WO2018040911A1 - 电池隔膜和锂离子电池及其制备方法 - Google Patents

电池隔膜和锂离子电池及其制备方法 Download PDF

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WO2018040911A1
WO2018040911A1 PCT/CN2017/097563 CN2017097563W WO2018040911A1 WO 2018040911 A1 WO2018040911 A1 WO 2018040911A1 CN 2017097563 W CN2017097563 W CN 2017097563W WO 2018040911 A1 WO2018040911 A1 WO 2018040911A1
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acrylate
weight
self
copolymer
segment
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PCT/CN2017/097563
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English (en)
French (fr)
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金丽娜
单军
胡刚
何龙
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比亚迪股份有限公司
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Priority to US16/319,602 priority Critical patent/US20210280946A1/en
Priority to KR1020197005838A priority patent/KR102207081B1/ko
Priority to EP17845213.2A priority patent/EP3490032B1/en
Priority to JP2019527943A priority patent/JP6915059B2/ja
Publication of WO2018040911A1 publication Critical patent/WO2018040911A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/42—Acrylic 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
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • 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
    • 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 disclosure relates to the field of lithium ion batteries, and in particular to a battery separator, a method of preparing a battery separator, a battery separator prepared by the method, a lithium ion battery including the battery separator, and the lithium ion battery. Preparation.
  • the polymer matrix which can swell the liquid electrolyte and has lithium ion-conducting properties mainly includes polyethers (such as polyethylene oxide PEO), polyacrylonitriles (PAN), and polyacrylates (such as polymethyl methacrylate PMMA). Its copolymer), polyvinylidene fluoride (including polyvinylidene fluoride PVDF and a copolymer of vinylidene fluoride and hexafluoropropylene P (VDF-HFP)) and the like.
  • polyacrylates are a kind of researched polymer matrix. These polymers have similar functional groups with carbonate solvents in the electrolyte, so their compatibility with electrolytes is good. It has a low interface impedance with a metal lithium electrode and good interface stability, and is an ideal polymer matrix.
  • CN103633367A discloses a self-crosslinking pure acrylic emulsion (the main component is an acrylate polymer) which is widely used in the fields of leather finishing, fiber treatment, plastic, metal anticorrosion, rust prevention, woodware, exterior wall decoration, etc.
  • the use of a large number of organic solvents has been abandoned, and green production of polymer lithium ion batteries has been realized.
  • the use of the substrate for a polymer lithium ion battery has the advantages of strong lyophilicity, high liquid retention rate, and good thermal stability.
  • the GPE body has a high impedance and a low ionic conductivity, resulting in poor performance of the lithium ion battery obtained at a high rate, and a large polarization at the time of charge and discharge at a high rate, thereby affecting the performance of the lithium ion battery.
  • the phase inversion method is one of the main methods for preparing a porous membrane, and mainly includes two forms: (1) solvent evaporation precipitation phase separation method; and (2) immersion precipitation phase separation method.
  • CN101062987A discloses a porous gel polymer electrolyte membrane and a method of preparing the same.
  • the porous gel polymer electrolyte film contains 33 to 54% by weight of polyvinylidene fluoride and 3 to 15% by weight of acrylonitrile-methyl Polyethylene glycol monomethyl ether acetate copolymer and 43-52% by weight of a 1 M lithium hexafluorophosphate electrolyte.
  • the preparation method of the porous gel polymer electrolyte membrane comprises synthesizing polyethylene glycol monomethyl ether methacrylate and acrylonitrile copolymer, and then blending it with polyvinylidene fluoride to dissolve N, N-di
  • a polymer solution is prepared in a methyl acetamide solvent, and the polymer solution is coated on a glass plate, immersed in deionized water to obtain a porous film, and then adsorbed by a lithium hexafluorophosphate electrolyte.
  • the pore forming method employed in this patent application is an immersion precipitation phase separation method.
  • the purpose of the present disclosure is to overcome the defects that the self-crosslinking GPE body of the prior art has a high impedance, a low ionic conductivity, and a large polarization at the time of charge and discharge at a high rate, resulting in a poor lithium-ion battery rate.
  • a novel battery separator a method for preparing a battery separator, a battery separator prepared by the method, a lithium ion battery including the battery separator, and a method of preparing the lithium ion battery.
  • the present disclosure provides a battery separator, wherein the battery separator includes a porous base film and an adhesive layer attached to at least one surface of the porous base film, the adhesive layer containing acrylate crosslinks A polymer and a styrene-acrylate crosslinked copolymer and/or a vinylidene fluoride-hexafluoropropylene copolymer, and the adhesive layer has a porosity of 40 to 65%.
  • the present disclosure also provides a method for preparing a battery separator, which comprises attaching a slurry containing a self-crosslinking type pure acrylic emulsion and a self-crosslinking type styrene-acrylic emulsion and/or a copolymer emulsion of vinylidene fluoride and hexafluoropropylene. On at least one side surface of the porous base film, drying is then performed to form a bonding layer having a porosity of 40 to 65% on at least one side surface of the porous base film.
  • the present disclosure also provides a battery separator prepared by the above method.
  • the present disclosure also provides a lithium ion battery including a positive electrode, a negative electrode, an electrolyte, and a battery separator, wherein the battery separator is the above battery separator.
  • the present disclosure also provides a method for preparing a lithium ion battery, which comprises sequentially laminating or winding a positive electrode sheet, a battery separator, and a negative electrode sheet into a polar core, and then injecting an electrolyte into the polar core and sealing the same.
  • the battery separator is the above battery separator.
  • the battery separator provided by the present disclosure adopts a slurry containing a self-crosslinking type pure acrylic emulsion and a self-crosslinking type styrene-acrylic emulsion and/or a copolymer emulsion of vinylidene fluoride and hexafluoropropylene to form a specific porosity on the porous base film.
  • An adhesive layer comprising an acrylate crosslinked polymer and a styrene-acrylate crosslinked copolymer and/or a vinylidene fluoride-hexafluoropropylene copolymer; the adhesive layer after absorbing the electrolyte It has excellent lithium ion-leading characteristics (GPE characteristics), significantly lowers the bulk resistance, and significantly improves the ionic conductivity.
  • GPE characteristics lithium ion-leading characteristics
  • the rate charge and discharge performance is remarkably improved, and the viscosity is improved.
  • the layer layer can inhibit the decomposition of the electrolyte at a high temperature inside the battery, thereby improving the high temperature cycle performance and high temperature. Storage performance.
  • the bonding layer can be used as a transition layer to tightly bond the positive electrode tab and the negative electrode tab together, not only to form an integrated battery core to improve the hardness of the soft pack battery, but also to enable the battery to circulate.
  • the pole piece can't afford Zou, ensuring that the positive electrode piece, the negative electrode piece and the battery separator are always in close contact, reducing the capacity loss, improving the cycle characteristics of the battery, and prolonging the service life of the battery.
  • Fig. 1 is a SEM image of the porous self-crosslinking polymer film Sa1 obtained in Example 1, and the magnification was 5000 times.
  • Example 2 is a SEM picture of the porous self-crosslinking polymer film Sa4 on the surface of the CCL obtained in Example 4, and the magnification is 20,000 times.
  • Example 3 is a SEM picture of the porous self-crosslinking polymer film Sa4 on the surface of PE obtained in Example 4, and the magnification is 20,000 times.
  • Example 4 is an anatomical photograph (positive electrode and separator) of a SL435573-type LiCoO 2 /graphite soft-package polymer lithium ion battery obtained in Example 1.
  • Example 5 is an anatomical photograph (negative electrode and separator) of a SL435573-type LiCoO 2 /graphite soft-package polymer lithium ion battery obtained in Example 1.
  • Example 6 is a graph showing discharge capacity of a SL435573-type LiCoO 2 /graphite soft-package polymer lithium ion battery obtained in Example 1 and Comparative Example 2 at 25 ° C for 1 C cycle as a function of cycle number.
  • Example 7 is a graph showing the discharge capacity of a SL435573-type LiCoO 2 /graphite soft-package polymer lithium ion battery obtained in Example 1 and Comparative Example 3 at a temperature of 45 ° C and 1 C cycle as a function of the number of cycles.
  • the battery separator provided by the present disclosure includes a porous base film and an adhesive layer attached to at least one surface of the porous base film, the adhesive layer containing an acrylate crosslinked polymer and a styrene-acrylate crosslinkage a copolymer and/or a vinylidene fluoride-hexafluoropropylene copolymer, and the tie layer has a porosity of 40 to 65%.
  • the tie layer contains an acrylate crosslinked polymer and a styrene-acrylate crosslinked copolymer and/or a vinylidene fluoride-hexafluoropropylene copolymer
  • the adhesive layer contains an acrylate Crosslinked polymer and styrene-acrylate crosslinked copolymer without containing a vinylidene fluoride-hexafluoropropylene copolymer, or containing an acrylate crosslinked polymer and a vinylidene fluoride-hexafluoropropylene copolymer without The styrene-acrylate crosslinked copolymer is contained, or both the acrylate crosslinked polymer and the styrene-acrylate crosslinked copolymer and the vinylidene fluoride-hexafluoropropylene copolymer are contained.
  • copolymer emulsion containing self-crosslinking type pure acrylic emulsion and self-crosslinking type styrene-acrylic emulsion and/or vinylidene fluoride and hexafluoropropylene can also be similarly explained.
  • the acrylate crosslinked polymer refers to a polymer obtained by crosslinking polymerization of a reactive acrylate monomer.
  • the acrylate crosslinked polymer may have a degree of crosslinking of 2 to 30%, alternatively 5 to 20%.
  • the degree of crosslinking refers to the percentage of the weight of the crosslinked polymer to the total weight of the polymer.
  • the glass transition temperature of the acrylate-based crosslinked polymer may be -20 ° C to 60 ° C, for example, -12 ° C to 54 ° C.
  • the acrylate crosslinked polymer is a crosslinked polymerization of a first acrylate crosslinked polymer and a second acrylate crosslinked polymer and/or a third acrylate. a mixture of substances, either a second acrylate crosslinked polymer or a third acrylate crosslinked polymer; wherein the first acrylate crosslinked polymer contains 70-80% by weight of polymethyl a methyl acrylate segment, 2 to 10% by weight of a polyethyl acrylate segment, 10 to 20% by weight of a polybutyl acrylate segment, and 2 to 10% by weight of a polyacrylic acid segment, the second acrylate
  • the cross-linked polymer contains 30-40% by weight of polymethyl methacrylate segments, 2-10% by weight of polyethyl acrylate segments, 50-60% by weight of polybutyl acrylate segments and 2-10%.
  • the third acrylate crosslinked polymer contains 50-80% by weight of polymethyl methacrylate segment, 2-10% by weight of polyethyl acrylate segment, 15- 40% by weight of polybutyl acrylate segment and 2-10% by weight of polyacrylic acid segment; said first propylene
  • the acid ester crosslinked polymer has a glass transition temperature of 50 ° C to 60 ° C
  • the second acrylate based crosslinked polymer has a glass transition temperature of -20 ° C to -5 ° C
  • the third acrylate The cross-linked polymer has a glass transition temperature of from 30 ° C to 50 ° C.
  • the styrene-acrylate crosslinked copolymer refers to a copolymer obtained by copolymerization of a styrene monomer and a reactive acrylate monomer.
  • the weight ratio of the styrene structural unit to the acrylate structural unit in the styrene-acrylate crosslinked copolymer may be from 0.5 to 2:1, optionally from 0.67 to 1.5:1.
  • the styrene-acrylate crosslinked copolymer may have a degree of crosslinking of 2 to 30%, alternatively 5 to 20%.
  • the glass transition temperature of the styrene-acrylate crosslinked copolymer may be selected from -30 ° C to 50 ° C, for example, from -20 ° C to 50 ° C.
  • the styrene-acrylic acid The ester crosslinked copolymer contains 40-50% by weight of polystyrene segments, 5-15% by weight of polymethyl methacrylate segments, 2-10% by weight of polyethyl acrylate segments, 30-40 The wt% polybutyl acrylate segment and the 2-10% by weight polyacrylic acid segment; the styrene-acrylate crosslinked copolymer has a glass transition temperature of 15-30 °C.
  • the glass transition temperature of the vinylidene fluoride-hexafluoropropylene copolymer may be selected from -65 ° C to -40 ° C, for example, from -60 ° C to -40 ° C.
  • the vinylidene fluoride-hexafluoropropylene copolymer contains 80 to 98% by weight of a polyvinylidene fluoride segment and 2 to 20% by weight of a polyhexafluoropropylene segment, optionally 90 96% by weight of a polyvinylidene fluoride segment and 4 to 10% by weight of a polyhexafluoropropylene segment; the vinylidene fluoride-hexafluoropropylene copolymer has a glass transition temperature of from -60 ° C to -40 ° C.
  • the adhesive layer contains an acrylate-based crosslinked polymer and a styrene-acrylate cross-linked copolymer and does not contain a vinylidene fluoride-hexafluoropropylene copolymer, and the acrylate-based copolymer
  • the weight ratio of the cross-polymer to the styrene-acrylate cross-linking copolymer is 1:0.05-2, optionally 1:1-2; or the bonding layer contains an acrylate cross-linked polymer and a partial a fluoroethylene-hexafluoropropylene copolymer and no styrene-acrylate crosslinked copolymer, the weight ratio of the acrylate crosslinked polymer to the vinylidene fluoride-hexafluoropropylene copolymer is 1:0.3-25 , optionally 1:0.4-19; or, the bonding layer contains an acrylate crosslinked polymer, a styrene-acrylate cross
  • the bonding layer contains a first acrylate-based crosslinked polymer, a second acrylate-based cross-linked polymer, and a styrene-acrylate cross-linked copolymer and does not contain vinylidene fluoride - a hexafluoropropylene copolymer, and the weight ratio of the first acrylate crosslinked polymer, the second acrylate crosslinked polymer to the styrene-acrylate crosslinked copolymer is 5-10:1:10 -13; or,
  • the adhesive layer contains a first acrylate-based crosslinked polymer, a second acrylate-based cross-linked polymer, and a vinylidene fluoride-hexafluoropropylene copolymer, and does not contain a styrene-acrylate cross-linked copolymer.
