and the total mass of monomers in reaction solution B are 7:3. The dropping time is 2 hours, and the temperature is maintained at 65°C for 2 hours. hour, add 1% of the plasticizer dodecanol ester based on the total monomer mass, raise the pressure to 4 atmospheres at the same time, continue to keep it warm for 2 hours, return to normal pressure to obtain a synthetic emulsion, and set aside.
步骤S40：在合成乳液中，添加总固含量0.6%的交联剂正硅酸乙酯和N-羟基苯并三氮唑，硅酸乙酯与N-羟基苯并三氮唑质量比1：1，通过155℃喷雾干燥塔中，得到合成的隔膜功能涂层粉体，备用。粉体一次平均粒径为350nm，二次粒径为5~40μm。Step S40: In the synthetic emulsion, add cross-linking agents ethyl orthosilicate and N-hydroxybenzotriazole with a total solid content of 0.6%. The mass ratio of ethyl silicate to N-hydroxybenzotriazole is 1: 1. Pass the 155°C spray drying tower to obtain the synthesized membrane functional coating powder for later use. The average primary particle size of the powder is 350nm, and the secondary particle size is 5~40μm.
步骤S50：通过气流粉碎机，粉碎得到D 50=5~8μm，D90＜20μm粉体，将粉碎后的粉末加入水中，加入分散剂硬脂酸钠，润湿剂聚醚改性的有机硅，消泡剂聚氧乙烯聚氧丙烯甘油醚，高速分散60分钟，再通过均质机，调整均质机压力600bar，过完均质机加入锂电池专用丙烯腈与丙烯酸锂的共聚物胶粘剂，增稠剂聚丙烯酰胺，配置成8 wt% 的均相浆料，其中，分散剂占功能涂层粉体质量的1wt%，润湿剂占浆料整体质量的0.2wt%，胶粘剂丙烯腈与丙烯酸锂的共聚物占功能粉体材料的8wt%，增稠剂聚丙烯酰胺占浆料质量的0.1wt%，消泡剂聚氧乙烯聚氧丙烯甘油醚占整体浆料质量的0.01%，该浆料用于隔膜涂布，浆料粒径D 50=5.2 μm，D 90=14.1μm，粘度44cps。 Step S50: Grind the powder with D 50 =5~8 μm and D90 <20 μm through a jet mill. Add the crushed powder to water, add the dispersant sodium stearate, and the wetting agent polyether-modified silicone. The defoaming agent polyoxyethylene polyoxypropylene glyceryl ether is dispersed at high speed for 60 minutes, and then passed through the homogenizer. Adjust the pressure of the homogenizer to 600 bar. After passing through the homogenizer, add a copolymer adhesive of acrylonitrile and lithium acrylate specially used for lithium batteries. The thickener polyacrylamide is configured into a homogeneous slurry of 8 wt%, in which the dispersant accounts for 1wt% of the functional coating powder mass, the wetting agent accounts for 0.2wt% of the overall mass of the slurry, and the adhesive acrylonitrile and acrylic acid The lithium copolymer accounts for 8wt% of the functional powder material, the thickener polyacrylamide accounts for 0.1wt% of the slurry mass, and the defoaming agent polyoxyethylene polyoxypropylene glyceryl ether accounts for 0.01% of the overall slurry mass. The material is used for separator coating. The particle size of the slurry is D 50 =5.2 μm, D 90 =14.1 μm, and the viscosity is 44cps.
本实施例第三方面提供了一种锂离子电池涂布隔膜，包括基膜和星型互传网络球状颗粒结构在基膜表面形成的功能涂层。具体将核壳树脂材料涂布在隔膜两面，基膜采用12μm+单面4μm干法陶瓷涂布隔膜，孔隙率45±2%，采用微凹辊涂布工艺，涂布密度在0.5±0.1g /m 2，透气增量小于30s，测试隔膜性能指标。 The third aspect of this embodiment provides a lithium-ion battery coating separator, which includes a base film and a functional coating formed on the surface of the base film by a star-shaped mutual transmission network spherical particle structure. Specifically, the core-shell resin material is coated on both sides of the separator. The base film uses a 12 μm + single-sided 4 μm dry ceramic coating separator with a porosity of 45±2%. A micro-gravure roller coating process is used, and the coating density is 0.5±0.1g/ m 2 , the air permeability increment is less than 30s, and the membrane performance index is tested.
