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WO2018209794A1 - 形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法 - Google Patents

形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法 Download PDF

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WO2018209794A1
WO2018209794A1 PCT/CN2017/093654 CN2017093654W WO2018209794A1 WO 2018209794 A1 WO2018209794 A1 WO 2018209794A1 CN 2017093654 W CN2017093654 W CN 2017093654W WO 2018209794 A1 WO2018209794 A1 WO 2018209794A1
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battery separator
molecular weight
polymer composition
forming
ribbon
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PCT/CN2017/093654
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English (en)
French (fr)
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程跃
熊磊
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上海恩捷新材料科技股份有限公司
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Publication of WO2018209794A1 publication Critical patent/WO2018209794A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B29C69/02—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • 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
    • H01M50/494—Tensile strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of lithium battery technology, and in particular to a polymer composition for forming a battery separator, a battery separator, and a preparation method.
  • Lithium-ion batteries are usually composed mainly of a positive electrode, a negative electrode, a separator, an electrolyte, and a battery casing.
  • the diaphragm is one of the key inner layer components.
  • the main function of the separator is to separate the positive and negative electrodes of the battery to prevent direct contact between the positive and negative electrodes and short circuit.
  • the electrolyte ions can pass smoothly during the charging and discharging process of the battery to form a current, and the battery operating temperature is abnormal. When rising, the electrolyte ion migration channel is turned off, and the current is cut off to ensure battery safety.
  • the performance of the diaphragm determines the interface structure and internal resistance of the battery, which directly affects the capacity, cycle and safety performance of the battery.
  • the separator with excellent performance plays an important role in improving the overall performance of the battery.
  • commercially available lithium ion battery separators generally employ a polyolefin porous membrane.
  • the main performance parameters of the battery separator include thickness, porosity, pore size, pore size distribution, strength, heat shrinkage, closed cell temperature and membrane rupture temperature.
  • the electrode area In order to reduce the internal resistance of the battery, the electrode area must be as large as possible, so the thickness of the diaphragm is required to be as thin as possible.
  • the battery separator itself is not electrically conductive, the conductive ions need to migrate through the diaphragm. This requires that the diaphragm itself needs a certain number of pores, that is, porosity, but the porosity is too high, which will cause the strength of the diaphragm to decrease, affecting the overall reliability of the battery.
  • the wettability of the electrolyte on the separator directly affects the resistance of ion migration.
  • the pore diameter is not very large, the more uniform the pore size distribution, the better the wettability of the electrolyte.
  • the battery assembly needs to pull the diaphragm during its production and assembly process. After the assembly is completed, it is also necessary to ensure that the diaphragm is not pierced by the electrode material, so the diaphragm not only needs sufficient tensile strength but also requires a certain piercing strength.
  • the polymer separator will undergo heat shrinkage under certain heating conditions.
  • the heat shrinkage rate of the separator is also required.
  • the internal temperature of the battery rises sharply due to excessive current, which requires the diaphragm to close the migration path of the conductive ions in time. Therefore, the temperature at which the micropores of the battery separator are melt-closed is referred to as a closed-cell temperature.
  • the isolation film is broken and the fracture temperature is called the film breaking temperature.
  • the closed-cell temperature and the membrane-breaking temperature of the diaphragm must have a certain temperature difference to ensure that even if the temperature continues to rise after the diaphragm is closed, the diaphragm will not rupture.
  • the conventional wet lithium ion battery separator needs to undergo an organic solvent extraction process in the production process, which is often a bottleneck restricting the production speed of the entire battery separator film, and there is also a significant gap between the two sides of the produced separator. Same In order to maintain the continuity of the entire production process, all heating components require external heat supply, high energy consumption and high production costs.
  • An object of the present invention is to provide a semi-dry and semi-wet battery separator manufacturing process and a product thereof, which can eliminate the extraction process in the wet process, and at the same time, the battery separator has excellent comprehensive performance, such as The lower micropore diameter, uniform concentration of pore size distribution, good porosity and film strength, the two sides of the separator prepared by this method have a closer microscopic morphology.
  • an object of the present invention is to provide a polymer composition, a battery separator, and a preparation method for forming a battery separator, which are used for solving a battery separator prepared by a wet process in the prior art.
  • the resulting micro-topography of the battery separator has significant differences, and in order to maintain the continuity of the entire production process, all heating components require external heat supply. The problem of high energy consumption and high production cost.
  • the present invention provides a polymer composition for forming a battery separator, the polymer composition forming the battery separator comprising: an average molecular weight of 1.0 ⁇ 10 5 to 10.0 ⁇ 10 6 and a high molecular weight polyethylene having a density of 0.940 to 0.976 g/cm 3 , a pore former, and an antioxidant, wherein
  • the pore former has a weight of 500 to 2000 parts by weight based on 100 parts by weight of the high molecular weight polyethylene, and the antioxidant has a weight of 0.1 to 10 parts.
  • the pore former comprises: natural mineral oil, C 6-15 alkane, C 8-15 aliphatic carboxylic acid C 1-4 alkyl ester , C 2-6 halogenated alkane, phthalate, trimellitate, adipate, sebacate, maleate, benzoate, epoxy vegetable oil, benzenesulfonamide, phosphoric acid At least one of a triester, a glycol ether, acetyl glyceryl monoacetate, a citric acid ester or a diisononyl cyclohexane-1,2-dicarboxylate.
  • the pore former has a kinematic viscosity at 40 ° C of 10 mm 2 /s to 100 mm 2 /s.
  • the pore former has an initial boiling point of greater than or equal to 110 °C.
  • the antioxidant comprises: 4,4-thiobis(6-tert-butylm-cresol), dibutylhydroxytoluene, sub- Phosphate ester, tert-butyl hydroquinone, ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl carbonate, 1,1,3-tris(2-methyl-) 4-hydroxy-5-tert-butylphenyl)butane, 2-tert-butyl-6-methylphenol, N,N'-di- ⁇ -naphthyl p-phenylenediamine, dilauryl thiodipropionate, At least one of tris(nonylphenyl)phosphite or triphenyl phosphite.