  • the weight ratio of the first acrylate crosslinked polymer, the second acrylate crosslinked polymer and the vinylidene fluoride-hexafluoropropylene copolymer is 5-15:1:5-12; or
  • the adhesive layer contains a second acrylate crosslinked polymer and a vinylidene fluoride-hexafluoropropylene copolymer and does not contain a styrene-acrylate crosslinked copolymer, and the second acrylate crosslinked polymer
  • the weight ratio to the vinylidene fluoride-hexafluoropropylene copolymer is 1:5-20; or,
  • the adhesive layer comprises a second acrylate crosslinked polymer, a styrene-acrylate crosslinked copolymer and a vinylidene fluoride-hexafluoropropylene copolymer, the second acrylate crosslinked polymer, benzene Ethylene-acrylate crosslinked copolymer and partial
  • the weight ratio of the fluoroethylene-hexafluoropropylene copolymer is 1:0.5-2:1-5; or
  • the adhesive layer contains a third acrylate crosslinked polymer, a styrene-acrylate crosslinked copolymer, and a vinylidene fluoride-hexafluoropropylene copolymer, the third acrylate crosslinked polymer, benzene
  • the weight ratio of the ethylene-acrylate crosslinked copolymer to the vinylidene fluoride-hexafluoropropylene copolymer is 1:0.5-2:1-5; or
  • the adhesive layer comprises a first acrylate crosslinked polymer, a second acrylate crosslinked polymer, a styrene-acrylate crosslinked copolymer, and a vinylidene fluoride-hexafluoropropylene copolymer, the first acrylic acid
  • the weight ratio of the ester crosslinked polymer, the second acrylate crosslinked polymer, the styrene-acrylate crosslinked copolymer and the vinylidene fluoride-hexafluoropropylene copolymer is 10-15:1:0.5-2 :5-10;
  • the first acrylate-based crosslinked polymer contains 70-80% by weight of polymethyl methacrylate segment, 2-10% by weight of polyethyl acrylate segment, and 10-20% by weight of polyacrylic acid.
  • the second acrylate-based crosslinked polymer containing 30 to 40% by weight of a polymethyl methacrylate segment, 2 to 10% by weight of a poly Ethyl acrylate segment, 50-60% by weight of polybutyl acrylate segment and 2-10% by weight of polyacrylic acid segment
  • the third acrylate crosslinked polymer contains 50-80% by weight of polymethyl a methyl acrylate segment, 2 to 10% by weight of a polyethyl acrylate segment, 15 to 40% by weight of a polybutyl acrylate segment, and 2 to 10% by weight of a polyacrylic acid segment, the styrene-acrylic acid
  • the ester crosslinked copolymer contains
  • the bonding layer further contains at least one of an acrylonitrile-acrylate copolymer, a chloropropene copolymer, and a styrene-butadiene copolymer.
  • the adhesive layer further contains an acrylonitrile-acrylate copolymer
  • the adhesive layer further contains a chloropropane copolymer and/or butylbenzene copolymer
  • the weight ratio of the acrylonitrile-acrylate copolymer to the acrylate crosslinked polymer may be 0.05-2:1, for example, 0.08. -1.85:1.
  • the weight ratio of the chloropropane copolymer to the acrylate crosslinked polymer may be from 0.15 to 7:1, for example, from 0.2 to 6:1.
  • the bonding layer further contains a styrene-butadiene copolymer, the styrene-butadiene copolymer and the acrylate-based cross-linking polymerization
  • the weight ratio of the substance may be selected from 0.05 to 2:1, for example, from 0.08 to 1.85:1.
  • the single layer density of the bonding layer may be selected from 0.05 to 0.9 mg/cm 2 , for example, from 0.1 to 0.6 mg/cm 2 .
  • the one-sided thickness of the bonding layer may be selected from 0.1 to 1 ⁇ m, for example, from 0.2 to 0.6 ⁇ m.
  • the type of the porous base film is not particularly limited in the present disclosure, and may be a conventional choice in the art, and may be, for example, a polymer base film or a ceramic base film, wherein the ceramic base film is conventional in the art. Like the ceramic base film, it includes both a polymer base film and a ceramic layer on at least one side surface of the polymer base film.
  • the above polymer base film may be a conventional polyolefin film.
  • the polyolefin film includes a polypropylene (PP) film, a polyethylene (PE) film, a PE/PP/PE three-layer film, and the like.
  • the ceramic layer typically contains ceramic particles and a binder, wherein the binder may be present in an amount of from 1 to 10% by weight, alternatively from 3 to 7% by weight, relative to 100 parts by weight of the ceramic particles.
  • the ceramic particles are generally selected from at least one of Al 2 O 3 , SiO 2 , SnO 2 , ZrO 2 , TiO 2 , SiC, Si 3 N 4 , CaO, MgO, ZnO, BaTiO 3 , LiAlO 2 , and BaSO 4 . .
  • the binder may generally be a polyacrylate, a copolymer of polyvinylidene fluoride and hexafluoropropylene, a copolymer of polyvinylidene fluoride and trichloroethylene, polyacrylonitrile, polyvinylpyrrolidone, polyimide, At least one of polyvinyl alcohol or the like may be selected from a polyacrylate such as a polyacrylate having a glass transition temperature of -40 ° C to 0 ° C.
  • the polyacrylate having a glass transition temperature of -40 ° C to 0 ° C may specifically be a copolymer of monomer units such as butyl acrylate, ethyl acrylate, methyl methacrylate or acrylic acid.
  • a polyacrylate having a glass transition temperature of -40 ° C to 0 ° C is used as a binder, the processing property can be improved without affecting the bonding strength and gas permeability of the ceramic base film, and the industrial application prospect is obtained.
  • the ceramic layer may have a single side thickness of 0.1 to 3 ⁇ m, alternatively 0.5 to 2 ⁇ m.
  • the total thickness of the porous base film may generally be 9-22 ⁇ m, alternatively 9-11 ⁇ m.
  • the method for preparing a battery separator comprises attaching a slurry containing a self-crosslinking type pure acrylic emulsion and a self-crosslinking type styrene-acrylic emulsion and/or a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene to at least a porous base film. On one side surface, drying is then performed to form a bonding layer having a porosity of 40 to 65% on at least one side surface of the porous base film.
  • the self-crosslinking type pure acrylic emulsion refers to an emulsion obtained by emulsion polymerization of a reactive acrylate monomer.
  • the degree of crosslinking of the acrylate crosslinked polymer in the self-crosslinking type pure acrylic emulsion may be 2 to 30%, alternatively 5 to 20%.
  • the glass transition temperature of the acrylate-based crosslinked polymer in the self-crosslinking type pure acrylic emulsion may be selected from -20 ° C to 60 ° C, for example, from -12 ° C to 54 ° C.
  • the self-crosslinking type pure acrylic emulsion is a mixture of a first self-crosslinking type pure acrylic emulsion and a second self-crosslinking type pure acrylic emulsion and/or a third self-crosslinking type pure acrylic emulsion.
  • the acrylate crosslinked polymer in the first self-crosslinking type pure acrylic emulsion contains 70-80 weight % polymethyl methacrylate segment, 2-10% by weight of polyethyl acrylate segment, 10-20% by weight Polybutyl acrylate segment and 2-10% by weight of polyacrylic acid segment
  • the acrylate crosslinked polymer in the second self-crosslinking pure acrylic emulsion contains 30-40% by weight of polymethacrylic acid a methyl ester segment, 2 to 10% by weight of a polyethyl acrylate segment, 50 to 60% by weight of a polybutyl acrylate segment, and 2 to 10% by weight of a polyacrylic acid segment
  • the third self-crosslinking type The acrylate crosslinked polymer in the pure acrylic emulsion contains 50-80% by weight of polymethyl methacrylate segments, 2-10% by weight of polyeth
  • the self-crosslinking type styrene-acrylic emulsion refers to a copolymer emulsion obtained by copolymerizing a styrene monomer and a reactive acrylate monomer.
  • the weight ratio of the styrene structural unit to the acrylate structural unit in the styrene-acrylate copolymer may be 0.5-2:1, and optionally 0.67-1.5:1.
  • the styrene-acrylate crosslinked copolymer in the self-crosslinking styrene-acrylic emulsion may have a crosslinking degree of 2 to 30%, alternatively 5 to 20%.
  • the glass transition temperature of the styrene-acrylate crosslinked copolymer in the self-crosslinking type styrene-acrylic emulsion may be selected from -30 ° C to 50 ° C, for example, from -20 ° C to 50 ° C.
  • the styrene-acrylate crosslinked copolymer in the self-crosslinking type styrene-acrylic emulsion contains 40 to 50% by weight of a polystyrene segment, and 5 to 15% by weight of a polymethyl group.
  • a methyl acrylate segment 2 to 10% by weight of a polyethyl acrylate segment, 30 to 40% by weight of a polybutyl acrylate segment, and 2 to 10% by weight of a polyacrylic acid segment;
  • the cross-linking copolymer has a glass transition temperature of 15 to 30 °C.
  • the glass transition temperature of the vinylidene fluoride-hexafluoropropylene copolymer in the copolymer emulsion of vinylidene fluoride and hexafluoropropylene may be selected from -65 ° C to -40 ° C, for example, from -60 ° C to -40 ° C.
  • the vinylidene fluoride-hexafluoropropylene copolymer in the copolymer emulsion of vinylidene fluoride and hexafluoropropylene contains 80 to 98% by weight of a polyvinylidene fluoride segment and 2 to 20% by weight.
  • the transition temperature can be selected from -60 ° C to -40 ° C.
  • the copolymer emulsion of vinylidene fluoride and hexafluoropropylene can be obtained commercially, or can be obtained by various existing methods, or can be obtained by disposing a vinylidene fluoride-hexafluoropropylene copolymer powder into an emulsion.
  • the copolymer emulsion of vinylidene fluoride and hexafluoropropylene is prepared by the following method:
  • the dispersant is a water-soluble polymer dispersant, and includes both an ionic (polyelectrolyte) and a nonionic. among them,
  • the ionic dispersant is a polycarboxylic acid dispersant which is homopolymerized by a carboxyl group-containing vinyl monomer (such as acrylic acid, maleic anhydride, etc.) or copolymerized with other monomers, and then esterified with an alkali neutralizing alcohol.
  • the ionic dispersing agent include, but are not limited to, polyacrylic acid (PAA), polyethyleneimine (PEI), cetyltrimethylammonium bromide (CTAB), polyamide, polyacrylamide (PAM).
  • the nonionic dispersing agent includes polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), fatty alcohol polyoxyethylene ether (JFC), and the like.
  • the dispersant has a weight average molecular weight of from 100 to 500 000 g/mol, optionally from 1000 to 100,000 g/mol.
  • the concentration of the aqueous solution A of the dispersant is from 0.01 to 10% by weight, alternatively from 0.05 to 5% by weight, for example from 0.1 to 2% by weight.
  • the dispersant is used in an amount of from 0.05 to 10% by weight, alternatively from 0.1 to 6% by weight, for example from 0.1 to 2% by weight, based on the amount of the vinylidene fluoride-hexafluoropropylene copolymer powder used.
  • the ionic dispersant used is an anionic polymer (such as PAM)
  • the ionic dispersant used is a cationic polymer (such as PEI, CTAB)
  • the propylene copolymer powder is effectively protected so that it is stably dispersed in the aqueous phase.
  • the dispersant used is a nonionic polymeric dispersant, the pH of the solution is not adjusted.
  • the slurry contains a self-crosslinking type pure acrylic emulsion and a self-crosslinking type styrene-acrylic emulsion and does not contain a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene, the self-crosslinking type pure acrylic emulsion
  • the weight ratio of the solid content to the self-crosslinking type styrene-acrylic emulsion is 1:0.05-2, optionally 1:1-2; or the slurry contains self-crosslinking pure acrylic emulsion with vinylidene fluoride and six a copolymerized emulsion of fluoropropene and containing no self-crosslinking type styrene-acrylic emulsion, the self-crosslinking type pure acrylic emulsion and the copolymerized emulsion of vinylidene fluoride and hexafluoropropylene have a solid content ratio
  • the slurry contains a first self-crosslinking type pure acrylic emulsion, a second self-crosslinking type pure acrylic emulsion, and a self-crosslinking type styrene-acrylic emulsion, and does not contain vinylidene fluoride and hexafluoropropylene.
