CN102942831A - 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
CN102942831A
CN102942831A CN2012104767600A CN201210476760A CN102942831A CN 102942831 A CN102942831 A CN 102942831A CN 2012104767600 A CN2012104767600 A CN 2012104767600A CN 201210476760 A CN201210476760 A CN 201210476760A CN 102942831 A CN102942831 A CN 102942831A
Authority
CN
China
Prior art keywords
ion secondary
lithium ion
secondary battery
coating
monomer
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.)
Granted
Application number
CN2012104767600A
Other languages
Chinese (zh)
Other versions
CN102942831B (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

Be used 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 simultaneously a kind of manufacture method of using the lithium ion secondary battery membrane of this coating composition.
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.Used diaphragm material great majority are polyolefine material in the market, mainly comprise polyethylene and polypropylene.
Because polyethylene and polyacrylic thermal characteristics difference, (Shut-down temperature) is relatively low for diaphragm current closing temperature take polyethylene as material produce, when overload occurs in battery, along with the microvoid structure of temperature rising barrier film inside is very fast destroyed and melting is closed, in time block electric current.Yet, weak point is that its melt fracture temperature (Melt-downtemperature) is also low, rising along with battery temperature, surpass about 15 ℃ of fusing points, barrier film is heated and breaks, cause the inside battery structural collapse and cause blast, so we wish that material has lower electric current blocking temperature and higher melt fracture temperature usually.And its raw material fusing point of the barrier film take polypropylene as material produce is higher, usually more than 160 ℃, has good high temperature resistant rupture of membranes performance, but its electric current closing temperature is also corresponding higher simultaneously, is 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 when trilamellar membrane raise in temperature, the PE at middle part shrank 130 ℃ of fusings and causes heat to close, but because outside PP temperature of fusion is 160 ℃, barrier film can also keep certain security.But three layers of barrier film do not solve the potential problem that fusing is shunk fully, and when temperature continued to raise, the PP film still can melt, and causes internal short-circuit of battery.
In order to improve the thermotolerance of barrier film, reduce the safety problems such as short circuit that the dividing plate thermal contraction causes, improve the reliability engineering of battery.Various barrier film manufacturing technology schemes take the non-woven fabrics of cheapness as base material have for example been proposed, publication number utilizes for the Chinese patent of " 101425570 " discloses that coating contains the refractory layer of mineral filler on the basis of weaving of thermal glass or stupalith manufacturing or non-woven fabrics, thereby finishes invention.Although the anodic aluminium oxide membrane of this patent manufacturing 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 take the 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, purpose provides a kind of high temperature resistant, barrier film of satisfying the high-multiplying-power battery requirement.Although yet the PET basement membrane has good thermotolerance, its fusing point is 256-265 ℃, 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 hereat is difficult to think such has reliable safety performance.
Summary of the invention
First purpose 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, adopt the secondary battery membrane of this coating composition preparation, not only have low closed pore temperature, high breaking temperature, have also simultaneously that percent thermal shrinkage is little, refractory coating and the characteristics such as the base material bonding force is high, the refractory coating surface wettability is good, the barrier film that is used as lithium-ion secondary cell has better over-all properties, has reliable safety performance.
Second purpose of the present invention is for a kind of manufacture method of lithium ion secondary battery membrane is provided.
First purpose 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, and its heat decomposition temperature is greater than 250 ℃; 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 comprises of described heat-resistant resin molecular chain, hydrophilic structural unit and structure of functional groups unit are transformed by oleophylic monomer, hydrophilic monomer and monomer respectively.
Preferably, the oleophylic monomer is that atomicity is the acrylate of 4-20, and its glass transition temperature Tg is-70 ℃～120 ℃.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 no more than 8 acrylate derivative of carbonatoms, and it contains at least a hydrophilic radical in carboxyl, hydroxyl or the amide group.Concrete being enumerated as is selected from following a kind of compound at least: 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, the monomer is the acrylate derivative of giving the tackiness agent response characteristic, and it contains one or more active function groups in acid anhydrides, carboxyl, epoxy group(ing), hydroxyl, amino or the 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 at the interior and synthetic heat-resistant resin of this proportional range and could satisfy requirement of the present invention.The effect that oleophylic unit, hydrophilic unit and functional group units are brought into play in the heat-resistant resin is different, but can produce synergistic effect.The oleophylic unit improves the interface interaction of refractory coating and non-polar polyolefinic substrate, gives simultaneously refractory coating good processing snappiness; Hydrophilic unit improves the interaction force between hydrophilic filler in the refractory coating, namely improves refractory coating force of cohesion; The chemically crosslinked effect can further occur in the functional monomer, improves refractory coating adhesive power, force of cohesion, thermotolerance, solvent resistance and electrochemical stability.Usually, for base adhesion force and the processing snappiness that improves refractory coating, can suitably improve the ratio of oleophylic unit in polymer molecular chain, more preferably the oleophylic monomer accounts for the 50-80% of oleophylic monomer, hydrophilic monomer and monomer's gross weight, and 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 the monomer often has strong polarity and the 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, account for oleophylic monomer, hydrophilic monomer and below 10% of monomer's gross weight, preferred accounting for below 5% so monomer's ratio is general.