  • the invention also provides a method for preparing a battery separator, the method for preparing the battery separator comprises:
  • step 1) the continuously extruded polymer composition is subjected to vacuum distillation to cast the cast piece to obtain a ribbon;
  • the strip obtained in the step 2) is subjected to vacuum distillation to biaxially stretch into a film to remove the pore former in the ribbon;
  • the step 1) comprises the following steps:
  • the high molecular weight polyethylene having an average molecular weight of 1.0 ⁇ 10 5 to 10.0 ⁇ 10 6 and a density of 0.940 to 0.976 g/cm 3 , the pore former and the antioxidant in a desired mass part Add into the continuous ingredient feeding kettle, stir and mix evenly;
  • step 1-1) adding the mixture obtained in the step 1-1) to the extruder, the high molecular weight polyethylene having an average molecular weight of 1.0 ⁇ 10 5 to 10.0 ⁇ 10 6 and a density of 0.940 to 0.976 g/cm 3 and The antioxidant is dissolved in the porogen and is continuously extruded from the extruder.
  • the step 2) comprises the following steps:
  • step 1) placing the polymer composition continuously extruded in step 1) into a slit die in a vacuum distillation chamber;
  • the polymer composition was extruded through a slit die onto a casting chill roll and cast into a ribbon at a casting temperature.
  • the ribbon obtained in the step 2) is subjected to vacuum distillation to biaxially stretch into a film to remove the pore former in the ribbon.
  • the specific method is as follows: the ribbon obtained in the step 2) is placed in a vacuum distillation chamber for vacuum distillation, and simultaneously fed to a biaxial stretching machine to stretch the ribbon.
  • the heat setting temperature is 100 to 150 ° C; and the heat setting time is 10 to 20 minutes.
  • the present invention also provides a battery separator obtained by the production method as described in any of the above schemes.
  • the battery separator has a thickness of 5 to 30 ⁇ m, a pore diameter of 0.3 to 0.8 ⁇ m, and a porosity of 30% to 60%.
  • the polymer separator, battery separator, and preparation method for forming a battery separator of the present invention have the following beneficial effects:
  • the battery separator forming polymer composition of the present invention is used to form a battery separator, using the polymer composition
  • the formed battery separator has a lower micropore diameter, a uniformly concentrated pore size distribution, a good porosity and a film strength, and the formed battery separator has a closer microscopic morphology on both sides;
  • the preparation method of the battery separator of the invention completely abandons the extraction process in the existing wet process, effectively breaks the bottleneck of the production speed of the existing battery separator, and the battery separator prepared by the method has excellent comprehensive performance:
  • the invention has a lower micropore diameter, a uniformly concentrated pore size distribution, a good porosity and a film strength.
  • the battery separator formed by the battery separator prepared by the method has a closer microscopic morphology on both sides.
  • the method for preparing a battery separator of the present invention has the advantages of low energy consumption and low production cost compared to the wet process in the prior art.
  • FIG. 1 is a flow chart showing a method of preparing a battery separator provided by the present invention.
  • Example 2 is a front and back photomicrograph of a battery separator prepared in Example 1 of the present invention, wherein a is a frontal photomicrograph and b is a reverse photomicrograph.
  • Example 3 is a front and back photomicrograph of a battery separator prepared in Example 2 of the present invention, wherein a is a frontal photomicrograph and b is a reverse photomicrograph.
  • Example 4 is a front and back photomicrograph of a battery separator prepared in Example 3 of the present invention, wherein a is a frontal photomicrograph and b is a reverse photomicrograph.
  • Figure 5 is a front and back photomicrograph of a battery separator prepared in Example 4 of the present invention, wherein a is a frontal photomicrograph and b is a reverse photomicrograph.
  • Figure 6 is a front and back photomicrograph of a battery separator prepared in Example 5 of the present invention, wherein a is a frontal photomicrograph and b is a reverse photomicrograph.
  • Figure 7 is a front and back photomicrograph of a battery separator prepared in Example 6 of the present invention, wherein a is a frontal photomicrograph and b is a reverse photomicrograph.
  • the present invention provides a polymer composition for forming a battery separator for preparing a battery separator, the polymer composition forming the battery separator comprising: an average molecular weight of 1.0 ⁇ 10 5 to 10.0 ⁇ 10 6 Daltons and a density of 0.940 ⁇ 0.976g / cm 3 of the high molecular weight polyethylene, an antioxidant porogen, wherein
  • the pore former has a weight of 500 to 2000 parts by weight based on 100 parts by weight of the high molecular weight polyethylene, and the antioxidant has a weight of 0.1 to 10 parts.
  • the high molecular weight polyethylene has an average molecular weight of 1.0 ⁇ 10 5 to 5.0 ⁇ 10 6 Daltons; more preferably, the high molecular weight polyethylene has an average molecular weight of 1.0 ⁇ 10 5 to 2.0 ⁇ 10 6 Dalton.
  • the high molecular weight polyethylene has a density of from 0.940 to 0.966 g/cm 3 ; more preferably, the high molecular weight polyethylene has a density of from 0.950 to 0.966 g/cm 3 .
  • the high molecular weight polyethylene may be a high molecular weight polyethylene having an average molecular weight or a mixture of two or more average molecular weight high molecular weight polyethylene.
  • the pore former may comprise: natural mineral oil, C 6-15 alkane, C 8-15 aliphatic carboxylic acid C 1-4 alkyl ester, C 2-6 halogenated alkane, phthalate, Trimellitic acid ester, adipate, sebacate, maleate, benzoate, epoxy vegetable oil, benzenesulfonamide, phosphotriester, glycol ether, acetyl monoglyceride, At least one of a citrate or a diisononyl cyclohexane-1,2-dicarboxylate.
  • the natural mineral oil may include CAS: 8020-83-5, 8042-47-5; MDL: MFCD00131611; E1NECS: 232-455-8, and the like.
  • the C 6-15 alkane may include decalin, decane, undecane or dodecane, and the like.
  • the C 8-15 aliphatic carboxylic acid C 1-4 alkyl ester may include methyl decanoate, ethyl decanoate, propyl citrate, n-butyl decanoate, methyl undecanoate, eleven Ethyl carbonate, propyl undecacrylate, n-butyl undecanoate, methyl dodecyl carbonate, ethyl dodecyl carbonate, propyl dodecyl carbonate or n-butyl dodecyl carbonate.