实施例6Example 6
本实施例提供了一种锂离子电池涂布隔膜，其与实施例5的区别在于，将实施例5制备的隔膜功能涂布浆料采用喷涂的工艺涂布在隔膜两面，涂层覆盖率15%，涂布面密度0.5±0.1 g /m 2，基膜采用12μm+单面4μm干法陶瓷涂布隔膜，制备的功能涂布隔膜透气增量小于30s，测试隔膜性能指标。 This embodiment provides a lithium-ion battery coated separator. The difference from Example 5 is that the separator functional coating slurry prepared in Example 5 is coated on both sides of the separator using a spraying process, and the coating coverage is 15 %, the coating surface density is 0.5±0.1 g/m 2 , the base film adopts 12μm + single-sided 4μm dry ceramic coating separator, the prepared functional coating separator has an air permeability increment of less than 30s, and the separator performance indicators are tested.
对比例1Comparative example 1
基膜湿法9μm+双面辊涂PVDF-HFP@LBG，涂布量0.5±0.1g/m 2。 The base film is 9μm wet + double-sided roller coated with PVDF-HFP@LBG, and the coating amount is 0.5±0.1g/m 2 .
对比例2Comparative example 2
基膜湿法9μm+单面3μm陶瓷+双面喷涂PVDF-HFP@LBG，涂布量0.5±0.1g/m 2。 The base film is 9μm wet + 3μm ceramic on one side + PVDF-HFP@LBG sprayed on both sides, coating amount 0.5±0.1g/m 2 .
对比例3Comparative example 3
基膜湿法9μm+双面辊涂AFL，涂布量0.2±0.1g/m 2。 Base film wet method 9μm + double-sided roller coating AFL, coating amount 0.2±0.1g/m 2 .
对比例4Comparative example 4
基膜湿法9μm +单面3μm陶瓷+双面喷涂AFL，涂布量0.2±0.1g/m 2。 The base film is 9μm wet + 3μm ceramic on one side + AFL sprayed on both sides, coating amount 0.2±0.1g/m 2 .
性能测试Performance Testing
进一步的，为了验证本申请实施例的进步性，对实施例1至实施例6和对比例1至对比例4进行如下性能测试：Further, in order to verify the progress of the embodiments of the present application, the following performance tests were conducted on Examples 1 to 6 and Comparative Examples 1 to 4:
1、干压粘接测试：将测试的极片和隔膜裁切成25±mm宽，200mm长的标准样，在80℃，1MPa的压力下热压60s，然后采用180°剥离强度测试方法。1. Dry pressure bonding test: Cut the tested pole pieces and diaphragms into standard samples with a width of 25±mm and a length of 200mm, hot press them at 80°C and a pressure of 1MPa for 60 seconds, and then use the 180° peel strength test method.
2、湿压粘接测试：将测试的极片和隔膜用电解液浸润后裁切成25±mm宽，200mm长的标准样，在80℃，1MPa的压力下热压60s，然后采用180°剥离强度测试方法。2. Wet pressure bonding test: Wet the tested pole pieces and separators with electrolyte and cut them into standard samples with a width of 25±mm and a length of 200mm, hot press them at 80°C and a pressure of 1MPa for 60s, and then use 180° Peel Strength Test Method.
