WO2019154275A1 - 聚合物隔膜及其制备方法和应用以及锂离子电池及其制备方法 - Google Patents

聚合物隔膜及其制备方法和应用以及锂离子电池及其制备方法 Download PDF

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WO2019154275A1
WO2019154275A1 PCT/CN2019/074196 CN2019074196W WO2019154275A1 WO 2019154275 A1 WO2019154275 A1 WO 2019154275A1 CN 2019074196 W CN2019074196 W CN 2019074196W WO 2019154275 A1 WO2019154275 A1 WO 2019154275A1
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hydrophilic
polymer
porous
layer
polymer separator
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French (fr)
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金丽娜
宣博文
曹晓东
吴金祥
单军
胡刚
何龙
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BYD Co Ltd
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BYD Co Ltd
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Priority to JP2020564304A priority Critical patent/JP7085026B2/ja
Priority to KR1020207024562A priority patent/KR102434640B1/ko
Priority to EP19751447.4A priority patent/EP3751639A4/en
Priority to US16/967,398 priority patent/US11824225B2/en
Publication of WO2019154275A1 publication Critical patent/WO2019154275A1/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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
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    • 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
    • H01M50/443—Particulate 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
    • 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
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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 a polymer separator and a preparation method and application thereof, and to a lithium ion battery using the polymer separator and a method of preparing the same.
  • Lithium-ion batteries are mainly composed of positive/negative materials, electrolytes, separators and battery casing packaging materials.
  • the separator is an important part of the lithium ion battery, which is used to separate the positive and negative electrodes to prevent internal short circuit of the battery; the diaphragm allows the electrolyte ions to pass freely, completing the electrochemical charging and discharging process.
  • the performance of the diaphragm determines the interface structure and internal resistance of the battery, which directly affects the rate performance, cycle performance and safety performance (high temperature resistance) of the battery.
  • the separator with excellent performance plays an important role in improving the overall performance of the battery.
  • the polyethylene and polypropylene microporous membranes prepared by mechanical stretching method are currently the main commercial lithium ion battery separators.
  • commercial microporous membrane shrinkage caused by closed cells near the melting temperature causes short circuit of the battery, which causes the battery to have the danger of burning and explosion at high temperature.
  • the polyolefin separator has poor adsorption to the electrolyte, which is not conducive to lithium ion during charging and discharging. Conduction.
  • polyethers such as polyethylene oxide
  • polyacrylonitriles such as polymethyl methacrylate and copolymers thereof
  • polyvinylidene fluoride are coated on both sides of the polyolefin microporous membrane.
  • a porous film of a polar polymer including polyvinylidene fluoride and a copolymer of vinylidene fluoride and hexafluoropropylene
  • 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.
  • PVdF polyvinylidene fluoride
  • PVdF coating technology uses solvent evaporation precipitation phase separation method to make pores on the surface of polyolefin microporous membrane to obtain PVdF porous membrane.
  • the specific operation process is: dissolving or dispersing polyvinylidene fluoride in acetone.
  • porogen DMC dimethyl carbonate
  • the existing polyvinylidene fluoride (PVdF) coating technology uses low boiling acetone as a solvent, and the operational safety needs to be improved.
  • the inventors of the present disclosure found in the research process that although the use of a high boiling solvent instead of acetone can improve the safety of operation, the performance of a lithium ion battery prepared by preparing a polyvinylidene fluoride polymer solution using a solvent having a high boiling point is markedly lowered. After research, the reason may be that the polyvinylidene fluoride polymer solution prepared by using a high boiling solvent is extremely permeable, and the polymer solution easily penetrates the separator to reach the other surface opposite to the coated surface.
  • the polyvinylidene fluoride-based polymer is also brought into the pores of the separator. Since the flowability and permeability of the polyvinylidene fluoride-based polymer are much lower than that of the organic solvent, the polyvinylidene fluoride-based polymerization carried by the organic solvent into the separator The material usually remains in the pores of the membrane, clogging the membrane, adversely affecting the permeability and porosity of the membrane, increasing the bulk impedance of the polymer membrane, reducing the ionic conductivity, and adversely affecting the performance of the finally prepared lithium ion battery.
  • the existing polyolefin separator surface generally forms a ceramic layer to improve the thermal stability of the separator and the ability to adsorb the electrolyte, even a polyolefin separator having the ceramic layer is difficult to block the polymer solution from penetrating the separator.
  • the inventors of the present disclosure conducted intensive studies on the problems in formulating a polyvinylidene fluoride-based polymer solution using a solvent having a high boiling point, and found that when a polyvinylidene fluoride-based polymer solution is prepared using a solvent having a high boiling point, Providing a hydrophilic retardation layer between a porous substrate (that is, a polyolefin porous film having a ceramic layer or not having a ceramic layer) and a polyvinylidene fluoride-based polymer can effectively inhibit a polyvinylidene fluoride-based polymer
  • the solution penetrates the hydrophilic retardation layer and enters the porous substrate, thereby effectively reducing the amount of the polyvinylidene fluoride-based polymer entering the porous substrate, improving the gas permeability and porosity of the polymer separator, and lowering the polymer.
  • the bulk impedance of the separator increases the ionic conductivity of the polymer separator, so that the
  • the present disclosure provides a polymer separator comprising a porous substrate, a hydrophilic retardation layer, and a porous polar polymer bonding layer, the hydrophilic barrier A hysteresis layer is disposed between the porous substrate and the porous polar polymer bonding layer, and the pore walls in the porous polar polymer bonding layer have a nodular structure.
  • the present disclosure provides a method of preparing a polymer separator, the method comprising:
  • hydrophilic retardation slurry on at least one surface of a porous substrate to form a hydrophilic retardation coating, the hydrophilic retardation slurry containing a dispersion medium, and hydrophilicity dispersed in the dispersion medium Inorganic particles and a binder, optionally drying the hydrophilic retardation coating to form a hydrophilic retardation layer;
  • the binder solution contains an organic solvent and a polar polymer binder and a pore former dissolved in the organic solvent;
  • the present disclosure provides a polymer membrane prepared by the method of the second aspect of the present disclosure.
  • the present disclosure provides the use of the polymer separator of the first or third aspect of the present disclosure in a lithium ion battery.
  • the present disclosure provides a lithium ion battery including a positive electrode tab, a negative electrode tab, and a polymer separator, wherein the polymer separator is the first aspect of the disclosure Or the polymeric separator of the third aspect.
  • the present disclosure provides a method of fabricating a lithium ion battery, the method comprising:
  • the polymer separator is disposed between the positive electrode tab and the negative electrode tab to form a battery pole core, and then packaged.
  • the polymer separator according to the present disclosure is used for a lithium ion battery, and can be firmly bonded to a positive electrode tab and a negative electrode tab of a lithium ion battery, and has strong binding force with the positive electrode tab and the negative electrode tab, so that lithium ion
  • the battery has a high hardness. Lithium ion batteries employing the polymer membranes of the present disclosure show better performance.
  • a low boiling point solvent such as acetone
  • a high boiling point with higher operational safety can be used.
  • a mixture of a low boiling point solvent and a high boiling point solvent can also be used.
  • a high boiling point solvent when a high boiling point solvent is used, not only the operation safety can be improved, but also the performance of the lithium ion battery is not significantly lowered.
  • FIG. 1A and FIG. 1B are photographs of the surface SEM topography of the hydrophilic retardation layer of the polymer separator prepared in Example 1-1, FIG. 1A is a photograph magnified 500 times, and FIG. 1B is a photograph magnified 5000 times.
  • FIG. 2A and 2B are SEM topographical images of the polymer separator prepared in Example 2-5A, FIG. 2A is a photograph magnified 500 times, and FIG. 2B is a photograph magnified 5000 times.
  • FIG. 3A and 3B are SEM topographical images of the polymer separator prepared in Example 2-4A, FIG. 3A is a photograph magnified 500 times, and FIG. 3B is a photograph magnified 5000 times.
  • FIG. 4A and 4B are SEM topographical images of the polymer separator prepared in Example 2-4B, FIG. 4A is a photograph magnified 500 times, and FIG. 4B is a photograph magnified 5000 times.
  • FIG. 5A and 5B are photographs of the surface SEM topography of the polymer separator prepared in Comparative Example 2, FIG. 5A is a photograph magnified 500 times, and FIG. 5B is a photograph magnified 5000 times.
  • FIG. 6A and 6B are photographs of the surface SEM topography of the polymer separator prepared in Comparative Example 3, FIG. 6A is a photograph magnified 500 times, and FIG. 6B is a photograph magnified 5000 times.
  • FIG. 7A and 7B are SEM topographic photographs of the polymer separator side (Fig. 7A) and the positive electrode side (Fig. 7B) after the polymer separator prepared in Example 2-4B was peeled off from the positive electrode bonding contact surface.
  • FIGS. 8A and 8B are SEM topographic photographs of the polymer separator side (Fig. 8A) and the negative electrode side (Fig. 8B) after the polymer separator prepared in Example 2-4B was peeled off from the negative electrode bonding contact surface.
  • FIG. 9A and 9B are graphs showing the peel strength test curves of the positive electrode and the polymer separator of the lithium ion battery prepared in Example 2-4B (FIG. 9A) and Comparative Example 2 (FIG. 9B), respectively.
  • FIG. 10A and 10B are graphs showing the peel strength test curves of the negative electrode and the polymer separator of the lithium ion battery prepared in Example 2-4B (FIG. 10A) and Comparative Example 2 (FIG. 10B), respectively.
  • the present disclosure provides a polymer separator comprising a porous substrate, a hydrophilic retardation layer, and a porous polar polymer bonding layer, the hydrophilic barrier A hysteresis layer is disposed between the porous substrate and the porous polar polymeric tie layer.
  • the hydrophilic retardation layer is a retardation layer having hydrophilic properties.
  • the contact angle of the hydrophilic retardation layer with water may be not higher than 40°, for example, 1°, 2°, 3°, 4°, 5°, 6°, 7°. , 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 21°, 22°, 23°, 24 °, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 .
  • the hydrophilic retardation layer has a contact angle with water of 20 or less.
  • the hydrophilic retardation layer has a contact angle with water of from 2 to 15 °, preferably from 5 to 10 °.
  • the contact angle is determined by the method specified in GB/T 30693-2014 plastic film and water contact angle measurement.
  • the hydrophilic retardation layer contains a binder and hydrophilic inorganic particles which are bonded to each other by the binder.
  • the hydrophilic inorganic particles are hydrophilic Al 2 O 3 , hydrophilic SiO 2 , hydrophilic SnO 2 , hydrophilic ZrO 2 , hydrophilic TiO 2 , hydrophilic SiC, hydrophilic Si 3 At least one of N 4 , hydrophilic CaO, hydrophilic MgO, hydrophilic ZnO, hydrophilic BaTiO 3 , hydrophilic LiAlO 2 and hydrophilic BaSO 4 , for example, the hydrophilic inorganic particles are preferably Hydrophilic Al 2 O 3 , hydrophilic SiO 2 , hydrophilic SnO 2 , hydrophilic ZrO 2 , hydrophilic TiO 2 , hydrophilic SiC, hydrophilic Si 3 N 4 , hydrophilic CaO One or more of hydrophilic MgO, hydrophilic ZnO, hydrophilic BaTiO 3 , hydrophilic LiAlO 2 and hydrophilic BaSO 4 .
  • the hydrophilic inorganic particles are hydrophilic Al 2 O 3 and/or hydrophilic SiO 2 . Further preferably, the hydrophilic inorganic particles are at least one of a vapor phase hydrophilic SiO 2 , a precipitation hydrophilic SiO 2 and a vapor phase hydrophilic Al 2 O 3 , for example, the hydrophilic inorganic The particles are one or more selected from the group consisting of a vapor phase hydrophilic SiO 2 , a precipitation method hydrophilic SiO 2 and a vapor phase hydrophilic Al 2 O 3 .
  • the hydrophilic inorganic particles may have a particle diameter of from 1 nm to 10 ⁇ m, preferably from 1 nm to 5 ⁇ m, more preferably from 1 nm to 2 ⁇ m.
  • the particle diameter of the hydrophilic inorganic particles is more preferably from 10 nm to 1 ⁇ m, further preferably from 20 nm, from the viewpoint of further improving the gas permeability and ionic conductivity of the polymer separator and the performance of the lithium ion battery using the polymer separator. 800 nm, still more preferably 50 nm to 350 nm.
  • the particle diameter is a volume average particle diameter, which is measured by a laser particle size analyzer.
  • the hydrophilic inorganic particles may have a specific surface area of from 10 to 600 m 2 /g.
  • the hydrophilic inorganic particles preferably have a specific surface area of from 100 to 500 m 2 /g, more preferably from the viewpoint of further improving the gas permeability and ionic conductivity of the polymer separator and the performance of the lithium ion battery using the polymer separator.
  • the specific surface area is determined by the method specified in the method for measuring the specific surface area of solid materials by the gas adsorption BET method of GB/T19587-2004.
  • the content of the hydrophilic inorganic particles may be 50 to 95% by weight, preferably 70 to 95% by weight, more preferably based on the total amount of the hydrophilic retardation layer. It is 80 to 95% by weight, and more preferably 85 to 95% by weight.
  • the binder is used on the one hand to bind and fix the hydrophilic inorganic particles, and on the other hand, it is possible to further increase the ability of the polymer membrane to adsorb the electrolyte.
  • the binder is an acrylate type polymer, a styrene-acrylate copolymer, a polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, an acrylonitrile-acrylate copolymer, a vinyl chloride-acrylate
  • At least one of a copolymer and a butadiene-styrene copolymer is preferably an acrylate type polymer, a styrene-acrylate copolymer, a polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, One or more of an acrylonitrile-acrylate copolymer, a vinyl
  • the hydrophilic retardation layer may have a thickness of 0.1 to 3 ⁇ m, for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m, 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, 2.6 ⁇ m, 2.7 ⁇ m, 2.8 ⁇ m, 2.9 ⁇ m, or 3 ⁇ m.
  • the hydrophilic retardation layer has a thickness of from 0.1 to 1 ⁇ m, more preferably from 0.3 to 0.8 ⁇ m.
  • the porous substrate contains a porous polymer layer which can be used to swell the liquid electrolyte and transport lithium ions.
  • the porous polymer layer is a porous polyolefin layer, for example, the porous polymer layer is at least one of a porous polyethylene layer, a porous polypropylene layer, a porous polyethylene, and a porous polypropylene composite layer, preferably porous One or more of a polyethylene (PE) layer, a porous polypropylene (PP) layer, a porous polyethylene, and a porous polypropylene composite layer.
  • the porous polyethylene and porous polypropylene composite layer may be a PE/PP/PE composite substrate layer.
  • the porous polymer layer may have a thickness of 1 to 50 ⁇ m, for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m.
  • the porous substrate may further contain a ceramic layer for improving thermal stability, mechanical properties, and electrolyte adsorption capacity of the porous polymer layer.
  • the ceramic particles in the ceramic layer may be selected from the group consisting 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.
  • At least one of 4 is formed by sintering, preferably selected from the group consisting 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 One or two or more ceramic particles formed by sintering in BaSO 4 .
  • the ceramic layer may have a thickness of 1-5 ⁇ m, for example, 1 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m, 2.0 ⁇ m, 2.1 ⁇ m.
  • the thickness of the ceramic layer is greater than the thickness of the hydrophilic retardation layer.
  • the ceramic layer may be disposed between the porous polymer layer and the hydrophilic retardation layer, or a porous polymer layer may be disposed on the ceramic layer between the hydrophilic retardation layer and the hydrophilic barrier layer, a combination of the above two modes may also be employed.
  • the porous polar polymer bonding layer serves to reduce the shrinkage ratio of the porous substrate near the melting temperature while functioning as a bond, and the polymer separator is adhered to the positive or negative electrode of the battery. Together, the ability of the porous substrate to adsorb the electrolyte can also be improved.
  • the polar polymer in the porous polar polymer bonding layer may be a polar polymer capable of achieving the above functions, and specific examples thereof may include, but are not limited to, polyvinylidene fluoride, vinylidene fluoride, and hexafluoropropylene.
  • the copolymer, and at least one of the copolymers of vinylidene fluoride and acrylate preferably including but not limited to copolymers of polyvinylidene fluoride, vinylidene fluoride and hexafluoropropylene, and copolymerization of vinylidene fluoride and acrylate
  • PVdF polyvinylidene fluoride
  • P(VdF-HFP) a copolymer of vinylidene fluoride and hexafluoropropylene
  • copolymerization of vinylidene fluoride and acrylate One or more of the substances.
  • the porous polar polymer bonding layer may have a thickness of 0.1 to 10 ⁇ m, preferably 0.2 to 5 ⁇ m, more preferably 0.7 to 3 ⁇ m, still more preferably 0.8 to 1.5 ⁇ m.
  • the pore walls in the porous polar polymer bonding layer have a nodular structure, that is, in the porous polar polymer bonding layer, the pore walls between the pores have a nodular structure.
  • the nodules in the nodule structure may be raised from the wall of the hole (i.e., protruded relative to the wall surface of the hole) or may not be raised from the wall of the hole (i.e., non-protruding with respect to the wall surface of the hole).
  • the "nodular structure" herein can be understood as the network structure shown in Fig.
  • the mesh wall is composed entirely of spherical particles or partially spherical particles, and its essence is that PVDF is homogeneously dissolved in a solvent. Thereafter, the pellet formed by secondary precipitation (which is different from the pellet of the commercial PVDF pellet itself) due to changes in certain specific conditions such as temperature and humidity.
  • the mesh wall is smooth, has no spherical particles, and is not a nodular structure.
  • the hydrophilic retardation layer and the porous polar polymer binder layer may be provided on one side of the porous substrate or on both sides of the porous substrate.
  • the porous polar polymer tie layer is attached to the surface of the hydrophilic retardation layer.
  • the polymer membrane is composed of a porous substrate, a hydrophilic retardation layer, and a porous polar polymer bonding layer, the porous substrate being a porous polymer Floor.
  • the hydrophilic retardation layer is attached to the surface of the porous substrate, and the porous polar polymer bonding layer is attached to the surface of the hydrophilic retardation layer.
  • the hydrophilic retardation layer and the porous polar polymer bonding layer may be sequentially disposed on one surface of the porous substrate (ie, the polymer separator has the following structure: porous polymer layer
  • the polymer membrane of the present disclosure is composed of a porous substrate, a hydrophilic retardation layer, and a porous polar polymer bonding layer, which is porously polymerized.
  • the layer consists of a layer of matter and a layer of ceramic.
  • the ceramic layer is attached to the surface of the porous polymer layer
  • the hydrophilic retardation layer is attached to the surface of the ceramic layer
  • the porous polar polymer is adhered
  • the junction layer is attached to the surface of the hydrophilic retardation layer (that is, the polymer membrane has the following structure: porous polymer layer
  • the porous polymer layer is attached to a surface of the ceramic layer, and the hydrophilic retardation layer is attached to a surface of the porous polymer layer, the porous polar polymer bonding layer Attached to the surface of the hydrophilic retardation layer (ie, the polymer membrane has the following structure: ceramic layer
  • the ceramic layer is attached to a surface of the porous polymer layer, and the other surface of the ceramic layer and the porous polymer layer are sequentially attached with a hydrophilic retardation layer and a porous polar polymerization.
  • the adhesive layer ie, the polymer separator has the following structure: porous polar polymer bonding layer
  • the polymer film according to the present disclosure may have a total thickness of conventionally selected, and may generally be 5 to 50 ⁇ m, preferably 8 to 30 ⁇ m, and more preferably 10 to 20 ⁇ m.
  • the polymer separator according to the present disclosure has a high gas permeability.
  • the polymer membrane according to the present disclosure has a Gurley value of 100-900 Sec/100 mL, preferably 120-600 Sec/100 mL, more preferably 120-500 Sec/100 mL. Further preferably, the polymer membrane has a Gurley value of from 150 to 350 Sec / 100 mL, such as from 200 to 300 Sec / 100 mL.
