CN102942831B - Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane - Google Patents

Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane Download PDF

Info

Publication number
CN102942831B
CN102942831B CN201210476760.0A CN201210476760A CN102942831B CN 102942831 B CN102942831 B CN 102942831B CN 201210476760 A CN201210476760 A CN 201210476760A CN 102942831 B CN102942831 B CN 102942831B
Authority
CN
China
Prior art keywords
monomer
coating
ion secondary
oleophylic
lithium ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210476760.0A
Other languages
Chinese (zh)
Other versions
CN102942831A (en
Inventor
邱钧锋
王松钊
蔡朝辉
吴耀根
廖凯明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Huiqiang New Energy Material Technology Co ltd
Original Assignee
Foshan Jinhui Hi-Tech Photoelectric Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foshan Jinhui Hi-Tech Photoelectric Material Co Ltd filed Critical Foshan Jinhui Hi-Tech Photoelectric Material Co Ltd
Priority to CN201210476760.0A priority Critical patent/CN102942831B/en
Publication of CN102942831A publication Critical patent/CN102942831A/en
Priority to PCT/CN2013/072585 priority patent/WO2014079177A1/en
Application granted granted Critical
Publication of CN102942831B publication Critical patent/CN102942831B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—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
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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

Abstract

The invention discloses a coating composite for a lithium ion secondary battery membrane and a method for manufacturing the membrane. The coating composite comprises heat resistant resins and inorganic non-conducting insulation particles, molecular chains of the heat resistant resins comprise oleophylic structural units, hydrophilic structural units and functional group structural units, and a thermal decomposition temperature is larger than 250 DEG C. The inorganic non-conducting insulation particles have the advantages of being high temperature resistant, low in density, rigidity and water absorption and the like; composite micro porous membranes prepared through the coating composite has the advantages of being low in hole closing temperature, high in membrane breaking temperature, low in thermal shrinkage rate, high in combining force between a heat resistant coating and a substrate, good in wettability of the heat resistant coating surface and the like simultaneously; and the membrane used for manufacturing a lithium ion secondary battery has good comprehensive properties and reliable safety performances.