3 、质量溶胀测试：将用于涂布隔膜功能涂层浆料120℃烘干，烘干的块状料浸入LiPF6 1mol/L EC:DMC:EMC=1:1:1的电解液中，60℃保持7天，取出块状料，表面电解液吸干，称种，计算质量增加值与干重比为质量溶胀度。3. Mass swelling test: Dry the functional coating slurry for separator coating at 120°C, and immerse the dried block material in LiPF6 1mol/L In the electrolyte of EC:DMC:EMC=1:1:1, keep it at 60°C for 7 days. Take out the block material, absorb the electrolyte on the surface, and weigh the seeds. Calculate the ratio of the mass increase value to the dry weight as the mass swelling degree.
4 、隔膜离子电导率测试：利用两块钢片组装模拟电池，采用交流阻抗的方法测出隔膜直流阻抗，然后计算其离子电导率。4. Separator ion conductivity test: Use two steel sheets to assemble a simulated battery, use the AC impedance method to measure the DC impedance of the separator, and then calculate its ion conductivity.
表1性能测试结果Table 1 Performance test results
其中，请参考表1所示，对比实施例1至实施例6与对比例1至对比例4的聚合物涂层隔膜与电极之间的界面粘结力以及隔膜在60℃电解液浸泡7天前后隔膜离子电导率变化，实施例1至实施例6均表现出优异的电极界面粘结性能，其中，辊涂正负极在干/湿压状态的粘结剥离力均能达到15 N/m以上，喷涂能达到5 N/m以上，功能涂层隔膜在60℃浸泡7天，离子电导率基本保持不变，这说明功能涂层具备优良的耐电解液性能。电解液浸泡并不会造成隔膜孔隙堵塞以及隔膜离子传导性能下降，而对比样涂布PVDF-HFP@LBG，有下降，而涂布AFL的隔膜，因材料溶胀度大，辊涂隔膜堵孔严重，电解液浸泡7天后，离子电导率下降明显，从2.8×10 -3 S.cm -1下降到0.2×10 -3 S.cm -1。 Among them, please refer to Table 1 for the interfacial adhesion between the polymer-coated separator and the electrode of Comparative Examples 1 to 6 and Comparative Examples 1 to 4 and the separator soaked in 60°C electrolyte for 7 days. The ionic conductivity of the front and rear separators changes. Examples 1 to 6 all show excellent electrode interface bonding performance. Among them, the bonding and peeling force of the roller-coated positive and negative electrodes in the dry/wet pressing state can reach 15 N/m. Above, spraying can reach more than 5 N/m. When the functional coating separator is soaked at 60°C for 7 days, the ionic conductivity remains basically unchanged, which shows that the functional coating has excellent electrolyte resistance. Soaking in the electrolyte will not cause clogging of the separator pores and a decrease in the ion conductivity of the separator. However, the control sample coated with PVDF-HFP@LBG has a decrease. However, the separator coated with AFL has serious pore blockage due to the large swelling degree of the material. , after 7 days of immersion in the electrolyte, the ionic conductivity dropped significantly, from 2.8×10 -3 S.cm -1 to 0.2×10 -3 S.cm -1 .
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (20)

  1. 一种核壳树脂材料，其特征在于，包括树脂内核和包裹在内核表面的树脂外层，所述树脂内核包括三维交联网络结构，所述树脂外层含有增塑的线性半互传网络结构。A core-shell resin material, characterized in that it includes a resin core and a resin outer layer wrapped on the surface of the core. The resin core includes a three-dimensional cross-linked network structure, and the resin outer layer contains a plasticized linear semi-reciprocal network structure. .
  2. 如权利要求1所述核壳树脂材料，其特征在于，所述核壳树脂材料包括星型互传网络球状颗粒。The core-shell resin material according to claim 1, characterized in that the core-shell resin material includes star-shaped mutual transmission network spherical particles.
  3. 如权利要求1所述核壳树脂材料，其特征在于，所述核壳树脂材料的一次粒径为200~400nm，二次粒径为5~40μm。The core-shell resin material according to claim 1, wherein the primary particle size of the core-shell resin material is 200~400 nm and the secondary particle size is 5~40 μm.