  • the hydrophilic retardation layer in the polymer separator according to the present disclosure is more hydrophilic and effective than the ceramic layer in the prior polymer separator for improving the thermal stability of the separator and the adsorption capacity of the electrolyte.
  • the polar polymer enters the porous substrate during the grounding process.
  • the pores in the porous polar polymer tie layer have a larger pore size in the polymer separator according to the present disclosure than the existing polymer separator (the porous polymer bond layer of the existing polymer separator)
  • the pore size is usually from 0.5 to 1 ⁇ m
  • the pore size in the porous polar polymer bonding layer of the polymer separator according to the present disclosure may be 3 ⁇ m or more, usually 3 to 10 ⁇ m
  • the porous polar polymer bonding layer is multilayered.
  • a wire mesh interlaced structure a portion of the surface of the hydrophilic retardation layer being exposed through the multilayer wire mesh interweaving structure; however, the porous polar polymer bonding layer in the existing polymer separator is more dense. It is honeycomb.
  • the present disclosure provides a method of preparing a polymer separator, the method comprising:
  • hydrophilic retardation slurry on at least one surface of the porous substrate to form a hydrophilic retardation coating, optionally drying the hydrophilic retardation coating to form a hydrophilic retardation layer;
  • the porous substrate may be a porous polymer film or a composite film of a porous polymer film and a ceramic film.
  • the porous polymer film is preferably a porous polyolefin film, for example, the porous polymer layer is at least one of a porous polyethylene layer, a porous polypropylene layer, a porous polyethylene, and a porous polypropylene composite layer, preferably a porous poly One or two or more of a vinyl film, a porous polypropylene film, a porous polyethylene, and a porous polypropylene composite film.
  • the porous polyethylene and porous polypropylene composite film may be a PE/PP/PE composite film.
  • the ceramic in the ceramic film may be selected from the group consisting of selected from the group consisting 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 At least one of BaSO 4 is formed by sintering, preferably selected from the group consisting 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 Ceramic particles formed by sintering one or more of BaSO 4 .
  • the porous polymer film may have a thickness of 1 to 50 ⁇ m, for example, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m.
  • the ceramic film may have a thickness of from 1 to 5 ⁇ m, preferably from 1.5 to 3 ⁇ m.
  • the hydrophilic retardation slurry contains a dispersion medium, and hydrophilic inorganic particles dispersed in the dispersion medium, and a binder.
  • the hydrophilic inorganic particles may have a particle diameter of from 1 nm to 10 ⁇ m, preferably from 1 nm to 5 ⁇ m, more preferably from 1 nm to 2 ⁇ m.
  • the particle diameter of the hydrophilic inorganic particles is more preferably from 1 nm to 2 ⁇ m from the viewpoint of further improving the gas permeability and ionic conductivity of the finally prepared polymer separator, and the performance of the lithium ion battery using the polymer separator. It is preferably 10 nm to 1 ⁇ m, still more preferably 20 nm to 800 nm, and particularly preferably 50 nm to 350 nm.
  • the hydrophilic inorganic particles may have a specific surface area of from 10 to 600 m 2 /g.
  • the hydrophilic inorganic particles preferably have a specific surface area of from 100 to 500 m 2 /g from the viewpoint of further improving the gas permeability and ionic conductivity of the finally prepared polymer separator and the performance of the lithium ion battery using the polymer separator. more preferably 150-400m 2 / g, more preferably 200-400m 2 / g, still more preferably 250-390m 2 / g, more preferably 300-380m 2 / g.
  • the hydrophilic inorganic particles are hydrophilic Al 2 O 3 , hydrophilic SiO 2 , hydrophilic SnO 2 , hydrophilic ZrO 2 , hydrophilic TiO 2 , hydrophilic SiC, hydrophilic Si 3 At least one of N 4 , hydrophilic CaO, hydrophilic MgO, hydrophilic ZnO, hydrophilic BaTiO 3 , hydrophilic LiAlO 2 , and hydrophilic BaSO 4 , such as the hydrophilic inorganic particles Specific examples may include, but are not limited to, hydrophilic Al 2 O 3 , hydrophilic SiO 2 , hydrophilic SnO 2 , hydrophilic ZrO 2 , hydrophilic TiO 2 , hydrophilic SiC, hydrophilic Si 3 N 4.
  • hydrophilic CaO hydrophilic CaO
  • hydrophilic MgO hydrophilic MgO
  • hydrophilic ZnO hydrophilic BaTiO 3
  • hydrophilic LiAlO 2 hydrophilic BaSO 4
  • the hydrophilic inorganic particles are hydrophilic Al 2 O 3 and/or hydrophilic SiO 2 .
  • the hydrophilic inorganic particles are at least one of vapor phase hydrophilic SiO 2 , precipitation hydrophilic SiO 2 and vapor phase hydrophilic Al 2 O 3 , for example, the hydrophilic inorganic The particles are one or more selected from the group consisting of a vapor phase hydrophilic SiO 2 , a precipitation method hydrophilic SiO 2 and a vapor phase hydrophilic Al 2 O 3 .
  • the binder is an acrylate type polymer, a styrene-acrylate copolymer, a polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, or an acrylonitrile-acrylic acid.
  • At least one of an ester copolymer, a vinyl chloride-acrylate copolymer, and a butadiene-styrene copolymer preferably an acrylate type polymer, a styrene-acrylate copolymer, a polyvinylidene fluoride, or a second One or more of a vinyl fluoride-hexafluoropropylene copolymer, an acrylonitrile-acrylate copolymer, a vinyl chloride-acrylate copolymer, and a butadiene-styrene copolymer.
  • the dispersion medium can be selected according to the kind of the hydrophilic inorganic particles and the binder, so that the hydrophilic inorganic particles and the binder form a uniform and stable slurry.
  • Specific examples of the dispersion medium may include, but are not limited to, at least one of water, ethanol, isopropanol, cyclohexane, tetrahydrofuran, dichloromethane, and chloroform, and preferably include, but are not limited to, water, ethanol, and isopropyl One or more of an alcohol, cyclohexane, tetrahydrofuran, dichloromethane, and chloroform.
  • the content of the hydrophilic inorganic particles may be 50 to 95% by weight, for example, 50% by weight, 52% by weight, 55% by weight, 57% by weight, 60% by weight, 62% by weight, 65 wt%, 67 wt%, 70 wt%, 72 wt%, 75 wt%, 77 wt%, 80 wt%, 82 wt%, 85 wt%, 87 wt%, 90 wt%, 92 wt%, 95 wt% % is preferably from 70 to 95% by weight, more preferably from 80 to 95% by weight, still more preferably from 85 to 95% by weight.
  • the amount of the binder can be selected in accordance with the amount of the hydrophilic inorganic particles to bind and fix the hydrophilic inorganic particles.
  • the binder may be included in an amount of 1 to 30 parts by weight, for example, 1 part by weight, 2 parts by weight, or 5 parts by weight per 100 parts by weight of the hydrophilic inorganic particles. Parts, 7 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, preferably 2 to 25 parts by weight, More preferably, it is 5-20 parts by weight.
  • the hydrophilic block slurry may also contain a dispersing agent to further increase the stability of the hydrophilic retarding slurry.
  • the dispersant may be a common substance which can promote the dispersibility of the inorganic particles in a liquid medium, and specific examples thereof may include, but are not limited to, polyvinyl alcohol (PVA) and/or sodium polyacrylate (PAANa).
  • PVA polyvinyl alcohol
  • PAANa sodium polyacrylate
  • the amount of the dispersant may be a conventional choice. Generally, the dispersant may be used in an amount of 0.1 to 10 parts by weight, such as 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1.0, based on 100 parts by weight of the hydrophilic inorganic particles.
  • Parts by weight 7.5 parts by weight, 7.7 parts by weight, 8.0 parts by weight, 8.2 parts by weight, 8.5 parts by weight, 8.7 parts by weight, 9.0 parts by weight, 9.2 parts by weight, 9.5 parts by weight, 9.7 parts by weight, 10.0 parts by weight, preferably 0.2. - 5 parts by weight, more preferably 0.3 to 2 parts by weight.
  • the hydrophilic barrier slurry may also contain a thickening agent to further enhance the coatability of the hydrophilic barrier slurry.
  • the thickener may be a cellulosic thickener and/or a polyacrylate alkali swellable thickener (such as BASF Latekoll D thickener).
  • the thickener may be used in an amount of 0.1 to 10 parts by weight, such as 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, per 100 parts by weight of the hydrophilic inorganic particles.
  • the parts by weight are preferably 0.5 to 5 parts by weight, more preferably 0.8 to 2 parts by weight.
  • the pH of the hydrophilic barrier slurry is adjusted to be alkaline, preferably 8-10, such as 8, 8.2, 8.5, 8.7, 9.0, 9.2, 9.5, 9.7, 10.0.
  • the solid content of the hydrophilic retardation slurry is preferably 2 to 30% by weight, for example, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 5% by weight, 7% by weight, 10% by weight, 12% by weight, 15% by weight, 17% by weight, 20% by weight, 22% by weight, 25% by weight, 27% by weight, 30% by weight, more preferably 5 to 25% by weight.
  • the coating amount of the hydrophilic retardation slurry on the surface of the porous substrate can be selected according to the thickness of the desired hydrophilic retardation layer.
  • the hydrophilic retardation slurry is applied in an amount such that the hydrophilic retardation layer has a thickness of 0.1 to 3 ⁇ m, for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m, 2 ⁇ m, 2.1 ⁇ m, 2.2 ⁇ m, 2.3 ⁇ m, 2.4 ⁇ m, 2.5 ⁇ m, 2.6 ⁇ m, 2.7 ⁇ m, 2.8 ⁇ m, 2.9 ⁇ m, or 3 ⁇ m
  • the hydrophilic retardation coating layer may be dried to form a hydrophilic retardation layer, and then the polar polymer binder solution may be coated, or the hydrophilic retardation coating layer may not be dried, but directly
  • the hydrophilic retardation coating is coated with a polar polymeric binder solution.
  • the hydrophilic retardation coating is dried to form a hydrophilic retardation layer and then coated with a polar polymer binder solution, which further improves the gas permeability and ionic conductivity of the finally prepared polymer separator, and further Improve the performance of lithium ion batteries using the polymer separator.
  • the drying temperature may be from 10 to 120 °C.
  • the drying temperature is not higher than 100 °C. More preferably, the drying temperature is not higher than 80 ° C, for example, 10-80 ° C, specifically 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 °C, 55°C, 60°C, 65°C, 70°C, 75°C, or 80°C.
  • the drying temperature is 40-60 ° C, such as 50-60 ° C.
  • the drying may be carried out under normal pressure or under reduced pressure.
  • the drying is carried out under normal pressure.
  • the drying can be carried out in a blast drying oven.
  • the duration of the drying may be selected depending on the drying temperature and the kind of the dispersing agent to be used. Generally, the duration of the drying in step (1) may be from 0.1 to 24 hours, such as 0.1 hours, 0.2 hours, 0.5 hours, 0.7 hours, 1 hour, 1.2 hours, 1.5 hours, 1.7 hours, 2.0 hours, 2.2.
  • the contact angle of the hydrophilic retardation layer with water may be not higher than 40°, for example, 1°, 2°, 3°, 4°, 5°, 6°, 7°, 8 °, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 21°, 22°, 23°, 24°, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40.
  • the hydrophilic retardation layer has a contact angle with water of 20 or less.
  • the hydrophilic retardation layer formed in the step (1) has a contact angle with water of from 2 to 15 °, more preferably from 5 to 10 °.
  • the polar polymer binder solution contains an organic solvent and a polar polymer binder and a pore former dissolved in the organic solvent.
  • the polar polymer binder may be at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, and a copolymer of vinylidene fluoride and acrylate, for example, may be a polyethylene One or more of a copolymer of vinyl fluoride, vinylidene fluoride and hexafluoropropylene, and a copolymer of vinylidene fluoride and acrylate.
  • the organic solvent may be a low boiling organic solvent (an organic solvent having a boiling point lower than 60 ° C), such as acetone; or a high boiling solvent such as a solvent having a boiling point of 60 ° C or higher; or a low boiling solvent and a high boiling solvent; mixture.
  • a low boiling organic solvent an organic solvent having a boiling point lower than 60 ° C
  • a high boiling solvent such as a solvent having a boiling point of 60 ° C or higher
  • a low boiling solvent and a high boiling solvent mixture.
  • it is preferred to control the content of the low boiling point solvent it is preferred to control the content of the low boiling point solvent to be not higher than the safety threshold at which the explosion occurs, from the viewpoint of further improving the operational safety.
  • the organic solvent is a low boiling solvent, preferably acetone.
  • the prepared polymer separator and lithium ion battery exhibit superior performance, and in particular, the lithium ion battery prepared by using the polymer separator exhibits markedly improved large rate discharge performance and high temperature. performance.
  • the preferred conditions include that the hydrophilic inorganic particles preferably have a particle diameter of from 1 nm to 2 ⁇ m, more preferably from 10 nm to 1 ⁇ m, further preferably from 20 nm to 800 nm, still more preferably from 50 nm to 350 nm, and the hydrophilic resistance
  • the contact angle of the hysteresis layer with water is preferably 20 or less, and the drying in the step (2) is carried out at a temperature not higher than 60 °C.
  • the organic solvent is a high boiling solvent, such as an organic solvent having a boiling point of 60 ° C or higher (eg, 60-260 ° C), preferably an organic solvent having a boiling point of 120 ° C or higher (eg, 120-260 ° C). More preferably, an organic solvent having a boiling point of 140 ° C or higher (for example, 140 to 260 ° C) is used. Further preferably, the organic solvent has a boiling point of 145 to 260 ° C, such as 150 to 230 ° C.
  • organic solvent may include, but are not limited to, triethyl phosphate, N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide. At least one, more preferably including but not limited to triethyl phosphate, N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide One or two or more. According to this embodiment, operational safety can be improved.
  • the organic solvent is a mixture of a low boiling solvent and a high boiling solvent.
  • the low boiling point solvent and the high boiling point solvent are each the same as described above.
  • the content of the high boiling point solvent may be from 0.1 to 99.9% by weight based on the total amount of the organic solvent, and the content of the low boiling point solvent may be from 0.1 to 99.9% by weight.
  • the pore former is preferably an organic pore former.
  • the boiling point of the pore former is preferably higher than the boiling point of the organic solvent, so that when drying, the organic solvent is first volatilized, and the pore former is volatilized to enhance the pore-forming effect.
  • the organic pore former has a boiling point of 61-261 ° C, such as 61 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C, 100 ° C, 105 ° C, 110 ° C , 115 ° C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C, 145 ° C, 150 ° C, 155 ° C, 160 ° C, 165 ° C, 170 ° C, 175 ° C, 180 ° C, 185 ° C, 190 ° C, 195 °C, 200 ° C, 205 ° C, 210 ° C, 215 ° C, 220 ° C, 225 ° C, 230 ° C, 235 ° C, 240 ° C, 245 ° C, 250 ° C, 255 ° C, 260 ° C, 2
  • the pore former may be a carbonate type compound and/or an alcohol ether type compound, and specific examples thereof may include, but are not limited to, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, At least one of vinylene carbonate, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol dimethyl ether, preferably including but not limited to ethylene carbonate, propylene carbonate, carbonic acid One or more of methyl ester, diethyl carbonate, ethyl methyl carbonate, vinylene carbonate, diethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol dimethyl ether .
  • the weight ratio of the organic solvent to the pore former may be 1:0.01-1, for example: 1:0.01, 1:0.05, 1:0.1, 1:0.15 , 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75,1 : 0.8, 1:0.85, 1:0.9, 1:0.95, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, or 1:1.
  • the weight ratio of the organic solvent to the pore former is 1:0.02-0.5. More preferably, in the polar polymer binder solution, the weight ratio of the organic solvent to the pore former is 1:0.03-0.3. Further preferably, in the polar polymer binder solution, the weight ratio of the organic solvent to the pore former is 1:0.05-0.1.
  • the polar polymer binder solution has a concentration of the polar polymer binder of 1 to 30% by weight, for example, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt% %, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, It is preferably 2 to 25% by weight.
  • the concentration of the polar polymer binder in the polar polymer binder solution is more preferably 5 from the viewpoint of further improving the properties of the finally prepared polymer separator and the performance of the lithium ion battery using the polymer separator. -20% by weight.
  • the concentration of the polar polymeric binder in the polar polymeric binder solution is a critical concentration (typically from 8 to 15% by weight, preferably from 10 to 12% by weight).
  • the critical concentration refers to the concentration of the polar polymer binder solution passing through the porous substrate, and the polar polymer can be bonded in an environment of 25 ° C, 1 standard atmospheric pressure and a relative humidity of RH 45% to 55%.
  • the solution is coated on one surface of the porous substrate, and it is observed whether the polar polymer binder solution permeates the porous substrate within 1 hour, and is at a concentration that is transmitted through the porous substrate and a concentration that does not penetrate the porous substrate.
  • the concentration between them is taken as the critical concentration.
  • concentration of the polar polymer binder is a critical concentration
  • the polar polymer binder is in a solution, which is microscopically gel-like, and the single molecule is difficult to flow and diffuse, which can strengthen the polar polymer molecules.
  • the interaction between the two forms an ideal physical cross-linking network structure during solvent evaporation, so that the polymer separator has more excellent gas permeability and ionic conductivity.
  • the lithium ion battery using the polymer separator has superior performance. performance.
  • the coating amount of the polar polymer binder solution can be selected according to the thickness of the desired polar polymer bonding layer.
  • the coating amount of the polar polymer binder solution may be such that the thickness of the finally formed porous polar polymer bonding layer is 0.1 to 10 ⁇ m, for example, 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m.
  • the drying may be carried out at a temperature not higher than 120 °C.
  • the drying is carried out at a temperature not higher than 60 ° C, and may be 10-60 ° C, for example: 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 55 ° C, or 60 ° C. Drying at a temperature not higher than 60 ° C enables the polar polymer bonding layer to have a more excellent pore structure, thereby further improving the gas permeability and ionic conductivity of the finally prepared polymer separator, and further improving The performance of a lithium ion battery using the polymer separator.
  • the drying is carried out at a temperature of from 20 to 55 °C. Further preferably, the drying is carried out at a temperature of from 30 to 45 °C.
  • the duration of the drying can be selected depending on the temperature of the drying. Specifically, the duration of the drying may be from 0.1 to 36 hours, preferably from 5 to 30 hours, more preferably from 10 to 24 hours, still more preferably from 15 to 24 hours.
  • one or a combination of two or more of a conventional coating method such as a roll coating method, a spray coating method, an immersion coating method, and a screen printing method may be employed.
  • a hydrophilic retardation layer and a porous polar polymer bonding layer may be formed on one side of the porous substrate, or a hydrophilic layer may be formed on both sides of the porous substrate.
  • a barrier layer and a porous polar polymeric tie layer may be formed on one side of the porous substrate, or a hydrophilic layer may be formed on both sides of the porous substrate.
  • the finally prepared polymer membrane is composed of a porous substrate, a hydrophilic retardation layer, and a porous polar polymer tie layer, the porous substrate being a porous polymer a film, the hydrophilic retardation layer is attached to a surface of the porous substrate, and the porous polar polymer bonding layer is attached to a surface of the hydrophilic retardation layer.
  • the hydrophilic retardation layer and the porous polar polymer bonding layer may be sequentially disposed on one surface of the porous substrate (that is, the polymer separator has the following structure: porous polymer film
  • the finally prepared polymer membrane is composed of a porous substrate, a hydrophilic retardation layer, and a porous polar polymer bonding layer, which is a porous polymerization.