Description

For the coating composition of lithium ion secondary battery membrane and the manufacture method of this barrier film
Technical field
The present invention relates to a kind of coating composition for lithium ion secondary battery membrane, also relate to a kind of manufacture method of the lithium ion secondary battery membrane that uses this coating composition simultaneously.
Background technology
Lithium-ion secondary cell has long, energy density advantages of higher of life-span and is widely used.Barrier film is the important component part of lithium ion battery, plays a part isolation positive and negative electrode and ionic conduction.Diaphragm material great majority used are polyolefine material in the market, mainly comprise polyethylene and polypropylene.
Due to polyethylene and polyacrylic thermal characteristics difference, diaphragm current closing temperature (Shut-down temperature) taking polyethylene as material produce is relatively low, in the time there is overload in battery, along with the microvoid structure of temperature rise barrier film inside is very fast destroyed and melting is closed, block in time electric current.But, weak point is that its melt fracture temperature (Melt-downtemperature) is also low, along with the rising of battery temperature, exceed 15 DEG C of left and right of fusing point, barrier film is heated and breaks, cause inside battery structural collapse and cause blast, so we wish that material has lower electric current blocking temperature and higher melt fracture temperature conventionally.And its raw material fusing point of barrier film taking polypropylene as material produce is higher, conventionally, more than 160 DEG C, there is good high temperature resistant rupture of membranes performance, but its electric current closing temperature is also corresponding higher simultaneously, be unfavorable for equally improving the safety performance of battery.Therefore, the developing direction of lithium cell diaphragm is sandwich diaphragm (PP/PE/PP) now, and trilamellar membrane is in the time that temperature raises, and the PE at middle part shrinks and causes heat to close 130 DEG C of fusings, but because outside PP temperature of fusion is 160 DEG C, barrier film can also keep certain security.But three layers of barrier film do not solve the potential problem that fusing is shunk completely, and in the time that temperature continues to raise, PP film still can melt, and causes internal short-circuit of battery.
In order to improve the thermotolerance of barrier film, the safety problems such as the short circuit that the thermal contraction of minimizing dividing plate causes, the reliability engineering of raising battery.Various barrier film manufacturing technology schemes taking cheap non-woven fabrics as base material have for example been proposed, publication number utilizes the refractory layer that on the basis of weaving of thermal glass or stupalith manufacture or non-woven fabrics, coating contains mineral filler for the Chinese patent of " 101425570 " discloses, thereby completes invention.Although the anodic aluminium oxide membrane of this patent manufacture has certain thermotolerance, exist base material fragility large, the shortcoming of intensity difference, the barrier film that is difficult to think such has reliable safety performance.
Publication number is a kind of taking PET film as base material for the Chinese patent of " 101471432 " discloses, and at the composite membrane of the heat-resisting organic polymer material of its surface coverage one deck, object is to provide a kind of high temperature resistant, barrier film of meeting high-multiplying-power battery requirement.Although but PET basement membrane has good thermotolerance, its fusing point is 256-265 DEG C, but based on the security consideration of lithium-ion secondary cell, ignored the low closed pore temperature that should provide as lithium ion secondary battery membrane, the barrier film that is hereat difficult to think such has reliable safety performance.
Summary of the invention
First object of the present invention is in order to overcome the problems referred to above, a kind of coating composition for lithium ion secondary battery membrane is provided, the secondary battery membrane that adopts this coating composition to prepare, not only there is low closed pore temperature, high breaking temperature, also have that percent thermal shrinkage is little simultaneously, refractory coating and the feature such as base material bonding force is high, refractory coating surface wettability is good, there is better over-all properties, there is reliable safety performance as the barrier film of lithium-ion secondary cell.
Second object of the present invention is the manufacture method for a kind of lithium ion secondary battery membrane is provided.
First object of the present invention adopts following technical scheme:
A kind of coating composition for lithium ion secondary battery membrane, it contains heat-resistant resin and inorganic non-conductive insulating particle, be characterized in: the molecular chain of described heat-resistant resin comprises oleophylic structural unit, hydrophilic-structure unit and structure of functional groups unit, its heat decomposition temperature is greater than 250 DEG C; Wherein, the weight ratio of oleophylic structural unit, hydrophilic-structure unit and structure of functional groups unit is 10～90:80～9:10～1.
Preferably, the oleophylic structural unit that described heat-resistant resin molecular chain comprises, hydrophilic structural unit and structure of functional groups unit are transformed by oleophylic monomer, hydrophilic monomer and monomer respectively.
Preferably, oleophylic monomer is that atomicity is the acrylate of 4-20, and its glass transition temperature Tg is-70 DEG C～120 DEG C.The concrete mixture that is enumerated as following a kind of monomer or two or more monomers: methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, vinyl acetate or vinyl cyanide etc., but the present invention is not limited to this.
Preferably, hydrophilic monomer is the acrylate derivative of no more than 8 of carbonatoms, and it contains at least one hydrophilic radical in carboxyl, hydroxyl or amide group.Concrete being enumerated as is at least selected from following a kind of compound: sodium acrylate, Lithium acrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic, NIPA, N, N-diethyl-2-acrylamide, N,N-DMAA, N methacrylamide, N-ethyl acrylamide or N hydroxymethyl acrylamide etc.
Preferably, monomer is the acrylate derivative of giving tackiness agent response characteristic, and it contains one or more active function groups in acid anhydrides, carboxyl, epoxy group(ing), hydroxyl, amino or amide group.Concrete be enumerated as following one or more compounds: methacrylic acid, vinylformic acid, hydroxyethyl methylacrylate, Rocryl 410, N-butoxymethyl acrylamide, dimethylaminoethyl methacrylic ester, two amido ethyl-methyl acrylate, Methacrylamide, glycidyl methacrylate etc., but be not restrictive.
Three kinds of comonomers of above-mentioned heat-resistant resin: oleophylic monomer, hydrophilic monomer and monomer's weight ratio is 10～90:80～9:10～1.Only be limited in this proportional range and synthetic heat-resistant resin could meet requirement of the present invention.The effect that in heat-resistant resin, oleophylic unit, hydrophilic unit and functional group units are brought into play is different, but can produce synergistic effect.Oleophylic unit improves the interface interaction of refractory coating and non-polar polyolefinic substrate, gives the processing snappiness that refractory coating is good simultaneously; Hydrophilic unit improves the interaction force between hydrophilic filler in refractory coating, improves refractory coating force of cohesion; Can further there is chemically crosslinked effect in functional monomer, improve refractory coating adhesive power, force of cohesion, thermotolerance, solvent resistance and electrochemical stability.Usually, in order to improve base adhesion force and the processing snappiness of refractory coating, can suitably improve the ratio of oleophylic unit in polymer molecular chain, more preferably oleophylic monomer accounts for the 50-80% of oleophylic monomer, hydrophilic monomer and monomer's gross weight, and what the ratio of hydrophilic monomer can be suitable is adjusted into the 20-50% that accounts for oleophylic monomer, hydrophilic monomer and monomer's gross weight; And monomer often has strong polarity and chemically crosslinked effect can further occur, although can further improve the force of cohesion of refractory coating, but crosslinked effect can cause coating to become hard and crisp, be unfavorable for processing, so what monomer's ratio was general accounts for oleophylic monomer, hydrophilic monomer and below 10% of monomer's gross weight, preferred accounting for below 5%.