  • the weight ratio of the co-emulsion, the first self-crosslinking type pure acrylic emulsion, the second self-crosslinking type pure acrylic emulsion and the self-crosslinking type styrene-acrylic emulsion is 5-10:1:10-13; or
  • the slurry comprises a first self-crosslinking type pure acrylic emulsion, a second self-crosslinking type pure acrylic emulsion, and a vinylidene fluoride and a hexafluoropropylene Copolymer emulsion of olefin and no self-crosslinking styrene-acrylic emulsion, solid content of the first self-crosslinking pure acrylic emulsion, the second self-crosslinking pure acrylic emulsion and the copolymerized emulsion of vinylidene fluoride and hexafluoropropylene
  • the weight ratio is 5-15:1:5-12; or,
  • the slurry comprises a second self-crosslinking type pure acrylic emulsion and a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene and does not contain a self-crosslinking type styrene-acrylic emulsion, and the second self-crosslinking type pure acrylic emulsion and partial fluorine
  • the copolymerized emulsion of ethylene and hexafluoropropylene has a solid content ratio of 1:5-20; or
  • the slurry comprises a second self-crosslinking type pure acrylic emulsion, a self-crosslinking type styrene-acrylic emulsion, and a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene, the second self-crosslinking type pure acrylic emulsion, self-crosslinking type
  • the weight ratio of the solid content of the styrene-acrylic emulsion to the copolymerized emulsion of vinylidene fluoride and hexafluoropropylene is 1:0.5-2:1-5; or
  • the slurry comprises a third self-crosslinking type pure acrylic emulsion, a self-crosslinking type styrene-acrylic emulsion, and a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene, the third self-crosslinking type pure acrylic emulsion, self-crosslinking type
  • the weight ratio of the solid content of the styrene-acrylic emulsion to the copolymerized emulsion of vinylidene fluoride and hexafluoropropylene is 1:0.5-2:1-5; or
  • the slurry comprises a first self-crosslinking type pure acrylic emulsion, a second self-crosslinking type pure acrylic emulsion, a self-crosslinking type styrene-acrylic emulsion, and a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene, and the first self-crosslinking type
  • the weight ratio of the solid content of the pure acrylic emulsion, the second self-crosslinking type pure acrylic emulsion, the self-crosslinking type styrene-acrylic emulsion and the copolymerized emulsion of vinylidene fluoride and hexafluoropropylene is 10-15:1:0.5-2:5 -10;
  • the acrylate crosslinked polymer in the first self-crosslinking type pure acrylic emulsion contains 70-80% by weight of polymethyl methacrylate segment, 2-10% by weight of polyethyl acrylate segment, 10 -20% by weight of polybutyl acrylate segment and 2-10% by weight of polyacrylic acid segment
  • the acrylate crosslinked polymer in the second self-crosslinking pure acrylic emulsion contains 30-40% by weight Polymethyl methacrylate segment, 2-10% by weight of polyethyl acrylate segment, 50-60% by weight of polybutyl acrylate segment and 2-10% by weight of polyacrylic acid segment
  • the acrylate crosslinked polymer in the self-crosslinking type pure acrylic emulsion contains 50-80% by weight of polymethyl methacrylate segment, 2-10% by weight of polyethyl acrylate segment, 15-40% by weight Polybutyl acrylate segment and 2-10% by weight of polyacrylic acid segment
  • the slurry further contains at least one of a copolymerized emulsion of acrylonitrile and acrylate, a chloropropene emulsion, and a styrene-butadiene latex.
  • the slurry further contains a copolymer emulsion of acrylonitrile and acrylate
  • the slurry further contains a chloropropene emulsion and/or a styrene-butadiene latex
  • the weight ratio of the solid content of the copolymer emulsion of acrylonitrile and acrylate to the solid content of the self-crosslinking type pure acrylic emulsion may be selected as 0.05- 2:1, for example, 0.08-1.85:1.
  • the weight ratio of the solid content of the chloropropene emulsion to the solid content of the self-crosslinking type pure acrylic emulsion may be 0.15-7:1, for example, 0.2-6: 1.
  • the weight ratio of the solid content of the styrene-butadiene latex to the solid content of the self-crosslinking type pure acrylic emulsion may be 0.05-2:1, for example, 0.08-1.85: 1.
  • the slurry has a total solid content of from 0.5 to 25% by weight, such as from 1 to 20% by weight, for example from 1 to 10 weight%.
  • the method of attaching may alternatively adopt a spray coating method and/or a screen printing method to form a porous film having the above porosity directly by a discontinuous coating by a spray coating method and/or a screen printing method, so that a porous film can be prepared (not Continuous) self-crosslinking polymer coating without the need for a phase separation process.
  • the spray temperature can be selected from 30 to 80 ° C, for example from 40 to 75 ° C.
  • the screen printing temperature can be selected from 30 to 80 ° C, for example from 40 to 75 ° C.
  • the slurry may be used in an amount such that the formed bonding layer has a single-sided thickness of 0.1 to 1 ⁇ m, for example, 0.2 to 0.6 ⁇ m.
  • the temperature at which the slurry is dried in the present disclosure is not particularly limited and may be, for example, 30 to 80 ° C, for example, 40 to 75 ° C.
  • the present disclosure also provides a battery separator prepared by the above method.
  • the present disclosure also provides a lithium ion battery including a positive electrode sheet, a negative electrode sheet, an electrolyte, and a battery separator, wherein the battery separator is the above battery separator.
  • the electrolyte is well known to those skilled in the art and typically consists of an electrolyte lithium salt and an organic solvent.
  • the lithium salt of the electrolyte is a dissociable lithium salt, for example, at least one selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), and the like, an organic solvent. It may be selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), vinylene carbonate (VC), and the like. At least one of them.
  • the concentration of the electrolyte lithium salt in the electrolyte is 0.8-1.5 mol/L.
  • the positive electrode sheet is prepared by coating a positive electrode material for a lithium ion battery, a conductive agent, and a binder onto an aluminum foil.
  • the positive electrode material used includes any positive electrode material usable for a lithium ion battery, for example, lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ). At least one of the others.
  • the negative electrode sheet is prepared by applying a negative electrode material for a lithium ion battery, a conductive agent, and a binder to a copper foil.
  • the negative electrode material used includes any negative electrode material usable for a lithium ion battery, for example, at least one of graphite, soft carbon, hard carbon, and the like.
  • the main improvement of the lithium ion battery provided by the present disclosure is that a new ceramic diaphragm is used, and the arrangement pattern (connection manner) of the positive electrode sheet, the negative electrode sheet, the battery separator and the electrolyte can be the same as the prior art, Those skilled in the art will be aware of this and will not be described herein.
  • the lithium ion battery provided by the present disclosure has the advantages of high hardness, good cycle performance, long service life, good rate charge and discharge performance, and high temperature performance.
  • the method for preparing a lithium ion battery comprises sequentially laminating or winding a positive electrode sheet, a battery separator and a negative electrode sheet into a polar core, and then injecting an electrolyte into the polar core and sealing the battery separator. Battery separator.
  • polybutyl acrylate segment accounts for 15% by weight
  • polymethyl methacrylate segment accounts for 75% by weight
  • polyethyl acrylate segment accounts for 5% by weight
  • polyacrylic acid segment accounts for 5% by weight
  • vitrification Transformation temperature Tg 54°C, solid content 50% by weight, Shanghai Aigao Chemical Co., Ltd.;
  • polystyrene segment accounts for 45% by weight
  • polybutyl acrylate segment accounts for 35% by weight
  • polymethyl methacrylate segment accounts for 10% by weight
  • polyethyl acrylate segment accounts for 5% by weight
  • polyacrylic acid chain The segment accounts for 5% by weight
  • the solid content is 50% by weight.
  • Polyvinylidene fluoride segment accounts for 95% by weight
  • polyhexafluoropropylene segment accounts for 5% by weight
  • weight average molecular weight Mw 450000
  • glass transition temperature is -55 ° C
  • solid content is 30% by weight
  • Kynar powerflex LBG The composition is the same as 10278, the difference is that after drying and purification, Arkema.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • LiCoO 2 , PVDF binder and carbon black were slurried in a mass ratio of 100:0.8:0.5, coated on an aluminum foil, and dried to form a LiCoO 2 positive electrode sheet having a thickness of 0.114 mm, the same below.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Sa1 were wound in a manner to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was designated as D1.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • Self-crosslinking type pure acrylic emulsion (Shanghai Aiyi Chemical Co., Ltd., grade 1040), copolymerized emulsion of vinylidene fluoride and hexafluoropropylene (Arkema, grade 10278), self-crosslinking type pure C Emulsion (Shanghai Aiyi Chemical Co., Ltd., grade 1005) and self-crosslinking type styrene-acrylic emulsion (Shanghai Aiyi Chemical Co., Ltd., grade S601) are mixed in a solid content of 12:6:1:1, and added Appropriate amount of water was stirred and uniformly formulated into a slurry having a total solid content of 10% by weight.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet and a battery separator Sa4 were prepared by winding a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was recorded as D4, wherein the CCL faces the positive electrode. sheet.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Sa5 were prepared in a wound manner to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which is designated as D5.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Sa6 were wound in a dry room to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was designated as D6.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Sa7 were prepared in a wound manner to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was designated as D7.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a CCL base film comprising a porous self-crosslinking polymer film Sa8 (referred to as a battery separator Sa8) and a porous self-crosslinking polymer film Sb8 on a PTFE plate, wherein the porous self-crosslinking polymer film has a single face density of 0.2 g/m 2 , single side thickness is 0.4 ⁇ m.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Sa8 were wound in a dry room to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was designated as D8.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a battery separator and a lithium ion battery were prepared according to the method of Example 1, except that the slurry forming the bonding layer further contained a copolymer emulsion of acrylonitrile and acrylate (Shanghai Ai Gao Chemical Co., Ltd., grade A1030, polypropylene).
  • the nitrile segment accounts for 15% by weight
  • the polybutyl acrylate segment accounts for 30% by weight
  • the polymethyl methacrylate segment accounts for 45% by weight
  • the polyethyl acrylate segment accounts for 5% by weight
  • the polyacrylic acid segment accounts for 5 wt%.
  • a porous self-crosslinking polymer film Sa10 a CCL/PE/CCL base film (denoted as battery separator Sa10), a porous self-crosslinking polymer film Sb10 on a PTFE plate, and a lithium ion battery (denoted as D10), wherein the single side of the porous self-crosslinking polymer film
  • the density was 0.1 g/m 2 and the thickness of one side was 0.2 ⁇ m.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a CCL/PE/CCL base film comprising a porous self-crosslinking polymer film Sa11 ( It is referred to as a battery separator Sa11), a porous self-crosslinking polymer film Sb11 on a PTFE plate, and a lithium ion battery (referred to as D11), wherein the porous self-crosslinking polymer film has a single face density of 0.1 g/m 2 , The thickness of one side is 0.2 ⁇ m.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a battery separator and a lithium ion battery were prepared according to the method of Example 4, except that a copolymerized emulsion of vinylidene fluoride and hexafluoropropylene was used.
  • the vinylidene fluoride and hexafluoropropylene copolymer powders having the same solid content were used (the glass transition temperature was -55 ° C, Arkema, grade Kynar powerflex LBG) dispersion, the specific preparation process of the dispersion is as follows:
  • PVA having a weight average molecular weight of 95,000 g/mol was dissolved in water at 100 ° C to form an aqueous solution of 2.5% by weight of PVA.
  • PAA having a weight average molecular weight of 9000 g/mol and a 10% by weight NaOH solution were mixed with water to form an aqueous solution of 5% by weight of PAANa.
  • the obtained slurry was printed on both sides of the PE/CCL (9 ⁇ m/2 ⁇ m) base film and one side surface of the PTFE plate according to the method of Example 4, and then dried at 50 ° C to obtain porous self-crosslinking, respectively.
  • the PE/CCL base film of the polymer film Sa13 (referred to as the battery separator Sa13) and the porous self-crosslinking polymer film Sb13 on the PTFE plate, wherein the porous self-crosslinking polymer film has a single face density of 0.1 g/m. 2 , the thickness of one side is 0.2 ⁇ m.
  • the obtained battery separator was subjected to the method of Example 4 to prepare a lithium ion battery separator, which is designated as D13.
  • This embodiment is for explaining a battery separator and a lithium ion battery provided by the present disclosure and a method of producing the same.
  • a battery separator and a lithium ion battery were prepared in the same manner as in Example 2, except that the self-crosslinking type pure acrylic emulsion 1005 was replaced with the same weight part of the self-crosslinking type pure acrylic emulsion 1020.
  • the obtained slurry was printed on both sides of the CCL/PE/CCL (1 ⁇ m/9 ⁇ m/1 ⁇ m) base film and one side surface of the PTFE plate according to the method of Example 2, and then dried at 50 ° C to obtain respectively.
  • CCL/PE/CCL base film of porous self-crosslinking polymer film Sa14 (referred to as battery separator Sa14) and porous self-crosslinking polymer film Sb14 on PTFE plate, wherein single-sided surface density of porous self-crosslinking polymer film Both were 0.2 g/m 2 and the thickness of one side was 0.4 ⁇ m.
  • the obtained battery separator was subjected to the method of Example 2 to prepare a lithium ion battery separator, which is designated as D14.
  • This comparative example is used to illustrate a reference battery separator and a lithium ion battery and a method of preparing the same.
  • the slurry and the bonding layer were prepared in the same manner as in Example 4 except that the bonding layer was formed by a doctor blade method to obtain a PE/CCL base film including a dense self-crosslinking polymer film Ra1 (recorded as a battery).
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Ra1 were prepared in a wound manner to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was designated as DD1.
  • This comparative example is used to illustrate a reference battery separator and a lithium ion battery and a method of preparing the same.
  • the slurry and the bonding layer were prepared in the same manner as in Example 1, except that the bonding layer was formed by a doctor blade method to obtain a CCL/PE/CCL base film including a dense self-crosslinking polymer film Ra2.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet, and a battery separator Ra2 were prepared in a wound manner to prepare a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was designated as DD2.
  • This comparative example is used to illustrate a reference battery separator and a lithium ion battery and a method of preparing the same.
  • a LiCoO 2 positive electrode sheet, a graphite negative electrode sheet and a PE/CCL (9 um / 2 um) separator were prepared by winding a SL435573 type LiCoO 2 /graphite soft-package polymer lithium ion battery, which was recorded as DD3, wherein CCL Facing the positive electrode.
  • a self-crosslinking polymer film having a very good porosity can be formed on the surface of the base film CCL by screen printing, and the self-crosslinking polymer is mostly spherical.
  • a self-crosslinking polymer film having a very good porosity can be formed on the surface of the base film PE by screen printing, and the self-crosslinking polymer is mostly spherical.
  • porous self-crosslinking polymer films Sb1-Sb14 obtained in Examples 1-14 were respectively cut into discs having a diameter of 17 mm, and the thickness was measured. After weighing the mass, it was immersed in n-butanol for 2 hours, and then taken out and blotted with a filter paper. The liquid on the surface of the membrane is weighed out at this time. Calculate the porosity according to the following formula:
  • M 0 is the mass of the dry film (g)
  • M is the mass (g) after soaking for 2 h in n-butanol
  • ⁇ BuOH is the density of n-butanol (g/cm 3 )
  • r is the film.