  4. 如权利要求1所述核壳树脂材料，其特征在于，形成所述树脂内核的材料包括第一主单体、第一功能单体、乳化剂、第一引发剂；The core-shell resin material of claim 1, wherein the material forming the resin core includes a first main monomer, a first functional monomer, an emulsifier, and a first initiator;
    形成所述树脂外层的材料包括第二主单体、第二功能单体、第二引发剂、有机溶剂和增塑剂。The material forming the resin outer layer includes a second main monomer, a second functional monomer, a second initiator, an organic solvent and a plasticizer.
  5. 如权利要求4所述核壳树脂材料，其特征在于，所述第一主单体、第二主单体分别独立包括甲基丙烯酸甲酯、2-甲基丙烯酸乙酯、丙烯酸甲酯、苯乙烯、丙烯腈、丙烯酸乙酯、丙烯酸异辛酯、丙烯酸十二酯、丙烯酸十八酯、1，3-丁二烯、丙烯酸丁酯、a-氰基丙烯酸酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯、丙烯酸羟丙酯、丙烯酸磷酸酯、醋酸乙烯酯中的至少一种。The core-shell resin material of claim 4, wherein the first main monomer and the second main monomer independently include methyl methacrylate, 2-ethyl methacrylate, methyl acrylate, and benzene. Ethylene, acrylonitrile, ethyl acrylate, isooctyl acrylate, dodecyl acrylate, stearyl acrylate, 1,3-butadiene, butyl acrylate, a-cyanoacrylate, butyl methacrylate, methyl At least one of ethyl acrylate, hydroxypropyl acrylate, phosphate acrylate, and vinyl acetate.
  6. 如权利要求4所述核壳树脂材料，其特征在于，所述第一功能单体、第二功能单体分别独立包括丙烯酸、丙烯酸羟乙酯、二乙烯基苯、N-羟甲基丙烯酰胺、N、N亚甲基双丙烯酰胺，1，4-丁二醇双丙烯酸酯，甲基丙烯酸、甲基丙烯酸羟乙酯、双丙酮丙烯酰胺、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、硅烷偶联剂KH570、二甲基丙烯酸乙二醇酯、聚丙二醇缩水甘油醚、双丙酮丙烯酰胺、二乙烯基苯中的中至少一种。The core-shell resin material of claim 4, wherein the first functional monomer and the second functional monomer independently include acrylic acid, hydroxyethyl acrylate, divinylbenzene, and N-methylol acrylamide. , N, N methylene bisacrylamide, 1,4-butanediol diacrylate, methacrylic acid, hydroxyethyl methacrylate, diacetone acrylamide, hydroxypropyl acrylate, hydroxypropyl methacrylate, Polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, silane coupling agent KH570, ethylene glycol dimethacrylate, polypropylene glycol shrink At least one of glyceryl ether, diacetone acrylamide, and divinylbenzene.
  7. 如权利要求4所述核壳树脂材料，其特征在于，所述乳化剂包括硬脂酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、烷基酚聚氧乙烯醚OP系列、硬脂酸聚氧乙烯醚系列，吐温系列、曲拉通100、烯丙基醚类磺酸盐、丙烯酰胺基磺酸盐、马来酸衍生物、烯丙基琥珀酸烷基酯磺酸钠至少一种。The core-shell resin material according to claim 4, characterized in that the emulsifier includes sodium stearate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene ether OP series , Stearic acid polyoxyethylene ether series, Tween series, Triton 100, allyl ether sulfonate, acrylamide sulfonate, maleic acid derivatives, allyl succinic acid alkyl ester sulfonate At least one sodium chloride.
  8. 如权利要求4所述核壳树脂材料，其特征在于，所述有机溶剂包括碳酸二甲酯，碳酸二乙酯，乙基甲基碳酸酯等至少一种。The core-shell resin material of claim 4, wherein the organic solvent includes at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and the like.