  • a composite film of a film and a ceramic film is attached to the surface of the porous polymer film, the hydrophilic retardation layer is attached to the surface of the ceramic film, and the porous polar polymer is adhered
  • the junction layer is attached to the surface of the hydrophilic retardation layer (that is, the polymer membrane has the following structure: porous polymer membrane
  • the porous polymer film is attached to a surface of the ceramic layer, and the hydrophilic retardation layer is attached to a surface of the porous polymer film, the porous polar polymer bonding layer Adhered to the surface of the hydrophilic retardation layer (that is, the polymer membrane has the following structure: ceramic membrane
  • the ceramic film is attached to the surface of the porous polymer film, and the other surface of the ceramic film and the porous polymer film are sequentially attached with a hydrophilic retardation layer and a porous polar polymer bonding layer.
  • the polymer separator has the following structure: porous polar polymer bonding layer
  • the present disclosure provides a polymer membrane prepared by the method of the second aspect of the present disclosure.
  • the polymer separator prepared by the method of the second aspect of the present disclosure may have a total thickness of 5 to 50 ⁇ m, for example, 5 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m. 23 ⁇ m, 25 ⁇ m, 28 ⁇ m, 30 ⁇ m, 32 ⁇ m, 35 ⁇ m, 38 ⁇ m, 40 ⁇ m, 42 ⁇ m, 44 ⁇ m, 46 ⁇ m, 48 ⁇ m, 50 ⁇ m, preferably 8-30 ⁇ m, more preferably 10-20 ⁇ m.
  • the polymer separator prepared by the method of the second aspect of the present disclosure has high gas permeability.
  • the polymer membrane prepared by the method of the second aspect of the present disclosure has a Gurley value of 100-900 Sec/100 mL, such as 100 Sec/100 mL, 120 Sec/100 mL, 150 Sec/100 mL, 170 Sec/100 mL, 190 Sec/100 mL, 200 Sec/ 100mL, 220Sec/100mL, 250Sec/100mL, 270Sec/100mL, 290Sec/100mL, 300Sec/100mL, 325Sec/100mL, 350Sec/100mL, 370Sec/100mL, 390Sec/100mL, 400Sec/100mL, 425Sec/100mL, 450Sec/100mL, 480Sec/100mL, 500Sec/100mL, 520Sec/100mL
  • the hydrophilic retardation layer in the polymer membrane prepared by the method of the second aspect of the present disclosure is compared with the ceramic layer in the prior polymer membrane for improving the thermal stability of the membrane and the adsorption capacity of the electrolyte. It is more water-based and can effectively block the polar polymer from entering the porous substrate during the preparation process.
  • the polymer separator prepared by the method of the second aspect of the present disclosure has a larger pore diameter in the porous polar polymer bonding layer (the porous pore of the existing polymer separator)
  • the pore diameter in the polymer polymer bonding layer is usually from 0.5 to 1 ⁇ m, and the pore diameter in the porous polar polymer bonding layer of the polymer separator according to the present disclosure may be 3 ⁇ m or more, usually 3 to 10 ⁇ m), and the porous polar polymerization
  • the adhesive layer is a multi-layered wire mesh interlaced structure, and a part of the surface of the hydrophilic retardation layer is exposed through the multilayered mesh interlaced structure; however, the porous polymer in the existing polymer separator
  • the bonding layer is more dense and honeycomb-like.
  • the pore walls may have a nodular structure, that is, a porous polar polymer bonding layer
  • the wall of the hole between the holes may have a nodular structure.
  • the nodules in the nodule structure may be raised from the wall of the hole (i.e., protruded relative to the wall surface of the hole) or may not be raised from the wall of the hole (i.e., non-protruding with respect to the wall surface of the hole).
  • the present disclosure provides the use of the polymer separator of the first or third aspect of the present disclosure in a lithium ion battery.
  • the present disclosure provides a lithium ion battery including a positive electrode tab, a negative electrode tab, and a polymer separator, wherein the polymer separator is the first aspect of the disclosure Or the polymeric separator of the third aspect.
  • the positive electrode tab is made 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 ), and lithium iron phosphate (LiFePO 4 ). One or more of them.
  • the negative electrode tab is made by coating a negative electrode material for a lithium ion battery, a conductive agent, and a binder onto a copper foil.
  • the negative electrode material used includes any negative electrode material usable for a lithium ion battery, for example, one or more of graphite, soft carbon, and hard carbon.
  • the lithium ion battery according to the present disclosure may or may not contain an electrolytic solution.
  • the electrolyte is well known to those skilled in the art and contains a lithium salt and an organic solvent.
  • the lithium salt may be a dissociable lithium salt, and may be, for example, one or more selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), and lithium tetrafluoroborate (LiBF 4 ).
  • the organic solvent may be selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) and vinylene carbonate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • VEC diethyl carbonate
  • the present disclosure provides a method of fabricating a lithium ion battery, the method comprising:
  • the polymer separator is disposed between the positive electrode tab and the negative electrode tab to form a battery pole core, and then packaged.
  • Step S2 can be carried out by a conventional method in the technical field of lithium ion battery preparation, which is not particularly limited in the present disclosure.
  • the electrolyte may be filled into the battery core, or may be directly packaged without filling the electrolyte.
  • the contact angle of the hydrophilic retardation layer and water is determined by the method specified in GB/T30693-2014 Plastic film and water contact angle measurement.
  • the particle size is measured by a laser particle size analyzer and is a volume average particle diameter.
  • Examples 1-1 to 1-4 were used to prepare a hydrophilic retardation layer according to the present disclosure.
  • Hydrophilic silica (specific surface area 380 m 2 /g, particle size 80 nm, purchased from Aladdin) and acrylate adhesive (P1005, purchased from Shanghai Aigao Chemical Co., Ltd.) prepared by gas phase method , dispersant (PVA, purchased from Aladdin), dispersant (PAANa, purchased from Showa Denko, Japan), carboxymethyl cellulose (CMC, purchased from Daicel, Japan) as a thickener to have a solid content of 92: 8: 0.4: 0.4: 1.2 (weight ratio) dispersed in water, control the solid content of 8% by weight, adjust the pH of the slurry to 8, and stir evenly to form a hydrophilic retardation slurry.
  • PVA dispersant
  • PAANa dispersant
  • CMC carboxymethyl cellulose
  • the hydrophilic retardation slurry was applied by a gravure roll coating to a single-sided ceramic separator (9 ⁇ m PE + 2 ⁇ m ceramic layer, and the ceramic particles in the ceramic layer were micron-sized alumina ceramic particles, purchased from Shandong Guozhu, Both sides are dried at 60 ° C for 12 hours to obtain a separator having a hydrophilic retardation layer, wherein the hydrophilic retardation layer has a thickness of 0.5 ⁇ m, and the contact angle of the hydrophilic retardation layer and water is 5°.
  • 1A and 1B show SEM images of the hydrophilic retardation layer
  • Hydrophilic silica prepared by precipitation method (specific surface area: 370 m 2 /g, particle size 150 nm, purchased from Aladdin), acrylate adhesive (P1005, purchased from Shanghai Aigao Chemical Co., Ltd.) , dispersant (PVA), dispersant (PAANa), thickener Latekoll D (purchased from BASF) dispersed in water at a solid content of 90:10:0.4:0.4:1.2 (weight ratio), controlling the solid content of the slurry to 8 % by weight, the pH of the slurry was adjusted to 10, and the mixture was stirred uniformly to form a hydrophilic retardation slurry.
  • PVA dispersant
  • PAANa dispersant
  • thickener Latekoll D purchased from BASF
  • the hydrophilic retardation slurry was applied to both sides of the single-sided ceramic separator by a gravure roll coating method, and dried at 60 ° C for 10 hours to obtain a separator having a hydrophilic retardation layer, wherein the hydrophilic retardation layer
  • the thickness was 0.7 ⁇ m, and the contact angle of the hydrophilic retardation layer and water was 8°.
  • Hydrophilic alumina prepared surface area 350 m 2 /g, particle size 200 nm, purchased from Aladdin), acrylate adhesive (P2010, purchased from Shanghai Aigao Chemical Co., Ltd.) ), dispersant (PVA), dispersant (PAANa), thickener Latekoll D (purchased from BASF) dispersed in water at a solids content of 85:15:0.2:0.3:1 (by weight) to control the solids content of the slurry 20% by weight, the pH of the slurry was adjusted to 10, and the mixture was stirred uniformly to form a hydrophilic retardation slurry.
  • the hydrophilic retardation slurry was applied to both sides of the single-sided ceramic separator by spraying, and dried at 50 ° C for 8 hours to obtain a separator having a hydrophilic retardation layer, wherein the thickness of the hydrophilic retardation layer was 0.6 ⁇ m, the contact angle of the hydrophilic barrier layer and water was 10°.
  • Hydrophilic alumina prepared surface area 320 m 2 /g, particle size 320 nm, purchased from Aladdin), acrylate adhesive (P2010, purchased from Shanghai Aigao Chemical Co., Ltd.) ), dispersant (PVA), dispersant (PAANa), thickener Latekoll D (purchased from BASF) dispersed in water at a solids content of 95:5:0.4:0.4:1.2 (weight ratio) to control the solids content of the slurry 17% by weight, the pH of the slurry was adjusted to 9, and the mixture was stirred uniformly to form a hydrophilic retardation slurry.
  • the hydrophilic retardation slurry was applied to both sides of the single-sided ceramic separator by a gravure roll coating method, and dried at 50 ° C for 12 hours to obtain a separator having a hydrophilic retardation layer, wherein the hydrophilic retardation layer
  • the thickness was 0.8 ⁇ m, and the contact angle of the hydrophilic retardation layer and water was 8°.
  • P(VdF-HFP) powder (Kynar powerflex LBG powder, purchased from Arkema, the same below) was dissolved in a mixture of N,N-dimethylformamide and propylene carbonate to control P (VdF)
  • concentration of -HFP was a critical concentration (10% by weight), and the mixture was uniformly stirred to obtain a polar polymer binder solution in which the weight ratio of N,N-dimethylformamide to propylene carbonate was 1:0.05.
  • the polar polymer binder solution was applied by gravure roll coating to the surface of the hydrophilic retardation layer on both sides of the separator having the hydrophilic retardation layer prepared in Example 1-1 at 35 ° C
  • the air was dried for 20 hours to form a porous polar polymer tie layer, thereby obtaining a polymer separator according to the present disclosure.
  • 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.
  • Styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) were dispersed in water, and stirred at a high speed of 2.5:1.5:90:6 at room temperature (25 ° C) for 3.5 hours with artificial graphite and conductive agent.
  • a good material is applied to the copper foil and dried to form a graphite negative pole piece having a thickness of 0.135 mm.
  • the LiCoO 2 positive electrode tab, the graphite negative electrode tab and the polymer separator prepared in the step (2) are prepared by winding to prepare a CSL454187 LiCoO 2 /graphite soft-packed lithium ion battery core.
  • the electrolyte is packaged to obtain a lithium ion battery; wherein the original ceramic surface faces the positive electrode, the electrolyte in the electrolyte is lithium hexafluorophosphate, the concentration is 1 mol/L, and the organic solvent is EC, EMC and DEC by weight ratio 1:1:1. Mix the resulting mixture.
  • Example 2-1B A lithium ion battery was prepared in the same manner as in Example 2-1A except that in the step (1), the polar polymer binder solution was applied by immersion coating method to the examples. a surface of a hydrophilic retardation layer on both sides of a separator having a hydrophilic retardation layer prepared by 1-3, wherein a separator having a hydrophilic retardation layer is immersed in a polar polymer binder solution, immersion time It is 30 seconds.
  • Example 2-2A A lithium ion battery was prepared in the same manner as in Example 2-1A except that a polymer separator was prepared by dissolving P(VdF-HFP) powder in N-methylpyrrolidone and propylene carbonate. In the mixture of esters, the concentration of P(VdF-HFP) is controlled to be a critical concentration (12% by weight), and the mixture is uniformly stirred to obtain a polar polymer binder solution, wherein the weight of N-methylpyrrolidone and propylene carbonate The ratio is 1:0.06.
  • the polar polymer binder solution was applied by gravure roll coating to the surface of the hydrophilic retardation layer on both sides of the separator having the hydrophilic retardation layer prepared in Example 1-2, respectively, at 30
  • the film was dried by blasting for 24 hours to form a porous polar polymer bonding layer, thereby obtaining a polymer separator according to the present disclosure.
  • Example 2-2B A lithium ion battery was prepared in the same manner as in Example 2-2A except that in the step (1), the polar polymer binder solution was applied by immersion coating method to the examples. a surface of a hydrophilic retardation layer on both sides of a separator having a hydrophilic retardation layer prepared by 1-4, wherein a separator having a hydrophilic retardation layer is immersed in a polar polymer binder solution, immersion time It is 30 seconds.
  • Example 2-3A A lithium ion battery was prepared in the same manner as in Example 2-1A except that a polymer separator was prepared by dissolving P(VdF-HFP) powder in triethyl phosphate and propylene carbonate. In the mixture, the concentration of P(VdF-HFP) is controlled to be a critical concentration (12% by weight), and the mixture is uniformly stirred to obtain a polar polymer binder solution, wherein the weight ratio of triethyl phosphate to propylene carbonate is 1:0.1.
  • the polar polymer binder solution was applied by gravure roll coating to the surface of the hydrophilic retardation layer on both sides of the separator having the hydrophilic retardation layer prepared in Example 1-2 at 40 ° C
  • the air was dried for 18 hours to form a porous polar polymer tie layer, thereby obtaining a polymer separator according to the present disclosure.
  • Example 2-3B A lithium ion battery was prepared in the same manner as in Example 2-3A except that in the step (1), the polar polymer binder solution was applied by immersion coating method to the examples. a surface of a hydrophilic retardation layer on both sides of a separator having a hydrophilic retardation layer prepared by 1-3, wherein a separator having a hydrophilic retardation layer is immersed in a polar polymer binder solution, immersion time It is 30 seconds.
  • Example 2-4A A lithium ion battery was prepared in the same manner as in Example 2-1A except that the polymer separator was prepared by dissolving P(VdF-HFP) powder in N,N-dimethyl group. a mixture of an amide and a dipropylene glycol dimethyl ether as a pore-forming agent, controlling a concentration of P(VdF-HFP) to a critical concentration (10% by weight), and uniformly obtaining a polar polymer binder solution, wherein The weight ratio of the mixture of N,N-dimethylformamide and dipropylene glycol dimethyl ether was 1:0.06.
  • the polar polymer binder solution was applied by gravure roll coating to the surface of the hydrophilic retardation layer on both sides of the separator having the hydrophilic retardation layer prepared in Example 1-1 at 45 ° C
  • the air was dried for 15 hours to form a porous polar polymer tie layer, thereby obtaining a polymer separator according to the present disclosure.
  • Example 2-4B A lithium ion battery was prepared in the same manner as in Example 2-4A except that in the step (1), the polar polymer binder solution was applied by immersion coating method to the examples. a surface of a hydrophilic retardation layer on both sides of a separator having a hydrophilic retardation layer prepared by 1-3, wherein a separator having a hydrophilic retardation layer is immersed in a polar polymer binder solution, immersion time It is 30 seconds.
  • Example 2-5A A lithium ion battery was prepared in the same manner as in Example 2-1A except that a polymer separator was prepared by dissolving P(VdF-HFP) powder in N-methylpyrrolidone and dipropylene glycol. In the mixture of dimethyl ether, the concentration of P(VdF-HFP) is controlled to be a critical concentration (12% by weight), and the mixture is uniformly stirred to obtain a polar polymer binder solution, wherein N-methylpyrrolidone and dipropylene glycol are used. The weight ratio of the methyl ether mixture was 1:0.08.
  • the polar polymer binder solution was applied by spray coating to the surface of the hydrophilic retardation layer on both sides of the separator having the hydrophilic retardation layer prepared in Example 1-1, and drummed at 45 ° C The air was dried for 15 hours to form a porous polar polymer tie layer, thereby obtaining a polymer separator according to the present disclosure.
  • Example 2-5B A lithium ion battery was prepared in the same manner as in Example 2-5A except that in the step (1), the polar polymer binder solution was applied by immersion coating method to the examples. a surface of a hydrophilic retardation layer on both sides of a separator having a hydrophilic retardation layer prepared by 1-3, wherein a separator having a hydrophilic retardation layer is immersed in a polar polymer binder solution, immersion time It is 30 seconds.
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-1A except that in the step (1), the separator having the hydrophilic retardation layer was the one-sided ceramic separator of Example 1-1. (9 ⁇ mPE+2 ⁇ m ceramic layer) instead, the polar polymer binder solution is directly applied to both sides of the single-sided ceramic separator, and N,N-dimethylformamide is replaced by an equal weight of acetone to obtain a polymer. Diaphragm.
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-4B except that the separator having a hydrophilic retardation layer was used as the one-sided ceramic of Examples 1-3 in the preparation of the polymer separator. Instead of the separator (9 ⁇ m PE + 2 ⁇ m ceramic layer), the polar polymer binder solution was directly applied to both sides of the single-sided ceramic separator, and N,N-dimethylformamide was replaced with an equal weight of acetone to obtain a polymerization. Membrane (the polymer membrane does not have a hydrophilic retardation layer).
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-4B except that the polar polymer binder solution contained no pore former.
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-4B except that in the step (1), the drying was not performed at 45 ° C for 15 hours, but at 120 ° C by air blowing. hour.
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-4B except that the concentration of P(VdF-HFP) was controlled to be 3.5% by weight in the preparation of the polar polymer binder solution (non- Critical concentration).
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-4B except that the concentration of P(VdF-HFP) was controlled to be 22% by weight in the preparation of the polar polymer binder solution (non- Critical concentration).
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-4B except that N,N-dimethylformamide was replaced with an equal weight of acetone in the preparation of a polar polymer binder solution. .
  • a separator having a hydrophilic retardation layer was prepared in the same manner as in Example 1-1, except that in the step (1), the vapor phase hydrophilic silica was made of quartz (having a specific surface area of 10 m 2 /g, The particle size was 10 ⁇ m instead, thereby obtaining a separator having a hydrophilic retardation layer, and the formed hydrophilic retardation layer and water had a contact angle of 40°; a polymer separator was prepared in the same manner as in Example 2-1A. Unlike the lithium ion battery, the separator having the hydrophilic retardation layer prepared in Example 7 was used.
  • a separator having a hydrophilic retardation layer was prepared in the same manner as in Example 1-3 except that the vapor phase hydrophilic aluminum oxide was aluminized aluminum oxide (having a specific surface area of 130 m 2 /g). Instead of the particle size of 5 ⁇ m, a separator having a hydrophilic retardation layer was obtained, and the hydrophilic retardation layer was formed to have a contact angle of 36° with water; a polymer was prepared in the same manner as in Example 2-4B. The separator and the lithium ion battery were different from the separator having the hydrophilic retardation layer prepared in Example 8.
  • a polymer separator and a lithium ion battery were prepared in the same manner as in Example 2-5A, except that the hydrophilic retardation slurry was applied to both sides of the single-sided ceramic separator in the same manner as in Example 1-1. After drying, the polar polymer binder solution was sprayed directly by the method of Example 2-5A, and then dried in the same manner as in Example 2-5A to obtain a polymer separator.
  • microstructure of the polymer separator prepared in each of the examples and the comparative examples was observed using a scanning electron microscope (SEM, JEOL, JSM-7600FE).
  • FIGS. 3A and 3B show SEM topography photographs of the polymer separator prepared in Example 2-4A
  • FIG. 4A And Figure 4B shows a SEM topographical photograph of the polymer separator prepared in Example 2-4B.
  • 2A, 2B, 3A, 3B, 4A and 4B it can be seen that the porous polar polymer bonding layer having a relatively good porosity can be prepared by the method of the present disclosure, and the porous polar polymerization is prepared at the same time.
  • the adhesive layer of the object has a nodule on the wall of the hole.
  • FIGS. 5A and 5B show SEM topography photographs of the polymer separator prepared in Comparative Example 2
  • FIGS. 6A and 6B show SEM topography photographs of the polymer separator prepared in Comparative Example 3.