  • the radius (cm) and d is the thickness (cm) of the film.
  • porous self-crosslinking polymer films Sb1-Sb14 obtained in Examples 1-14 were cut into discs having a diameter of 17 mm, dried, and weighed into a good mass and then immersed in an electrolyte (the electrolyte contained 32.5% by weight of EC (carbonic acid). Vinyl ester), 32.5% by weight of EMC (ethyl methyl carbonate), 32.5% by weight of DMC (dimethyl carbonate), 2.5% by weight of VC (vinylene carbonate) and 1 mol/L of LiPF 6 (lithium hexafluorophosphate) ))) 24h, then take out the liquid on the surface of the membrane with filter paper and weigh the mass at this time. The operation is carried out in a glove box filled with argon, and then calculate the liquid absorption rate according to the following formula:
  • Liquid absorption rate% (Wi-W)/W ⁇ 100%
  • the porous self-crosslinking polymer films Sb1-Sb14 obtained in Examples 1-14 and the dense self-crosslinking polymer films Rb1 and Rb2 obtained in Comparative Example 1-2 were cut into discs having a diameter of 17 mm, and after drying, Placed between two stainless steel (SS) electrodes, absorbing a sufficient amount of electrolyte (the electrolyte contains 32.5% by weight of EC (ethylene carbonate), 32.5% by weight of EMC (ethyl methyl carbonate), 32.5 weight % DMC (dimethyl carbonate), 2.5% by weight VC (vinylene carbonate) and 1 mol/L LiPF 6 (lithium hexafluorophosphate), sealed in a 2016 type button cell for AC impedance test, linear and real axis
  • Example 2 The finished battery obtained in Example 1 (pressure hot pressing at 1 MPa for 4 h at 85 ° C) was dissected in a fully charged state, and the obtained positive and negative electrode sheets and a separator were photographed. The results are shown in Fig. 2. As can be seen from Fig. 2, the black positive electrode material is all adhered to the porous self-crosslinking membrane; part of the negative electrode material is adhered to the porous self-crosslinking membrane. It can be seen that the porous self-crosslinking polymer film obtained by the present disclosure has a large viscosity to the positive and negative electrodes of the lithium ion battery, thereby greatly improving the hardness of the soft pack battery.
  • the capacity-discharge performance tests of the divided polymer lithium ion batteries obtained in Examples 1-14 and Comparative Examples 1-3 were carried out using a lithium ion battery performance test cabinet (Guangzhou Lanqi, BK6016).
  • the rate discharge test results are listed in Table 2.
  • test results show that the high-rate discharge performance of the porous self-crosslinking GPE lithium ion battery is higher than that of the dense self-crosslinking GPE lithium ion battery, which is due to the improved conductivity and the reduction of the pole during charge and discharge.
  • the phenomenon is beneficial to lithium ion migration.
  • the lithium ion battery performance test cabinet (Guangzhou Lanqi, BK6016) was used to test the 25 ° C cycle performance of the divided polymer lithium ion batteries obtained in Example 1 and Comparative Example 2.
  • the test method is as follows: the battery is charged to 4.35 V at 1 C, 0.1 C is cut off, left for 10 min, discharged at 1 C to 3.0 V, and thus circulated.
  • the cycle results are shown in Figure 3.
  • the test results show that the cycle performance of the porous self-crosslinking gel polymer electrolyte lithium ion battery prepared by the present disclosure is much better than that of using dense Self-crosslinking polymer electrolyte battery.
  • a battery using a porous self-crosslinking gel polymer electrolyte does not have such a disadvantage, and thus the cycle performance is greatly improved.
  • the lithium ion battery performance test cabinet (Guangzhou Lanqi, BK6016) was used to test the 45 ° C cycle performance of the divided polymer lithium ion batteries obtained in Example 1 and Comparative Example 3.
  • the test method is as follows: the battery is charged to 4.35 V at 1 C, 0.1 C is cut off, left for 10 min, discharged at 1 C to 3.0 V, and thus circulated.
  • the cycle results are shown in Figure 4.
  • the test results show that the high temperature cycle performance of the porous self-crosslinking gel polymer electrolyte lithium ion battery prepared by the present disclosure is better than that of the ceramic separator battery. It can be seen that the porous self-crosslinking polymer film provided by the present disclosure is useful for improving the high temperature performance of the battery when used in a battery.
  • the lithium ion batteries obtained in Example 1 and Comparative Example 3 were subjected to a storage performance test at 85 ° C for 4 hours.
  • the test method is as follows: 1 using lithium ion battery performance test cabinet (Guangzhou Lanqi, BK6016) to charge the battery to 0.55V to 4.35V, 0.02C cut off; set aside for 5min, discharge to 3.0V at 0.2C, record the discharge capacity before; 2 The battery was charged to 4.35V at 0.5C, 0.02C cut off; the voltage, internal resistance and thickness before the test was left for 1h; 3 the battery was placed in the oven at 85 °C for 4 hours; 4 the thickness was tested immediately after storage, and the test was cooled after 2 hours at room temperature.
  • Example 1 62 263 8.33
  • Example 2 48 192 7.52
  • Example 3 51 300 7.14
  • Example 4 53 311 7.52
  • Example 5 46 220 7.39
  • Example 6 55 287 7.91 Example 7 59 252 8.12 Example 8 54 76 7.86 Example 9 47 112 7.40 Example 10 48 293 7.88 Example 11 50 214 7.31 Example 12 46 182 7.26 Example 13 54 315 7.53 Example 14 47 160 7.16 Comparative example 1 - 156 5.25 Comparative example 2 - 130 5.11 Comparative example 3 - - -

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Abstract

本公开涉及锂离子电池领域，公开了一种电池隔膜和锂离子电池及其制备方法。所述电池隔膜包括多孔基膜和附着在所述多孔基膜至少一侧表面上的粘结层，所述粘结层含有丙烯酸酯类交联聚合物以及苯乙烯-丙烯酸酯类交联共聚物和/或偏氟乙烯-六氟丙烯共聚物，且所述粘结层的孔隙率为40-65％。

Description

电池隔膜和锂离子电池及其制备方法
相关申请的交叉引用
本公开主张在2016年8月29日在中国提交的中国专利申请号No.201610753606.1的优先权，其全部内容通过引用包含于此。
技术领域
本公开涉及锂离子电池领域，具体地，涉及一种电池隔膜、一种电池隔膜的制备方法、由该方法制备得到的电池隔膜、包括所述电池隔膜的锂离子电池以及所述锂离子电池的制备方法。
背景技术
可溶胀液态电解液并具有导锂离子特性的聚合物基体主要有聚醚类(如聚氧化乙烯PEO)、聚丙烯腈类(PAN)、聚丙烯酸酯类(如聚甲基丙烯酸甲酯PMMA及其共聚物)、聚偏氟乙烯类(包括聚偏二氟乙烯PVDF和偏氟乙烯和六氟丙烯的共聚物P(VDF-HFP))等。其中，聚丙烯酸酯类是研究比较多的一类聚合物基体，此类聚合物与电解液中的碳酸酯类溶剂在结构上有相似的官能团，因此，其与电解液的相容性好，与金属锂电极的界面阻抗低，界面稳定性较好，是理想的聚合物基体。
将丙烯酸酯类聚合物作为凝胶聚合物电解液(GPE)基体应用于锂离子电池已有很多专利文献报道。CN103633367A公开了将广泛应用于皮革涂饰、纤维处理、塑料、金属的防腐、防锈、木器、外墙装饰等领域的自交联纯丙乳液(主体成分为丙烯酸酯类聚合物)借鉴到聚合物锂离子电池领域，摒弃了大量有机溶剂的使用，实现了聚合物锂离子电池的绿色化生产。将该基体用于聚合物锂离子电池具有亲液性强、保液率高、热稳定好等优点。但是该GPE本体阻抗偏高、离子电导率偏低，导致得到的锂离子电池倍率性能较差，在高倍率下充放电时极化较大，从而影响了锂离子电池的性能。
为了减小自交联型GPE的本体阻抗、提高离子电导率，可对其进行造孔。倒相法是制备多孔膜的主要方法之一，其主要包括两种形式：(1)溶剂蒸发沉淀相分离法；(2)浸入沉淀相分离法。例如，CN101062987A公开了一种多孔型凝胶聚合物电解液薄膜及其制备方法。该多孔型凝胶聚合物电解液薄膜含有33-54重量％的聚偏氟乙烯、3-15重量％的丙烯腈-甲基 丙烯酸聚乙二醇单甲醚酯共聚物以及43-52重量％的1M六氟合磷酸锂碳酸酯电解液。该多孔型凝胶聚合物电解液薄膜的制备方法包括先合成甲基丙烯酸聚乙二醇单甲醚酯和丙烯腈共聚物，然后将其与聚偏氟乙烯共混溶解于N,N-二甲基乙酰胺溶剂中配制成聚合物溶液，将该聚合物溶液涂覆在玻璃板上，浸渍入去离子水中，得到多孔薄膜，再吸附六氟合磷酸锂碳酸酯电解液制得。此外，该专利申请所采用的造孔方法为浸入沉淀相分离法。
发明内容
本公开的目的是为了克服现有技术存在的自交联型GPE本体阻抗偏高、离子电导率偏低、在高倍率下充放电时极化较大而导致锂离子电池倍率较差的缺陷，而提供一种新的电池隔膜、一种电池隔膜的制备方法、由该方法制备得到的电池隔膜、包括该电池隔膜的锂离子电池以及所述锂离子电池的制备方法。
具体地，本公开提供了一种电池隔膜，其中所述电池隔膜包括多孔基膜和附着在所述多孔基膜至少一侧表面上的粘结层，所述粘结层含有丙烯酸酯类交联聚合物以及苯乙烯-丙烯酸酯类交联共聚物和/或偏氟乙烯-六氟丙烯共聚物，且所述粘结层的孔隙率为40-65％。
本公开还提供了一种电池隔膜的制备方法，该方法包括将含有自交联型纯丙乳液以及自交联型苯丙乳液和/或偏氟乙烯和六氟丙烯的共聚乳液的浆料附着在多孔基膜的至少一侧表面上，接着进行干燥，以在所述多孔基膜的至少一侧表面上形成孔隙率为40-65％的粘结层。
本公开还提供了由上述方法制备得到的电池隔膜。