  9. 如权利要求4所述核壳树脂材料，其特征在于，所述第一引发剂、第二引发剂各自独立包括氧化苯甲酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙酯、偶氮二异丁腈、偶氮二异庚腈、过氧化二碳酸二环己酯、异丙苯过氧化氢中、过硫酸钾、过硫酸铵中的至少一种。The core-shell resin material according to claim 4, wherein the first initiator and the second initiator each independently include benzoyl oxide, tert-butyl peroxybenzoate, and diisopropyl peroxydicarbonate. , at least one of azobisisobutyronitrile, azobisisoheptanitrile, dicyclohexyl peroxydicarbonate, cumene hydroperoxide, potassium persulfate, and ammonium persulfate.
  10. 如权利要求4所述核壳树脂材料，其特征在于，所述增塑剂包括邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛酯、邻苯二甲酸丁苄酯、十二醇酯、双季戊四醇酯、甘油三乙酸酯、柠檬酸酯中的至少一种。The core-shell resin material according to claim 4, wherein the plasticizer includes dimethyl phthalate, diethyl phthalate, dioctyl phthalate, butyl phthalate. At least one of benzyl ester, dodecanol ester, dipentaerythritol ester, glycerol triacetate, and citrate ester.
  11. 如权利要求2所述核壳树脂材料，其特征在于，所述交联剂包括丙二胺、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、N-羟基苯并三氮唑、N-羟基琥珀酰亚胺、正硅酸乙酯、正硅酸甲酯、三羟甲基丙烷中的至少一种。The core-shell resin material according to claim 2, wherein the cross-linking agent includes propylene diamine, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, At least one of N-hydroxybenzotriazole, N-hydroxysuccinimide, ethyl orthosilicate, methyl orthosilicate, and trimethylolpropane.
  12. 一种核壳树脂材料的制备方法，其特征在于，包括如下步骤：A method for preparing core-shell resin materials, which is characterized by including the following steps:
    制备树脂颗粒，在所述树脂颗粒的表面形成含增塑剂的树脂包覆层，得到核壳树脂颗粒；Preparing resin particles, forming a resin coating layer containing a plasticizer on the surface of the resin particles to obtain core-shell resin particles;
    对所述树脂内核和树脂包覆层进行交联反应，得到核壳树脂材料。The resin core and the resin coating layer are cross-linked to obtain a core-shell resin material.
  13. 如权利要求12所述核壳树脂材料的制备方法，其特征在于，所述制备树脂颗粒，在所述树脂颗粒的表面形成树脂包覆层的方法包括如下步骤：The method for preparing a core-shell resin material according to claim 12, wherein the method of preparing resin particles and forming a resin coating layer on the surface of the resin particles includes the following steps:
    将第一主单体、第一功能单体、乳化剂与水进行乳化处理，得到第一乳液；emulsify the first main monomer, the first functional monomer, the emulsifier and water to obtain a first emulsion;
    将第二主单体、第二功能单体与有机溶剂进行混合处理，得到第一反应液；Mix the second main monomer, the second functional monomer and the organic solvent to obtain the first reaction liquid;
    向所述第一乳液中加入第一引发剂进行第一聚合反应，得到第二反应液；Adding a first initiator to the first emulsion to perform a first polymerization reaction to obtain a second reaction liquid;
    向所述第二反应液中加入所述第一反应液和第二引发剂进行第二聚合反应，得到第三反应液；Adding the first reaction liquid and a second initiator to the second reaction liquid to perform a second polymerization reaction to obtain a third reaction liquid;
    向所述第三反应液中加入增塑剂，得到含所述核壳树脂颗粒第四反应液。A plasticizer is added to the third reaction liquid to obtain a fourth reaction liquid containing the core-shell resin particles.
  14. 如权利要求13所述核壳树脂材料的制备方法，其特征在于，所述交联剂按照所述第一主单体、第二主单体、第一功能单体、第二功能单体总质量之和与所述交联剂质量比为100：0.5~5的比例添加所述第四反应液中。The preparation method of core-shell resin material according to claim 13, characterized in that the cross-linking agent is in accordance with the total of the first main monomer, the second main monomer, the first functional monomer and the second functional monomer. The ratio of the sum of the masses to the mass of the cross-linking agent is 100:0.5~5 and is added to the fourth reaction solution.