  • 4A and 4B can be seen in comparison with FIG. 5A and FIG. 5B, the pores in the porous polar polymer bonding layer on the surface of the polymer membrane according to the present disclosure have a larger pore diameter, and are multi-layered wire mesh interwoven structure. a part of the surface of the hydrophilic retardation layer is exposed through the multilayered wire mesh interweaving structure; the porous polar polymer bonding layer in the polymer separator prepared in Comparative Example 2 is denser and honeycomb-shaped . 4A and 4B can be seen in comparison with FIGS.
  • the porous polar polymer bonding layer of the polymer separator prepared by the method of the present disclosure has a nodular structure on the pore wall, which may be due to The introduction of the pore former in the polar polymer binder solution results in phase separation of the polar polymer in the precipitation.
  • the apparent porosity of the polymer membrane can be calculated according to the following formula:
  • ⁇ M is the apparent density
  • ⁇ f is the areal density
  • ⁇ P is the bulk density
  • d is the thickness of the polymer membrane.
  • the polymer membranes according to the present disclosure have a higher apparent porosity.
  • the polymer separator (area 5 mm ⁇ 5 mm) was isothermally heat treated at 90 ° C and 120 ° C for 2 h and 1 h, respectively, to characterize the temperature resistance of the polymer separator.
  • the experimental results are listed in Table 1. From the results of Table 1, it is known that the polymer separator according to the present disclosure has a lower heat shrinkage rate.
  • the diameter of the steel needle is 1 mm using a universal testing machine.
  • the experimental results are listed in Table 1.
  • the polymer separator according to the present disclosure has a higher puncture strength.
  • Thickness of polymer membrane 2 single-plane density of polar polymer coating on both surfaces of polymer membrane
  • the polymer diaphragm is cut into a disk having a diameter of 17 mm. After drying, it is overlapped by three layers and placed between two stainless steel (SS) electrodes to absorb a sufficient amount of electrolyte (electrolyte is lithium hexafluorophosphate, the concentration is 1 mol/L, organic
  • the solvent is a mixture of EC, EMC and DEC at a weight ratio of 1:1:1. It is sealed in a 2016 type button cell.
  • the electrochemical impedance workstation (Shanghai Chenhua, CHI 660C) is used for AC impedance test and AC signal. The frequency range is from 0.01 Hz to 1 MHz, and the sinusoidal potential amplitude is 5 mV.
  • the intersection of the linear and real axes is the bulk resistance of the polymer membrane.
  • the ionic conductivity of the polymer membrane is calculated by the following formula:
  • A is the contact area between the stainless steel plate and the polymer separator.
  • R is the bulk impedance of the polymer electrolyte.
  • the polymer separator according to the present disclosure exhibits excellent ionic conductivity.
  • the prepared lithium ion battery (after 85 ° C, 4 h, 1 MPa hot pressing) was dissected in a fully charged state, and the mechanical strength of the peeling was measured by a universal testing machine.
  • the test standard was tested with reference to the peel strength of the adhesive tape of GBT 2792-2014. Method; and taking the obtained positive and negative pole pieces and the separator to take a picture.
  • 7A and 7B and FIGS. 8A and 8B respectively show SEM topographic photographs of the positive electrode and the negative electrode of the lithium ion battery prepared in Example 2-4B after peeling off from the polymer separator, and FIG. 9A and FIG.
  • FIG. 10A respectively show The peeling strength test curves of the positive electrode and the negative electrode of the lithium ion battery prepared in Example 2-4B
  • FIG. 9B and FIG. 10B respectively show the peeling strength test curves of the positive electrode and the negative electrode of the lithium ion battery prepared in Comparative Example 2 as a comparison .
  • the polymer membrane according to the present disclosure is quite viscous to the positive electrode of a lithium ion battery.
  • the polymer separator according to the present disclosure also has a higher bond strength to the negative electrode viscosity.
  • the test results are listed in Table 3. As shown in Table 3, the lithium ion battery according to the present disclosure has a higher hardness.
  • the 25 °C cycle performance test was carried out on the lithium ion battery after the separation of the sample and the comparative examples prepared by using the (Guangzhou Lanqi, BK6016) lithium ion battery performance test cabinet.
  • the specific method is as follows.
  • the batteries were charged to 0.70 V cutoff at 0.7 C, 0.2 C, respectively; left for 10 min, put at 3.0 C or 0.2 C to 3.0 V, and cycled.
  • the test results of Table 4 indicate that the lithium ion battery according to the present disclosure exhibits more excellent cycle performance.
  • the lithium ion battery performance test cabinet (Guangzhou Lanqi, BK6016) was used to test the cycle performance of the 45 °C lithium ion battery obtained in the examples and the comparative examples.
  • the test method is: charging the battery to 0.70 V cutoff at 0.7 C; leaving it for 10 min, putting it at 0.7 C to 3.0 V, and circulating.
  • the cycle results are shown in Table 5.
  • the test results show that the lithium ion battery according to the present disclosure exhibits more excellent high temperature cycle performance. It can thus be seen that the polymer membrane according to the present disclosure is advantageous for improving the high temperature performance of the battery.
  • the lithium ion battery performance test cabinet (Guangzhou Lanqi, BK6016) was used to conduct the rate discharge performance test on the Lithium ion batteries obtained in the examples and the comparative examples.
  • the specific test method is as follows.
  • the rate discharge test results are shown in Table 6.
  • the test results show that the lithium ion battery according to the present disclosure shows good rate discharge performance.
  • the lithium ion batteries obtained in the examples and the comparative examples were subjected to a storage performance test at 85 ° C for 4 hours.
  • the test method is as follows.
  • Example 2-1A 2574 97.5%
  • Example 2-1B 2561 97.0%
  • Example 2-2A 2563 97.1%
  • Example 2-2B 2564 97.1%
  • Example 2-3A 2569 97.3%
  • Example 2-3B 2568 97.3%
  • Example 2-4A 2555 96.8%
  • Example 2-4B 2568 97.3%
  • Example 2-5A 2570 97.4%
  • Example 2-5B 2561 97.0%
  • Comparative example 1 2541 96.3%
  • Comparative example 3 2564 97.1%
  • Example 3 2550 96.6%
  • Example 4 2543 96.3%
  • Example 5 2534 96.0%
  • Example 6 2535 96.0%
  • Example 7 2534 96.0%
  • Example 8 2543 96.3%
  • Example 9 2550 96.6%
  • Example 2-1A Comparative Example 1, and comparing Example 2-4B with Comparative Example 2, it can be seen that by providing a hydrophilic retardation layer, a polar polymer solution is prepared even with a high boiling point solvent.
  • the prepared lithium ion battery also has good rate discharge performance, and particularly exhibits significantly improved discharge performance under large rate discharge conditions.
  • Example 2-4B Comparing Example 2-4B with Example 3, it can be seen that drying the polar polymer binder coating at a temperature not higher than 60 ° C can significantly improve the gas permeability of the prepared polymer separator and The ionic conductivity significantly improves the performance of the final prepared lithium ion battery. Comparing Examples 2-4B with Examples 4 and 5, it can be seen that controlling the concentration of the polar polymer in the polar polymer binder solution to a critical concentration can significantly improve the gas permeability of the prepared polymer separator and The ionic conductivity significantly improves the performance of the final prepared lithium ion battery.
  • Example 2-1A and Example 2-4B Comparing Example 2-1A and Example 2-4B with Examples 7 and 8, respectively, it can be seen that making the contact angle of the hydrophilic retardation layer with water not higher than 20° can further improve the finally prepared lithium.
  • the performance of the ion battery Comparing Example 2-5A with Example 9, it can be seen that by drying the hydrophilic retardation coating and coating the polar polymer binder solution to form a polar polymer bonding layer, the preparation can be further improved.
  • the gas permeability and ionic conductivity of the polymer membrane increase the performance of the final prepared lithium ion battery.

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Abstract

本公开公开了一种聚合物隔膜及其制备方法以及含有该聚合物隔膜的锂离子电池及其制备方法，所述聚合物隔膜含有多孔基材、亲水性阻滞层以及多孔极性聚合物粘结层，所述亲水性阻滞层设置在所述多孔基材和所述多孔极性聚合物粘结层之间，所述多孔极性聚合物粘结层中的孔壁具有结节结构。

Description

聚合物隔膜及其制备方法和应用以及锂离子电池及其制备方法 技术领域
本公开涉及一种聚合物隔膜及其制备方法和应用，本公开还涉及采用该聚合物隔膜的锂离子电池及其制备方法。
背景技术
锂离子电池主要由正/负极材料、电解质、隔膜及电池外壳包装材料组成。隔膜是锂离子电池的重要组成部分，用于分隔正、负极，防止电池内部短路；隔膜允许电解质离子自由通过，完成电化学充放电过程。隔膜的性能决定了电池的界面结构、内阻等，直接影响电池的倍率性能、循环性能以及安全性能(耐高温性能)等特性，性能优异的隔膜对提高电池的综合性能具有重要的作用。
由于具有原料价格低廉、制备工艺简单、机械强度高、电化学稳定性强等特点，机械拉伸法制备的聚乙烯、聚丙烯微孔膜是目前主要商用的锂离子电池隔膜。但是，商用微孔膜在熔融温度附近闭孔收缩造成电池短路，使电池具有高温下燃烧和爆炸的危险；除此之外，聚烯烃隔膜对电解液吸附性差，不利于充放电过程中锂离子的传导。
目前，在聚烯烃微孔膜两侧涂覆聚醚类(如聚氧化乙烯)、聚丙烯腈类、聚丙烯酸酯类(如聚甲基丙烯酸甲酯及其共聚物)、聚偏氟乙烯类(包括聚偏二氟乙烯、以及偏氟乙烯和六氟丙烯的共聚物)等极性聚合物的多孔膜是可以改善隔膜吸附电解液性能，同时降低微孔膜在熔融温度附近收缩比率的主要方法。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。