  • the C 2-6 haloalkane may include dichloroethane, dichloropropane, fluorochloroethane or chlorofluoropropane, and the like.
  • the pore former has a kinematic viscosity at 40 ° C of 10 mm 2 /s to 100 mm 2 /s; preferably, the pore former has a kinematic viscosity at 40 ° C of 20 mm 2 /s to 80 mm 2 /s; more preferably The pore former has a kinematic viscosity at 40 ° C of 30 mm 2 /s to 70 mm 2 /s.
  • the porogen has an initial boiling point greater than or equal to 110 °C.
  • the pore former has a weight of 700 to 1800 parts by weight of the high molecular weight polyethylene, and more preferably, the weight of the high molecular weight polyethylene is 100 parts.
  • the pore former has a weight of 800 to 1600 parts.
  • the antioxidant may include: 4,4-thiobis(6-tert-butylm-cresol), dibutylhydroxytoluene, phosphite, tert-butyl hydroquinone, ⁇ -(3 , 5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl carbonate, 1,1,3-tris(2-methyl-4hydroxy-5-tert-butylphenyl)butane, 2- Tert-butyl-6-methylphenol, N,N'-di- ⁇ -naphthyl p-phenylenediamine, dilauryl thiodipropionate, tris(nonylphenyl) phosphite or triphenyl phosphite At least one of the esters.
  • 4,4-thiobis(6-tert-butylm-cresol) dibutylhydroxytoluene
  • phosphite
  • the antioxidant has a weight of 0.5 to 8 parts by weight based on 100 parts by weight of the high molecular weight polyethylene; more preferably, the weight of the high molecular weight polyethylene is 100 parts, The antioxidant has a weight of 1 to 6 parts.
  • the present invention also provides a method for preparing a battery separator, and the method for preparing the battery separator includes:
  • step 1) the continuously extruded polymer composition is subjected to vacuum distillation to cast the cast piece to obtain a ribbon;
  • the strip obtained in the step 2) is subjected to vacuum distillation to biaxially stretch into a film to remove the pore former in the ribbon;
  • step 1) referring to step S1 in Figure 1, a polymer composition as described in any of the above schemes is prepared and the polymer composition is continuously extruded.
  • composition and characteristics of the polymer composition are described in detail above with respect to the contents of the polymer composition, and are not described herein.
  • preparing the polymer composition and continuously extruding the polymer composition comprises the steps of:
  • the stirring speed can be set according to actual needs.
  • the stirring speed can be 50 rpm; of course, in other examples, the stirring speed can also be other Any value;
  • the oxidant is dissolved in the porogen, it is continuously extruded by the extruder; the speed of continuous extrusion of the extruder can be set according to actual needs, and in an example, the extruder is continuously extruded
  • the speed of the exit may be 200 rpm; of course, in other examples, the speed at which the extruder is continuously extruded may also be any other value.
  • the extruder may be a single screw extruder, a twin screw extruder or a multi-screw extruder, or may be any other existing extruder.
  • step 2) referring to step S2 in Fig. 1, the polymer composition continuously extruded in step 1) is subjected to vacuum distillation casting to obtain a ribbon.
  • performing the step 1) continuous extrusion of the polymer composition by vacuum distillation casting the cast sheet comprises the following steps:
  • step 1) placing the polymer composition continuously extruded in step 1) into a slit die in a vacuum distillation chamber;
  • the polymer composition was extruded through a slit die onto a casting chill roll and cast into a ribbon at a casting temperature.
  • the casting temperature may be 50 to 100 ° C.
  • the casting temperature is 80 ° C.
  • step 3 referring to the step S3 in FIG. 1, the ribbon obtained in the step 2) is biaxially drawn into a film by vacuum distillation to remove the pore former in the ribbon. .
  • the strip obtained in the step 2) is subjected to vacuum distillation biaxially to form a film
  • the specific method for removing the pore former in the ribbon is: the step obtained in the step 2)
  • the ribbon is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine to stretch the ribbon to obtain a film from which the pore former is removed.
  • step 4 referring to step S4 in Fig. 1, the film obtained in step 3) is heat set.
  • the heat setting temperature and heat setting time can be set according to actual needs; preferably, the heat setting temperature is 100 to 150 ° C; the heat setting time is 10 to 20 minutes; more preferably, the heat setting temperature is It is 120 ° C; the heat setting time is 15 minutes.
  • step 5 referring to step S5 in Fig. 1, the heat-set film is wound up.
  • the heat-set film is placed in a winding device to be wound up to obtain the battery separator, which is a semi-dry and semi-wet battery separator.
  • the speed at which the heat-set film is wound may be set according to actual needs.
  • the speed of winding the heat-set film may be 20 to 100 m/min; more preferably, The heat-set film was wound at a speed of 50 m/min.
  • the above preparation method of the battery separator completely eliminates the extraction process in the existing wet process, effectively breaks the bottleneck of the production speed of the existing battery separator, and the battery separator prepared by the method has excellent comprehensive performance: for example, It has a low pore size, a uniform concentration of pore size distribution, good porosity and film strength. At the same time, the battery separator formed by the battery separator has a closer microscopic morphology on both sides.
  • the method for preparing a battery separator of the present invention has the advantages of low energy consumption and low production cost compared to the wet process in the prior art.
  • test instruments and test methods used in each performance test are first described as follows:
  • German Malt film thickness gauge 1216 was measured according to the method for measuring the thickness of plastic film and sheet of GB/T6672-2001.
  • results were measured using a multimeter at two points where the separators were 10 cm apart, and the results were the average of 10 measurements at different measurement points.
  • Gurley permeability tester 4110 was used to measure according to the GB/T 1037 plastic film and sheet water vapor permeability test method.
  • the Shanghai Jiaoji QJ210A universal testing machine was used to measure the peeling strength of the paper according to GB/T 2679.7.
  • test was carried out according to ASTM d882-2002 tensile standard test method for plastic sheets using a Shanghai TQ QJ210A universal testing machine.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the substance is placed in a vacuum distillation chamber for distillation under reduced pressure. At the same time, it is fed into a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • FIG. 2 A photomicrograph of the battery separator obtained in this example is shown in Fig. 2.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • FIG. 1 A photomicrograph of the battery separator obtained in this example is shown in FIG.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • FIG. 1 A photomicrograph of the battery separator obtained in this example is shown in FIG.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • FIG. 1 A photomicrograph of the battery separator obtained in this example is shown in FIG.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • FIG. 6 A photomicrograph of the battery separator obtained in this example is shown in Fig. 6.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • FIG. 1 A photomicrograph of the battery separator obtained in this example is shown in FIG.