Preferably, described inorganic non-conductive insulating particle has following performance perameter: thermotolerance is greater than 400 DEG C, and true density is less than 3g/cm 3, knoop hardness is less than 600kgf/mm 2, dry air 4.0h at 100 DEG C, per unit volume water content is less than 5mg/cm 3.The feature such as that inorganic non-conductive insulating particle has is high temperature resistant, density is little, hardness is low and water-intake rate is low.
The thermotolerance of the inorganic non-conductive insulating particle in the present invention is greater than 400 DEG C, refers at 400 DEG C, to be at least stable, and quality change does not occur, and there is no special stipulation about testing method.For example, can adopt gravitational thermal analysis method, measure the quality of inorganic non-conductive insulating particle and the relation of temperature variation, be heated to more than 400 DEG C with the temperature rise rate of 10 DEG C/min, there is not quality change in inorganic non-conductive insulating particle, just can think and requirement according to the invention be not particularly limited about the upper limit of heat resisting temperature.
In addition, the true density of the inorganic non-conductive insulating particle in the present invention is less than 3g/cm 3, be particularly limited for the density of inorganic non-conductive insulating particle, be mainly the proportion problem of considering coating and composite diaphragm, more particularly consider coating and the energy density problem of composite diaphragm in lithium-ion secondary cell that application the present invention manufactures.In known refractory coating barrier film, aluminum oxide is widely used, and the true density of aluminum oxide is 3.9g/cm 3, the inorganic non-conductive insulating particle density in the present invention by comparison, reduces more than 20%, can go out by theoretical calculate, and the inorganic non-conductive insulating particle in application the present invention can reach the feature that improves lithium-ion secondary cell energy density.
In addition, the knoop hardness of the inorganic non-conductive insulating particle in the present invention is less than 600kgf/mm 2, with respect to the alumina material of applying in known refractory coating barrier film, lower hardness ratio exceedes 50%, the inorganic materials that the present invention uses is because hardness is low, can reduce that refractory coating slurry is manufactured and coating processing in wearing and tearing, and then work-ing life that can extension device, thereby by preferably.
In addition, the inorganic non-conductive insulating particle in the present invention has the feature that water-intake rate is low, and it is dried 4.0h at 100 DEG C under air, and per unit volume water content is less than 5mg/cm 3.About the regulation of eigen, mainly to consider the hazardness of moisture in lithium-ion secondary cell, for example, due to the reason of micro-moisture, ionogen in lithium ion battery and the water generation hydrogen fluoride gas that reacts, thus the dangerous features such as battery bulging caused, and hydrogen fluoride is dissolved in electrolytic solution simultaneously, can reduce electrolyte ph, and then worsen battery performance.Therefore,, in battery manufacture process, moisture controlled is extremely important.Therefore, the water content of barrier film is to need strict control, preferably has the inorganic non-conductive insulating particle that water-intake rate is low, and this point is particularly important.Inorganic non-conductive insulating particle in the present invention is dried 4.0h at 100 DEG C under air, per unit volume water content is less than 5mg/cm 3, be more preferably less than 1mg/cm 3, it is more few better that the above-mentioned water content of inorganic non-conductive insulating particle should say, is most preferably 0mg/cm 3, but there is theoretical possibility in this, and practical situation are very difficult to realize.
Preferably, described inorganic non-conductive insulating particle is silicate compound.Can be the compound that silicon, oxygen and other chemical element (such as aluminium, iron, calcium, magnesium, potassium, sodium, lead, titanium etc.) are combined into, concrete be selected from following one or more mixture: water glass, asbestos, feldspar, glass, cement, clay, peridotites, pistacite, tourmalinite, pyroxene, hornblende, mica, carclazyte, feldspar, quartz etc. natural or the compound of synthetic.
Preferred, described inorganic non-conductive insulating particle is glass powder.Its median size is 0.8-1.5 μ m, and pore size distribution μ m is 0.1-2.2 μ m.The size distribution that is inorganic non-conductive insulating particle should meet: 0.8≤D50≤1.5 μ m, 0.1≤D0, D100≤2.2 μ m.Wherein, more preferably median size meets: 0.8≤D50≤1.2 μ m, the inorganic non-conductive insulating particle of D100≤2.0 μ m.On the one hand, if inorganic non-conductive insulating particle particle diameter is less than 0.1 μ m,, in the time preparing refractory coating slurry, there is the problem of inorganic non-conductive insulating particle difficulties in dispersion, thereby affect the homogeneity of refractory coating; On the other hand, if inorganic non-conductive insulating particle particle diameter is greater than 2.0 μ m, there is the uncontrollable anxiety of refractory coating thickness, thereby cause the deterioration of the battery performance that uses this barrier film.
After coating composition of the present invention is disperseed in solvent, drying forms thermotolerance coating after solidifying; Wherein, inorganic non-conductive insulating particle accounts for the 60-95% of inorganic non-conductive insulating particle and heat-resistant resin gross weight.
Second object of the present invention adopts following technical scheme:
A kind of manufacture method of lithium ion secondary battery membrane, the method comprises: the coating fluid that comprises heat-resistant resin and inorganic non-conductive insulating particle at least one surface coated at the polyolefin-based end, drying forms after thermotolerance coating after solidifying, and finally obtains composite microporous film; Described coating fluid comprises coating composition and the solvent described in first object of the present invention.
The manufacture method of lithium ion secondary battery membrane of the present invention can be exemplified as preparation method hereinafter described, but the present invention is not limited to this.
The manufacture method of lithium ion secondary battery membrane, comprises the following steps:
1) oleophylic monomer, hydrophilic monomer, monomer's copolymer emulsion is dissolved in solvent as heat-resistant resin binding agent, prepares polymer bonding agent solution;
2) inorganic non-conductive insulating particle is joined in above-mentioned polymer bonding agent solution, after disperseing, make coating fluid;
3) scattered slurry is coated after the single or double at the polyolefin-based end, through the operation of dry solidification, to be obtained final product.