在实际生产中，聚偏氟乙烯系(PVdF)涂覆技术已得到了广泛应用。聚偏氟乙烯系(PVdF)涂覆技术采用溶剂蒸发沉淀相分离法在聚烯烃微孔膜表面造孔得到PVdF多孔膜，其具体操作工艺为：将聚偏氟乙烯溶解或分散于丙酮中，并添加一定量的致孔剂DMC(二甲基碳酸酯)，形成浆液，将该浆液涂布在聚烯烃微孔膜表面并进行干燥。干燥的过程中，先挥发除去潜溶剂丙酮，再蒸发除去致孔剂DMC，从而留下孔隙。
公开内容
现有的聚偏氟乙烯系(PVdF)涂覆技术采用低沸点丙酮作为溶剂，操作安全性有待提高。本公开的发明人在研究过程中发现尽管采用高沸点的溶剂代替丙酮，可以提高操作安全性，但是采用高沸点的溶剂配制聚偏氟乙烯系聚合物溶液而制备的锂离子电池的性能明显下降，经过研究发现，其原因可能在于：采用高沸点的溶剂配制的聚偏氟乙烯系聚合物 溶液渗透性极强，聚合物溶液极易穿透隔膜而到达与涂布面相对的另一个表面，从而将聚偏氟乙烯系聚合物也带入隔膜的孔隙中，由于聚偏氟乙烯系聚合物的流动性和渗透性远低于有机溶剂，被有机溶剂携带进入隔膜的聚偏氟乙烯系聚合物通常存留在隔膜的孔隙中，堵塞隔膜，对隔膜的透气性和孔隙率产生不利影响，提高聚合物隔膜的本体阻抗，降低离子电导率，对最终制备的锂离子电池的性能产生不良影响。尽管现有的聚烯烃隔膜表面通常形成陶瓷层以提高隔膜的热稳定性以及吸附电解液的能力，但是即便具有所述陶瓷层的聚烯烃隔膜也难以阻挡聚合物溶液穿透隔膜。
针对采用高沸点的溶剂配制聚偏氟乙烯系聚合物溶液时存在的问题，本公开的发明人进行了深入的研究，发现：采用高沸点的溶剂配制聚偏氟乙烯系聚合物溶液时，如果在多孔基材(即，具有陶瓷层或不具有陶瓷层的聚烯烃多孔膜)与聚偏氟乙烯系聚合物之间设置亲水性阻滞层，能有效地抑制聚偏氟乙烯系聚合物溶液透过亲水性阻滞层而进入多孔基材中，从而有效地降低进入多孔基材中的聚偏氟乙烯系聚合物的量，提高聚合物隔膜的透气性和孔隙率，降低聚合物隔膜的本体阻抗，提高聚合物隔膜的离子电导率，使得制备的锂离子电池仍然具有较好的性能。在此基础上完成了本公开。
根据本公开的第一个方面，本公开提供了一种聚合物隔膜，该聚合物隔膜含有多孔基材、亲水性阻滞层以及多孔极性聚合物粘结层，所述亲水性阻滞层设置在所述多孔基材和所述多孔极性聚合物粘结层之间，所述多孔极性聚合物粘结层中的孔壁具有结节结构。
根据本公开的第二个方面，本公开提供了一种聚合物隔膜的制备方法，该方法包括：
(1)将亲水阻滞浆液涂布在多孔基材的至少一个表面形成亲水阻滞涂层，所述亲水阻滞浆液含有分散介质、以及分散在所述分散介质中的亲水性无机颗粒以及粘合剂，可选地将所述亲水阻滞涂层干燥，形成亲水性阻滞层；
(2)将极性聚合物粘结剂溶液涂布在所述亲水阻滞涂层或者所述亲水性阻滞层的表面形成极性聚合物粘结剂涂层，所述极性聚合物粘结剂溶液含有有机溶剂以及溶解在所述有机溶剂中的极性聚合物粘结剂和造孔剂；
(3)，将所述亲水阻滞涂层和所述极性聚合物粘结剂涂层进行干燥，形成亲水性阻滞层和多孔极性聚合物粘结层，或者将所述极性聚合物粘结剂涂层进行干燥，形成多孔极性聚合物粘结层。
根据本公开的第三个方面，本公开提供了由本公开第二个方面所述方法制备的聚合物隔膜。
根据本公开的第四个方面，本公开提供了本公开第一个方面或者第三个方面所述的聚合物隔膜在锂离子电池中的应用。
根据本公开的第五个方面，本公开提供了一种锂离子电池，该锂离子电池包括正极极 片、负极极片以及聚合物隔膜，其中，所述聚合物隔膜为本公开第一个方面或者第三个方面所述的聚合物隔膜。
根据本公开的第六个方面，本公开提供了一种锂离子电池的制备方法，该方法包括：
S1、采用本公开第二个方面所述的方法制备聚合物隔膜；
S2、将所述聚合物隔膜设置在正极极片和负极极片之间，形成电池极芯后，进行封装。
将根据本公开的聚合物隔膜用于锂离子电池，能与锂离子电池的正极极片和负极极片牢固地粘结在一起，与正极极片和负极极片的结合力强，使得锂离子电池具有较高的硬度。采用本公开的聚合物隔膜的锂离子电池显示出较好的性能。
根据本公开的聚合物隔膜的制备方法，在配制极性聚合物粘结剂溶液时，既可以采用现有工艺中的低沸点溶剂(如丙酮)，也可以采用操作安全性更高的高沸点溶剂，还可以采用低沸点溶剂和高沸点溶剂的混合物。其中，采用高沸点溶剂时，不仅能提高操作安全性，而且不会导致锂离子电池的性能明显下降。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
图1A和图1B为实施例1-1制备的聚合物隔膜的亲水性阻滞层的表面SEM形貌图片，图1A为放大500倍的照片，图1B为放大5000倍的照片。
图2A和图2B为实施例2-5A制备的聚合物隔膜的表面SEM形貌图片，图2A为放大500倍的照片，图2B为放大5000倍的照片。
图3A和图3B为实施例2-4A制备的聚合物隔膜的表面SEM形貌图片，图3A为放大500倍的照片，图3B为放大5000倍的照片。
图4A和图4B为实施例2-4B制备的聚合物隔膜的表面SEM形貌图片，图4A为放大500倍的照片，图4B为放大5000倍的照片。
图5A和图5B为对比例2制备的聚合物隔膜的表面SEM形貌图片，图5A为放大500倍的照片，图5B为放大5000倍的照片。
图6A和图6B为对比例3制备的聚合物隔膜的表面SEM形貌图片，图6A为放大500倍的照片，图6B为放大5000倍的照片。
图7A和图7B为将实施例2-4B制备的聚合物隔膜与正极粘结接触面剥离后，聚合物隔膜侧(图7A)以及正极侧(图7B)的SEM形貌照片。
图8A和图8B为将实施例2-4B制备的聚合物隔膜与负极粘结接触面剥离后，聚合物隔膜侧(图8A)以及负极侧(图8B)的SEM形貌照片。
图9A和图9B分别为实施例2-4B(图9A)以及对比例2(图9B)制备的锂离子电池的正极与聚合物隔膜的剥离强度测试曲线图。
图10A和图10B分别为实施例2-4B(图10A)以及对比例2(图10B)制备的锂离子电池的负极与聚合物隔膜的剥离强度测试曲线图。
公开详细描述
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。
根据本公开的第一个方面，本公开提供了一种聚合物隔膜，该聚合物隔膜包括多孔基材、亲水性阻滞层以及多孔极性聚合物粘结层，所述亲水性阻滞层设置在所述多孔基材和所述多孔极性聚合物粘结层之间。
所述亲水性阻滞层为具有亲水特性的阻滞层。根据本公开的聚合物隔膜，所述亲水性阻滞层与水的接触角可以为不高于40°，例如1°、2°、3°、4°、5°、6°、7°、8°、9°、10°、11°、12°、13°、14°、15°、16°、17°、18°、19°、20°、21°、22°、23°、24°、25°、26°、27°、28°、29°、30°、31°、32°、33°、34°、35°、36°、37°、38°、39°、或者40°。优选地，所述亲水性阻滞层与水的接触角为20°以下。在所述亲水性阻滞层与水接触角为20°以下时，能更为明显地提高聚合物隔膜的性能，例如：更为明显地提高聚合物隔膜的透气性和离子电导率，使得采用该聚合物隔膜的锂离子电池显示出更为优异的性能。更优选地，所述亲水性阻滞层与水的接触角为2-15°，优选为5-10°。所述接触角采用GB/T30693-2014塑料薄膜与水接触角的测量中规定的方法测定。
所述亲水性阻滞层含有粘合剂以及亲水性无机颗粒，所述亲水性无机颗粒通过所述粘合剂相互粘合。
所述亲水性无机颗粒为亲水性Al 2O 3、亲水性SiO 2、亲水性SnO 2、亲水性ZrO 2、亲水性TiO 2、亲水性SiC、亲水性Si 3N 4、亲水性CaO、亲水性MgO、亲水性ZnO、亲水性BaTiO 3、亲水性LiAlO 2和亲水性BaSO 4中的至少一种，例如所述亲水性无机颗粒优选为亲水性Al 2O 3、亲水性SiO 2、亲水性SnO 2、亲水性ZrO 2、亲水性TiO 2、亲水性SiC、亲水性Si 3N 4、亲水性CaO、亲水性MgO、亲水性ZnO、亲水性BaTiO 3、亲水性LiAlO 2和亲水性BaSO 4中的一种或两种以上。更优选地，所述亲水性无机颗粒为亲水性Al 2O 3和/或亲水性SiO 2。进一步优选地，所述亲水性无机颗粒为气相法亲水性SiO 2、沉淀法亲水性SiO 2和气相法亲水性Al 2O 3中的至少一种，例如所述亲水性无机颗粒为气相法亲水性SiO 2、沉淀法亲水性SiO 2 和气相法亲水性Al 2O 3中的一种或两种以上。
所述亲水性无机颗粒的粒径可以为1nm至10μm，优选为1nm至5μm，更优选1nm至2μm。从进一步提高聚合物隔膜的透气性和离子电导率以及采用该聚合物隔膜的锂离子电池性能的角度出发，所述亲水性无机颗粒的粒径更优选为10nm至1μm，进一步优选为20nm至800nm，更进一步优选为50nm至350nm。所述粒径为体积平均粒径，采用激光粒度仪测定。
所述亲水性无机颗粒的比表面积可以为10-600m 2/g。从进一步提高聚合物隔膜的透气性和离子电导率以及采用该聚合物隔膜的锂离子电池性能的角度出发，所述亲水性无机颗粒的比表面积优选为100-500m 2/g，更优选为150-400m 2/g，进一步优选为200-400m 2/g，更进一步优选为250-390m 2/g，特别优选为300-380m 2/g。所述比表面积采用GB/T19587-2004气体吸附BET法测定固态物质比表面积方法中规定的方法测定。
根据本公开的聚合物隔膜，以所述亲水性阻滞层的总量为基准，所述亲水性无机颗粒的含量可以为50-95重量％，优选为70-95重量％，更优选为80-95重量％，进一步优选为85-95重量％。
所述粘合剂一方面用于粘合并固定亲水性无机颗粒，另一方面还可以进一步提高聚合物隔膜的吸附电解液的能力。所述粘合剂为丙烯酸酯型聚合物、苯乙烯-丙烯酸酯共聚物、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物、丙烯腈-丙烯酸酯共聚物、氯乙烯-丙烯酸酯共聚物和丁二烯-苯乙烯共聚物中的至少一种，优选为丙烯酸酯型聚合物、苯乙烯-丙烯酸酯共聚物、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物、丙烯腈-丙烯酸酯共聚物、氯乙烯-丙烯酸酯共聚物和丁二烯-苯乙烯共聚物中的一种或两种以上。
根据本公开的聚合物隔膜，所述亲水性阻滞层的厚度可以为0.1-3μm，例如：0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm、2μm、2.1μm、2.2μm、2.3μm、2.4μm、2.5μm、2.6μm、2.7μm、2.8μm、2.9μm、或者3μm。优选地，所述亲水性阻滞层的厚度为0.1-1μm，更优选为0.3-0.8μm。
根据本公开的聚合物隔膜，所述多孔基材含有多孔聚合物层，可以用于溶胀液体电解液并传输锂离子。优选地，所述多孔聚合物层为多孔聚烯烃层，例如所述多孔聚合物层为多孔聚乙烯层、多孔聚丙烯层、多孔聚乙烯和多孔聚丙烯复合层中的至少一种，优选多孔聚乙烯(PE)层、多孔聚丙烯(PP)层、多孔聚乙烯和多孔聚丙烯复合层中的一种或两种以上。所述多孔聚乙烯和多孔聚丙烯复合层可以为PE/PP/PE复合基材层。
根据本公开的聚合物隔膜，所述多孔聚合物层的厚度可以为1-50μm，例如1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、 16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34μm、35μm、36μm、37μm、38μm、39μm、40μm、41μm、42μm、43μm、44μm、45μm、46μm、47μm、48μm、49μm、50μm，优选为5-20μm，更优选为8-15μm。
根据本公开的聚合物隔膜，所述多孔基材还可以含有陶瓷层，所述陶瓷层用于提高多孔聚合物层的热稳定性、力学性能和电解液吸附能力。所述陶瓷层中的陶瓷颗粒可以为由选自Al 2O 3、SiO 2、SnO 2、ZrO 2、TiO 2、SiC、Si 3N 4、CaO、MgO、ZnO、BaTiO 3、LiAlO 2和BaSO 4中的至少一种烧结形成，优选为由选自Al 2O 3、SiO 2、SnO 2、ZrO 2、TiO 2、SiC、Si 3N 4、CaO、MgO、ZnO、BaTiO 3、LiAlO 2和BaSO 4中的一种或两种以上烧结形成的陶瓷颗粒。一般地，所述陶瓷层的厚度可以为1-5μm，例如1μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm、2.0μm、2.1μm、2.2μm、2.3μm、2.4μm、2.5μm、2.6μm、2.7μm、2.8μm、2.9μm、3μm、3.1μm、3.2μm、3.3μm、3.4μm、3.5μm、3.6μm、3.7μm、3.8μm、3.9μm、4.0μm、4.1μm、4.2μm、4.3μm、4.4μm、4.5μm、4.6μm、4.7μm、4.8μm、4.9μm、5.0μm，优选为1.5-3μm。优选地，所述陶瓷层的厚度大于所述亲水性阻滞层的厚度。
根据本公开的聚合物隔膜含有陶瓷层时，所述陶瓷层可以设置在所述多孔聚合物层和所述亲水性阻滞层之间，也可以是多孔聚合物层设置在所述陶瓷层和所述亲水性阻滞层之间，还可以为上述两种方式的组合。
根据本公开的聚合物隔膜，所述多孔极性聚合物粘结层用于降低多孔基材在熔融温度附近收缩比率，同时起到粘结的作用，将聚合物隔膜与电池的正极或负极粘结在一起，还可以提高多孔基材的吸附电解液的能力。所述多孔极性聚合物粘结层中的极性聚合物可以为能实现上述功能的极性聚合物，其具体实例可以包括但不限于聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的至少一种，优选包括但不限于聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的至少一种，更优选包括但不限于聚偏二氟乙烯(PVdF)、偏氟乙烯和六氟丙烯的共聚物(P(VdF-HFP))、以及偏氟乙烯和丙烯酸酯的共聚物中的一种或两种以上。
所述多孔极性聚合物粘结层的厚度可以为0.1-10μm，优选为0.2-5μm，更优选为0.7-3μm，进一步优选为0.8-1.5μm。
根据本公开的聚合物隔膜，所述多孔极性聚合物粘结层中的孔壁具有结节结构，即多孔极性聚合物粘结层中，孔之间的孔壁上具有结节结构。所述结节结构中的结节可以隆起于孔壁(即，相对于孔壁面为突出)，也可以不隆起于孔壁(即，相对于孔壁面为非突出)。需要说明的是，本文中的“结节结构”可以理解为图4B所示网状结构，其网壁全部由球状颗粒组成、或部分为球状颗粒组成，其本质为PVDF在溶剂中均相溶解后，因某些特定的 温湿度等条件变化，二次析出形成的小球(该球与商品化PVDF颗粒本身的小球不同)。而参考图6B，其为普通网状结构，网壁光滑，没有球状颗粒，并不是结节结构。
根据本公开的聚合物隔膜，所述亲水性阻滞层、以及所述多孔极性聚合物粘结层可以设置在多孔基材的一面，也可以设置在多孔基材的两面。优选地，所述多孔极性聚合物粘结层附着在所述亲水性阻滞层的表面。
根据本公开的聚合物隔膜，在一种实施方式中，该聚合物隔膜由多孔基材、亲水性阻滞层和多孔极性聚合物粘结层组成，所述多孔基材为多孔聚合物层。所述亲水性阻滞层附着在所述多孔基材的表面，所述多孔极性聚合物粘结层附着在所述亲水性阻滞层的表面。根据该实施方式，可以在多孔基材的一个表面依次设置所述亲水性阻滞层和所述多孔极性聚合物粘结层(即，聚合物隔膜具有以下结构：多孔聚合物层|亲水性阻滞层|多孔极性聚合物粘结层)，也可以在多孔基材的两个相对的表面各自依次设置所述亲水性阻滞层和所述多孔极性聚合物粘结层(即，聚合物隔膜具有以下结构：多孔极性聚合物粘结层|亲水性阻滞层|多孔聚合物层|亲水性阻滞层|多孔极性聚合物粘结层)。
根据本公开的聚合物隔膜，在另一种实施方式中，该聚合物隔膜由多孔基材、亲水性阻滞层和多孔极性聚合物粘结层组成，所述多孔基材由多孔聚合物层和陶瓷层组成。根据该实施方式，在一个实例中，所述陶瓷层附着在所述多孔聚合物层的表面，所述亲水性阻滞层附着在所述陶瓷层的表面，所述多孔极性聚合物粘结层附着在所述亲水性阻滞层的表面(即，聚合物隔膜具有以下结构：多孔聚合物层|陶瓷层|亲水性阻滞层|多孔极性聚合物粘结层)。在另一个实例中，所述多孔聚合物层附着在所述陶瓷层的表面，所述亲水性阻滞层附着在所述多孔聚合物层的表面，所述多孔极性聚合物粘结层附着在所述亲水性阻滞层的表面(即，聚合物隔膜具有以下结构：陶瓷层|多孔聚合物层|亲水性阻滞层|多孔极性聚合物粘结层)。在又一个实例中，所述陶瓷层附着在所述多孔聚合物层的表面，所述陶瓷层和所述多孔聚合物层的另一个表面各自依次附着亲水性阻滞层和多孔极性聚合物粘结层(即，聚合物隔膜具有以下结构：多孔极性聚合物粘结层|亲水性阻滞层|陶瓷层|多孔聚合物层|亲水性阻滞层|多孔极性聚合物粘结层)。
根据本公开的聚合物隔膜，其总厚度可以为常规选择，一般可以为5-50μm，优选为8-30μm，更优选为10-20μm。
根据本公开的聚合物隔膜，具有较高的透气性。一般地，根据本公开的聚合物隔膜，Gurley值为100-900Sec/100mL，优选为120-600Sec/100mL，更优选为120-500Sec/100mL。进一步优选地，所述聚合物隔膜的Gurley值为150-350Sec/100mL，如200-300Sec/100mL。
与现有的聚合物隔膜中用于提高隔膜热稳定性和电解液吸附能力的陶瓷层相比，根据本公开的聚合物隔膜中的亲水性阻滞层，亲水性更强，能有效地阻滞制备过程中极性聚合 物进入多孔基材中。与现有的聚合物隔膜相比，根据本公开的聚合物隔膜，多孔极性聚合物粘结层中的孔的孔径更大(现有的聚合物隔膜的多孔极性聚合物粘结层中的孔径通常为0.5-1μm，根据本公开的聚合物隔膜的多孔极性聚合物粘结层中的孔径可以为3μm以上，通常为3-10μm)，多孔极性聚合物粘结层为多层丝网交织结构，所述亲水性阻滞层的部分表面通过所述多层丝网交织结构而暴露可见；然而现有的聚合物隔膜中的多孔极性聚合物粘结层更为致密，呈蜂窝状。
根据本公开的第二个方面，本公开提供了一种聚合物隔膜的制备方法，该方法包括：
(1)将亲水阻滞浆液涂布在多孔基材的至少一个表面形成亲水阻滞涂层，可选地将所述亲水阻滞涂层干燥，形成亲水性阻滞层；
(2)将极性聚合物粘结剂溶液涂布在所述亲水阻滞涂层或者所述亲水性阻滞层的表面形成极性聚合物粘结剂涂层；
(3)将所述亲水阻滞涂层和所述极性聚合物粘结剂涂层进行干燥，形成亲水性阻滞层和多孔极性聚合物粘结层，或者将所述极性聚合物粘结剂涂层进行干燥，形成多孔极性聚合物粘结层。
所述多孔基材可以为多孔聚合物膜，也可以为多孔聚合物膜和陶瓷膜的复合膜。所述多孔聚合物膜优选为多孔聚烯烃膜，例如所述多孔聚合物层为多孔聚乙烯层、多孔聚丙烯层、多孔聚乙烯和多孔聚丙烯复合层中的至少一种，优选为多孔聚乙烯膜、多孔聚丙烯膜、多孔聚乙烯和多孔聚丙烯复合膜中的一种或两种以上。所述多孔聚乙烯和多孔聚丙烯复合膜可以为PE/PP/PE复合膜。所述陶瓷膜中的陶瓷可以为由选自选自Al 2O 3、SiO 2、SnO 2、ZrO 2、TiO 2、SiC、Si 3N 4、CaO、MgO、ZnO、BaTiO 3、LiAlO 2和BaSO 4中的至少一种烧结形成，优选为由选自Al 2O 3、SiO 2、SnO 2、ZrO 2、TiO 2、SiC、Si 3N 4、CaO、MgO、ZnO、BaTiO 3、LiAlO 2和BaSO 4中的一种或两种以上烧结形成的陶瓷颗粒。所述复合膜中，所述多孔聚合物膜的厚度可以为1-50μm，例如1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34μm、35μm、36μm、37μm、38μm、39μm、40μm、41μm、42μm、43μm、44μm、45μm、46μm、47μm、48μm、49μm、50μm，优选为5-20μm，更优选为8-15μm。所述陶瓷膜的厚度可以为1-5μm，优选为1.5-3μm。
步骤(1)中，所述亲水阻滞浆液含有分散介质、以及分散在所述分散介质中的亲水性无机颗粒以及粘合剂。
所述亲水性无机颗粒的粒径可以为1nm至10μm，优选为1nm至5μm，更优选1nm至2μm。从进一步提高最终制备的聚合物隔膜的透气性和离子电导率，以及采用该聚合物隔膜 的锂离子电池性能的角度出发，所述亲水性无机颗粒的粒径更优选为1nm至2μm，进一步优选为10nm至1μm，更进一步优选为20nm至800nm，特别优选为50nm至350nm。
所述亲水性无机颗粒的比表面积可以为10-600m 2/g。从进一步提高最终制备的聚合物隔膜的透气性和离子电导率以及采用该聚合物隔膜的锂离子电池性能的角度出发，所述亲水性无机颗粒的比表面积优选为100-500m 2/g，更优选为150-400m 2/g，进一步优选为200-400m 2/g，更进一步优选为250-390m 2/g，特别优选为300-380m 2/g。
所述亲水性无机颗粒为亲水性Al 2O 3、亲水性SiO 2、亲水性SnO 2、亲水性ZrO 2、亲水性TiO 2、亲水性SiC、亲水性Si 3N 4、亲水性CaO、亲水性MgO、亲水性ZnO、亲水性BaTiO 3、亲水性LiAlO 2和亲水性BaSO 4中的至少一种，例如所述亲水性无机颗粒的具体实例可以包括但不限于亲水性Al 2O 3、亲水性SiO 2、亲水性SnO 2、亲水性ZrO 2、亲水性TiO 2、亲水性SiC、亲水性Si 3N 4、亲水性CaO、亲水性MgO、亲水性ZnO、亲水性BaTiO 3、亲水性LiAlO 2、以及亲水性BaSO 4中的一种或两种以上。优选地，所述亲水性无机颗粒为亲水性Al 2O 3和/或亲水性SiO 2。更优选地，所述亲水性无机颗粒为气相法亲水性SiO 2、沉淀法亲水性SiO 2和气相法亲水性Al 2O 3中的至少一种，例如所述亲水性无机颗粒为气相法亲水性SiO 2、沉淀法亲水性SiO 2和气相法亲水性Al 2O 3中的一种或两种以上。