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • the mixture was continuously fed into an extruder, and at 180 ° C, the high molecular weight polyethylene, the antioxidant was continuously dissolved in mineral oil in an extruder, and then continuously extruded by an extruder at a speed of 200 rpm. Out.
  • the continuously extruded mixture was introduced into a slit die placed in a vacuum distillation chamber, and the mixture was extruded through a slit die to a casting cooling roll, and cast into a ribbon at 80 ° C to obtain a belt.
  • the material is placed in a vacuum distillation chamber for distillation under reduced pressure, and simultaneously fed to a biaxial stretching machine for stretching to remove mineral oil from the ribbon.
  • the obtained film was heat-set at 120 ° C for 15 minutes, and the film was wound up at a speed of 50 m / min to finally obtain a semi-dry and semi-wet battery separator.
  • the battery separator obtained in the present embodiment was tested by the above test instrument and test method, and the test results are as follows:
  • the present invention also provides a battery separator obtained by the production method as described in any of the above schemes.
  • the battery separator has a thickness of 5 to 30 ⁇ m, a pore diameter of 0.3 to 0.8 ⁇ m, and a porosity of 30% to 60%.
  • the present invention provides a polymer composition for forming a battery separator, a battery separator, and a preparation method, the polymer composition for forming a battery separator comprising: an average molecular weight of 1.0 ⁇ 10 5 to 10.0 ⁇ 106 and a density of 0.940 ⁇ 0.976g / cm 3 of the high molecular weight polyethylene, an antioxidant porogen, wherein the high molecular weight polyethylene by weight of 100 parts of the weight of porogen 500 ⁇ 2000 parts, the antioxidant has a weight of 0.1 to 10 parts.
  • the polymer separator forming battery separator of the present invention is used for forming a battery separator, and the battery separator formed using the polymer composition has a low pore diameter, a uniformly concentrated pore size distribution, a good porosity, and Membrane strength, and the formed battery separator has more close microscopic morphology on both sides; the preparation method of the battery separator of the invention completely abandons the extraction process in the existing wet process, effectively breaks through the production of the existing battery separator
  • the bottleneck of speed, and the battery separator prepared by the method has excellent comprehensive properties: for example, having a low pore diameter, a uniformly concentrated pore size distribution, good porosity and film strength, and the battery isolation prepared by the method
  • the battery separator formed by the film has a closer microscopic morphology on both sides.
  • the method for producing a battery separator of the present invention has the advantages of low energy consumption and low production cost as compared with the wet process of the prior art.

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Abstract