Solvent is preferably the solvent of good solvent with respect to heat-resistant resin, uses the principle of similar compatibility to remove to find suitable solvent, preferably has the solvent of similar polarity and solubility parameters to heat-resistant resin binding agent.More preferably, this solvent has lower boiling characteristic simultaneously, is particularly conducive to like this dry solidification operation after coating gluing.Such solvent can roughly be enumerated as following a kind of solvent or the mixture of both above solvents: ethanol, acetone, butanone, methylene dichloride, sherwood oil, tetrahydrofuran (THF), N, dinethylformamide, N,N-dimethylacetamide, water, N-Methyl pyrrolidone etc.Based on environmental protection demand and economy principle, the preferably solvent using the mixture of water and ethanol as heat-resistant resin binding agent, more preferably separately using water as solvent.
The ratio of inorganic non-conductive insulating particle and heat-resistant resin binding agent, can be the 60-95% that inorganic non-conductive insulating particle account for inorganic non-conductive insulating particle and heat-resistant resin binding agent gross weight, more preferably accounts for 75-95%.About the solid content of coating fluid (slurry) that includes heat-resistant resin binding agent and inorganic non-conductive insulating particle, can be 10-50%, more preferably 20-45%.About the dispersing apparatus of the solution that contains inorganic non-conductive insulating particle and binding agent, can be enumerated as: high speed dispersor, sand mill, three-roll grinder, ball mill, colloidal mill etc.The feature and the requirement of the present invention that disperse for wet type, the method that preferably adopts sand mill to disperse, now suitable jitter time is 0.5-20 hour, and after slurry disperses, the size distribution of inorganic non-conductive insulating particle is to meet within the scope of 0.1～2.2 μ m of the claims in the present invention as good.
For the known coating method in this area, can enumerate nonrestrictive example and be: scraper plate coating, spraying coating, the print roll coating that coincide, wound rod coating, air doctor blade coating, intaglio plate print roll coating, slit die head are extrusion coated etc.In the present invention, can adopt above one or more array configuration to be coated with, as long as can realize slurry evenly coating on polyethylene base material, be not particularly limited.
Preferably, the described polyolefin-based end is ultrahigh molecular weight polyethylene(UHMWPE) barrier film, and its surface is through photochemical treatment.The described polyolefin-based end, in general, can adopt tri-layers of barrier film of polypropylene diaphragm, PP/PE/PP of dry process or polyethylene barrier film prepared by wet processing, the polyethylene barrier film that the present invention preferably adopts wet processing to prepare because wet method barrier film has, pore distribution is even, hole size evenly, even thickness, porosity and Gas permeability is good, puncture intensity and biaxial tensile strength advantages of higher.The ultrahigh molecular weight polyethylene(UHMWPE) barrier film preferred, the present invention adopts wet processing to prepare, this barrier film possesses outside all advantages of wet method barrier film, further improves especially in intensity and thermotolerance.
In addition, thickness and the porosity of the ultrahigh molecular weight polyethylene(UHMWPE) barrier film adopting for the present invention are not particularly limited, can adopt known scope: thickness 9～30 μ m, voidage 30～60%, but be not limited to this, can select flexibly according to the needs of composite microporous film of the present invention.
In addition, the ultrahigh molecular weight polyethylene(UHMWPE) substrate in the present invention, surface is through photochemical treatment.Common all kinds of polyolefine (for example PP, PE) are non-polar molecule, are difficult to adhere to the ink molecules of polarity on its surface.Usually, before carrying out polyolefin film printing, carry out chemistry or physical method processing, make the binding strength of its upper layer that forms polarity with raising and polarity ink.Usually, polyolefin film surface treatment method can be enumerated as: solvent treatment method, chromic acid oxidation, flame treating method, Corona discharge Treatment method, Low Temperature Plasma Treating method, uviolizing, radiation exposure, radiation grafting, air heat oxidation, power chemical treatment, cladding process and maleic anhydride graft surface method etc.Photochemical treatment method particularly preferably in the present invention, improves surface tension thereby reach, and improves wettability and fusible object.For example, use photosensitizers benzophenone pre-treatment polyethylene surface, the uviolizing polyethylene surface that is 184mm with wavelength, can make its surface occur crosslinked, and benzophenone also can be sublimated and remove afterwards, noresidue.
Composite microporous film of the present invention, its thermotolerance coating is less than 30 ° to the contact angle of water droplet.Contact angle is that the one of degree of wetting is measured, and degree of wetting can reflect the surface tension at interface, outermost layer thermotolerance coating that can composite microporous film of the present invention has excellent hydrophilic wettability energy, because electrolytic solution is intensive polar solvent, similar to aqueous polar, known, thermotolerance coating has excellent close electrolytic solution wettability equally.The electrolytic solution wettability that barrier film is good, can expand the contact area of barrier film and electrolytic solution, thereby increases ionic conductivity, improves charge-discharge performance and the capacity of battery.For the testing method of the water droplet contact angle of refractory coating, can be enumerated as: deionized water is dropped in to refractory coating surface, then with contact angle measurement test, the contact angle of water droplet is tested, can take to test many group panel datas, the method of finally averaging, thus the contact angle of refractory coating to water droplet obtained.
The base adhesion force (sticking power between refractory coating and base material) of the thermotolerance coating in the present invention is greater than 120N/m, and force of cohesion (reactive force between refractory coating molecule) is greater than 100N/m.Usually, if thermotolerance coating cannot form reliable bonding in polyalkene diaphragm substrate,, in battery manufacturing procedure, there will be barrier film dry linting problem, cause the generation of defective products, such refractory layer cannot effectively be brought into play the effect that suppresses thermal contraction simultaneously.Thermotolerance coating base adhesion force of the present invention and force of cohesion are all greater than 100N/m, can avoid the generation of the problems referred to above.About the testing tool of base adhesion force and force of cohesion, can be enumerated as: peeling strength testing machine, adhesion-force tester etc., preferably adopt adhesive tape 180 to spend peeling strength test machine.
The tensile strength of the MD of composite microporous film of the present invention and TD direction is all greater than 120MPa, in 150-180 DEG C of temperature range, heats 1 hour, and the percent thermal shrinkage of MD and TD direction remains within the scope of 1-5%.Known, the barrier film of wet processing manufacture has the feature of intensity significantly better than dry method, and TD and MD tensile strength more even, be conducive to like this improve the safety performance of battery.Composite microporous film basement membrane of the present invention is ultrahigh molecular weight polyethylene(UHMWPE), this barrier film possesses outside all advantages of wet method barrier film, in intensity and thermotolerance, further improve especially, therefore given the feature that the MD of composite microporous film of the present invention and the tensile strength of TD direction are all greater than 120MPa.