所述亲水阻滞浆液中，所述粘合剂为丙烯酸酯型聚合物、苯乙烯-丙烯酸酯共聚物、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物、丙烯腈-丙烯酸酯共聚物、氯乙烯-丙烯酸酯共聚物和丁二烯-苯乙烯共聚物中的至少一种，优选为丙烯酸酯型聚合物、苯乙烯-丙烯酸酯共聚物、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物、丙烯腈-丙烯酸酯共聚物、氯乙烯-丙烯酸酯共聚物和丁二烯-苯乙烯共聚物中的一种或两种以上。
所述亲水阻滞浆液中，分散介质可以根据亲水性无机颗粒以及粘合剂的种类进行选择，以能使得亲水性无机颗粒和粘合剂形成均匀稳定的浆液为准。所述分散介质的具体实例可以包括但不限于水、乙醇、异丙醇、环己烷、四氢呋喃、二氯甲烷和三氯甲烷中的至少一种，优选包括但不限于水、乙醇、异丙醇、环己烷、四氢呋喃、二氯甲烷和三氯甲烷中的一种或两种以上。
所述亲水阻滞浆液中，亲水性无机颗粒的含量可以为50-95重量％，例如，50重量％、52重量％、55重量％、57重量％、60重量％、62重量％、65重量％、67重量％、70重量％、72重量％、75重量％、77重量％、80重量％、82重量％、85重量％、87重量％、90重量％、92重量％、95重量％，优选为70-95重量％，更优选为80-95重量％，进一步优选为85-95重量％。粘合剂的用量可以根据亲水性无机颗粒的用量进行选择，以能将亲水性无机颗粒粘合并固定为准。一般地，所述亲水阻滞浆液中，相对于100重量份亲水性无机颗粒，所述粘合剂的含量可以为1-30重量份，例如，1重量份、2重量份、5重量份、7重量份、10重 量份、12重量份、15重量份、17重量份、20重量份、22重量份、25重量份、27重量份、30重量份，优选为2-25重量份，更优选为5-20重量份。
所述亲水阻滞浆液还可以含有分散剂，以进一步提高亲水阻滞浆液的稳定性。所述分散剂可以为常见的可以促进无机颗粒在液体介质中的分散性的物质，其具体实例可以包括但不限于聚乙烯醇(PVA)和/或聚丙烯酸钠(PAANa)。所述分散剂的用量可以为常规选择。一般地，相对于100重量份亲水性无机颗粒，所述分散剂的用量可以为0.1-10重量份，例如0.1重量份、0.2重量份、0.3重量份、0.5重量份、0.7重量份、1.0重量份、1.2重量份、1.5重量份、1.7重量份、2.0重量份、2.2重量份、2.5重量份、2.7重量份、3.0重量份、3.2重量份、3.5重量份、3.7重量份、4.0重量份、4.2重量份、4.5重量份、4.7重量份、5.0重量份、5.2重量份、5.5重量份、5.7重量份、6.0重量份、6.2重量份、6.5重量份、6.7重量份、7.0重量份、7.2重量份、7.5重量份、7.7重量份、8.0重量份、8.2重量份、8.5重量份、8.7重量份、9.0重量份、9.2重量份、9.5重量份、9.7重量份、10.0重量份，优选为0.2-5重量份，更优选为0.3-2重量份。
所述亲水阻滞浆液还可以含有增稠剂，以进一步提高亲水阻滞浆液的可涂布性能。所述增稠剂可以为纤维素型增稠剂和/或聚丙烯酸酯类碱溶胀型增稠剂(如巴斯夫Latekoll D增稠剂)。相对于100重量份亲水性无机颗粒，所述增稠剂的用量可以为0.1-10重量份，例如0.1重量份、0.2重量份、0.3重量份、0.5重量份、0.6重量份、0.7重量份、0.8重量份、1.0重量份、1.2重量份、1.5重量份、1.7重量份、2.0重量份、2.2重量份、2.5重量份、2.7重量份、3.0重量份、3.2重量份、3.5重量份、3.7重量份、4.0重量份、4.2重量份、4.5重量份、4.7重量份、5.0重量份、5.2重量份、5.5重量份、5.7重量份、6.0重量份、6.2重量份、6.5重量份、6.7重量份、7.0重量份、7.2重量份、7.5重量份、7.7重量份、8.0重量份、8.2重量份、8.5重量份、8.7重量份、9.0重量份、9.2重量份、9.5重量份、9.7重量份、10.0重量份，优选为0.5-5重量份，更优选为0.8-2重量份。
优选地，将所述亲水阻滞浆液的pH值调节为碱性，优选为8-10，例如8、8.2、8.5、8.7、9.0、9.2、9.5、9.7、10.0。
所述亲水阻滞浆液的固含量优选为2-30重量％，例如2重量％、3重量％、重量％、4重量％、5重量％、7重量％、10重量％、12重量％、15重量％、17重量％、20重量％、22重量％、25重量％、27重量％、30重量％，更优选为5-25重量％。
所述亲水阻滞浆液在所述多孔基材表面的涂布量可以根据预期的亲水性阻滞层的厚度进行选择。一般地，所述亲水阻滞浆液的涂布量使得所述亲水性阻滞层的厚度为0.1-3μm，例如：0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm、2μm、2.1μm、2.2μm、2.3μm、 2.4μm、2.5μm、2.6μm、2.7μm、2.8μm、2.9μm、或者3μm。优选地，所述亲水阻滞浆液的涂布量使得所述亲水性阻滞层的厚度为0.1-1μm，更优选为0.3-0.8μm。
步骤(1)中，可以将亲水阻滞涂层干燥形成亲水性阻滞层后涂布极性聚合物粘结剂溶液，也可以不将亲水阻滞涂层干燥，而是直接在亲水阻滞涂层表面涂布极性聚合物粘结剂溶液。优选地，将亲水阻滞涂层干燥形成亲水性阻滞层后涂布极性聚合物粘结剂溶液，这样能进一步提高最终制备的聚合物隔膜的透气性和离子电导率，并进一步提高采用该聚合物隔膜的锂离子电池的性能。
步骤(1)中，所述干燥的温度可以为10-120℃。优选地，所述干燥的温度为不高于100℃。更优选地，所述干燥的温度为不高于80℃，例如10-80℃，具体可以为10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、或者80℃。优选地，所述干燥的温度为40-60℃，如50-60℃。步骤(1)中，所述干燥可以在常压下进行，也可以在减压下进行。优选地，所述干燥在常压下进行。所述干燥可以在鼓风干燥箱中进行。步骤(1)中，所述干燥的持续时间可以根据干燥的温度以及采用的分散剂的种类进行选择。一般地，步骤(1)中所述干燥的持续时间可以为0.1-24小时，例如0.1小时、0.2小时、0.5小时、0.7小时、1小时、1.2小时、1.5小时、1.7小时、2.0小时、2.2小时、2.5小时、2.7小时、3.0小时、3.2小时、3.5小时、3.7小时、4.0小时、4.2小时、4.5小时、4.7小时、5.0小时、5.2小时、5.5小时、5.7小时、6.0小时、6.2小时、6.5小时、6.7小时、7.0小时、7.2小时、7.5小时、7.7小时、8.0小时、8.2小时、8.5小时、8.7小时、9.0小时、9.2小时、9.5小时、9.7小时、10.0小时、10.5小时、11小时、11.5小时、12小时、12.5小时、13小时、13.5小时、14小时、14.5小时、15小时、15.5小时、16小时、16.5小时、17小时、17.5小时、18小时、18.5小时、19小时、19.5小时、20.0小时、20.5小时、21小时、21.5小时、22小时、22.5小时、23小时、23.5小时、24小时，优选为5-18小时，更优选为8-12小时。
根据本公开的方法，所述亲水性阻滞层与水的接触角可以为不高于40°，例如1°、2°、3°、4°、5°、6°、7°、8°、9°、10°、11°、12°、13°、14°、15°、16°、17°、18°、19°、20°、21°、22°、23°、24°、25°、26°、27°、28°、29°、30°、31°、32°、33°、34°、35°、36°、37°、38°、39°、或者40°。优选地，所述亲水性阻滞层与水的接触角为20°以下。在所述亲水性阻滞层与水接触角为20°以下时，能更为明显地提高聚合物隔膜的性能，例如：更为明显地提高聚合物隔膜的透气性和离子电导率，使得采用该聚合物隔膜的锂离子电池显示出更为优异的性能。更优选地，步骤(1)形成的亲水性阻滞层与水的接触角为2-15°，更优选为5-10°。
步骤(2)中，所述极性聚合物粘结剂溶液含有有机溶剂以及溶解在所述有机溶剂中的 极性聚合物粘结剂和造孔剂。
所述极性聚合物粘结剂可以为聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的至少一种，例如可以为聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的一种或两种以上。
所述有机溶剂可以为低沸点有机溶剂(沸点低于60℃的有机溶剂)，例如丙酮；也可以为高沸点溶剂，例如沸点为60℃以上的溶剂；还可以为低沸点溶剂和高沸点溶剂的混合物。对于低沸点溶剂和高沸点溶剂的混合物，从进一步提高操作安全性的角度出发，优选将低沸点溶剂的含量控制为不高于发生燃爆的安全阀值。
在一种实施方式中，所述有机溶剂为低沸点溶剂，优选为丙酮。根据该实施方式，在优选条件下，制备的聚合物隔膜和锂离子电池显示出更为优异的性能，特别是采用该聚合物隔膜制备的锂离子电池显示出明显提高的大倍率放电性能和高温性能。所述优选条件包括：所述亲水性无机颗粒的粒径优选为1nm至2μm，更优选为10nm至1μm，进一步优选为20nm至800nm，更进一步优选为50nm至350nm，所述亲水性阻滞层与水的接触角优选为20°以下，并且步骤(2)中所述干燥在不高于60℃的温度下进行。
在另一种实施方式中，所述有机溶剂为高沸点溶剂，例如沸点为60℃以上的有机溶剂(如60-260℃)，优选沸点为120℃以上的有机溶剂(如120-260℃)，更优选沸点为140℃以上的有机溶剂(如140-260℃)。进一步优选地，所述有机溶剂的沸点为145-260℃，如150-230℃。所述有机溶剂的具体实例可以包括但不限于磷酸三乙酯、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、以及二甲基亚砜中的至少一种，更优选包括但不限于磷酸三乙酯、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、以及二甲基亚砜中的一种或两种以上。根据该实施方式，能提高操作安全性。
在又一种实施方式中，所述有机溶剂为低沸点溶剂和高沸点溶剂的混合。所述低沸点溶剂和所述高沸点溶剂各自与前文所述相同。在该实施方式中，以所述有机溶剂的总量为基准，高沸点溶剂的含量可以为0.1-99.9重量％，低沸点溶剂的含量可以为0.1-99.9重量％。
所述造孔剂优选为有机造孔剂。所述造孔剂的沸点优选为高于所述有机溶剂的沸点，这样在进行干燥时，有机溶剂先挥发，造孔剂后挥发以增强造孔效果。优选地，所述有机造孔剂的沸点为61-261℃，例如61℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃、220℃、225℃、230℃、235℃、240℃、245℃、250℃、255℃、260℃、261℃。所述造孔剂可以为碳酸酯型化合物和/或醇醚型化合物，其具体实例可以包括但不限于碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、二乙二醇二甲醚、二丙二醇 单甲醚、二丙二醇单乙醚和二丙二醇二甲醚中的至少一种，优选包括但不限于碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、二乙二醇二甲醚、二丙二醇单甲醚、二丙二醇单乙醚和二丙二醇二甲醚中的一种或两种以上。
所述极性聚合物粘结剂溶液中，所述有机溶剂与所述造孔剂的重量比可以为1：0.01-1，例如：1：0.01、1：0.05、1：0.1、1：0.15、1：0.2、1：0.25、1：0.3、1：0.35、1：0.4、1：0.45、1：0.5、1：0.55、1：0.6、1：0.65、1：0.7、1：0.75、1：0.8、1：0.85、1：0.9、1：0.95、1：0.1、1：0.15、1：0.2、1：0.25、1：0.3、1：0.35、1：0.4、1：0.45、1：0.5、1：0.55、1：0.6、1：0.65、1：0.7、1：0.75、1：0.8、1：0.85、1：0.9、1：0.95、或者1：1。优选地，所述极性聚合物粘结剂溶液中，所述有机溶剂与所述造孔剂的重量比为1：0.02-0.5。更优选地，所述极性聚合物粘结剂溶液中，所述有机溶剂与所述造孔剂的重量比为1：0.03-0.3。进一步优选地，所述极性聚合物粘结剂溶液中，所述有机溶剂与所述造孔剂的重量比为1：0.05-0.1。
步骤(2)中，所述极性聚合物粘结剂溶液中极性聚合物粘结剂的浓度为1-30重量％，例如2重量％、3重量％、4重量％、5重量％、6重量％、7重量％、8重量％、9重量％、10重量％、11重量％、12重量％、13重量％、14重量％、15重量％、16重量％、17重量％、18重量％、19重量％、20重量％、21重量％、22重量％、23重量％、24重量％、25重量％、26重量％、27重量％、28重量％、29重量％、30重量％，优选为2-25重量％。从进一步提高最终制备的聚合物隔膜的性能以及采用该聚合物隔膜的锂离子电池性能的角度出发，所述极性聚合物粘结剂溶液中极性聚合物粘结剂的浓度更优选为5-20重量％。进一步优选地，所述极性聚合物粘结剂溶液中极性聚合物粘结剂的浓度为临界浓度(一般为8-15重量％，优选为10-12重量％)。所述临界浓度是指极性聚合物粘结剂溶液透过多孔基材的浓度，可以在25℃、1标准大气压且相对湿度为RH45％～55％的环境下，将极性聚合物粘结剂溶液涂布在多孔基材一个表面，观察极性聚合物粘结剂溶液在1小时内是否透过多孔基材，将处于透过多孔基材的浓度和不透过多孔基材的浓度之间的浓度作为临界浓度。在所述极性聚合物粘结剂的浓度为临界浓度时，极性聚合物粘结剂在溶液中，微观上呈凝胶状，单分子难以流动扩散，这样能加强极性聚合物分子之间的相互作用，在溶剂蒸发过程中形成理想的物理交联网络结构，从而使得聚合物隔膜具有更为优异的透气性和离子电导率，采用该聚合物隔膜的锂离子电池具有更为优异的性能。
所述极性聚合物粘结剂溶液的涂布量可以根据预期的极性聚合物粘结层的厚度进行选择。所述极性聚合物粘结剂溶液的涂布量可以使得最终形成的多孔极性聚合物粘结层的厚度为0.1-10μm，例如，0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1.0μm、1.2μm、1.5μm、1.6μm、1.7μm、2.0μm、2.2μm、2.5μm、2.7μm、3.0μm、3.2μm、 3.5μm、3.7μm、4.0μm、4.2μm、4.5μm、4.7μm、5.0μm、5.2μm、5.4μm、5.7μm、6.0μm、6.2μm、6.5μm、6.7μm、7.0μm、7.2μm、7.5μm、7.7μm、8.0μm、8.2μm、8.5μm、8.7μm、9.0μm、9.2μm、9.4μm、9.7μm、10μm,优选为0.2-5μm，更优选为0.7-3μm，进一步优选为0.8-1.5μm。
步骤(3)中，所述干燥可以在不高于120℃的温度下进行。优选地，所述干燥在不高于60℃的温度下进行，可以为10-60℃，例如：10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、或者60℃。在不高于60℃的温度下进行干燥，能使得极性聚合物粘结层具有更为优异的孔结构，从而能进一步提高最终制备的聚合物隔膜的透气性和离子电导率，并进一步提高采用该聚合物隔膜的锂离子电池的性能。更优选地，所述干燥在20-55℃的温度下进行。进一步优选地，所述干燥在30-45℃的温度下进行。所述干燥的持续时间可以根据干燥的温度进行选择。具体地，所述干燥的持续时间可以为0.1-36小时，优选为5-30小时，更优选为10-24小时，进一步优选为15-24小时。
步骤(1)和步骤(2)中，可以采用常规涂布方法，例如辊涂法、喷涂法、浸入涂布法和丝网印刷法中的一种或两种以上的组合。
根据本公开的方法，制备的聚合物隔膜中，可以在多孔基材的单面形成亲水性阻滞层和多孔极性聚合物粘结层，也可以在多孔基材的双面形成亲水性阻滞层和多孔极性聚合物粘结层。
根据本公开的方法，在一种实施方式中，最终制备的聚合物隔膜由多孔基材、亲水性阻滞层和多孔极性聚合物粘结层组成，所述多孔基材为多孔聚合物膜，所述亲水性阻滞层附着在所述多孔基材的表面，所述多孔极性聚合物粘结层附着在所述亲水性阻滞层的表面。根据该实施方式，可以在多孔基材的一个表面依次设置所述亲水性阻滞层和所述多孔极性聚合物粘结层(即，聚合物隔膜具有以下结构：多孔聚合物膜|亲水性阻滞层|多孔极性聚合物粘结层)，也可以在多孔基材的两个相对的表面各自设置所述亲水性阻滞层和所述多孔极性聚合物粘结层(即，聚合物隔膜具有以下结构：多孔极性聚合物粘结层|亲水性阻滞层|多孔聚合物膜|亲水性阻滞层|多孔极性聚合物粘结层)。
根据本公开的方法，在另一种实施方式中，最终制备的聚合物隔膜由多孔基材、亲水性阻滞层和多孔极性聚合物粘结层组成，所述多孔基材为多孔聚合物膜和陶瓷膜的复合膜。根据该实施方式，在一个实例中，所述陶瓷膜附着在所述多孔聚合物膜的表面，所述亲水性阻滞层附着在所述陶瓷膜的表面，所述多孔极性聚合物粘结层附着在所述亲水性阻滞层的表面(即，聚合物隔膜具有以下结构：多孔聚合物膜|陶瓷膜|亲水性阻滞层|多孔极性聚合物粘结层)。在另一个实例中，所述多孔聚合物膜附着在所述陶瓷层的表面，所述亲水性阻滞层附着在所述多孔聚合物膜的表面，所述多孔极性聚合物粘结层附着在所述亲水 性阻滞层的表面(即，聚合物隔膜具有以下结构：陶瓷膜|多孔聚合物膜|亲水性阻滞层|多孔极性聚合物粘结层)。在又一个实例中，陶瓷膜附着在多孔聚合物膜的表面，所述陶瓷膜和所述多孔聚合物膜的另一个表面各自依次附着亲水性阻滞层和多孔极性聚合物粘结层(即，聚合物隔膜具有以下结构：多孔极性聚合物粘结层|亲水性阻滞层|陶瓷膜|多孔聚合物膜|亲水性阻滞层|多孔极性聚合物粘结层)。
根据本公开的第三个方面，本公开提供了由本公开第二个方面所述方法制备的聚合物隔膜。
由本公开第二个方面所述方法制备的聚合物隔膜，其总厚度可以为常规选择，一般可以为5-50μm，例如5μm、8μm、9μm、10μm、11μm、12μm、13μm、15μm、18μm、20μm、23μm、25μm、28μm、30μm、32μm、35μm、38μm、40μm、42μm、44μm、46μm、48μm、50μm，优选为8-30μm，更优选为10-20μm。
由本公开第二个方面所述方法制备的聚合物隔膜，具有较高的透气性。一般地，由本公开第二个方面所述方法制备的聚合物隔膜，Gurley值为100-900Sec/100mL，例如100Sec/100mL、120Sec/100mL、150Sec/100mL、170Sec/100mL、190Sec/100mL、200Sec/100mL、220Sec/100mL、250Sec/100mL、270Sec/100mL、290Sec/100mL、300Sec/100mL、325Sec/100mL、350Sec/100mL、370Sec/100mL、390Sec/100mL、400Sec/100mL、425Sec/100mL、450Sec/100mL、480Sec/100mL、500Sec/100mL、520Sec/100mL、550Sec/100mL、575Sec/100mL、600Sec/100mL、625Sec/100mL、650Sec/100mL、675Sec/100mL、690Sec/100mL、700Sec/100mL、720Sec/100mL、740Sec/100mL、770Sec/100mL、790Sec/100mL、800Sec/100mL、825Sec/100mL、850Sec/100mL、875Sec/100mL、900Sec/100mL，优选为120-600Sec/100mL，更优选为120-500Sec/100mL。进一步优选地，由本公开第二个方面所述方法制备的聚合物隔膜的Gurley值为150-350Sec/100mL，如200-300Sec/100mL。
与现有的聚合物隔膜中用于提高隔膜热稳定性和电解液吸附能力的陶瓷层相比，由本公开第二个方面所述方法制备的聚合物隔膜中的亲水性阻滞层，亲水性更强，能有效地阻滞制备过程中极性聚合物进入多孔基材中。与现有的聚合物隔膜相比，由本公开第二个方面所述方法制备的聚合物隔膜，多孔极性聚合物粘结层中的孔的孔径更大(现有的聚合物隔膜的多孔极性聚合物粘结层中的孔径通常为0.5-1μm，根据本公开的聚合物隔膜的多孔极性聚合物粘结层中的孔径可以为3μm以上，通常为3-10μm)，多孔极性聚合物粘结层为多层丝网交织结构，所述亲水性阻滞层的部分表面通过所述多层丝网交织结构而暴露可见；然而现有的聚合物隔膜中的多孔极性聚合物粘结层更为致密，呈蜂窝状。
由本公开第二个方面所述的方法制备的聚合物隔膜，制备的聚合物隔膜的多孔极性聚合物粘结层中，孔壁可以具有结节结构，即多孔极性聚合物粘结层中，孔之间的孔壁上可 以具有结节结构。所述结节结构中的结节可以隆起于孔壁(即，相对于孔壁面为突出)，也可以不隆起于孔壁(即，相对于孔壁面为非突出)。
根据本公开的第四个方面，本公开提供了本公开第一个方面或者第三个方面所述的聚合物隔膜在锂离子电池中的应用。
根据本公开的第五个方面，本公开提供了一种锂离子电池，所述锂离子电池包括正极极片、负极极片、以及聚合物隔膜，其中，聚合物隔膜为本公开第一个方面或者第三个方面所述的聚合物隔膜。
所述正极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(LiCoO 2)、氧化镍锂(LiNiO 2)、氧化锰锂(LiMn 2O 4)和磷酸亚铁锂(LiFePO 4)中的一种或两种以上。所述负极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、硬碳中的一种或两种以上。