一种形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法，所述形成电池隔离膜的聚合物组合物包括：平均分子量为1.0×10 5～10.0×10 6且密度为0.940～0.976g/cm 3的高分子量聚乙烯、成孔剂及抗氧化剂，其中，按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为500～2000份，所述抗氧化剂的重量为0.1～10份。所述形成电池隔离膜的聚合物组合物用于形成电池隔离膜，使用所述聚合物组合物形成的电池隔离膜具有较低的微孔孔径、均匀集中的孔径分布、良好的孔隙率和膜强度，且形成的电池隔离膜两面具有更为接近的微观形貌。

Description

形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法 技术领域
本发明涉及锂电池技术领域，特别是涉及一种形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法。
背景技术
锂离子电池通常主要由正极，负极，隔膜，电解液，电池外壳组成。锂离子电池结构中，隔膜是关键的内层组件之一。隔膜的主要作用是将电池的正、负极分隔开来，防止正负极直接接触而短路，同时还要使电解质离子能够在电池充放电过程中顺利通过，形成电流，在电池工作温度发生异常升高时，关闭电解质离子的迁移通道，切断电流保证电池安全。由此可见，隔膜的性能决定了电池的界面结构、内阻等，直接影响电池的容量、循环以及安全性能等特性，性能优异的隔膜对提高电池的综合性能具有重要的作用。目前市售的锂离子电池隔膜一般采用聚烯烃多孔膜。
电池隔离膜的主要性能参数包括厚度，孔隙率，孔径大小，孔径分布，强度，热收缩率，闭孔温度和破膜温度等。为了减少电池内阻，电极面积必须尽可能大，所以对于隔膜的厚度要求尽可能的薄。电池隔膜本身虽然不导电，但是导电离子需要通过隔膜进行迁移，这就要求隔膜本身需要存在一定数量的孔，即孔隙率，但是孔隙率过高势必导致隔膜强度降低，影响电池整体可靠性。除此之外，电解液在隔膜上的浸润性直接影响离子迁移的阻力，浸润性越好，离子通过隔膜进行迁移的阻力越小，电池内阻也就越小。通常，在孔径不是非常大的情况下，孔径分布越均匀，电解液的浸润性越好。电池组件在其生产组装过程中需要对隔膜进行牵引，在组装完成后还需要保证隔膜不会被电极材料刺穿，因此隔膜不仅需要足够的拉伸强度还需要一定的刺穿强度。聚合物隔离膜在一定的受热条件下会发生热收缩，为避免热收缩带来的正负极直接接触而造成的内部短路，对隔离膜的热收缩率也有一定的要求。锂离子电池在异常条件下，如外部线路发生短路时，由于电流过大，电池内部温度急剧升高，这就需要隔膜能够及时关闭导电离子的迁移通道。因此，将电池隔离膜的微孔发生熔融闭合的温度称为闭孔温度。当温度继续升高时，发生隔离膜熔断破裂，将此熔断破裂温度称为破膜温度。从锂离子电池的安全角度来考虑，隔膜的闭孔温度和破膜温度必须有一定的温度差，以保证隔膜闭孔切断电流后即使温度继续上升，也有足够温度缓冲区间不发生隔膜破裂。
常规湿法锂离子电池隔离膜在生产过程中需要经过有机溶剂的萃取过程，此过程往往是限制整个电池隔离膜生产速度的瓶颈，生产出来的隔离膜两面微观形貌也存在明显差距。同 时为了维持整个生产过程的连续性，所有加热部件都需要外部热能供给，能耗大，生产成本高。本发明的一个发明目的是提供一种半干半湿法电池隔离膜制造工艺及其产品，使其能够摒弃湿法工艺中的萃取工艺，同时使该电池隔离膜具有优异的综合性能，如具有较低的微孔孔径，均匀集中的孔径分布，良好的孔隙率和膜强度，该方法制备的隔离膜两面具有更为接近的微观形貌。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法，用于解决现有技术中采用湿法工艺制备电池隔离膜需要萃取存在的限制整个电池隔离膜生产速度的瓶颈，生产出来的电池隔膜两面微观形貌存在明显差异的问题，以及为了维持整个生产过程的连续性，所有加热部件都需要外部热能供给而存在的能耗大、生产成本高的问题。
为实现上述目的及其他相关目的，本发明提供一种形成电池隔离膜的聚合物组合物，所述形成电池隔离膜的聚合物组合物包括：平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的高分子量聚乙烯、成孔剂及抗氧化剂，其中，
按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为500～2000份，所述抗氧化剂的重量为0.1～10份。
作为本发明的形成电池隔离膜的聚合物组合物的一种优选方案，所述成孔剂包括：天然矿物油、C6-15烷烃、C8-15脂族羧酸C1-4烷酯、C2-6卤代烷烃、邻苯二甲酸酯、偏苯三酸酯、己二酸酯、癸二酸酯、马来酸酯、苯甲酸酯、环氧植物油、苯磺酰胺、磷酸三酯、二元醇醚、乙酰单酸甘油乙酯、柠檬酸酯或环己烷-1，2-二羧酸二异壬酯中的至少一种。
作为本发明的形成电池隔离膜的聚合物组合物的一种优选方案，所述成孔剂40℃运动粘度为10mm2/s～100mm2/s。
作为本发明的形成电池隔离膜的聚合物组合物的一种优选方案，所述成孔剂的初馏点大于或等于110℃。
作为本发明的形成电池隔离膜的聚合物组合物的一种优选方案，所述抗氧化剂包括：4，4-硫代双(6-叔丁基间甲酚)、二丁基羟基甲苯、亚磷酸酯、特丁基对苯二酚、β-(3，5-二叔丁基-4-羟基苯基)丙酸正十八碳酸酯、1，1，3-三(2-甲基-4羟基-5-叔丁苯基)丁烷、2-特丁基-6-甲基苯酚、N，N’-二-β-萘基对苯二胺、硫代二丙酸双月桂酯、亚磷酸三(壬基苯基)酯或亚磷酸三苯酯中的至少一种。
本发明还提供一种电池隔膜的制备方法，所述电池隔离膜的制备方法包括：
1)制备如上述任一方案中所述的聚合物组合物，并将所述聚合物组合物连续挤出；
2)将步骤1)连续挤出的聚合物组合物进行减压蒸馏流延铸片，以得到带状物；
3)将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂；
4)将步骤3)得到的所述薄膜进行热定型；
5)将热定型后的薄膜进行收卷。
作为本发明的电池隔膜的制备方法的一种优选方案，步骤1)包括如下步骤：
1-1)将平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的所述高分子量聚乙烯、所述成孔剂及所述抗氧化剂按所需质量份加入连续配料加料釜中，搅拌混合均匀；
1-2)将步骤1-1)得到的混合物加入挤出机中，待平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的所述高分子量聚乙烯及所述抗氧化剂溶解于所述成孔剂之后，由所述挤出机连续挤出。
作为本发明的电池隔膜的制备方法的一种优选方案，步骤2)包括如下步骤：
2-1)将步骤1)连续挤出的聚合物组合物置于减压蒸馏室内的狭缝模头内；
2-2)通过所述狭缝模头将所述聚合物组合物挤出至流延冷却辊上，并于流延温度下流延呈带状物。