Composite microporous film has in 150-180 DEG C of temperature range, heat 1 hour, the percent thermal shrinkage of MD and TD direction remains on the notable feature within the scope of 1-5%, like this, even the excessive heating that electrochemical device causes because of non-normal use, thereby cause the overheated of barrier film, because barrier film of the present invention has excellent resistance toheat, also can not cause the generation of internal short-circuit of battery.Even if there is short circuit, short-circuited region can not continue to expand yet, thereby has ensured the safety performance of battery.
Beneficial effect of the present invention is:
1, the heat-resistant resin molecular chain of coating composition of the present invention comprises oleophylic structural unit, hydrophilic structural unit and structure of functional groups unit, and heat decomposition temperature is greater than 250 DEG C.Described mineral filler has high temperature resistant, density is little, the features such as the low and water-intake rate of hardness is low, because the single or double of the substrate at composite microporous film has adhered to the coating being formed by coating composition of the present invention, make this composite microporous film not only there is low closed pore temperature, high breaking temperature, its percent thermal shrinkage is little simultaneously, refractory coating and base material bonding force are high, the features such as refractory coating surface wettability is good, barrier film as lithium-ion secondary cell has better over-all properties, there is reliable safety performance, specific performance parameter can be with reference to table one.
2, composite microporous film of the present invention also can address the problem: most of plastics films (as polyolefin film) belong to non-polar polymer, surface tension is lower, generally at 29-30mN/m, theoretically, if the surface tension of object is lower than 33mN/m, according to the adsorption theory of one of cementation theory, there is all problems of adhere firmly in the above of at present known ink and tackiness agent, so usually, also there is the problem that cannot form reliable bonding in polyalkene diaphragm substrate in thermotolerance coating, and then can cause refractory layer cannot effectively bring into play the effect that suppresses thermal contraction.And thermotolerance coating base adhesion force of the present invention and force of cohesion are all greater than 100N/m, can avoid the generation of the problems referred to above, effectively solve the above-mentioned interface illusive problem that bonds, thereby can improve greatly the safety performance of composite microporous film.
3, composite microporous film of the present invention, its thermotolerance coating is less than 30 ° to the contact angle of water droplet, make thermotolerance coating there is excellent close electrolytic solution wettability, the electrolytic solution wettability that barrier film is good, can expand the contact area of barrier film and electrolytic solution, thereby increase ionic conductivity, charge-discharge performance and the capacity of raising battery.
4, the tensile strength of the MD of composite microporous film of the present invention and TD direction is all greater than 120MPa, in 150-180 DEG C of temperature range, heat 1 hour, the percent thermal shrinkage of MD and TD direction remains within the scope of 1-5%, there is excellent intensity and resistance toheat, can not cause the generation of internal short-circuit of battery.Even if there is short circuit, short-circuited region can not continue to expand yet, thereby has ensured the safety performance of battery.And TD and MD tensile strength are more even, be conducive to like this improve the safety performance of battery.
Embodiment
Be described further content in the present invention below in conjunction with specific embodiment for better illustrating.
Embodiment 1:
Select oleophylic monomer n-butyl acrylate, hydrophilic monomer sodium acrylate, the acrylic acid copolymer emulsion of monomer as (consisting of of multipolymer, n-butyl acrylate: sodium acrylate: vinylformic acid=6:3:1, weight ratio) be heat-resistant resin binding agent, using water as solvent, under room temperature, dissolve and disperse 1 hour.Then in 80 parts of glass powder (median size be 0.8 μ m), the ratio of 20 parts of above-mentioned heat-resistant resin binder solutions joins in 100 parts of deionized waters, then by sand mill dispersing and mixing 3 hours, thereby makes coating fluid.
The above-mentioned coating fluid making is coated on two surfaces of ultrahigh molecular weight polyethylene(UHMWPE) basement membrane (being called for short UHMWPE, lower same) of 20 μ m with line rod, then in blast dry oven, is dried, drying temperature is 50 DEG C.Making coated on both sides total thickness is that 6 μ m(are respectively 3 μ composite microporous film m).
Above-mentioned prepared lithium-ion secondary cell by composite microporous film performance in table 1.
Embodiment 2
The difference of the present embodiment and embodiment 1 is: the coating fluid that embodiment 1 is made is coated on a surface of UHMWPE basement membrane, then at the baking oven inner drying of 50 DEG C and obtain.Make the composite microporous film that one side coat-thickness is 6 μ m.
Above-mentioned prepared lithium-ion secondary cell by composite microporous film performance in table 1.
Embodiment 3
The difference of the present embodiment and embodiment 1 is: the median size of its inorganic non-conductive insulating particle (glass powder) is 1.2 μ m, and it is in identical with embodiment 1.
Above-mentioned prepared lithium-ion secondary cell by composite microporous film performance in table 1.
Embodiment 4
The difference of the present embodiment and embodiment 1 is: the ratio of component in heat-resistant resin binding agent is replaced by: oleophylic monomer n-butyl acrylate, hydrophilic monomer sodium acrylate, the acrylic acid copolymer emulsion of monomer are as heat-resistant resin binding agent (consisting of of multipolymer, n-butyl acrylate: sodium acrylate: vinylformic acid=16:3:1), all the other are identical with embodiment 1.
Above-mentioned prepared lithium-ion secondary cell by composite microporous film performance in table 1.
Embodiment 5
The difference of the present embodiment and embodiment 1 is: the kind of heat-resistant resin binding agent and ratio are changed into simultaneously: oleophylic monomer vinyl cyanide, hydrophilic monomer N, N-DMAA, the acrylic acid copolymer emulsion of monomer are as heat-resistant resin binding agent (consisting of of multipolymer, vinyl cyanide: N, N-DMAA: vinylformic acid=10:9:1), all the other are identical with embodiment 1.
Above-mentioned prepared lithium-ion secondary cell by composite microporous film performance in table 1.
Comparative example 1
The UHMWPE barrier film of selecting uncoated refractory coating as a comparison case 1.
UHMWPE membrane properties is in table 1.
Comparative example 2
This comparative example is with the difference of embodiment 1: the kind of heat-resistant resin binding agent and ratio are changed into simultaneously: (ratio of composition is the composition of butadiene-styrene copolymer (SBR) and Xylo-Mucine (CMC), SBR:CMC=1:1), all the other are identical with embodiment 1.
Comparative example 3
This comparative example difference from Example 1 is: inorganic particulate is replaced by aluminum oxide, and all the other and embodiment 1 are together.
Above-mentioned prepared lithium-ion secondary cell by composite microporous film performance in table 1.
The performance synopsis of the composite diaphragm of table 1: embodiment and comparative example
Remarks:
1, heat-resistant resin kind: A: n-butyl acrylate/sodium acrylate/acrylic acid multipolymer; B: vinyl cyanide/N,N-DMAA/vinylformic acid; C:SBR/CMC.
2, test condition: 180 DEG C, 1.0 hours.
3, represent that test septation occurs curling, cannot measure.
4, unit: N/m.
For a person skilled in the art, can be according to technical scheme described above and design, make other various corresponding changes and distortion, and these all changes and distortion all should belong to the protection domain of the claims in the present invention within.