根据本公开的锂离子电池，可以含有电解液，也可以不含有电解液。所述电解液为本领域技术人员公知，含有锂盐和有机溶剂。所述锂盐可以为可离解的锂盐，例如，可以为选自六氟磷酸锂(LiPF 6)、高氯酸锂(LiClO 4)和四氟硼酸锂(LiBF 4)中的一种或两种以上。所述有机溶剂可以为选自碳酸乙烯酯(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)和碳酸亚乙烯酯(VC)中的一种或两种以上。优选地，所述电解液中，锂盐的浓度可以为0.8-1.5mol/L。
根据本公开的第六个方面，本公开提供了一种锂离子电池的制备方法，该方法包括：
S1、采用本公开第二个方面所述的方法制备聚合物隔膜；
S2、将所述聚合物隔膜设置在正极极片和负极极片之间，形成电池极芯后，进行封装。
步骤S2可以采用锂离子电池制备技术领域的常规方法进行，本公开对此没有特别限定。步骤S2中，可以向电池极芯中灌装电解液，也可以不灌装电解液直接进行封装。
以下结合实施例详细说明本公开，但并不因此限定本公开的范围。
以下实施例和对比例涉及以下测试方法。
(1)面密度采用重量法测定。
(2)亲水性阻滞层和水的接触角采用GB/T30693-2014塑料薄膜与水接触角的测量中规定的方法。
(3)粒径采用激光粒度仪测定，为体积平均粒径。
(4)比表面积采用GB/T 19587-2004气体吸附BET法测定固态物质比表面积中规定的方法。
下面通过实施例对本公开做进一步说明，但并不因此而限制本公开的内容。
实施例1-1至1-4用于制备根据本公开的亲水性阻滞层。
实施例1-1
将用气相法制备的亲水性二氧化硅(比表面积为380m 2/g，粒径为80nm，购自阿拉丁)、丙烯酸酯类粘合剂(P1005，购自上海爱高化工有限公司)、分散剂(PVA，购自阿拉丁)、分散剂(PAANa，购自日本昭和电工)、作为增稠剂的羧甲基纤维素(CMC，购自日本大赛璐)以浆液的固含量92：8：0.4：0.4：1.2(重量比)分散在水中，控制固含量为8重量％，调节浆液的pH值为8，搅拌均匀，形成亲水阻滞浆液。将亲水阻滞浆液以凹版辊涂布的方法，涂布至单面陶瓷隔膜(9μmPE+2μm陶瓷层，陶瓷层中的陶瓷颗粒为微米级三氧化二铝陶瓷颗粒，购自山东国瓷，下同)两侧，在60℃干燥12小时，得到具有亲水性阻滞层的隔膜，其中，亲水性阻滞层的厚度为0.5μm，亲水性阻滞层和水的接触角为5°。图1A和图1B示出了该亲水性阻滞层的SEM形貌图片
实施例1-2
将用沉淀法制备的亲水性二氧化硅(比表面积为370m 2/g，粒径为150nm，购自阿拉丁)、丙烯酸酯类粘合剂(P1005，购自上海爱高化工有限公司)、分散剂(PVA)、分散剂(PAANa)、增稠剂Latekoll D(购自巴斯夫)以固含量90：10：0.4：0.4：1.2(重量比)分散在水中，控制浆液的固含量为8重量％，调节浆液的pH值为10，搅拌均匀，形成亲水阻滞浆液。将亲水阻滞浆液以凹版辊涂布的方法，涂布至单面陶瓷隔膜两侧，在60℃干燥10小时，得到具有亲水性阻滞层的隔膜，其中，亲水性阻滞层的厚度为0.7μm，亲水性阻滞层和水的接触角为8°。
实施例1-3
将用气相法制备的亲水性三氧化二铝(比表面积为350m 2/g，粒径为200nm，购自阿拉丁)、丙烯酸酯类粘合剂(P2010，购自上海爱高化工有限公司)、分散剂(PVA)、分散剂(PAANa)、增稠剂Latekoll D(购自巴斯夫)以固含量85：15：0.2：0.3：1(重量比)分散在水中，控制浆液的固含量为20重量％，调节浆液的pH值为10，搅拌均匀，形成亲水阻滞浆液。将亲水阻滞浆液以喷涂的方法，涂布至单面陶瓷隔膜两侧，在50℃干燥8小时，得到具有亲水性阻滞层的隔膜，其中，亲水性阻滞层的厚度为0.6μm，亲水性阻滞层和水的接触角为10°。
实施例1-4
将用气相法制备的亲水性三氧化二铝(比表面积为320m 2/g，粒径为320nm，购自阿拉丁)、丙烯酸酯类粘合剂(P2010，购自上海爱高化工有限公司)、分散剂(PVA)、分散剂(PAANa)、增稠剂Latekoll D(购自巴斯夫)以固含量95：5：0.4：0.4：1.2(重量比)分散在水中，控制浆液的固含量为17重量％，调节浆液的pH为9，搅拌均匀，形成亲水阻滞浆液。将亲水阻滞浆液以凹版辊涂布的方法，涂布至单面陶瓷隔膜两侧，在50℃干燥12小时，得到具有亲水性阻滞层的隔膜，其中，亲水性阻滞层的厚度为0.8μm，亲水性阻滞层和水的接触角为8°。
以下实施例用于制备根据本公开的聚合物隔膜以及锂离子电池。
实施例2-1A
(1)将P(VdF-HFP)粉末(Kynar powerflex LBG粉末，购自阿科玛，下同)溶解于N,N-二甲基甲酰胺和碳酸丙烯酯的混合液中，控制P(VdF-HFP)的浓度为临界浓度(为10重量％)，搅拌均匀得到极性聚合物粘结剂溶液，其中，N,N-二甲基甲酰胺与碳酸丙烯酯的重量比为1：0.05。
将极性聚合物粘结剂溶液以凹版辊涂布的方法，涂布至实施例1-1制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，在35℃鼓风烘干20小时，形成多孔极性聚合物粘结层，从而得到根据本公开的聚合物隔膜。
(2)将LiCoO 2、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LiCoO 2正极极片。
将丁苯橡胶(SBR)和羧甲基纤维素(CMC)分散在水中，与人造石墨、导电剂按照质量比为2.5：1.5：90：6在室温(25℃)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的石墨负极极片。
(3)在干燥房中，将LiCoO 2正极极片、石墨负极极片和步骤(2)制备的聚合物隔膜以卷绕的方式制备CSL454187型LiCoO 2/石墨软包锂离子电池极芯，灌装电解液后进行封装得到锂离子电池；其中，原陶瓷面朝向正极，电解液中的电解质为六氟磷酸锂，其浓度为1mol/L，有机溶剂为EC、EMC和DEC按重量比1：1：1混合得到的混合液。
实施例2-1B
实施例2-1B采用与实施例2-1A相同的方法制备锂离子电池，不同的是，步骤(1)中，将极性聚合物粘结剂溶液以浸入涂布法，涂布至实施例1-3制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，其中，将具有亲水性阻滞层的隔膜浸入极性聚合物粘结剂溶液 中，浸渍时间为30秒。
实施例2-2A
实施例2-2A采用与实施例2-1A相同的方法制备锂离子电池，不同的是，采用以下方法制备聚合物隔膜：将P(VdF-HFP)粉末溶解于N-甲基吡咯烷酮和碳酸丙烯酯的混合液中，控制P(VdF-HFP)的浓度为临界浓度(为12重量％)，搅拌均匀得到极性聚合物粘结剂溶液，其中，N-甲基吡咯烷酮与碳酸丙烯酯的重量比为1：0.06。将极性聚合物粘结剂溶液以凹版辊涂布的方法，分别涂布至实施例1-2制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，在30℃鼓风烘干24小时，形成多孔极性聚合物粘结层，从而得到根据本公开的聚合物隔膜。
实施例2-2B
实施例2-2B采用与实施例2-2A相同的方法制备锂离子电池，不同的是，步骤(1)中，将极性聚合物粘结剂溶液以浸入涂布法，涂布至实施例1-4制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，其中，将具有亲水性阻滞层的隔膜浸入极性聚合物粘结剂溶液中，浸渍时间为30秒。
实施例2-3A
实施例2-3A采用与实施例2-1A相同的方法制备锂离子电池，不同的是，采用以下方法制备聚合物隔膜：将P(VdF-HFP)粉末溶解于磷酸三乙酯和碳酸丙烯酯的混合液中，控制P(VdF-HFP)的浓度为临界浓度(为12重量％)，搅拌均匀得到极性聚合物粘结剂溶液，其中，磷酸三乙酯与碳酸丙烯酯的重量比为1：0.1。将极性聚合物粘结剂溶液以凹版辊涂布的方法，涂布至实施例1-2制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，在40℃鼓风烘干18小时，形成多孔极性聚合物粘结层，从而得到根据本公开的聚合物隔膜。
实施例2-3B
实施例2-3B采用与实施例2-3A相同的方法制备锂离子电池，不同的是，步骤(1)中，将极性聚合物粘结剂溶液以浸入涂布法，涂布至实施例1-3制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，其中，将具有亲水性阻滞层的隔膜浸入极性聚合物粘结剂溶液中，浸渍时间为30秒。
实施例2-4A
实施例2-4A采用与实施例2-1A相同的方法制备锂离子电池，不同的是，采用以下方法制备聚合物隔膜：将P(VdF-HFP)粉末溶解于N,N-二甲基甲酰胺和作为造孔剂的二丙二醇二甲醚的混合液中，控制P(VdF-HFP)的浓度为临界浓度(为10重量％)，搅拌均匀得到极性聚合物粘结剂溶液，其中，N,N-二甲基甲酰胺与二丙二醇二甲醚的混合液的重量比为1：0.06。
将极性聚合物粘结剂溶液以凹版辊涂布的方法，涂布至实施例1-1制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，在45℃鼓风烘干15小时，形成多孔极性聚合物粘结层，从而得到根据本公开的聚合物隔膜。
实施例2-4B
实施例2-4B采用与实施例2-4A相同的方法制备锂离子电池，不同的是，步骤(1)中，将极性聚合物粘结剂溶液以浸入涂布法，涂布至实施例1-3制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，其中，将具有亲水性阻滞层的隔膜浸入极性聚合物粘结剂溶液中，浸渍时间为30秒。
实施例2-5A
实施例2-5A采用与实施例2-1A相同的方法制备锂离子电池，不同的是，采用以下方法制备聚合物隔膜：将P(VdF-HFP)粉末溶解于N-甲基吡咯烷酮和二丙二醇二甲醚的混合液中，控制P(VdF-HFP)的浓度为临界浓度(为12重量％)，搅拌均匀得到极性聚合物粘结剂溶液，其中，N-甲基吡咯烷酮与二丙二醇二甲醚的混合液的重量比为1：0.08。
将极性聚合物粘结剂溶液以喷涂涂布的方法，涂布至实施例1-1制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，在45℃鼓风烘干15小时，形成多孔极性聚合物粘结层，从而得到根据本公开的聚合物隔膜。
实施例2-5B
实施例2-5B采用与实施例2-5A相同的方法制备锂离子电池，不同的是，步骤(1)中，将极性聚合物粘结剂溶液以浸入涂布法，涂布至实施例1-3制备的具有亲水性阻滞层的隔膜两侧的亲水性阻滞层表面，其中，将具有亲水性阻滞层的隔膜浸入极性聚合物粘结剂溶液中，浸渍时间为30秒。
对比例1
采用与实施例2-1A相同的方法制备聚合物隔膜和锂离子电池，不同的是，步骤(1)中，具有亲水性阻滞层的隔膜用实施例1-1中的单面陶瓷隔膜(9μmPE+2μm陶瓷层)代替， 即极性聚合物粘结剂溶液直接涂布至单面陶瓷隔膜两侧表面，并且N,N-二甲基甲酰胺用等重量的丙酮代替，得到聚合物隔膜。
对比例2
采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，在制备聚合物隔膜时，具有亲水性阻滞层的隔膜用实施例1-3中的单面陶瓷隔膜(9μmPE+2μm陶瓷层)代替，即极性聚合物粘结剂溶液直接涂布至单面陶瓷隔膜两侧表面，并且N,N-二甲基甲酰胺用等重量的丙酮代替，得到聚合物隔膜(该聚合物隔膜不具有亲水性阻滞层)。
对比例3
采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，极性聚合物粘结剂溶液不含造孔剂。
实施例3
采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，步骤(1)中，不是在45℃鼓风烘干15小时，而是在120℃鼓风烘干8小时。
实施例4
采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，在制备极性聚合物粘结剂溶液时，控制P(VdF-HFP)的浓度为3.5重量％(非临界浓度)。
实施例5
采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，在制备极性聚合物粘结剂溶液时，控制P(VdF-HFP)的浓度为22重量％(非临界浓度)。
实施例6
采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，在制备极性聚合物粘结剂溶液时，N,N-二甲基甲酰胺用等重量的丙酮代替。
实施例7
采用与实施例1-1相同的方法制备具有亲水性阻滞层的隔膜，不同的是，步骤(1)中，气相法亲水性二氧化硅用石英(比表面积为10m 2/g，粒径为10μm)代替，从而得到具有亲水性阻滞层的隔膜，形成的亲水性阻滞层和水的接触角为40°；采用与实施例2-1A相同的 方法制备聚合物隔膜和锂离子电池，不同的是，采用实施例7制备的具有亲水性阻滞层的隔膜。
实施例8
采用与实施例1-3相同的方法制备具有亲水性阻滞层的隔膜，不同的是，气相法亲水性三氧化二铝用醇铝法三氧化二铝(比表面积为130m 2/g，粒径为5μm)代替，从而得到具有亲水性阻滞层的隔膜，形成的亲水性阻滞层和水的接触角为36°；采用与实施例2-4B相同的方法制备聚合物隔膜和锂离子电池，不同的是，采用实施例8制备的具有亲水性阻滞层的隔膜。
实施例9
采用与实施例2-5A相同的方法制备聚合物隔膜和锂离子电池，不同的是，采用与实施例1-1相同的方法将亲水阻滞浆液涂布在单面陶瓷隔膜两侧之后不进行烘干，而是直接采用实施例2-5A的方法喷涂极性聚合物粘结剂溶液后，采用与实施例2-5A相同的方法进行烘干，从而得到聚合物隔膜。
测试例
(1)聚合物隔膜表面形貌的观察：
采用扫描电子显微镜(SEM，JEOL，JSM-7600FE)观察各实施例和对比例制备的聚合物隔膜的微观形貌。
图2A和图2B示出了实施例2-5A制备的聚合物隔膜的SEM形貌照片，图3A和图3B示出了实施例2-4A制备的聚合物隔膜的SEM形貌照片，图4A和图4B示出了实施例2-4B制备的聚合物隔膜的SEM形貌照片。由图2A、图2B、图3A、图3B、图4A和图4B可以看出，采用本公开的方法能制备多孔性颇佳的多孔极性聚合物粘结层，同时制备的多孔极性聚合物粘结层的孔壁上具有结节。图5A和图5B示出了对比例2制备的聚合物隔膜的SEM形貌照片，图6A和图6B示出了对比例3制备的聚合物隔膜的SEM形貌照片。将图4A和图4B与图5A和图5B进行比较可以看出，根据本公开的聚合物隔膜表面的多孔极性聚合物粘结层中的孔的孔径更大，呈多层丝网交织结构，所述亲水性阻滞层的部分表面通过所述多层丝网交织结构而暴露可见；对比例2制备的聚合物隔膜中的多孔极性聚合物粘结层则较为致密，呈蜂窝状。将图4A和图4B与图6A和6B进行比较可以看出，采用本公开的方法制备的聚合物隔膜的多孔极性聚合物粘结层中的孔壁上具有结节结构，这可能是由于在极性聚合物粘结剂溶液中引入造孔剂导致极性聚合物在析出发生相分离所致。
(2)聚合物隔膜透气性(Gurley值)和表观孔隙率测试
采用型号为Gurley 4110N的透气度仪进行测试。测试100mL空气在1标准大气压下通过面积为1.0平方英寸的聚合物隔膜的时间。聚合物隔膜的透气性的测试结果列于表1。由表1的结果可以看出，根据本公开的聚合物隔膜显示出较好的透气性。
聚合物隔膜的表观孔隙率可根据如下公式计算得到：
Figure PCTCN2019074196-appb-000001
上式中，ρM为表观密度，
ρf为面密度，
ρP为体密度，
d为聚合物隔膜的厚度。
由表1的数据可以看出，根据本公开的聚合物隔膜具有较高的表观孔隙率。
(3)聚合物隔膜热收缩率测试
在90℃和120℃温度下分别利用恒温烘箱对聚合物隔膜(面积为5mm×5mm)进行等温热处理2h和1h，表征聚合物隔膜的耐温性能。实验结果在表1中列出，由表1的结果可知，根据本公开的聚合物隔膜具有较低的热收缩率。
(4)聚合物隔膜拉伸强度测试
根据GB/T 13022-1991中规定的方法，使用万能力学试验机测定。实验结果在表1中列出，由表1的结果可知，根据本公开的聚合物隔膜具有较高的拉伸强度。
(5)聚合物隔膜穿刺强度测试
根据GB/T 1004-2008中规定的方法，使用万能力学试验机测定，钢针直径为1毫米。实验结果在表1中列出，由表1可知，根据本公开的聚合物隔膜具有较高的穿刺强度。表1
Figure PCTCN2019074196-appb-000002
Figure PCTCN2019074196-appb-000003
1：聚合物隔膜的厚度 2：极性聚合物涂层分别在聚合物隔膜两个表面的单面面密度
(6)聚合物隔膜离子电导率测试
采用交流阻抗法测试，具体操作步骤如下。
聚合物隔膜裁成直径为17mm的圆片，烘干后，重叠三层，放在两个不锈钢(SS)电极之间，吸收足量电解液(电解质为六氟磷酸锂，其浓度为1mol/L，有机溶剂为EC、EMC和DEC按重量比1：1：1混合得到的混合液)，密封于2016型扣式电池中，采用电化学工作站(上海辰华，CHI 660C)进行交流阻抗实验，交流信号频率范围为0.01Hz至1MHz，正弦波电位幅值为5mV，线性与实轴的交点即为聚合物隔膜的本体电阻，采用以下公式计算得到聚合物隔膜的离子电导率：
σ＝L/(A·R)，
其中，L表示凝胶聚合物电解质的厚度，
A为不锈钢板与聚合物隔膜的接触面积，
R为聚合物电解质的本体阻抗。
本体阻抗和聚合物隔膜的离子电导率列于表2。
由表2可知，根据本公开的聚合物隔膜显示出优异的离子电导率。
表2
Figure PCTCN2019074196-appb-000004
(7)聚合物隔膜对正负极粘性与剥离强度测试
将制备的锂离子电池(经过85℃，4h，1MPa热压)在满电态下进行解剖，采用万能力学试验机测定其剥离力学强度，测定标准参照GBT 2792-2014胶粘带剥离强度的试验方法；并对所得到的正负极极片和隔膜进行拍照。图7A和图7B以及图8A和图8B分别给出了实施例2-4B制备的锂离子电池的正极和负极与聚合物隔膜剥离后的SEM形貌照片，图9A和图10A分别示出了实施例2-4B制备的锂离子电池的正极和负极的剥离强度测试曲线图，图9B和图10B分别示出了对比例2制备的锂离子电池的正极和负极的剥离强度测试曲线图作为对比。
由图7A和图7B以及图8A和图8B可知：采用本公开的聚合物隔膜制备的锂离子电池进行剥离后，聚合物隔膜的多孔极性聚合物粘结层均黏在正极材料上；部分负极料粘在 聚合物隔膜上。
由图9A和图9B可以看出，根据本公开的聚合物隔膜对锂离子电池的正极的粘性相当大。由图10A和图10B可以看出，根据本公开的聚合物隔膜对负极粘性亦具有更高的粘接强度。
(8)锂离子电池硬度测试
测试结果在表3中列出。如表3所示，根据本公开的锂离子电池具有较高的硬度。
表3
Figure PCTCN2019074196-appb-000005
Figure PCTCN2019074196-appb-000006
(9)电池常温循环性能测试
采用(广州兰奇，BK6016)锂离子电池性能测试柜，对实施例和对比例制备得到的分容后的锂离子电池进行25℃循环性能测试，具体方法如下。
将电池分别以0.7C、0.2C充电至4.40V截止；搁置10min，以0.7C或0.2C放至3.0V，如此循环。表4的测试结果表明：根据本公开的锂离子电池显示出更为优异的循环性能。
表4
Figure PCTCN2019074196-appb-000007
Figure PCTCN2019074196-appb-000008
(10)电池高温循环性能测试
采用(广州兰奇，BK6016)锂离子电池性能测试柜，对实施例和对比例得到的分容后的锂离子电池，进行45℃循环性能的测试。测试方法为：将电池以0.7C充电至4.40V截止；搁置10min，以0.7C放至3.0V，如此循环。循环结果见表5。
测试结果表明：根据本公开的锂离子电池显示出更为优异的高温循环性能。由此可见，根据本公开的聚合物隔膜有利于提高电池的高温性能。
表5
Figure PCTCN2019074196-appb-000009
Figure PCTCN2019074196-appb-000010
(11)电池倍率性能测试
采用(广州兰奇，BK6016)锂离子电池性能测试柜，对实施例和对比例得到的分容后的锂离子电池进行倍率放电性能测试。具体测试方法如下。
将电池用0.5C(1C＝2640mA)恒流恒压充电至4.40V，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6。测试结果表明，根据本公开的锂离子电池显示出良好的倍率放电性能。
表6
Figure PCTCN2019074196-appb-000011
(12)电池高温储存性能测试
对实施例和对比例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(广州兰奇，BK6016)锂离子电池性能测试柜将电池以0.5C充电至4.40V，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4.40V，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；
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7。由表7可知：根据本公开的锂离子电池高温储存后在容量保持率和容量恢复率均更好。由此可见，根据本公开的聚合物隔膜有利于提高电池的高温性能。
表7
编号 恢复容量(mAh) 容量恢复率(％)
实施例2-1A 2574 97.5％
实施例2-1B 2561 97.0％
实施例2-2A 2563 97.1％
实施例2-2B 2564 97.1％
实施例2-3A 2569 97.3％
实施例2-3B 2568 97.3％
实施例2-4A 2555 96.8％
实施例2-4B 2568 97.3％
实施例2-5A 2570 97.4％
实施例2-5B 2561 97.0％
对比例1 2541 96.3％
对比例2 2490 94.3％
对比例3 2564 97.1％
实施例3 2550 96.6％