本公开还提供了一种锂离子电池，所述锂离子电池包括正极、负极、电解液和电池隔膜，其中，所述电池隔膜为上述电池隔膜。
此外，本公开还提供了一种锂离子电池的制备方法，该方法包括将正极片、电池隔膜和负极片依次层叠或卷绕成极芯，然后往所述极芯中注入电解液并封口，其中，所述电池隔膜为上述电池隔膜。
本公开提供的电池隔膜采用含有自交联型纯丙乳液以及自交联型苯丙乳液和/或偏氟乙烯和六氟丙烯的共聚乳液的浆料在多孔基膜上形成具有特定孔隙率的粘结层，所述粘结层含有丙烯酸酯类交联聚合物以及苯乙烯-丙烯酸酯类交联共聚物和/或偏氟乙烯-六氟丙烯共聚物；该粘结层在吸收电解液后，具有优良的导锂离子特性(GPE特性)，本体阻抗显著降低，离子电导率显著提高，将含有该粘结层的电池隔膜用于锂离子电池时，倍率充放电性能显著提高，并且该粘结层可抑制电池内部高温下电解液的分解，从而提高了高温循环性能和高温 存储性能。此外，该粘结层可作为过渡层将正极片和负极片紧紧地粘结在一起，不仅可以形成一体化的电池极芯以提高软包电池的硬度，而且还可以使电池在循环的过程中，极片不起邹，保证正极片、负极片和电池隔膜始终紧密接触，减少容量损失，提高电池的循环特性，延长电池的使用寿命。
本公开的其它特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本公开的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本公开，但并不构成对本公开的限制。在附图中：
图1为实施例1得到的多孔自交联聚合物膜Sa1的SEM图片，放大倍数为5000倍。
图2为实施例4得到的CCL表面的多孔自交联聚合物膜Sa4的SEM图片，放大倍数为20000倍。
图3为实施例4得到的PE表面的多孔自交联聚合物膜Sa4的SEM图片，放大倍数为20000倍。
图4为实施例1所得SL435573型LiCoO2/石墨软包聚合物锂离子电池的解剖照片(正极与隔膜)。
图5为实施例1所得SL435573型LiCoO2/石墨软包聚合物锂离子电池的解剖照片(负极与隔膜)。
图6为实施例1和对比例2所得SL435573型LiCoO2/石墨软包聚合物锂离子电池在25℃、1C循环过程中的放电容量随循环次数的变化关系曲线图。
图7为实施例1和对比例3所得SL435573型LiCoO2/石墨软包聚合物锂离子电池在45℃、1C循环过程中的放电容量随循环次数的变化关系曲线图。
具体实施方式
以下对本公开的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本公开，并不用于限制本公开。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本公开提供的电池隔膜包括多孔基膜和附着在所述多孔基膜至少一侧表面上的粘结层，所述粘结层含有丙烯酸酯类交联聚合物以及苯乙烯-丙烯酸酯类交联共聚物和/或偏氟乙烯-六氟丙烯共聚物，且所述粘结层的孔隙率为40-65％。
“所述粘结层含有丙烯酸酯类交联聚合物以及苯乙烯-丙烯酸酯类交联共聚物和/或偏氟乙烯-六氟丙烯共聚物”指的是所述粘结层含有丙烯酸酯类交联聚合物与苯乙烯-丙烯酸酯类交联共聚物而不含有偏氟乙烯-六氟丙烯共聚物，或者，含有丙烯酸酯类交联聚合物与偏氟乙烯-六氟丙烯共聚物而不含有苯乙烯-丙烯酸酯类交联共聚物，或者，同时含有丙烯酸酯类交联聚合物与苯乙烯-丙烯酸酯类交联共聚物以及偏氟乙烯-六氟丙烯共聚物。此外，“含有自交联型纯丙乳液以及自交联型苯丙乳液和/或偏氟乙烯和六氟丙烯的共聚乳液”也可类似地进行解释。
所述丙烯酸酯类交联聚合物是指由反应型丙烯酸酯类单体发生交联聚合得到的聚合物。所述丙烯酸酯类交联聚合物的交联度可以为2-30％，可选为5-20％。在本公开中，所述交联度是指交联聚合物的重量占聚合物总重量的百分比。此外，所述丙烯酸酯类交联聚合物的玻璃化转变温度可选为-20℃至60℃，例如为-12℃至54℃。根据本公开的一种具体实施方式，所述丙烯酸酯类交联聚合物为第一丙烯酸酯类交联聚合物与第二丙烯酸酯类交联聚合物和/或第三丙烯酸酯类交联聚合物的混合物，或为第二丙烯酸酯类交联聚合物，或为第三丙烯酸酯类交联聚合物；其中，所述第一丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；所述第一丙烯酸酯类交联聚合物的玻璃化转变温度为50℃-60℃，所述第二丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三丙烯酸酯类交联聚合物的玻璃化转变温度为30℃-50℃。
所述苯乙烯-丙烯酸酯类交联共聚物是指由苯乙烯单体与反应型丙烯酸酯类单体发生共聚得到的共聚物。所述苯乙烯-丙烯酸酯类交联共聚物中苯乙烯结构单元与丙烯酸酯结构单元的重量比可以为0.5-2:1，可选为0.67-1.5:1。所述苯乙烯-丙烯酸酯类交联共聚物的交联度可以为2-30％，可选为5-20％。此外，所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度可选为-30℃至50℃，例如为-20℃至50℃。根据本公开的实施方式，所述苯乙烯-丙烯酸 酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃。
所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度可选为-65℃至-40℃，例如为-60℃至-40℃。根据本公开的实施方式，所述偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段，可选地含有90-96重量％的聚偏氟乙烯链段和4-10重量％的聚六氟丙烯链段；所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
根据本公开的实施方式，所述粘结层含有丙烯酸酯类交联聚合物和苯乙烯-丙烯酸酯类交联共聚物且不含有偏氟乙烯-六氟丙烯共聚物，所述丙烯酸酯类交联聚合物与苯乙烯-丙烯酸酯类交联共聚物的重量比为1：0.05-2，可选为1：1-2；或者，所述粘结层含有丙烯酸酯类交联聚合物和偏氟乙烯-六氟丙烯共聚物且不含有苯乙烯-丙烯酸酯类交联共聚物，所述丙烯酸酯类交联聚合物与偏氟乙烯-六氟丙烯共聚物的重量比为1：0.3-25，可选地为1：0.4-19；或者，所述粘结层含有丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物和偏氟乙烯-六氟丙烯共聚物，所述丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物与偏氟乙烯-六氟丙烯共聚物的重量比为1：0.01-2：0.3-5，可选为1：0.05-1.5：0.45-3。本公开的发明人经过深入研究后发现，当采用以上几种聚合物按照上述特定的比例配合使用时，非常有利于电池隔膜吸液率和电导率的提高以及加工性的改善。
根据本公开的实施方式，所述粘结层含有第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物和苯乙烯-丙烯酸酯类交联共聚物且不含有偏氟乙烯-六氟丙烯共聚物，且所述第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物与苯乙烯-丙烯酸酯类交联共聚物的重量比为5-10：1：10-13；或者，
所述粘结层含有第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物和偏氟乙烯-六氟丙烯共聚物且不含有苯乙烯-丙烯酸酯类交联共聚物，所述第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物与偏氟乙烯-六氟丙烯共聚物的重量比为5-15：1：5-12；或者，
所述粘结层含有第二丙烯酸酯类交联聚合物和偏氟乙烯-六氟丙烯共聚物且不含有苯乙烯-丙烯酸酯类交联共聚物，所述第二丙烯酸酯类交联聚合物与偏氟乙烯-六氟丙烯共聚物的重量比为1：5-20；或者，
所述粘结层含有第二丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物和偏氟乙烯-六氟丙烯共聚物，所述第二丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物与偏 氟乙烯-六氟丙烯共聚物的重量比为1：0.5-2：1-5；或者，
所述粘结层含有第三丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物和偏氟乙烯-六氟丙烯共聚物，所述第三丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物与偏氟乙烯-六氟丙烯共聚物的重量比为1：0.5-2：1-5；或者，
所述粘结层含有第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物和偏氟乙烯-六氟丙烯共聚物，第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物与偏氟乙烯-六氟丙烯共聚物的重量比为10-15：1：0.5-2：5-10；
其中，所述第一丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段；所述第一丙烯酸酯类交联聚合物的玻璃化转变温度为50℃-60℃，所述第二丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三丙烯酸酯类交联聚合物的玻璃化转变温度为30℃-50℃，所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃，所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
根据本公开，可选地，所述粘结层中还含有丙烯腈-丙烯酸酯共聚物、氯丙共聚物和丁苯共聚物中的至少一种。当所述粘结层中还含有丙烯腈-丙烯酸酯共聚物时，有利于提高电池隔膜在电池内部的离子电导率；当所述粘结层中还含有氯丙共聚物和/或丁苯共聚物时，有利于降低电池隔膜的吸液率，使吸液率不至于太高，因为吸液率过高会使得电池内部正极和负极缺乏电解液而裂化电池性能。
当所述粘结层中还含有丙烯腈-丙烯酸酯共聚物时，所述丙烯腈-丙烯酸酯共聚物与丙烯酸酯类交联聚合物的重量比可选为0.05-2：1，例如为0.08-1.85：1。当所述粘结层中还含有氯丙共聚物时，所述氯丙共聚物与丙烯酸酯类交联聚合物的重量比可选为0.15-7：1，例如为0.2-6：1。当所述粘结层中还含有丁苯共聚物时，所述丁苯共聚物与丙烯酸酯类交联聚合 物的重量比可选为0.05-2：1，例如为0.08-1.85：1。
根据本公开提供的电池隔膜，所述粘结层的单面面密度可选为0.05-0.9mg/cm2，例如为0.1-0.6mg/cm2。
根据本公开提供的电池隔膜，所述粘结层的单面厚度可选为0.1-1μm，例如为0.2-0.6μm。
本公开对所述多孔基膜的种类没有特别地限定，可以为本领域的常规选择，例如，可以为聚合物基膜，也可以为陶瓷基膜，其中，所述陶瓷基膜与本领域常规的陶瓷基膜一样，同时包括聚合物基膜和位于所述聚合物基膜至少一侧表面上的陶瓷层。上述聚合物基膜可采用现有的聚烯烃膜。所述聚烯烃膜包括聚丙烯(PP)膜、聚乙烯(PE)膜和PE/PP/PE三层膜等。所述陶瓷层通常含有陶瓷颗粒和粘结剂，其中，相对于100重量份的陶瓷颗粒，所述粘结剂的含量可以为1-10重量％，可选为3-7重量％。所述陶瓷颗粒通常选自Al2O3、SiO2、SnO2、ZrO2、TiO2、SiC、Si3N4、CaO、MgO、ZnO、BaTiO3、LiAlO2、BaSO4中的至少一种。所述粘结剂通常可以为聚丙烯酸酯、聚偏氟乙烯与六氟丙烯的共聚物、聚偏氟乙烯与三氯乙烯的共聚物、聚丙烯腈、聚乙烯基吡咯烷酮、聚酰亚胺、聚乙烯醇等中的至少一种，可选为聚丙烯酸酯，例如为玻璃化温度满足-40℃至0℃的聚丙烯酸酯。玻璃化温度满足-40℃至0℃的聚丙烯酸酯具体可以为丙烯酸丁酯、丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸等单体单元的共聚物。当采用玻璃化温度满足-40℃至0℃的聚丙烯酸酯作为粘结剂时，能够在不影响陶瓷基膜的粘结强度和透气性的基础上，改善其加工性能，更具工业应用前景。此外，所述陶瓷层的单面厚度可以为0.1-3μm，可选为0.5-2μm。
根据本公开提供的电池隔膜，所述多孔基膜的总厚度通常可以为9-22μm，可选为9-11μm。
本公开提供的电池隔膜的制备方法包括将含有自交联型纯丙乳液以及自交联型苯丙乳液和/或偏氟乙烯和六氟丙烯的共聚乳液的浆料附着在多孔基膜的至少一侧表面上，接着进行干燥，以在所述多孔基膜的至少一侧表面上形成孔隙率为40-65％的粘结层。
所述自交联型纯丙乳液是指由反应型丙烯酸酯类单体发生乳液聚合得到的乳液。所述自交联型纯丙乳液中的丙烯酸酯类交联聚合物的交联度可以为2-30％，可选为5-20％。此外，所述自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度可选为-20℃至60℃，例如为-12℃至54℃。根据本公开的实施方式，所述自交联型纯丙乳液为第一自交联型纯丙乳液与第二自交联型纯丙乳液和/或第三自交联型纯丙乳液的混合物，或为第二自交联型纯丙乳液，或为第三自交联型纯丙乳液；所述第一自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％ 的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；所述第一自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为50℃-60℃，所述第二自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为30℃-50℃。
所述自交联型苯丙乳液是指由苯乙烯单体与反应型丙烯酸酯类单体发生共聚得到共聚物乳液。其中，所述苯乙烯-丙烯酸酯类共聚物中苯乙烯结构单元与丙烯酸酯结构单元的重量比可以为0.5-2:1，可选为0.67-1.5:1。所述自交联型苯丙乳液中的苯乙烯-丙烯酸酯类交联共聚物的交联度可以为2-30％，可选为5-20％。此外，所述自交联型苯丙乳液中的苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度可选为-30℃至50℃，例如为-20℃至50℃。根据本公开的实施方式，所述自交联型苯丙乳液中的苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃。
所述偏氟乙烯和六氟丙烯的共聚乳液中的偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度可选为-65℃至-40℃，例如为-60℃至-40℃。根据本公开的实施方式，所述偏氟乙烯和六氟丙烯的共聚乳液中的偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段，可选地含有90-96重量％的聚偏氟乙烯链段和4-10重量％的聚六氟丙烯链段；所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度可选为-60℃至-40℃。
所述偏氟乙烯和六氟丙烯的共聚乳液可以通过商购得到，也可以通过现有的各种方法制备得到，还可以通过将偏氟乙烯-六氟丙烯共聚物粉末配置成乳液而得到。根据本公开的一种具体实施方式，所述偏氟乙烯和六氟丙烯的共聚乳液通过以下方法制备得到：
(1)将分散剂溶解于水中，并选择性地调节其pH值，得到分散剂的水溶液A；
(2)将偏氟乙烯-六氟丙烯共聚物粉末在搅拌下缓慢加入到分散剂的水溶液A中，待偏氟乙烯-六氟丙烯共聚物粉末加完之后，先低速搅拌，后高速搅拌，最后再高压均质分散，形成偏氟乙烯和六氟丙烯的共聚乳液。
所述分散剂为水溶性聚合物分散剂，包括离子型(聚电解质)和非离子型两类。其中， 所述离子型分散剂为聚羧酸类分散剂，其由含羧基的乙烯基单体(如丙烯酸、马来酸酐等)均聚或与其他单体共聚，后用碱中和醇酯化得到。所述离子型分散剂的实例包括但不限于：聚丙烯酸(PAA)、聚乙烯亚胺(PEI)、十六烷基三甲基溴化铵(CTAB)、聚酰胺、聚丙烯酰胺(PAM)、丙烯酸-丙烯酸酯类共聚物、丙烯酸-丙烯酰胺的共聚物[P(AA/AM)]、丙烯酸铵-丙烯酸酯类的共聚物、苯乙烯-马来酸酐共聚物(SMA)、苯乙烯-丙烯酸共聚物、丙烯酸-马来酸酐共聚物、马来酸酐-丙烯酰胺共聚物等。所述非离子型分散剂包括聚乙二醇(PEG)、聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、脂肪醇聚氧乙烯醚(JFC)等。所述分散剂的重均分子量为100-500 000g/mol，可选1000-100000g/mol。所述分散剂的水溶液A的浓度为0.01-10重量％，可选为0.05-5重量％，例如为0.1-2重量％。所述分散剂的用量为所用偏氟乙烯-六氟丙烯共聚物粉末用量的0.05-10重量％，可选0.1-6重量％，例如0.1-2重量％。当所采用的离子型分散剂为阴离子型聚合物(如PAM)时，将溶液调节至pH＝8-9，可使阴离子型聚合物完全解离，从而对偏氟乙烯-六氟丙烯共聚物粉末进行有效地保护，并使其稳定地分散在水相里。当所采用的离子型分散剂为阳离子型聚合物(如PEI，CTAB)时，将溶液调节至pH＝4-5，可使阳离子型聚合物很好地解离，从而对偏氟乙烯-六氟丙烯共聚物粉末进行有效地保护，使其稳定地分散在水相里。当所采用的分散剂为非离子型聚合物分散剂时，不调节溶液的pH值。