作为本发明的电池隔膜的制备方法的一种优选方案，将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂的具体方法为：将步骤2)得到的所述带状物置于减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机将所述带状物进行拉伸。
作为本发明的电池隔膜的制备方法的一种优选方案，步骤4)中，热定型的温度为100～150℃；热定型的时间为10～20分钟。
本发明还提供一种电池隔膜，所述电池隔膜由如上述任一方案中所述的制备方法制备而得到。
作为本发明的电池隔膜的一种优选方案，所述电池隔离膜的厚度为5～30μm，微孔孔径为0.3～0.8μm，孔隙率为30％～60％。
如上所述，本发明的形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法，具有以下有益效果：
本发明的形成电池隔离膜的聚合物组合物用于形成电池隔离膜，使用所述聚合物组合物 形成的电池隔离膜具有较低的微孔孔径、均匀集中的孔径分布、良好的孔隙率和膜强度，且形成的电池隔离膜两面具有更为接近的微观形貌；
本发明的电池隔离膜的制备方法完全摒弃了现有湿法工艺中的萃取工艺，有效突破了现有电池隔离膜生产速度的瓶颈，且该方法制备的电池隔离膜具有优异的综合性能：譬如，具有较低的微孔孔径、均匀集中的孔径分布、良好的孔隙率和膜强度，同时，该方法制备的电池隔离膜形成的电池隔离膜两面具有更为接近的微观形貌。此外，本发明的电池隔离膜的制备方法相较于现有技术中的湿法工艺还具有能耗低、生产成本低的优点。
附图说明
图1显示为本发明提供的电池隔离膜的制备方法的流程图。
图2显示为本发明实施例1中制备的电池隔离膜的正面及反面显微照片，其中，a为正面显微照片，b为反面显微照片。
图3显示为本发明实施例2中制备的电池隔离膜的正面及反面显微照片，其中，a为正面显微照片，b为反面显微照片。
图4显示为本发明实施例3中制备的电池隔离膜的正面及反面显微照片，其中，a为正面显微照片，b为反面显微照片。
图5显示为本发明实施例4中制备的电池隔离膜的正面及反面显微照片，其中，a为正面显微照片，b为反面显微照片。
图6显示为本发明实施例5中制备的电池隔离膜的正面及反面显微照片，其中，a为正面显微照片，b为反面显微照片。
图7显示为本发明实施例6中制备的电池隔离膜的正面及反面显微照片，其中，a为正面显微照片，b为反面显微照片。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。
请参阅图1至图7。须知，本说明书所附图示所绘示的结构、比例、大小等，均仅用以配合说明书所揭示的内容，以供熟悉此技术的人士了解与阅读，并非用以限定本发明可实施的限定条件，故不具技术上的实质意义，任何结构的修饰、比例关系的改变或大小的调整，在不影响本发明所能产生的功效及所能达成的目的下，均应仍落在本发明所揭示的技术内容得能涵盖的范围内。同时，本说明书中所引用的如“上”、“下”、“左”、“右”、“中部”及“一”等 的用语，亦仅为便于叙述的明了，而非用以限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容下，当亦视为本发明可实施的范畴。
本发明提供一种形成电池隔离膜的聚合物组合物，所述聚合物组合物用于制备电池隔离膜，所述形成电池隔离膜的聚合物组合物包括：平均分子量为1.0×105～10.0×106道尔顿且密度为0.940～0.976g/cm3的高分子量聚乙烯、成孔剂及抗氧化剂，其中，
按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为500～2000份，所述抗氧化剂的重量为0.1～10份。
优选地，所述高分子量聚乙烯的平均分子量为1.0×105～5.0×106道尔顿；更为优选地，所述高分子量聚乙烯的平均分子量为1.0×105～2.0×106道尔顿。
优选地，所述高分子量聚乙烯的密度为0.940～0.966g/cm3；更为优选地，所述高分子量聚乙烯的密度为0.950～0.966g/cm3。
需要说明的是，所述高分子量聚乙烯可以为一种平均分子量的高分子量聚乙烯，也可以为两种或多种平均分子量高分子量聚乙烯的混合物。
作为示例，所述成孔剂可以包括：天然矿物油、C6-15烷烃、C8-15脂族羧酸C1-4烷酯、C2-6卤代烷烃、邻苯二甲酸酯、偏苯三酸酯、己二酸酯、癸二酸酯、马来酸酯、苯甲酸酯、环氧植物油、苯磺酰胺、磷酸三酯、二元醇醚、乙酰单酸甘油乙酯、柠檬酸酯或环己烷-1，2-二羧酸二异壬酯中的至少一种。
作为示例，所述天然矿物油可以包括CAS：8020-83-5、8042-47-5；MDL：MFCD00131611；E1NECS：232-455-8等。
作为示例，所述C6-15烷烃可以包括萘烷、癸烷、十一烷或十二烷等。
作为示例，所述C8-15脂族羧酸C1-4烷酯可以包括癸酸甲酯、癸酸乙酯、癸酸丙酯、癸酸正丁酯、十一碳酸甲酯、十一碳酸乙酯、十一碳酸丙酯、十一碳酸正丁酯、十二碳酸甲酯、十二碳酸乙酯、十二碳酸丙酯或十二碳酸正丁酯等。
作为示例，所述C2-6卤代烷烃可以包括二氯乙烷、二氯丙烷、氟氯乙烷或氟氯丙烷等。
作为示例，所述成孔剂40℃运动粘度为10mm2/s～100mm2/s；优选地，所述成孔剂40℃运动粘度为20mm2/s～80mm2/s；更为优选地，所述成孔剂40℃运动粘度为30mm2/s～70mm2/s。
作为示例，所述成孔剂的初馏点大于或等于110℃。
优选地，按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为700～1800份；更为优选地，按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为800～1600份。
作为示例，所述抗氧化剂可以包括：4，4-硫代双(6-叔丁基间甲酚)、二丁基羟基甲苯、亚磷酸酯、特丁基对苯二酚、β-(3，5-二叔丁基-4-羟基苯基)丙酸正十八碳酸酯、1，1，3-三(2-甲基-4羟基-5-叔丁苯基)丁烷、2-特丁基-6-甲基苯酚、N，N’-二-β-萘基对苯二胺、硫代二丙酸双月桂酯、亚磷酸三(壬基苯基)酯或亚磷酸三苯酯中的至少一种。
优选地，按所述高分子量聚乙烯的重量为100份计，所述抗氧化剂的重量为0.5～8份；更为优选地，按所述高分子量聚乙烯的重量为100份计，所述抗氧化剂的重量为1～6份。
请参阅图1，本发明还提供一种电池隔膜的制备方法，所述电池隔离膜的制备方法包括：
1)制备如上述任一方案中所述的聚合物组合物，并将所述聚合物组合物连续挤出；
2)将步骤1)连续挤出的聚合物组合物进行减压蒸馏流延铸片，以得到带状物；
3)将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂；
4)将步骤3)得到的所述薄膜进行热定型；
5)将热定型后的薄膜进行收卷。
在步骤1)中，请参阅图1中的S1步骤，制备如上述任一方案中所述的聚合物组合物，并将所述聚合物组合物连续挤出。
作为示例，所述聚合物组合物的组分及特性详见上述关于所述聚合物组合物的内容，此处不再累述。
作为示例，制备所述聚合物组合物，并将所述聚合物组合物连续挤出包括如下步骤：