实施例4 2543 96.3％
实施例5 2534 96.0％
实施例6 2535 96.0％
实施例7 2534 96.0％
实施例8 2543 96.3％
实施例9 2550 96.6％
将实施例2-1A与对比例1进行比较、将实施例2-4B与对比例2进行比较，可以看出，通过设置亲水性阻滞层，即便采用高沸点溶剂配制极性聚合物溶液，制备的锂离子电池也具有良好的倍率放电性能，特别是在大倍率放电条件下显示出明显提高的放电性能。
将实施例2-4B与实施例3进行比较可以看出，将极性聚合物粘结剂涂层在不高于60℃ 的温度下进行干燥，能显著提高制备的聚合物隔膜的透气性和离子电导率，明显提高最终制备的锂离子电池的各项性能。将实施例2-4B与实施例4和5进行比较可以看出，控制极性聚合物粘结剂溶液中极性聚合物的浓度为临界浓度，能显著提高制备的聚合物隔膜的透气性和离子电导率，明显提高最终制备的锂离子电池的各项性能。将实施例2-1A和实施例2-4B分别与实施例7和8进行比较可以看出，使得亲水性阻滞层与水的接触角为不高于20°能进一步提高最终制备的锂离子电池的各项性能。将实施例2-5A与实施例9进行比较可以看出，将亲水阻滞涂层干燥后涂布极性聚合物粘结剂溶液，形成极性聚合物粘结层，能进一步提高制备的聚合物隔膜的透气性和离子电导率，从而提高最终制备的锂离子电池的各项性能。
以上详细描述了本公开的优选实施方式，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。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (118)

  1. 一种聚合物隔膜，其中，所述聚合物隔膜含有多孔基材、亲水性阻滞层以及多孔极性聚合物粘结层，所述亲水性阻滞层设置在所述多孔基材和所述多孔极性聚合物粘结层之间，所述多孔极性聚合物粘结层中的孔壁具有结节结构。
  2. 根据权利要求1所述的聚合物隔膜，其中，所述亲水性阻滞层的水接触角为不高于40度。
  3. 根据权利要求1或2所述的聚合物隔膜，其中，所述亲水性阻滞层的水接触角为不高于20度以下。
  4. 根据权利要求1-3中任一项所述的聚合物隔膜，其中，所述亲水性阻滞层的水接触角为2-15度。
  5. 根据权利要求1-4中任一项所述的聚合物隔膜，其中，所述亲水性阻滞层的水接触角为5-10度。
  6. 根据权利要求1-5中任一项所述的聚合物隔膜，其中，所述亲水性阻滞层含有粘合剂以及亲水性无机颗粒，所述亲水性无机颗粒通过所述粘合剂相互粘合。
  7. 根据权利要求1-6中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒为亲水性Al 2O 3、亲水性SiO 2、亲水性SnO 2、亲水性ZrO 2、亲水性TiO 2、亲水性SiC、亲水性Si 3N 4、亲水性CaO、亲水性MgO、亲水性ZnO、亲水性BaTiO 3、亲水性LiAlO 2和亲水性BaSO 4中的至少一种。
  8. 根据权利要求1-7中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒为亲水性Al 2O 3和/或亲水性SiO 2。
  9. 根据权利要求1-8中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒为气相法亲水性SiO 2、沉淀法亲水性SiO 2和气相法亲水性Al 2O 3中的至少一种。
  10. 根据权利要求1-9中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的粒径为1nm至10μm。
  11. 根据权利要求1-10中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的粒径为1nm至5μm。
  12. 根据权利要求1-11中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的粒径为1nm至2μm。
  13. 根据权利要求1-12中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的粒径为10nm至1μm。
  14. 根据权利要求1-13中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的粒径为20nm至800nm。
  15. 根据权利要求1-14中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的粒径为50nm至350nm。
  16. 根据权利要求1-15中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的比表面积为10-600m 2/g。
  17. 根据权利要求1-16中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的比表面积为100-500m 2/g。
  18. 根据权利要求1-17中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的比表面积为150-400m 2/g。
  19. 根据权利要求1-18中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的比表面积为200-400m 2/g。
  20. 根据权利要求1-19中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的比表面积为250-390m 2/g。
  21. 根据权利要求1-20中任一项所述的聚合物隔膜，其中，所述亲水性无机颗粒的比表面积为300-380m 2/g。
  22. 根据权利要求1-21中任一项所述的聚合物隔膜，其中，所述粘合剂为丙烯酸酯型聚合物、苯乙烯-丙烯酸酯共聚物、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物、丙烯腈-丙烯酸酯共聚物、氯乙烯-丙烯酸酯共聚物和丁二烯-苯乙烯共聚物中的至少一种。
  23. 根据权利要求1-22中任一项所述的聚合物隔膜，其中，以所述亲水性阻滞层的总量为基准，所述亲水性颗粒的含量为50-95重量％。
  24. 根据权利要求1-23中任一项所述的聚合物隔膜，其中，以所述亲水性阻滞层的总量为基准，所述亲水性颗粒的含量为70-95重量％。
  25. 根据权利要求1-24中任一项所述的聚合物隔膜，其中，以所述亲水性阻滞层的总量为基准，所述亲水性颗粒的含量为80-95重量％。
  26. 根据权利要求1-25中任一项所述的聚合物隔膜，其中，以所述亲水性阻滞层的总量为基准，所述亲水性颗粒的含量为85-95重量％。
  27. 根据权利要求1-26中任一项所述的聚合物隔膜，其中，所述亲水性阻滞层的厚度为0.1-3μm。
  28. 根据权利要求1-27中任一项所述的聚合物隔膜，其中，所述亲水性阻滞层的厚度为0.1-1μm。
  29. 根据权利要求1-28中任一项所述的聚合物隔膜，其中，所述亲水性阻滞层的厚度为0.3-0.8μm。
  30. 根据权利要求1-29中任一项所述的聚合物隔膜，其中，所述多孔极性聚合物粘结层含有极性聚合物，所述极性聚合物为聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的至少一种。
  31. 根据权利要求1-30中任一项所述的聚合物隔膜，其中，所述极性聚合物为聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的至少一种。
  32. 根据权利要求1-31中任一项所述的聚合物隔膜，其中，所述多孔极性聚合物粘结层的厚度为0.1-10μm。
  33. 根据权利要求1-32中任一项所述的聚合物隔膜，其中，所述多孔极性聚合物粘结层的厚度为0.2-5μm。
  34. 根据权利要求1-33中任一项所述的聚合物隔膜，其中，所述多孔极性聚合物粘结层的厚度为0.7-3μm。
  35. 根据权利要求1-34中任一项所述的聚合物隔膜，其中，所述多孔极性聚合物粘结层的厚度为0.8-1.5μm。
  36. 根据权利要求1-35中任一项所述的聚合物隔膜，其中，所述多孔基材含有多孔聚合物层。
  37. 根据权利要求1-36中任一项所述的聚合物隔膜，其中，所述多孔聚合物层为多孔聚烯烃层。
  38. 根据权利要求1-37中任一项所述的聚合物隔膜，其中，所述多孔聚合物层为多孔聚乙烯层、多孔聚丙烯层、多孔聚乙烯和多孔聚丙烯复合层中的至少一种。
  39. 根据权利要求1-38中任一项所述的聚合物隔膜，其中，所述多孔聚乙烯和多孔聚丙烯复合层为PE/PP/PE复合基材层。
  40. 根据权利要求1-39中任一项所述的聚合物隔膜，其中，所述多孔聚合物层的厚度为1-50μm。
  41. 根据权利要求1-40中任一项所述的聚合物隔膜，其中，所述多孔聚合物层的厚度为5-20μm。
  42. 根据权利要求1-41中任一项所述的聚合物隔膜，其中，所述多孔聚合物层的厚度为8-15μm。
  43. 根据权利要求1-42中任一项所述的聚合物隔膜，其中，所述多孔基材还含有陶瓷层，所述陶瓷层设置在所述多孔聚合物层和所述亲水性阻滞层之间；和/或
    所述多孔聚合物层设置在所述陶瓷层和所述亲水性阻滞层之间。
  44. 根据权利要求1-43中任一项所述的聚合物隔膜，其中，所述陶瓷层中的陶瓷颗粒由选自Al 2O 3、SiO 2、SnO 2、ZrO 2、TiO 2、SiC、Si 3N 4、CaO、MgO、ZnO、BaTiO 3、LiAlO 2和BaSO 4中的至少一种烧结形成。
  45. 根据权利要求1-44中任一项所述的聚合物隔膜，其中，所述陶瓷层的厚度为1-5μm。
  46. 根据权利要求1-45中任一项所述的聚合物隔膜，其中，所述陶瓷层的厚度为1.5-3μm。
  47. 根据权利要求1-46中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的厚度为5～50μm。
  48. 根据权利要求1-47中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的厚度为8～30μm。
  49. 根据权利要求1-48中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的厚度为10～20μm。
  50. 根据权利要求1-49中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的Gurley值为100-900Sec/100mL。
  51. 根据权利要求1-50中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的Gurley值为120-600Sec/100mL。
  52. 根据权利要求1-51中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的Gurley 值为120-500Sec/100mL。
  53. 根据权利要求1-52中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的Gurley值为150-350Sec/100mL。
  54. 根据权利要求1-53中任一项所述的聚合物隔膜，其中，所述聚合物隔膜的Gurley值为200-300Sec/100mL。
  55. 根据权利要求1-54中任一项所述的聚合物隔膜，其中，所述多孔极性聚合物粘结层为多层丝网交织结构，所述亲水性阻滞层的部分表面通过所述多层丝网交织结构而暴露可见。
  56. 一种制备聚合物隔膜的方法，其中，包括：
    (1)将亲水阻滞浆液涂布在多孔基材的至少一个表面形成亲水阻滞涂层，所述亲水阻滞浆液含有分散介质、以及分散在所述分散介质中的亲水性无机颗粒以及粘合剂；
    (2)将极性聚合物粘结剂溶液涂布在所述亲水阻滞涂层或者所述亲水性阻滞层的表面形成极性聚合物粘结剂涂层，所述极性聚合物粘结剂溶液含有有机溶剂以及溶解在所述有机溶剂中的极性聚合物粘结剂和造孔剂；
    (3)将所述亲水阻滞涂层和所述极性聚合物粘结剂涂层进行干燥，形成亲水性阻滞层和多孔极性聚合物粘结层，或者将所述极性聚合物粘结剂涂层进行干燥，形成多孔极性聚合物粘结层。
  57. 根据权利要求56所述的方法，其中，在步骤(1)中，进一步包括：将所述亲水阻滞涂层干燥，形成亲水性阻滞层。
  58. 根据权利要求56或57所述的方法，其中，所述亲水性阻滞层的水接触角为40度以下。
  59. 根据权利要求56-58中任一项所述的方法，其中，所述亲水性阻滞层的水接触角为20度以下。
  60. 根据权利要求56-59中任一项所述的方法，其中，所述亲水性阻滞层的水接触角 为2-15度。
  61. 根据权利要求56-60中任一项所述的方法，其中，所述亲水阻滞浆液的涂布量使得最终形成的亲水性阻滞层的厚度为0.1-3μm。
  62. 根据权利要求56-61中任一项所述的方法，其中，所述亲水阻滞浆液的涂布量使得最终形成的亲水性阻滞层的厚度为0.1-1μm。
  63. 根据权利要求56-62中任一项所述的方法，其中，所述亲水阻滞浆液的涂布量使得最终形成的亲水性阻滞层的厚度为0.3-0.8μm。
  64. 根据权利要求56-63中任一项所述的方法，其中，所述亲水性无机颗粒为亲水性Al 2O 3、亲水性SiO 2、亲水性SnO 2、亲水性ZrO 2、亲水性TiO 2、亲水性SiC、亲水性Si 3N 4、亲水性CaO、亲水性MgO、亲水性ZnO、亲水性BaTiO 3、亲水性LiAlO 2和亲水性BaSO 4中的至少一种。
  65. 根据权利要求56-64中任一项所述的方法，其中，所述亲水阻滞浆液中，所述亲水性无机颗粒的含量为50-95重量％。
  66. 根据权利要求56-65中任一项所述的方法，其中，所述亲水阻滞浆液中，所述亲水性无机颗粒的含量为70-95重量％。
  67. 根据权利要求56-66中任一项所述的方法，其中，所述亲水阻滞浆液中，所述亲水性无机颗粒的含量为80-95重量％。
  68. 根据权利要求56-67中任一项所述的方法，其中，相对于100重量份所述亲水性无机颗粒，所述粘合剂的含量为1-30重量份。
  69. 根据权利要求56-68中任一项所述的方法，其中，相对于100重量份所述亲水性无机颗粒，所述粘合剂的含量为2-25重量份。
  70. 根据权利要求56-69中任一项所述的方法，其中，相对于100重量份所述亲水性 无机颗粒，所述粘合剂的含量为5-20重量份。
  71. 根据权利要求56-70中任一项所述的方法，其中，所述亲水性无机颗粒的粒径为1nm至10μm。
  72. 根据权利要求56-71中任一项所述的方法，其中，所述亲水性无机颗粒的粒径为1nm至5μm。
  73. 根据权利要求56-72中任一项所述的方法，其中，所述亲水性无机颗粒的粒径为1nm至2μm。
  74. 根据权利要求56-73中任一项所述的方法，其中，所述亲水性无机颗粒的粒径为10nm至1μm。
  75. 根据权利要求56-74中任一项所述的方法，其中，所述亲水性无机颗粒的粒径为20nm至800nm。
  76. 根据权利要求56-75中任一项所述的方法，其中，所述亲水性无机颗粒的粒径为优选为50nm至350nm。
  77. 根据权利要求56-76中任一项所述的方法，其中，所述亲水性无机颗粒的比表面积为10-600m 2/g。
  78. 根据权利要求56-77中任一项所述的方法，其中，所述亲水性无机颗粒的比表面积为100-500m 2/g。
  79. 根据权利要求56-78中任一项所述的方法，其中，所述亲水性无机颗粒的比表面积为150-400m 2/g。
  80. 根据权利要求56-79中任一项所述的方法，其中，所述粘合剂为丙烯酸酯型聚合物、苯乙烯-丙烯酸酯共聚物、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物、丙烯腈-丙烯酸酯共聚物、氯乙烯-丙烯酸酯共聚物和丁二烯-苯乙烯共聚物中的至少一种。
  81. 根据权利要求56-80中任一项所述的方法，其中，所述分散介质为水、乙醇、异丙醇、环己烷、四氢呋喃、二氯甲烷和三氯甲烷中的至少一种。
  82. 根据权利要求56-81中任一项所述的方法，其中，所述极性聚合物粘结剂溶液中，极性聚合物的浓度为1-30重量％。
  83. 根据权利要求56-82中任一项所述的方法，其中，所述极性聚合物粘结剂溶液中，极性聚合物的浓度为2-25重量％。
  84. 根据权利要求56-83中任一项所述的方法，其中，所述极性聚合物粘结剂溶液中，极性聚合物的浓度为5-20重量％。
  85. 根据权利要求56-84中任一项所述的方法，其中，所述极性聚合物粘结剂溶液中，极性聚合物的浓度为临界浓度。
  86. 根据权利要求56-85中任一项所述的方法，其中，所述极性聚合物粘结剂为聚偏二氟乙烯、偏氟乙烯和六氟丙烯的共聚物、以及偏氟乙烯和丙烯酸酯的共聚物中的至少一种。
  87. 根据权利要求56-86中任一项所述的方法，其中，所述有机溶剂的沸点低于60摄氏度。
  88. 根据权利要求56-87中任一项所述的方法，其中，所述有机溶剂为丙酮。
  89. 根据权利要求56-88中任一项所述的方法，其中，所述有机溶剂的沸点为60-260摄氏度。
  90. 根据权利要求56-89中任一项所述的方法，其中，所述有机溶剂的沸点为120摄氏度以上。
  91. 根据权利要求56-90中任一项所述的方法，其中，所述有机溶剂的沸点为140摄氏度以上。
  92. 根据权利要求56-91中任一项所述的方法，其中，所述有机溶剂的沸点为150-230摄氏度。
  93. 根据权利要求56-92中任一项所述的方法，其中，所述有机溶剂为磷酸三乙酯、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺和二甲基亚砜中的至少一种。
  94. 根据权利要求56-93中任一项所述的方法，其中，所述造孔剂为有机造孔剂，所述有机造孔剂的沸点高于所述有机溶剂。
  95. 根据权利要求56-94中任一项所述的方法，其中，所述有机造孔剂的沸点为61-261摄氏度。
  96. 根据权利要求56-95中任一项所述的方法，其中，所述造孔剂为碳酸酯型化合物和/或醇醚型化合物。
  97. 根据权利要求56-96中任一项所述的方法，其中，所述造孔剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸亚乙烯酯、二乙二醇二甲醚、二丙二醇单甲醚、二丙二醇单乙醚和二丙二醇二甲醚中的至少一种。
  98. 根据权利要求56-97中任一项所述的方法，其中，所述有机溶剂与所述造孔剂的重量比为1：0.01-1。
  99. 根据权利要求56-98中任一项所述的方法，其中，所述有机溶剂与所述造孔剂的重量比为1：0.02-0.5。
  100. 根据权利要求56-99中任一项所述的方法，其中，所述有机溶剂与所述造孔剂的重量比为1：0.03-0.3。
  101. 根据权利要求56-100中任一项所述的方法，其中，所述有机溶剂与所述造孔剂的重量比为1：0.05-0.1。
  102. 根据权利要求56-101中任一项所述的方法，其中，所述极性聚合物粘结剂溶液 的涂布量使得所述多孔极性聚合物粘结层的厚度为0.1-10μm。
  103. 根据权利要求56-102中任一项所述的方法，其中，所述极性聚合物粘结剂溶液的涂布量使得所述多孔极性聚合物粘结层的厚度为0.2-5μm。
  104. 根据权利要求56-103中任一项所述的方法，其中，所述极性聚合物粘结剂溶液的涂布量使得所述多孔极性聚合物粘结层的厚度为0.7-3μm。
  105. 根据权利要求56-104中任一项所述的方法，其中，所述极性聚合物粘结剂溶液的涂布量使得所述多孔极性聚合物粘结层的厚度为0.8-1.5μm。
  106. 根据权利要求56-105中任一项所述的方法，其中，步骤(2)中，所述干燥在不高于120摄氏度的温度下进行。
  107. 根据权利要求56-106中任一项所述的方法，其中，步骤(2)中，所述干燥在不高于60摄氏度的温度下进行。
  108. 根据权利要求56-107中任一项所述的方法，其中，步骤(2)中，所述干燥在20-55摄氏度的温度下进行。
  109. 根据权利要求56-108中任一项所述的方法，其中，步骤(2)中，所述干燥的持续时间为0.1-36小时。
  110. 根据权利要求56-109中任一项所述的方法，其中，所述多孔基材为多孔聚合物膜、或者多孔聚合物膜和陶瓷膜的复合膜。
  111. 根据权利要求56-110中任一项所述的方法，其中，所述多孔聚合物膜为聚烯烃膜。
  112. 根据权利要求56-111中任一项所述的方法，其中，所述多孔聚合物膜为多孔聚乙烯膜、多孔聚丙烯膜、或者多孔聚乙烯和多孔聚丙烯复合膜。
  113. 根据权利要求56-112中任一项所述的方法，其中，所述陶瓷膜的厚度为1-5μm。
  114. 根据权利要求56-113中任一项所述的方法，其中，所述陶瓷膜的厚度为1.5-3μm。
  115. 一种由权利要求56-114中任一项所述的方法制备的聚合物隔膜。
  116. 权利要求1-55和115中任一项所述的聚合物隔膜在锂离子电池中的应用。
  117. 一种锂离子电池，所述锂离子电池包括正极极片、负极极片以及聚合物隔膜，其中，所述聚合物隔膜为权利要求1-55和115中任一项所述的聚合物隔膜。
  118. 一种制备锂离子电池的方法，其中，包括：
    S1、采用权利要求56-114中任一项所述的方法制备聚合物隔膜；
    S2、将所述聚合物隔膜设置在正极极片和负极极片之间，形成电池极芯后，进行封装。
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