Claims (6)

1. for the coating composition of lithium ion secondary battery membrane, it contains heat-resistant resin and inorganic non-conductive insulating particle, it is characterized in that: the molecular chain of described heat-resistant resin comprises oleophylic structural unit, hydrophilic-structure unit and structure of functional groups unit, its heat decomposition temperature is greater than 250 DEG C; Oleophylic structural unit, hydrophilic-structure unit and structure of functional groups unit that heat-resistant resin molecular chain comprises are transformed by oleophylic monomer, hydrophilic monomer and monomer respectively, wherein, oleophylic monomer accounts for the 50-80% of oleophylic monomer, hydrophilic monomer and monomer's gross weight, the ratio of hydrophilic monomer accounts for the 20-50% of oleophylic monomer, hydrophilic monomer and monomer's gross weight, and monomer accounts for oleophylic monomer, hydrophilic monomer and below 10% of monomer's gross weight;
described inorganic non-conductive insulating particle has following performance perameter: thermotolerance is greater than 400 DEG C, and true density is less than 3g/cm 3 , knoop hardness is less than 600kgf/mm 2 , dry air 4.0h at 100 DEG C, per unit volume water content is less than 5mg/cm 3 ;
described inorganic non-conductive insulating particle is silicate compound;
described silicate compound is glass powder; Median size is 0.8-1.5 μ m, and pore size distribution is 0.1-2.2 μ m.
2. coating composition for lithium ion secondary battery membrane according to claim 1, is characterized in that: described oleophylic monomer is that carbonatoms is the acrylate of 4-20, and its glass transition temperature Tg is-70 DEG C～120 DEG C; Described hydrophilic monomer is the acrylate derivative of no more than 8 of carbonatoms, and it contains any one hydrophilic radical in carboxyl, hydroxyl or amide group; Described monomer is acrylate derivative, and it contains any one active function groups in acid anhydrides, carboxyl, epoxy group(ing), hydroxyl, amino or amide group.
3. coating composition for lithium ion secondary battery membrane according to claim 1, is characterized in that: inorganic non-conductive insulating particle accounts for the 60-95% of inorganic non-conductive insulating particle and heat-resistant resin gross weight.
4. the manufacture method of lithium ion secondary battery membrane, the method comprises: the coating fluid that comprises heat-resistant resin and inorganic non-conductive insulating particle at least one surface coated at the polyolefin-based end, drying forms thermotolerance coating after solidifying, and finally obtains composite microporous film; It is characterized in that: described coating fluid comprises the coating composition described in any one and solvent in claim 1-3.
5. the manufacture method of lithium ion secondary battery membrane according to claim 4, is characterized in that: the described polyolefin-based end is ultrahigh molecular weight polyethylene(UHMWPE) barrier film, and its surface is through photochemical treatment.
6. the manufacture method of lithium ion secondary battery membrane according to claim 4, is characterized in that: described thermotolerance coating is less than 30 to the contact angle of water droplet o ; The base adhesion force of described thermotolerance coating is greater than 120N/m, and force of cohesion is greater than 100N/m; The tensile strength of the MD of described composite microporous film and TD direction is all greater than 120MPa, in 150-180 DEG C of temperature range, heats 1 hour, and the percent thermal shrinkage of MD and TD direction remains within the scope of 1-5%.
CN201210476760.0A 2012-11-21 2012-11-21 Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane Active CN102942831B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201210476760.0A CN102942831B (en) 2012-11-21 2012-11-21 Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane
PCT/CN2013/072585 WO2014079177A1 (en) 2012-11-21 2013-03-14 Coating composition for lithium ion secondary battery separator and method for manufacturing the separator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210476760.0A CN102942831B (en) 2012-11-21 2012-11-21 Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane

Publications (2)

Publication Number Publication Date
CN102942831A CN102942831A (en) 2013-02-27
CN102942831B true CN102942831B (en) 2014-10-29

Family

ID=47725829

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210476760.0A Active CN102942831B (en) 2012-11-21 2012-11-21 Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane

Country Status (2)

Country Link
CN (1) CN102942831B (en)
WO (1) WO2014079177A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942831B (en) * 2012-11-21 2014-10-29 佛山市金辉高科光电材料有限公司 Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane
CN103811702B (en) * 2014-02-12 2016-02-10 佛山市金辉高科光电材料有限公司 A kind of new ceramics coating of polyolefins composite membrane and preparation method thereof
EP3163653B1 (en) * 2014-06-26 2024-01-03 Zeon Corporation Laminate for nonaqueous secondary cell, method for producing same, and nonaqueous secondary cell
CN106537643B (en) * 2014-07-11 2019-10-25 帝人株式会社 Membrane coil and non-aqueous secondary battery
CN108134036B (en) * 2014-12-16 2020-06-16 东莞新能源科技有限公司 Organic-inorganic composite electrolyte membrane, preparation method and application thereof
CN104868081A (en) * 2014-12-22 2015-08-26 上海恩捷新材料科技股份有限公司 Water-based multi-layer membrane for lithium ion battery
CN105789538A (en) * 2016-04-20 2016-07-20 宁德时代新能源科技股份有限公司 Separator, preparation method thereof and secondary battery containing separator
TWI624105B (en) * 2017-06-13 2018-05-11 中興應用材料科技股份有限公司 Fire-resistant and isolating composite film used in energy storage device and manufacture thereof
KR102477422B1 (en) * 2017-10-17 2022-12-14 에스케이아이이테크놀로지주식회사 Separator for secondary battery, method for manufacturing the same and lithium secondary battery containing the same
KR102414896B1 (en) * 2017-11-29 2022-07-01 에스케이이노베이션 주식회사 Composite separator for secondary battery and lithium secondary battery containing the same
CN110120485B (en) * 2018-02-06 2021-06-18 比亚迪股份有限公司 Polymer diaphragm and preparation method and application thereof, and lithium ion battery and preparation method thereof
CN109524601B (en) * 2018-10-16 2021-09-24 上海恩捷新材料科技有限公司 Power lithium ion battery diaphragm and preparation method thereof
KR20200065814A (en) * 2018-11-30 2020-06-09 삼성에스디아이 주식회사 Separator for rechargeable lithium battery and rechargeable lithium battery including the same
US20220094019A1 (en) 2019-01-04 2022-03-24 Ceigard, LLC Coated microporous membranes, and battery separators, batteries, vehicles, and devices comprising the same
CN112952289B (en) * 2021-01-27 2022-07-01 江苏厚生新能源科技有限公司 High-performance lithium ion battery diaphragm and preparation method thereof
CN113416270B (en) * 2021-05-31 2024-01-16 珠海辰玉新材料科技有限公司 Polymer and preparation method and application thereof
CN114231105A (en) * 2021-12-10 2022-03-25 河北金力新能源科技股份有限公司 Low-moisture high-insulation lithium ion battery diaphragm and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246958A (en) * 2008-03-21 2008-08-20 成都中科来方能源科技有限公司 Lithium ion battery and combination electrode used for the same and production method thereof
CN102394282A (en) * 2011-11-25 2012-03-28 佛山市金辉高科光电材料有限公司 Lithium ion secondary battery porous multilayer diaphragm and manufacture method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62262366A (en) * 1986-05-08 1987-11-14 Ejison Watanabe Lead storage battery
JP2689473B2 (en) * 1988-04-20 1997-12-10 松下電器産業株式会社 Hydrogen storage alloy electrode and its manufacturing method
CN102942831B (en) * 2012-11-21 2014-10-29 佛山市金辉高科光电材料有限公司 Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246958A (en) * 2008-03-21 2008-08-20 成都中科来方能源科技有限公司 Lithium ion battery and combination electrode used for the same and production method thereof
CN102394282A (en) * 2011-11-25 2012-03-28 佛山市金辉高科光电材料有限公司 Lithium ion secondary battery porous multilayer diaphragm and manufacture method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP平1-267960A 1989.10.25