1-1)将平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的所述高分子量聚乙烯、所述成孔剂及所述抗氧化剂按所需质量份加入连续配料加料釜中，搅拌混合均匀；搅拌的速度可以根据实际需要设定，在一示例中，搅拌的速度可以为50转/分；当然，在其他示例中，搅拌的速度还可以为其他任意数值；
1-2)将步骤1-1)得到的混合物加入挤出机中，在所述挤出机中一定的温度条件下(譬如180℃)，所述高分子量聚乙烯及所述抗氧剂在所述挤出机中连续溶解于所述成孔剂中；待平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的所述高分子量聚乙烯及所述抗氧化剂溶解于所述成孔剂之后，由所述挤出机连续挤出；所述挤出机连续挤出的速度可以根据实际需要进行设定，在一示例中，所述挤出机连续挤出的速度可以为200转/分；当然，在其他示例中，所述挤出机连续挤出的速度还可以为其他任意数值。
需要说明的是，所述挤出机可以为单螺杆挤出机、双螺杆挤出机或多螺杆挤出机，也可以为现有其他任意一种形式的挤出机。
在步骤2)中，请参阅图1中的S2步骤，将步骤1)连续挤出的聚合物组合物进行减压蒸馏流延铸片，以得到带状物。
作为示例，将步骤1)连续挤出的聚合物组合物进行减压蒸馏流延铸片包括如下步骤：
2-1)将步骤1)连续挤出的聚合物组合物置于减压蒸馏室内的狭缝模头内；
2-2)通过所述狭缝模头将所述聚合物组合物挤出至流延冷却辊上，并于流延温度下流延呈带状物。
作为示例，所述流延温度可以为50～100℃，优选地，本实施例中，所述流延温度为80℃。
在步骤3)中，请参阅图1中的S3步骤，将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂。
作为示例，将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂的具体方法为：将步骤2)得到的所述带状物置于减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机将所述带状物进行拉伸，即可得到去除了所述成孔剂的薄膜。
在步骤4)中，请参阅图1中的S4步骤，将步骤3)得到的所述薄膜进行热定型。
作为示例，热定型的温度及热定型时间可以根据实际需要进行设定；优选地，热定型的温度为100～150℃；热定型的时间为10～20分钟；更优选地，热定型的温度为120℃；热定型的时间为15分钟。
在步骤5)中，请参阅图1中的S5步骤，将热定型后的薄膜进行收卷。
作为示例，将热定型后的薄膜置于收卷设备中进行收卷即可得到所述电池隔离膜，所述电池隔离膜为半干半湿法电池隔离膜。
作为示例，将热定型后的薄膜进行收卷的速度可以根据实际需要进行设定，优选地，将热定型后的薄膜进行收卷的速度可以为20～100米/分；更为优选地，将热定型后的薄膜进行收卷的速度为50米/分。
上述的电池隔离膜的制备方法完全摒弃了现有湿法工艺中的萃取工艺，有效突破了现有电池隔离膜生产速度的瓶颈，且该方法制备的电池隔离膜具有优异的综合性能：譬如，具有较低的微孔孔径、均匀集中的孔径分布、良好的孔隙率和膜强度，同时，该方法制备的电池隔离膜形成的电池隔离膜两面具有更为接近的微观形貌。此外，本发明的电池隔离膜的制备方法相较于现有技术中的湿法工艺还具有能耗低、生产成本低的优点。
下面结合具体实施例，对本发明进行进一步说明。在给出具体实施例之前，为了便于理解后续的性能测试结构，先将各性能测试所用到的测试仪器及测试方法说明如下：
1.厚度
采用德国马尔薄膜测厚仪1216根据GB/T6672-2001塑料薄膜与薄片厚度的测定方法测定。
2.电阻
采用万用表在隔离膜相距10cm的两个点上测得，采用的结果为不同的测量点上10次测定的平均值。
3.透过率
采用Gurley透气度测试仪4110根据GB/T1037塑料薄膜和片材透水蒸汽性试验方法进行测定。
4.孔隙率
采用PMI AAQ-3K-A-1全自动压水仪测定。
5.孔径
采用PMI AAQ-3K-A-1全自动压水仪测定。
6.刺穿强度
采用上海倾技QJ210A万能试验机根据GB/T 2679.7纸板戳穿强度进行测定。
7.拉伸强度
采用上海倾技QJ210A万能试验机根据ASTM d882-2002塑料薄片的拉伸标准测试方法进行测定。
8.收缩率
在常温(23℃)试验环境下测量隔膜上两点之间的距离L0，将试样放置于120℃±1℃烘箱中的不锈钢加上，保温1h后取出，待隔膜冷却到常温试验环境时，测量隔膜上两点之间的距离L1，收缩率S按以下公式计算：S＝(L0-L1)/L0×100％。
下面结合具体实施例对本发明进行进一步说明。
实施例1
将100克密度为0.957g/cm3的，平均分子量为3.0×105高分子量聚乙烯，0.5克抗氧剂，700克40℃运动粘度为50mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏， 同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000001
本实施例中得到的电池隔离膜的显微照片如图2所示。
实施例2
将100克密度为0.953g/cm3的，平均分子量为5.0×105高分子量聚乙烯，0.5克抗氧剂，700克40℃运动粘度为50mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000002
本实施例中得到的电池隔离膜的显微照片如图3所示。
实施例3
将100克密度为0.951g/cm3的，平均分子量为1.0×106高分子量聚乙烯，0.5克抗氧剂，800克40℃运动粘度为40mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000003
本实施例中得到的电池隔离膜的显微照片如图4所示。
实施例4
将100克密度为0.947g/cm3的，平均分子量为2.0×106高分子量聚乙烯，1.0克抗氧剂，900克40℃运动粘度为40mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000004
本实施例中得到的电池隔离膜的显微照片如图5所示。
实施例5
将100克密度为0.948g/cm3的，平均分子量为5.0×106高分子量聚乙烯，1.0克抗氧剂，1000克40℃运动粘度为40mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000005
本实施例中得到的电池隔离膜的显微照片如图6所示。
实施例6
将100克密度为0.953g/cm3的，平均分子量为5.0×105高分子量聚乙烯，200克密度为0.940g/cm3的，平均分子量为8.0×106高分子量聚乙烯，1.0克抗氧剂，3600克40℃运动粘度为40mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000006
本实施例中得到的电池隔离膜的显微照片如图7所示。
比较例1