根据本公开的实施方式，所述浆料含有自交联型纯丙乳液与自交联型苯丙乳液且不含有偏氟乙烯和六氟丙烯的共聚乳液，所述自交联型纯丙乳液与自交联型苯丙乳液的固含量的重量比为1：0.05-2，可选为1：1-2；或者，所述浆料含有自交联型纯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液且不含有自交联型苯丙乳液，所述自交联型纯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：0.3-25，可选为1：0.4-19；或者，浆料含有自交联型纯丙乳液、自交联型苯丙乳液、偏氟乙烯和六氟丙烯的共聚乳液，所述自交联型纯丙乳液、自交联型苯丙乳液、偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：0.05-2：0.30-5，可选为1：0.05-1.5：0.45-3。本公开的发明人经过深入研究后发现，当采用以上几种聚合物乳液按照上述特定的比例配合使用时，非常有利于陶瓷隔膜吸液率和电导率的提高以及加工性的改善。
根据本公开的实施方式，所述浆料含有第一自交联型纯丙乳液、第二自交联型纯丙乳液和自交联型苯丙乳液且不含有偏氟乙烯和六氟丙烯的共聚乳液，第一自交联型纯丙乳液、第二自交联型纯丙乳液与自交联型苯丙乳液的固含量的重量比为5-10：1：10-13；或者，
所述浆料含有第一自交联型纯丙乳液、第二自交联型纯丙乳液以及偏氟乙烯和六氟丙 烯的共聚乳液且不含有自交联型苯丙乳液，所述第一自交联型纯丙乳液、第二自交联型纯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为5-15：1：5-12；或者，
所述浆料含有第二自交联型纯丙乳液以及偏氟乙烯和六氟丙烯的共聚乳液且不含有自交联型苯丙乳液，所述第二自交联型纯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：5-20；或者，
所述浆料含有第二自交联型纯丙乳液、自交联型苯丙乳液以及偏氟乙烯和六氟丙烯的共聚乳液，所述第二自交联型纯丙乳液、自交联型苯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：0.5-2：1-5；或者，
所述浆料含有第三自交联型纯丙乳液、自交联型苯丙乳液以及偏氟乙烯和六氟丙烯的共聚乳液，所述第三自交联型纯丙乳液、自交联型苯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：0.5-2：1-5；或者，
所述浆料含有第一自交联型纯丙乳液、第二自交联型纯丙乳液、自交联型苯丙乳液以及偏氟乙烯和六氟丙烯的共聚乳液，第一自交联型纯丙乳液、第二自交联型纯丙乳液、自交联型苯丙乳液与偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为10-15：1：0.5-2：5-10；
所述第一自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述自交联型苯丙乳液中的苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述偏氟乙烯和六氟丙烯的共聚乳液中的偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段；所述第一自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为50℃-60℃，所述第二自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为30℃-50℃，所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃，所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
根据本公开，可选地，所述浆料中还含有丙烯腈和丙烯酸酯的共聚乳液、氯丙乳液和丁苯胶乳中的至少一种。当所述浆料中还含有丙烯腈和丙烯酸酯的共聚乳液时，有利于提高电池隔膜在电池内部的离子电导率；当所述浆料中还含有氯丙乳液和/或丁苯胶乳时，有利于降低电池隔膜的吸液率，使吸液率不至于太高，因为吸液率过高会使得电池内部正极和负极缺乏电解液而裂化电池性能。
当所述浆料中还含有丙烯腈和丙烯酸酯的共聚乳液时，所述丙烯腈和丙烯酸酯的共聚乳液的固含量与自交联型纯丙乳液的固含量的重量比可选为0.05-2：1，例如为0.08-1.85：1。当所述浆料中还含有氯丙乳液时，所述氯丙乳液的固含量与自交联型纯丙乳液的固含量的重量比可选为0.15-7：1，例如为0.2-6：1。当所述浆料中还含有丁苯胶乳时，所述丁苯胶乳的固含量与自交联型纯丙乳液的固含量的重量比可选为0.05-2：1，例如为0.08-1.85：1。
此外，为了便于将所述浆料附着于所述多孔基膜上，可选地，所述浆料的总固含量为0.5-25重量％，如为1-20重量％，例如为1-10重量％。
所述附着的方法可选采用喷涂法和/或丝网印刷法，通过喷涂法和/或丝网印刷法形成不连续覆盖从而直接形成具有上述孔隙率的多孔膜，这样能够制备出多孔(不连续)自交联聚合物涂层，而不需要相分离的过程。
本公开对所述喷涂和丝网印刷的条件没有特别地限定。例如，所述喷涂温度可选为30-80℃，例如为40-75℃。所述丝网印刷的温度可选为30-80℃，例如为40-75℃。
所述浆料的用量可选使得形成的粘结层的单面厚度为0.1-1μm，例如为0.2-0.6μm。
本公开对将所述浆料进行干燥的温度没有特别地限定，可选为30-80℃，例如为40-75℃。
所述多孔基膜的种类以及厚度已经在上文中有所描述，在此不作赘述。
本公开还提供了由上述方法制备得到的电池隔膜。
此外，本公开还提供了一种锂离子电池，所述锂离子电池包括正极片、负极片、电解液和电池隔膜，其中，所述电池隔膜为上述电池隔膜。
所述电解液为本领域技术人员公知，其通常由电解液锂盐和有机溶剂组成。其中，电解液锂盐采用可离解的锂盐，例如，可以选自六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、四氟硼酸锂(LiBF4)等中的至少一种，有机溶剂可以选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)、碳酸亚乙烯酯(VC)等中的至少一种。可选地，所述电解液中电解液锂盐的浓度为0.8-1.5mol/L。
所述正极片是由用于锂离子电池的正极材料、导电剂和粘结剂调成浆料涂布于铝箔上 制成。所用的正极材料包括任意可用于锂离子电池的正极材料，例如，氧化钴锂(LiCoO2)、氧化镍锂(LiNiO2)、氧化锰锂(LiMn2O4)、磷酸亚铁锂(LiFePO4)等中的至少一种。
所述负极片是由用于锂离子电池的负极材料、导电剂和粘结剂调成浆料涂布于铜箔上制成。所用负极材料包括任意可用于锂离子电池的负极材料，例如，石墨、软碳、硬碳等中的至少一种。
本公开提供的锂离子电池的主要改进之处在于采用了一种新的陶瓷隔膜，而正极片、负极片、电池隔膜和电解液的排布方式(连接方式)可以与现有技术相同，对此本领域技术人员均能知悉，在此不作赘述。
本公开提供的锂离子电池具有硬度高、循环性能好、使用寿命长、倍率充放电性能好、高温性能好的优点。
本公开提供的锂离子电池的制备方法包括将正极片、电池隔膜和负极片依次层叠或卷绕成极芯，然后往所述极芯中注入电解液并封口，其中，所述电池隔膜为上述电池隔膜。
其中，所述正极片、负极片和电解液的材质或组成已经在上文中有所描述，在此不作赘述。
以下将通过实施例对本公开进行详细描述。
以下实施例和对比例中，原料的物化参数如下：
(1)自交联型纯丙乳液的成分：
1.1)1040：聚丙烯酸丁酯链段占15重量％，聚甲基丙烯酸甲酯链段占75重量％，聚丙烯酸乙酯链段占5重量％，聚丙烯酸链段占5重量％，玻璃化转变温度Tg＝54℃，固含量为50重量％，上海爱高化工有限公司；
1.2)1005：聚丙烯酸丁酯链段占55重量％，聚甲基丙烯酸甲酯链段占35重量％，聚丙烯酸乙酯链段占5重量％，聚丙烯酸链段占5重量％，玻璃化转变温度Tg＝-12℃，固含量为50重量％，上海爱高化工有限公司；
1.3)1020：聚丙烯酸丁酯链段占25重量％，聚甲基丙烯酸甲酯链段占65重量％，聚丙烯酸乙酯链段占5重量％，聚丙烯酸链段占5重量％，玻璃化转变温度Tg＝40℃，固含量为50重量％，上海爱高化工有限公司。
(2)自交联型苯丙乳液的成分：
S601：聚苯乙烯链段占45重量％，聚丙烯酸丁酯链段占35重量％，聚甲基丙烯酸甲酯链段占10重量％，聚丙烯酸乙酯链段占5重量％，聚丙烯酸链段占5重量％，玻璃化转变温度Tg＝22℃，固含量为50重量％，上海爱高化工有限公司。
(3)偏氟乙烯和六氟丙烯的共聚乳液：
10278：聚偏氟乙烯链段占95重量％，聚六氟丙烯链段占5重量％，重均分子量Mw＝450000，玻璃化温度为-55℃，固含量为30重量％，阿科玛。
(4)偏氟乙烯-六氟丙烯共聚物粉末：
Kynar powerflex LBG:成分同10278，区别在于经过了干燥和提纯，阿科玛。
以下实施例和对比例中，粘结层的面密度按照以下方法进行测定：分别取0.2m×0.2m的PTFE板和含有粘结层的PTFE板，称其重量分别为M0(g)和M(g)，面密度＝[(M-M0)/0.04]g/m2。
实施例1
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1040)、自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)和自交联型苯丙乳液(上海爱髙化工有限公司，牌号为S601)以固含量9:1:10的质量比混合，并加入适量水，搅拌均匀配成总固含量为1重量％的浆料。
(2)将上述浆料以喷涂的方法(喷涂温度为40℃)喷涂到CCL/PE/CCL(1μm/9μm/1μm，其中，PE层购自日本SK公司且牌号为BD1201，CCL层为由95重量％二氧化二铝陶瓷颗粒和5重量％的玻璃化转变温度为-20℃的聚丙烯酸酯组成的陶瓷层，下同)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜(粘结层，下同)Sa1的CCL/PE/CCL基膜(记为电池隔膜Sa1)和PTFE板上的多孔自交联聚合物膜Sb1，其中多孔自交联聚合物膜的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
(3)将LiCoO2、PVDF粘结剂和炭黑按照质量比100:0.8:0.5调成浆料涂布于铝箔上并烘干制成厚度为0.114mm的LiCoO2正极片，下同。将丁苯橡胶(SBR)和羧甲基纤维素(CMC)溶于水后，与人造石墨、导电剂按照质量比为2.5:1.5:90:6在室温下高速搅拌3.5小时，将搅拌好的材料涂于铜箔上并烘干制成厚度为0.135mm的石墨负极片，下同。
在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa1以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D1。
实施例2
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)、自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)和自交联型苯丙乳液(上海爱髙化工有限公司，牌号为S601)以固含量12:4:4的质量比混合，并加入适量水，搅拌均匀配成总固含量为5重量％的浆料。
(2)将上述浆料以丝网印刷的方法(温度为75℃)印到CCL/PE/CCL(1μm/9μm/1μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa2的CCL/PE/CCL基膜(记为陶瓷隔膜Sa2)和PTFE板上的多孔自交联聚合物膜Sb2，其中多孔自交联聚合物膜的单面面密度均为0.2g/m2，单面厚度均为0.4μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa2以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D2。
实施例3
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1040)、偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)、自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)和自交联型苯丙乳液(上海爱髙化工有限公司，牌号为S601)以固含量12:6:1:1的质量比混合，并加入适量水，搅拌均匀配成总固含量为10重量％的浆料。
(2)将上述浆料以喷涂的方法(喷涂温度为58℃)喷涂到PE(9μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa3的PE基膜(记为电池隔膜Sa3)和PTFE板上的多孔自交联聚合物膜Sb3，其中多孔自交联聚合物膜的单面面密度均为0.3g/m2，单面厚度均为0.6μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa3以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D3。
实施例4
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1040)、偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)和自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)以固含量12.7:6.3:1的质量比混合，并加入适量水，搅拌均匀配成总固含量为1重量％的浆料。
(2)将上述浆料以丝网印刷的方法(温度为40℃)印到PE/CCL(9μm/2μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa4的PE/CCL基膜(记为陶瓷隔膜Sa4)和PTFE板上的多孔自交联聚合物膜Sb4，其中多孔自交联聚合物涂层的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa4以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D4，其中CCL面朝正极片。
实施例5
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1040)、自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)和自交联型苯丙乳液(上海爱髙化工有限公司，牌号为S601)以固含量6:1:13的质量比混合，并加入适量水，搅拌均匀配成总固含量为5重量％的浆料。
(2)将上述浆料以喷涂的方法(喷涂温度为75℃)喷涂到PE(9μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa5的PE基膜(记为电池隔膜Sa5)和PTFE板上的多孔自交联聚合物膜Sb5，其中多孔自交联聚合物膜的单面面密度均为0.2g/m2，单面厚度均为0.4μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa5以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D5。
实施例6
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1040)、偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)和自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)以固含量11.4:7.6:1的质量比混合，并加入适量水，搅拌均匀配成总固含量为10重量％的浆料。