Also Published As

Publication number Publication date
WO2014079177A1 (en) 2014-05-30
CN102942831A (en) 2013-02-27

Similar Documents

Publication Publication Date Title
CN102942831B (en) Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane
CN103811702B (en) A kind of new ceramics coating of polyolefins composite membrane and preparation method thereof
CN101226994B (en) Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof
CN101434708B (en) Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof
CN104521028B (en) For the improved diaphragm and correlation technique of lithium ion battery
CN103199209B (en) There is lithium ion battery nonwoven fabrics ceramic diaphragm and the technique of excellent closed pore performance
CN104979515B (en) Aramid fiber polymer coated lithium ion battery membrane and preparation method thereof
CN108281592A (en) A kind of heat safe composite battery separator film and preparation method thereof
CN105633326B (en) Aromatic polyamide composite diaphragm
CN106030858B (en) Non-aqueous secondary batteries perforated membrane adhesive, the porous film composition of non-aqueous secondary batteries, non-aqueous secondary batteries perforated membrane and non-aqueous secondary batteries
CN108305972A (en) A kind of ceramic-coated separator and preparation method and application
CN104638217A (en) Modified composite diaphragm and method for preparing diaphragm
CN106784534A (en) The preparation method of PVDF and its copolymer ceramic coating membrane
CN103474602B (en) A kind of lithium ion battery pore-creating ceramics barrier film and preparation method thereof
CN102148344B (en) Preparation method of lithium ion battery diaphragm
CN104766937B (en) A kind of environment-friendlylithium lithium ion battery membrane and preparation method thereof
CN109964338A (en) A kind of lithium ion battery multilayer complex functional diaphragm
CN105552285B (en) A kind of ceramic-coated separator and preparation method thereof and the application in lithium ion battery
CN103531736A (en) High-heat-resistance lithium-ion battery diaphragm and preparation method thereof
WO2013075524A1 (en) Porous multi-layer separating film for lithium ion secondary battery and method for manufacturing same
CN106898720B (en) Lithium ion battery diaphragm and preparation method thereof
CN104993084A (en) Biomass nanocrystal coated polyolefin lithium ion battery diaphragm and production method thereof
CN109509855A (en) A kind of aramid fiber ceramic diaphragm and its preparation method and application
CN108258171A (en) A kind of high-temperaure coating composite diaphragm and its preparation method and application
CN102651466A (en) High-safety ceramic composite lithium-ion isolating membrane and lithium battery thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Coating composite for lithium ion secondary battery membrane and method for manufacturing membrane

Effective date of registration: 20150630

Granted publication date: 20141029

Pledgee: Guangdong Guangxin Holdings Group Co. Ltd.

Pledgor: FOSHAN JINHUI HIGH-TECH OPTOELECTRONIC MATERIAL Co.,Ltd.

Registration number: 2015440000010

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20161202

Granted publication date: 20141029

Pledgee: Guangdong Guangxin Holdings Group Co. Ltd.

Pledgor: FOSHAN JINHUI HIGH-TECH OPTOELECTRONIC MATERIAL Co.,Ltd.

Registration number: 2015440000010

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
CP03 Change of name, title or address

Address after: Chancheng District of Guangdong city in Foshan province 528000 quarter of Huayi Road No. 28, a two building 17 layer (residence declaration)

Patentee after: Foshan Jinhui Gao Ke photoelectric material Limited by Share Ltd.

Address before: 528000 Chancheng City, Foshan Province Light District, No. three road, No. 7, No.

Patentee before: FOSHAN JINHUI HIGH-TECH OPTOELECTRONIC MATERIAL Co.,Ltd.

CP03 Change of name, title or address
TR01 Transfer of patent right

Effective date of registration: 20230109

Address after: 463000 industrial cluster area, Suiping County, Zhumadian City, Henan Province

Patentee after: HENAN HUIQIANG NEW ENERGY MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 528000 Guangdong, Foshan, Chancheng, Ji Hua Road 28, a two 17 story (residence declaration)

Patentee before: Foshan Jinhui Gao Ke photoelectric material Limited by Share Ltd.

TR01 Transfer of patent right