将100克密度为0.935g/cm3的，平均分子量为5.0×104的聚乙烯，0.5克抗氧剂，700克40℃运动粘度为40mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000007
比较例2
将100克密度为0.935g/cm3的，平均分子量为10.0×106的聚乙烯，1.0克抗氧剂，2500克40℃运动粘度为30mm2/s的矿物油加入连续配料加料釜中，以50转/分的速度搅拌，将原料混合均匀。
将混合物连续加入挤出机，在180℃条件下，所述高分子量聚乙烯，抗氧剂在挤出机中连续溶解于矿物油中，再由挤出机以200转/分的速度连续挤出。
连续挤出的混合物进入到置于减压蒸馏室中的狭缝模头内，混合物通过狭缝模头挤出到流延冷却辊，在80℃条件下流延成带状物，将得到的带状物置入减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机进行拉伸，用以除去带状物中的矿物油。将所得薄膜在120℃条件下热定型15分钟，将薄膜以50米/分的速度收卷，最终得到半干半湿法电池隔离膜。
将本实施例中得到的电池隔离膜采用上述测试仪器及测试方法进行测试，测试结果如下：
Figure PCTCN2017093654-appb-000008
从以上实验结果可以看出，随着聚乙烯分子量的增加，所述电池隔膜的强度有所增加，收缩率也在不断减小。但是过大的分子量不利于隔膜的开孔，孔径和孔隙率相对较低，进而导致透过率也相对较高；较低的分子量虽然更容易使隔膜开孔，但孔径和孔隙率相对较大，强度较低，收缩率也较高，丧失了实际的应用优势。从附图2至附图7可以进一步看出，所有实施例中隔膜两面的微观形貌均非常接近，没有显著差异。
本发明还提供一种电池隔膜，所述电池隔膜由如上述任一方案中所述的制备方法制备而得到。
作为本发明的电池隔膜的一种优选方案，所述电池隔离膜的厚度为5～30μm，微孔孔径为0.3～0.8μm，孔隙率为30％～60％。
综上所述，本发明提供一种形成电池隔离膜的聚合物组合物、电池隔离膜及制备方法，所述形成电池隔离膜的聚合物组合物包括：平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的高分子量聚乙烯、成孔剂及抗氧化剂，其中，按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为500～2000份，所述抗氧化剂的重量为0.1～10份。本发明的形成电池隔离膜的聚合物组合物用于形成电池隔离膜，使用所述聚合物组合物形成的电池隔离膜具有较低的微孔孔径、均匀集中的孔径分布、良好的孔隙率和膜强度，且形成的电池隔离膜两面具有更为接近的微观形貌；本发明的电池隔离膜的制备方法完全摒弃了现有湿法工艺中的萃取工艺，有效突破了现有电池隔离膜生产速度的瓶颈，且该方法制备的电池隔离膜具有优异的综合性能：譬如，具有较低的微孔孔径、均匀集中的孔径分布、良好的孔隙率和膜强度，同时，该方法制备的电池隔离膜形成的电池隔离膜两面具有更为接近的微观形貌。此外，本发明的电池隔离膜的制备方法相较于现有技术中的湿法工艺还具有能耗低、生 产成本低的优点。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (12)

  1. 一种形成电池隔离膜的聚合物组合物，其特征在于，所述形成电池隔离膜的聚合物组合物包括：平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的高分子量聚乙烯、成孔剂及抗氧化剂，其中，
    按所述高分子量聚乙烯的重量为100份计，所述成孔剂的重量为500～2000份，所述抗氧化剂的重量为0.1～10份。
  2. 根据权利要求1所述的形成电池隔离膜的聚合物组合物，其特征在于：所述成孔剂包括：天然矿物油、C6-15烷烃、C8-15脂族羧酸C1-4烷酯、C2-6卤代烷烃、邻苯二甲酸酯、偏苯三酸酯、己二酸酯、癸二酸酯、马来酸酯、苯甲酸酯、环氧植物油、苯磺酰胺、磷酸三酯、二元醇醚、乙酰单酸甘油乙酯、柠檬酸酯或环己烷-1，2-二羧酸二异壬酯中的至少一种。
  3. 根据权利1要求所述的形成电池隔离膜的聚合物组合物，其特征在于：所述成孔剂40℃运动粘度为10mm2/s～100mm2/s。
  4. 根据权利1要求所述的形成电池隔离膜的聚合物组合物，其特征在于：所述成孔剂的初馏点大于或等于110℃。
  5. 根据权利1要求所述的形成电池隔离膜的聚合物组合物，其特征在于：所述抗氧化剂包括：4，4-硫代双(6-叔丁基间甲酚)、二丁基羟基甲苯、亚磷酸酯、特丁基对苯二酚、β-(3，5-二叔丁基-4-羟基苯基)丙酸正十八碳酸酯、1，1，3-三(2-甲基-4羟基-5-叔丁苯基)丁烷、2-特丁基-6-甲基苯酚、N，N’-二-β-萘基对苯二胺、硫代二丙酸双月桂酯、亚磷酸三(壬基苯基)酯或亚磷酸三苯酯中的至少一种。
  6. 一种电池隔离膜的制备方法，其特征在于，所述电池隔离膜的制备方法包括：
    1)制备如权利要求1至5中任一项所述的聚合物组合物，并将所述聚合物组合物连续挤出；
    2)将步骤1)连续挤出的聚合物组合物进行减压蒸馏流延铸片，以得到带状物；
    3)将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂；
    4)将步骤3)得到的所述薄膜进行热定型；
    5)将热定型后的薄膜进行收卷。
  7. 根据权利要求6所述的电池隔离膜的制备方法，其特征在于：步骤1)包括如下步骤：
    1-1)将平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的所述高分子量聚乙烯、所述成孔剂及所述抗氧化剂按所需质量份加入连续配料加料釜中，搅拌混合均匀；
    1-2)将步骤1-1)得到的混合物加入挤出机中，待平均分子量为1.0×105～10.0×106且密度为0.940～0.976g/cm3的所述高分子量聚乙烯及所述抗氧化剂溶解于所述成孔剂之后，由所述挤出机连续挤出。
  8. 根据权利要求6所述的电池隔离膜的制备方法，其特征在于：步骤2)包括如下步骤：
    2-1)将步骤1)连续挤出的聚合物组合物置于减压蒸馏室内的狭缝模头内；
    2-2)通过所述狭缝模头将所述聚合物组合物挤出至流延冷却辊上，并于流延温度下流延呈带状物。
  9. 根据权利6要求所述的电池隔离膜的制备方法，其特征在于：将步骤2)得到的所述带状物进行减压蒸馏双向拉伸成薄膜，以去除所述带状物中的所述成孔剂的具体方法为：将步骤2)得到的所述带状物置于减压蒸馏室中进行减压蒸馏，同时送入双向拉伸机将所述带状物进行拉伸。
  10. 根据权利6要求所述的电池隔离膜的制备方法，其特征在于：步骤4)中，热定型的温度为100～150℃；热定型的时间为10～20分钟。
  11. 一种电池隔离膜，其特征在于，所述电池隔离膜由如权利要求6至10中任一项所述的制备方法制备而得到。
  12. 根据权利11要求所述的电池隔离膜，其特征在于：所述电池隔离膜的厚度为5～30μm，微孔孔径为0.3～0.8μm，孔隙率为30％～60％。
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