(2)将上述浆料以丝网印刷的方法(温度为58℃)印到CCL(1μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa6的CCL基膜(记为电池隔膜Sa6)和PTFE板上的多孔自交联聚合物膜Sb6，其中多孔自交联聚合物膜的单面面密度均为0.3g/m2，单面厚度均为0.6μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa6以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D6。
实施例7
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1040)、偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)和自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)以固含量9.5:9.5:1的质量比混合，并加入适量水，搅拌均匀配成总固含量为1重量％的浆料。
(2)将上述浆料以喷涂的方法(喷涂温度为40℃)喷涂到PE(9μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa7的PE基膜(记为电池隔膜Sa7)和PTFE板上的多孔自交联聚合物膜Sb7，其中多孔自交联聚合物膜的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa7以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D7。
实施例8
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)和自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)以固含量19:1的质量比混合，并加入适量水，搅拌均匀配成总固含量为5重量％的浆料。
(2)将上述浆料以丝网印刷的方法(温度为75℃)印到CCL(1μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa8的CCL基膜(记为电池隔膜Sa8)和PTFE板上的多孔自交联聚合物膜Sb8，其中多孔自交联聚合物膜的单面面密度均为0.2g/m2，单面厚度均为0.4μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa8以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D8。
实施例9
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
(1)将偏氟乙烯和六氟丙烯的共聚乳液(阿科玛，牌号为10278)和自交联型纯丙乳液(上海爱髙化工有限公司，牌号为1005)以固含量18:2的质量比混合，并加入适量水，搅拌均匀配成总固含量为10重量％的浆料。
(2)将上述浆料以喷涂的方法(喷涂温度为58℃)喷涂到PE(9μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa9的PE基膜(记为电池隔膜Sa9)和PTFE板上的多孔自交联聚合物膜Sb9，其中多孔自交联聚合物膜的单面面密度均为0.3g/m2，单面厚度均为0.6μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Sa9以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为D9。
实施例10
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
按照实施例1的方法制备电池隔膜和锂离子电池，不同的是，形成粘结层的浆料中还含有丙烯腈和丙烯酸酯的共聚乳液(上海爱高化工有限公司，牌号为A1030，聚丙烯腈链段占15重量％，聚丙烯酸丁酯链段占30重量％，聚甲基丙烯酸甲酯链段占45重量％，聚丙烯酸乙酯链段占5重量％，聚丙烯酸链段占5重量％，玻璃化转变温度Tg＝28℃，固含量为50重量％)，且A1030的固含量与1040和1005的总固含量的重量比为1：1，得到包括多孔自交联聚合物膜Sa10的CCL/PE/CCL基膜(记为电池隔膜Sa10)、PTFE板上的多孔自交联聚合物膜Sb10以及锂离子电池(记为D10)，其中多孔自交联聚合物膜的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
实施例11
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
按照实施例1的方法制备电池隔膜和锂离子电池，不同的是，形成粘结层的浆料中还含有氯丙乳液(上海爱高化工有限公司，牌号为C056，玻璃化转变温度Tg＝10℃，固含量为45重量％)，且C056的固含量与1040和1005的总固含量的重量比为3：1，得到包括多孔自交联聚合物膜Sa11的CCL/PE/CCL基膜(记为电池隔膜Sa11)、PTFE板上的多孔自交联聚合物膜Sb11以及锂离子电池(记为D11)，其中多孔自交联聚合物膜的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
实施例12
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
按照实施例1的方法制备电池隔膜和锂离子电池，不同的是，形成粘结层的浆料中还含有丁苯胶乳(日本瑞翁公司，牌号为9074，玻璃化温度Tg＝-61℃，固含量为50重量％)，且9074的固含量与1040和1005的总固含量的重量比为1：1，得到包括多孔自交联聚合物膜Sa12的CCL/PE/CCL基膜(记为电池隔膜Sa12)、PTFE板上的多孔自交联聚合物膜Sb12以及锂离子电池(记为D12)，其中多孔自交联聚合物膜的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
实施例13
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
按照实施例4的方法制备电池隔膜和锂离子电池，不同的是，将偏氟乙烯和六氟丙烯的共聚乳液采用含固含量相等的偏氟乙烯和六氟丙烯共聚物粉末(玻璃化温度为-55℃，阿科玛，牌号Kynar powerflex LBG)的分散液代替，该分散液的具体制备过程如下：
(1)将重均分子量为95000g/mol的PVA溶解于100℃的水中，形成2.5重量％PVA的水溶液。
(2)将重均分子量为9000g/mol的PAA、10重量％的NaOH溶液与水混合，形成5重量％PAANa的水溶液。
(3)在转速为30HZ的机械搅拌下，将上述PVA的水溶液、PAANa的水溶液和水混合，使得PVA和PAANa在水中的浓度均为0.05重量％，混合均匀后，形成PVA和PAANa二元分散剂的水溶液。将Kynar powerflex LBG在转速为30HZ机械搅拌下，缓慢加入到足量PVA和PAANa二元分散剂的水溶液中，使得分散剂PVA相对于LBG的质量比为0.4重量％，分散剂PAANa相对于LBG的质量比为0.4重量％，使得LBG的固含量为12.5重量％，加完后，先以50HZ的转速高速搅拌1h，然后用均质机在80MPa的压力下均质5次，形成LBG的分散液。
将所得浆料按照实施例4的方法印到PE/CCL(9μm/2μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa13的PE/CCL基膜(记为电池隔膜Sa13)和PTFE板上的多孔自交联聚合物膜Sb13，其中多孔自交联聚合物膜的单面面密度均为0.1g/m2，单面厚度均为0.2μm。
将所得电池隔膜按照实施例4的方法制备锂离子电池隔膜，记为D13。
实施例14
该实施例用于说明本公开提供的电池隔膜和锂离子电池及其制备方法。
按照实施例2的方法制备电池隔膜和锂离子电池，不同的是，将自交联型纯丙乳液1005采用相同重量份的自交联型纯丙乳液1020代替。
将所得浆料按照实施例2的方法印到CCL/PE/CCL(1μm/9μm/1μm)基膜两侧表面上以及PTFE板的一侧表面上，再在50℃下烘干，分别得到包括多孔自交联聚合物膜Sa14的CCL/PE/CCL基膜(记为电池隔膜Sa14)和PTFE板上的多孔自交联聚合物膜Sb14，其中多孔自交联聚合物膜的单面面密度均为0.2g/m2，单面厚度均为0.4μm。
将所得电池隔膜按照实施例2的方法制备锂离子电池隔膜，记为D14。
对比例1
该对比例用于说明参比的电池隔膜和锂离子电池及其制备方法。
按照实施例4的方法制备浆料和粘结层，不同的是，形成粘结层的方法为刮涂法，分别得到包括致密自交联聚合物膜Ra1的PE/CCL基膜(记为电池隔膜Ra1)和PTFE板上的致密自交联聚合物膜Rb1，其中致密自交联聚合物膜的单面面密度均为1g/m2，单面厚度均为2μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Ra1以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为DD1。
对比例2
该对比例用于说明参比的电池隔膜和锂离子电池及其制备方法。
按照实施例1的方法制备浆料和粘结层，不同的是，形成粘结层的方法为刮涂法，分别得到包括致密自交联聚合物膜Ra2的CCL/PE/CCL基膜(记为电池隔膜Ra2)和PTFE板上的致密自交联聚合物膜Rb2，其中致密自交联聚合物膜的单面面密度均为1.5g/m2，单面厚度均为3μm。
(3)在干燥房中，将LiCoO2正极片、石墨负极片和电池隔膜Ra2以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为DD2。
对比例3
该对比例用于说明参比的电池隔膜和锂离子电池及其制备方法。
在干燥房中，将LiCoO2正极片、石墨负极片和PE/CCL(9um/2um)隔膜以卷绕的方式制备SL435573型LiCoO2/石墨软包聚合物锂离子电池，记为DD3，其中CCL面朝正极片。
测试例
(1)表面形貌的观察：
采用扫描电子显微镜(SEM，JEOL，JSM-7600FE)观察实施例1和实施例4得到的多孔自交联聚合物膜Sa1以及Sa4CCL表面和Sa4PE表面的微观形貌，所得结果分别如图1(a)、图1(b)和图1(c)所示。从图1(a)中可以看出，采用喷涂法在CCL基膜表面能够形成多孔性非常好的自交联聚合物膜(粘结层，下同)。从图1(b)中可以看出，采用丝网印刷法在基膜CCL表面也能够形成多孔性非常好的自交联聚合物膜，自交联聚合物多呈球状。从图1(c)中可以看出，采用丝网印刷法在基膜PE表面也可以形成多孔性非常好的自交联聚合物膜，自交联聚合物多呈球状。
(2)孔隙率测试：
将实施例1-14得到的多孔自交联聚合物膜Sb1-Sb14分别裁成直径为17mm的圆片，测量厚度，称好质量后在正丁醇中浸泡2h，然后取出且用滤纸吸干膜表面的液体并称量出此时的质量。按照如下公式计算孔隙率：
Figure PCTCN2017097563-appb-000001
P为孔隙率，M0为干膜的质量(g)，M为在正丁醇中浸泡2h后的质量(g)，ρBuOH为正丁醇的密度(g/cm3)，r为膜的半径(cm)，d为膜的厚度(cm)。孔隙率的测试结果列于表1。由表1的结果可以看出，多孔自交联聚合物膜的孔隙率较高。
(3)吸液率测试：
将实施例1-14得到的多孔自交联聚合物膜Sb1-Sb14裁成直径为17mm的圆片，干燥好，称好质量后浸入到电解液(该电解液含有32.5重量％的EC(碳酸乙烯酯)、32.5重量％的EMC(乙基甲基碳酸酯)、32.5重量％的DMC(二甲基碳酸酯)、2.5重量％的VC(碳酸亚乙烯酯)和1mol/L LiPF6(六氟磷酸锂))中24h，然后取出用滤纸吸干膜表面的液体并称量出此时的质量，操作都在充满氩气的手套箱中进行，接着按照以下公式计算吸液率：
吸液率％＝(Wi-W)/W×100％
其中，W为干膜的质量(g)；Wi为干膜在电解液中浸泡了24h后的质量(g)。吸液率 的测试结果见表1。由表1的结果可以看出，多孔自交联聚合物膜的吸液率远远高于致密自交联聚合物膜。
(4)凝胶聚合物电解液的离子电导率的测试：
将实施例1-14得到的多孔自交联聚合物膜Sb1-Sb14以及对比例1-2得到的致密的自交联聚合物膜Rb1和Rb2裁成直径为17mm的圆片，烘干后，放在两个不锈钢(SS)电极之间，吸收足够量的电解液(该电解液含有32.5重量％的EC(碳酸乙烯酯)、32.5重量％的EMC(乙基甲基碳酸酯)、32.5重量％的DMC(二甲基碳酸酯)、2.5重量％的VC(碳酸亚乙烯酯)和1mol/L LiPF6(六氟磷酸锂))，密封于2016型扣式电池后进行交流阻抗实验，线性与实轴的交点即为电解液的本体电阻，由此可以得到离子电导率：σ＝L/A·R(其中L表示膜的厚度(cm)，A为不锈钢板与膜的接触面积(cm2)，R为电解液的本体电阻(mS))。所得电导率结果列于表1。由表1的结果可以看出，多孔自交联型GPE的本体阻抗较致密自交联型GPE有显著降低，离子电导率显著升高。
(5)膜对正负极的粘性测试：
对实施例1得到的成品电池(在85℃下经1MPa压力热压4h)在满电态下进行解剖，并对所得到的正负极片和隔膜进行拍照，结果如图2。由图2可以看出，黑色正极料全部粘在多孔自交联隔膜上；部分负极料粘在多孔自交联隔膜上。由此可见，本公开得到的多孔自交联聚合物膜对锂离子电池正负极的粘性较大，从而使软包电池的硬度大大提高。
(6)电池倍率性能的测试：
采用锂离子电池性能测试柜(广州兰奇，BK6016)对实施例1-14和对比例1-3得到的分容后的聚合物锂离子电池进行倍率放电性能测试。倍率放电测试方法为：将电池用0.5C(1C＝2520mA)恒流恒压充电至4.35V，截止电流为0.02C，搁置5min，用0.2C/0.5C/1C/2C/3C/4C放电至3.0V，记录放电容量。倍率放电测试结果列于表2。测试结果表明：多孔自交联型GPE锂离子电池高倍率放电性能较致密自交联型GPE锂离子电池有较大程度提高，这是由于其电导率提高，能够减小充放电过程中的极化现象，有利于锂离子迁移所致。
(7)常温循环性能的测试：
采用锂离子电池性能测试柜(广州兰奇，BK6016)对实施例1和对比例2得到的分容后的聚合物锂离子电池进行25℃循环性能的测试。测试方法为：将电池以1C充电至4.35V，0.1C截止，搁置10min，以1C放电至3.0V，如此循环。循环结果见图3。测试结果表明：采用本公开制备的多孔自交联凝胶聚合物电解液锂离子电池的循环性能远远好于采用致密 的自交联聚合物电解液的电池。锂离子在致密的自交联聚合物电解液中迁移较慢，从而导致采用致密自交联聚合物电解液的电池在充放电时极化较大，在每次循环的充电步骤均会产生锂枝晶将锂消耗掉，从而导致容量衰减较快。而采用多孔自交联凝胶聚合物电解液的电池则不存在这样的缺点，因此循环性能大幅度提高。
(8)高温循环性能的测试：
采用锂离子电池性能测试柜(广州兰奇，BK6016)对实施例1和对比例3得到的分容后的聚合物锂离子电池进行45℃循环性能的测试。测试方法为：将电池以1C充电至4.35V，0.1C截止，搁置10min，以1C放电至3.0V，如此循环。循环结果见图4。测试结果表明：采用本公开制备的多孔自交联凝胶聚合物电解液锂离子电池的高温循环性能好于陶瓷隔膜电池。可见，本公开提供的多孔自交联聚合物膜用于电池时有利于提高电池的高温性能。
(9)高温储存性能测试：
对实施例1和对比例3得到的锂离子电池进行85℃4h储存性能测试。测试方法如下：①采用锂离子电池性能测试柜(广州兰奇，BK6016)将电池以0.5C充电至4.35V，0.02C截止；搁置5min，以0.2C放电至3.0V，记录前放电容量；②将电池以0.5C充电至4.35V，0.02C截止；搁置1h后测试前电压、内阻、厚度；③将电池放入85℃烤箱储存4h；④储存后测试立即厚度，常温放置2h后测试冷却厚度、后电压、后内阻；⑤将电池以0.2C放电至3.0V，记录剩余容量，并计算容量剩余率(剩余容量除以前放电容量)；⑥以0.5C充满电，搁置5min，以0.2C放电至3.0V，记录恢复容量，并计算容量恢复率(恢复容量除以前容量)；测试结果见表3。由表3可知：采用本公开制备的多孔凝胶聚合物锂离子电池高温储存后在容量剩余率、容量恢复率、电压变化率、厚度变化率方面均远远好于陶瓷隔膜电池。由此可见，本公开提供的多孔自交联聚合物膜用于电池时有利于提高电池的高温性能。
表1
编号 孔隙率(％) 吸液率(％) 电导率(mS/cm)
实施例1 62 263 8.33
实施例2 48 192 7.52
实施例3 51 300 7.14
实施例4 53 311 7.52
实施例5 46 220 7.39
实施例6 55 287 7.91
实施例7 59 252 8.12
实施例8 54 76 7.86
实施例9 47 112 7.40
实施例10 48 293 7.88
实施例11 50 214 7.31
实施例12 46 182 7.26
实施例13 54 315 7.53
实施例14 47 160 7.16
对比例1 - 156 5.25