  15. 如权利要求13所述核壳树脂材料的制备方法，其特征在于，所述交联剂包括丙二胺、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、N-羟基苯并三氮唑、N-羟基琥珀酰亚胺、正硅酸乙酯、正硅酸甲酯、三羟甲基丙烷中的至少一种。The preparation method of core-shell resin material according to claim 13, characterized in that the cross-linking agent includes propylene diamine, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane At least one of diisocyanate, N-hydroxybenzotriazole, N-hydroxysuccinimide, ethyl orthosilicate, methyl orthosilicate, and trimethylolpropane.
  16. 如权利要求13所述核壳树脂材料的制备方法，其特征在于，所述第一主单体与第一功能单体的质量比为80~95：5~20，所述第一主单体和第一功能单体的总质量之和与乳化剂、第一引发剂的质量比为100：0.1~5：0.05~0.5。The preparation method of core-shell resin material according to claim 13, characterized in that the mass ratio of the first main monomer to the first functional monomer is 80~95:5~20, and the first main monomer The mass ratio of the sum of the total mass of the first functional monomer and the emulsifier and the first initiator is 100:0.1~5:0.05~0.5.
  17. 如权利要求13所述核壳树脂材料的制备方法，其特征在于，所述第二主单体与第一功能单体的质量比为50~80：20~50，第二主单体和第二功能单体的总质量之和与第二引发剂、有机溶剂的质量比为100：0.1~1：10~50。The preparation method of core-shell resin material according to claim 13, characterized in that the mass ratio of the second main monomer and the first functional monomer is 50~80:20~50, and the second main monomer and the first functional monomer are The mass ratio of the total mass of the bifunctional monomers to the second initiator and organic solvent is 100:0.1~1:10~50.
  18. 一种水性聚合物涂料，其特征在于，包括核壳树脂材料和其他助剂的混合物，其中，所述核壳树脂材料为权利要求1-11任一项所述核壳树脂材料或由权利要求12-17任一项制备方法制备的核壳树脂材料。A water-based polymer coating, characterized in that it includes a mixture of core-shell resin material and other auxiliaries, wherein the core-shell resin material is the core-shell resin material of any one of claims 1-11 or is composed of the core-shell resin material of any one of claims 1-11. Core-shell resin material prepared by any of the preparation methods 12-17.
  19. 一种电池隔膜，其特征在于，包括隔膜本体和权利要求18所述水性聚合物涂料在所述隔膜本体表面形成的功能涂层。A battery separator, characterized by comprising a separator body and a functional coating formed on the surface of the separator body by the water-based polymer coating of claim 18.
  20. 一种二次电池，其特征在于，包括正极和负极以及用于隔绝所述正极与所述负极的隔膜，所述隔膜为权利要求19所述的电池隔膜。 A secondary battery, characterized in that it includes a positive electrode and a negative electrode and a separator for isolating the positive electrode and the negative electrode, and the separator is the battery separator according to claim 19.
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CN114716696A (en) * 2022-04-06 2022-07-08 深圳市德立新材料科技有限公司 Core-shell resin material, preparation method thereof, water-based polymer coating, battery diaphragm and secondary battery

Cited By (4)

* Cited by examiner, † Cited by third party
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CN117106133A (en) * 2023-10-25 2023-11-24 宁德时代新能源科技股份有限公司 Polymer, primer paste, composite current collector, secondary battery and electricity utilization device
CN117106133B (en) * 2023-10-25 2024-04-09 宁德时代新能源科技股份有限公司 Polymer, primer paste, composite current collector, secondary battery and electricity utilization device
CN117458084A (en) * 2023-12-19 2024-01-26 宁德新能源科技有限公司 Secondary battery and electronic device
CN117458084B (en) * 2023-12-19 2024-03-19 宁德新能源科技有限公司 Secondary battery and electronic device

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