对比例2 - 130 5.11
对比例3 - - -
表2
Figure PCTCN2017097563-appb-000002
Figure PCTCN2017097563-appb-000003
表3
编号 实施例1 对比例3
前电压(V) 4.346 4.342
前内阻(mΩ) 25.4 27.1
前厚度(mm) 4.47 4.82
前容量(mAh) 2575 2512
后电压(V) 4.273 3.987
后内阻(mΩ) 29.9 35.4
立即厚度(mm) 4.58 5.15
冷却厚度(mm) 4.52 5.09
剩余容量(mAh) 2374 2135
恢复容量(mAh) 2504 2261
立即厚度变化率 2.5％ 6.8％
冷却厚度变化率 1.1％ 5.6％
容量剩余率 92.2％ 85.0％
容量恢复率 97.2％ 89.9％
电压变化率 1.7％ 8.2％
以上详细描述了本公开的实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。

Claims (22)

  1. 一种电池隔膜，包括多孔基膜，和
    附着在所述多孔基膜至少一侧表面上的粘结层，
    所述粘结层含有丙烯酸酯类交联聚合物以及苯乙烯-丙烯酸酯类交联共聚物和/或偏氟乙烯-六氟丙烯共聚物，和
    所述粘结层的孔隙率为40-65％。
  2. 根据权利要求1所述的电池隔膜，其中，所述丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至60℃，所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为-30℃至50℃，所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-65℃至-40℃。
  3. 根据权利要求1所述的电池隔膜，其中，
    所述粘结层含有所述丙烯酸酯类交联聚合物和所述苯乙烯-丙烯酸酯类交联共聚物且不含有所述偏氟乙烯-六氟丙烯共聚物，所述丙烯酸酯类交联聚合物与所述苯乙烯-丙烯酸酯类交联共聚物的重量比为1：0.05至1：2；或者，
    所述粘结层含有所述丙烯酸酯类交联聚合物和所述偏氟乙烯-六氟丙烯共聚物且不含有所述苯乙烯-丙烯酸酯类交联共聚物，所述丙烯酸酯类交联聚合物与所述偏氟乙烯-六氟丙烯共聚物的重量比为1：0.3至1：25；或者，
    所述粘结层含有所述丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物和所述偏氟乙烯-六氟丙烯共聚物，所述丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物和所述偏氟乙烯-六氟丙烯共聚物的重量比为1：(0.01至2)：(0.3至5)。
  4. 根据权利要求1所述的电池隔膜，其中，所述丙烯酸酯类交联聚合物为第一丙烯酸酯类交联聚合物与第二丙烯酸酯类交联聚合物和/或第三丙烯酸酯类交联聚合物的混合物，或为所述第二丙烯酸酯类交联聚合物，或为所述第三丙烯酸酯类交联聚合物；
    所述第一丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述 第三丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；
    所述第一丙烯酸酯类交联聚合物的玻璃化转变温度为50℃至60℃，所述第二丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三丙烯酸酯类交联聚合物的玻璃化转变温度为30℃至50℃。
  5. 根据权利要求1所述的电池隔膜，其中，所述苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃。
  6. 根据权利要求1所述的电池隔膜，其中，所述偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段；所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
  7. 根据权利要求4至6中任一项所述的电池隔膜，其中，
    所述粘结层含有第一丙烯酸酯类交联聚合物、第二丙烯酸酯类交联聚合物和所述苯乙烯-丙烯酸酯类交联共聚物且不含有所述偏氟乙烯-六氟丙烯共聚物，且所述第一丙烯酸酯类交联聚合物、所述第二丙烯酸酯类交联聚合物与所述苯乙烯-丙烯酸酯类交联共聚物的重量比为(5至10)：1：(10至13)；或者，
    所述粘结层含有所述第一丙烯酸酯类交联聚合物、所述第二丙烯酸酯类交联聚合物和所述偏氟乙烯-六氟丙烯共聚物且不含有所述苯乙烯-丙烯酸酯类交联共聚物，所述第一丙烯酸酯类交联聚合物、所述第二丙烯酸酯类交联聚合物与所述偏氟乙烯-六氟丙烯共聚物的重量比为(5至15)：1：(5至12)；或者，
    所述粘结层含有所述第二丙烯酸酯类交联聚合物和所述偏氟乙烯-六氟丙烯共聚物且不含有所述苯乙烯-丙烯酸酯类交联共聚物，所述第二丙烯酸酯类交联聚合物与所述偏氟乙烯-六氟丙烯共聚物的重量比为1：5至1：20；或者，
    所述粘结层含有所述第二丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物和所述偏氟乙烯-六氟丙烯共聚物，所述第二丙烯酸酯类交联聚合物、苯乙烯-丙烯酸酯类交联共聚物与偏氟乙烯-六氟丙烯共聚物的重量比为1：(0.5至2)：(1至5)；或者，
    所述粘结层含有第三丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物和所述偏氟乙烯-六氟丙烯共聚物，所述第三丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物与所述偏氟乙烯-六氟丙烯共聚物的重量比为1：(0.5至2)：(1至5)；或者，
    所述粘结层含有所述第一丙烯酸酯类交联聚合物、所述第二丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物和所述偏氟乙烯-六氟丙烯共聚物，所述第一丙烯酸酯类交联聚合物、所述第二丙烯酸酯类交联聚合物、所述苯乙烯-丙烯酸酯类交联共聚物与所述偏氟乙烯-六氟丙烯共聚物的重量比为(10至15)：1：(0.5至2)：(5至10)；
    其中，所述第一丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段；所述第一丙烯酸酯类交联聚合物的玻璃化转变温度为50℃至60℃，所述第二丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三丙烯酸酯类交联聚合物的玻璃化转变温度为30℃至50℃，所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃，所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
  8. 根据权利要求1至6中任一项所述的电池隔膜，其中，所述粘结层中还含有丙烯腈-丙烯酸酯共聚物、氯丙共聚物和丁苯共聚物中的至少一种；
    可选地，当所述粘结层中还含有所述丙烯腈-丙烯酸酯共聚物时，所述丙烯腈-丙烯酸酯共聚物与所述丙烯酸酯类交联聚合物的重量比为0.05：1至2：1；
    可选地，当所述粘结层中还含有所述氯丙共聚物时，所述氯丙共聚物与所述丙烯酸酯类交联聚合物的重量比为0.15：1至7：1；
    可选地，当所述粘结层中还含有所述丁苯共聚物时，所述丁苯共聚物与所述丙烯酸酯类交联聚合物的重量比为0.05：1至2：1。
  9. 根据权利要求1至6中任一项所述的电池隔膜，其中，所述粘结层的单面面密度为0.05-0.9mg/cm2；所述粘结层的单面厚度为0.1-1μm。
  10. 根据权利要求1至6中任一项所述的电池隔膜，其中，所述多孔基膜为聚合物基膜或陶瓷基膜，所述陶瓷基膜包括聚合物基膜和位于所述聚合物基膜至少一侧表面上的陶瓷层；所述多孔基膜的总厚度为9-22μm。
  11. 一种电池隔膜的制备方法，该方法包括将含有自交联型纯丙乳液以及自交联型苯丙乳液，和/或，偏氟乙烯和六氟丙烯的共聚乳液的浆料附着在多孔基膜的至少一侧表面上，接着进行干燥，以在所述多孔基膜的至少一侧表面上形成孔隙率为40-65％的粘结层。
  12. 根据权利要求11所述的方法，其中，所述自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至60℃，所述自交联型苯丙乳液中的苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为-30℃至50℃，所述偏氟乙烯和六氟丙烯的共聚乳液中的偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-65℃至-40℃。
  13. 根据权利要求11所述的方法，其中，所述浆料含有所述自交联型纯丙乳液与所述自交联型苯丙乳液且不含有所述偏氟乙烯和六氟丙烯的共聚乳液，所述自交联型纯丙乳液与所述自交联型苯丙乳液的固含量的重量比为1：0.05至1：2；或者，
    所述浆料含有所述自交联型纯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液且不含有所述自交联型苯丙乳液，所述自交联型纯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：0.3:至1：25；或者，
    所述浆料含有所述自交联型纯丙乳液、所述自交联型苯丙乳液、所述偏氟乙烯和六氟丙烯的共聚乳液，所述自交联型纯丙乳液、所述自交联型苯丙乳液、所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：(0.01至2)：(0.3至5)。
  14. 根据权利要求11所述的方法，其中，所述自交联型纯丙乳液为第一自交联型纯丙乳液与第二自交联型纯丙乳液和/或第三自交联型纯丙乳液的混合物，或为所述第二自交联型纯丙乳液，或为所述第三自交联型纯丙乳液；
    所述第一自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙 烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三自交联型纯丙乳液中的丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；
    所述第一自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为50℃至60℃，所述第二自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三自交联型纯丙乳液中的丙烯酸酯类交联聚合物的玻璃化转变温度为30℃至50℃。
  15. 根据权利要求11所述的方法，其中，所述自交联型苯丙乳液中的苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段；所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃。
  16. 根据权利要求11所述的方法，其中，所述偏氟乙烯和六氟丙烯的共聚乳液中的偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段；所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
  17. 根据权利要求11至16中任一项所述的方法，其中，
    所述浆料含有第一自交联型纯丙乳液、第二自交联型纯丙乳液和所述自交联型苯丙乳液且不含有所述偏氟乙烯和六氟丙烯的共聚乳液，所述第一自交联型纯丙乳液、所述第二自交联型纯丙乳液与所述自交联型苯丙乳液的固含量的重量比为(5至10)：1：(10至13)；或者，
    所述浆料含有所述第一自交联型纯丙乳液、所述第二自交联型纯丙乳液以及所述偏氟乙烯和六氟丙烯的共聚乳液且不含有所述自交联型苯丙乳液，所述第一自交联型纯丙乳液、所述第二自交联型纯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为(5至15)：1：(5至12)；或者，
    所述浆料含有所述第二自交联型纯丙乳液和所述偏氟乙烯和六氟丙烯的共聚乳液且不 含有所述自交联型苯丙乳液，所述第二自交联型纯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：5至1：20；或者，
    所述浆料含有所述第二自交联型纯丙乳液、所述自交联型苯丙乳液以及所述偏氟乙烯和六氟丙烯的共聚乳液，所述第二自交联型纯丙乳液、所述自交联型苯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：(0.5至2)：(1至5)；或者，
    所述浆料含有第三自交联型纯丙乳液、所述自交联型苯丙乳液和所述偏氟乙烯和六氟丙烯的共聚乳液，所述第三自交联型纯丙乳液、所述自交联型苯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为1：(0.5至2)：(1至5)；或者，
    所述浆料含有所述第一自交联型纯丙乳液、所述第二自交联型纯丙乳液、所述自交联型苯丙乳液以及所述偏氟乙烯和六氟丙烯的共聚乳液，所述第一自交联型纯丙乳液、所述第二自交联型纯丙乳液、所述自交联型苯丙乳液与所述偏氟乙烯和六氟丙烯的共聚乳液的固含量的重量比为(10至15)：1：(0.5至2)：(5至10)；
    所述第一自交联型纯丙乳液中的所述丙烯酸酯类交联聚合物含有70-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、10-20重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第二自交联型纯丙乳液中的所述丙烯酸酯类交联聚合物含有30-40重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、50-60重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述第三自交联型纯丙乳液中的所述丙烯酸酯类交联聚合物含有50-80重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、15-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述自交联型苯丙乳液中的所述苯乙烯-丙烯酸酯类交联共聚物含有40-50重量％的聚苯乙烯链段、5-15重量％的聚甲基丙烯酸甲酯链段、2-10重量％的聚丙烯酸乙酯链段、30-40重量％的聚丙烯酸丁酯链段和2-10重量％的聚丙烯酸链段，所述偏氟乙烯和六氟丙烯的共聚乳液中的所述偏氟乙烯-六氟丙烯共聚物含有80-98重量％的聚偏氟乙烯链段和2-20重量％的聚六氟丙烯链段；所述第一自交联型纯丙乳液中的所述丙烯酸酯类交联聚合物的玻璃化转变温度为50℃至60℃，所述第二自交联型纯丙乳液中的所述丙烯酸酯类交联聚合物的玻璃化转变温度为-20℃至-5℃，所述第三自交联型纯丙乳液中的所述丙烯酸酯类交联聚合物的玻璃化转变温度为30℃至50℃，所述苯乙烯-丙烯酸酯类交联共聚物的玻璃化转变温度为15-30℃，所述偏氟乙烯-六氟丙烯共聚物的玻璃化转变温度为-60℃至-40℃。
  18. 根据权利要求11至16任一项所述的方法，其中，所述浆料中还含有丙烯腈和丙 烯酸酯的共聚乳液、氯丙乳液和丁苯胶乳中的至少一种；
    可选地，当所述浆料中还含有所述丙烯腈和丙烯酸酯的共聚乳液时，所述丙烯腈和丙烯酸酯的共聚乳液与所述自交联型纯丙乳液的固含量的重量比为0.05：1至2：1；
    可选地，当所述浆料中还含有所述氯丙乳液时，所述氯丙乳液与所述自交联型纯丙乳液的固含量的重量比为0.15：1至7：1；
    可选地，当所述浆料中还含有所述丁苯胶乳时，所述丁苯胶乳与所述自交联型纯丙乳液的固含量的重量比为0.05：1至2：1。
  19. 根据权利要求11至16中任一项所述的方法，其中，所述附着的方法为喷涂法和/或丝网印刷法；所述喷涂法和丝网印刷法的操作温度各自独立地为30-80℃；所述干燥的温度为30-80℃。
  20. 由权利要求11至19中任一项所述的方法制备得到的电池隔膜。
  21. 一种锂离子电池，所述锂离子电池包括正极片、负极片、电解液和电池隔膜，其中所述电池隔膜为权利要求1至10和20中任一项所述的电池隔膜。
  22. 一种锂离子电池的制备方法，该方法包括将正极片、电池隔膜和负极片依次层叠或卷绕成极芯，然后往所述极芯中注入电解液并封口，其中所述电池隔膜为权利要求1至10和20中任意一项所述的电池隔膜。
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