Preferably, described inorganic non-conductive insulating particle has following performance perameter: thermotolerance is greater than 400 ℃, and true density is less than 3g/cm 3, knoop hardness is less than 600kgf/mm 2, 100 ℃ of lower dry air 4.0h, the per unit volume water content is less than 5mg/cm 3The characteristics 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 among the present invention refers to be stable at least greater than 400 ℃ under 400 ℃, quality change does not occur, and does not have 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, temperature rise rate with 10 ℃/min is heated to more than 400 ℃, quality change does not occur in inorganic non-conductive insulating particle, just can think 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 among the present invention is less than 3g/cm 3, be particularly limited for the density of inorganic non-conductive insulating particle, mainly be 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 the present invention makes of using.In the known refractory coating barrier film, aluminum oxide is widely used, and the true density of aluminum oxide is 3.9g/cm 3, namely the inorganic non-conductive insulating particle density among the present invention by comparison reduces more than 20%, can go out by theoretical calculate, and the inorganic non-conductive insulating particle of using among the present invention can reach the characteristics that improve the lithium-ion secondary cell energy density.
In addition, the knoop hardness of the inorganic non-conductive insulating particle among the present invention is less than 600kgf/mm 2, with respect to the alumina material of using in the known refractory coating barrier film, the lower hardness ratio surpasses 50%, the inorganic materials that the present invention uses is because hardness is low, can reduce that the refractory coating slurry is made and coating processing in wearing and tearing, and then work-ing life that can extension device, thereby by preferred.
In addition, the inorganic non-conductive insulating particle among the present invention has the low feature of water-intake rate, i.e. its dry 4.0h under 100 ℃ of lower air, and the per unit volume water content is less than 5mg/cm 3Regulation about eigen, mainly be to consider the hazardness of moisture in lithium-ion secondary cell, for example, reason owing to micro-moisture, ionogen in the lithium ion battery and steeping in water for reconstitution are given birth to reaction and are produced hydrogen fluoride gas, thereby cause the dangerous feature such as battery bulging, and hydrogen fluoride is dissolved in the electrolytic solution simultaneously, can reduce electrolyte ph, and then worsen battery performance.Therefore, in the battery manufacture process, moisture controlled is extremely important.Therefore, the water content of barrier film is to need strict control, preferably has the low inorganic non-conductive insulating particle of water-intake rate, and this point is particularly important.Inorganic non-conductive insulating particle among the present invention is dry 4.0h under 100 ℃ of lower air, and the per unit volume water content is less than 5mg/cm 3, more preferably be less than 1mg/cm 3, it is more few better that the above-mentioned water content of inorganic non-conductive insulating particle should say, most preferably is 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: the compounds natural or synthetic such as water glass, asbestos, feldspar, glass, cement, clay, peridotites, pistacite, tourmalinite, pyroxene, hornblende, mica, carclazyte, feldspar, quartz.
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 satisfy: 0.8≤D50≤1.5 μ m, 0.1≤D0, D100≤2.2 μ m.Wherein, more preferably median size satisfies: 0.8≤D50≤1.2 μ m, the inorganic non-conductive insulating particle of D100≤2.0 μ m.On the one hand, if less than 0.1 μ m, then when preparation refractory coating slurry, there is the problem of inorganic non-conductive insulating particle difficulties in dispersion in inorganic non-conductive insulating particle particle diameter, thereby affects the homogeneity of refractory coating; On the other hand, if then there is the uncontrollable anxiety of refractory coating thickness in inorganic non-conductive insulating particle particle diameter greater than 2.0 μ m, thereby cause using the deterioration of the battery performance of this barrier film.
After coating composition of the present invention disperseed, after solidifying, drying forms the thermotolerance coating in solvent; Wherein, inorganic non-conductive insulating particle accounts for the 60-95% of inorganic non-conductive insulating particle and heat-resistant resin gross weight.
Second purpose 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, after forming the thermotolerance coating after drying is solidified, finally obtain composite microporous film; Described coating fluid comprises the described coating composition of first purpose of the present invention and solvent.
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 may further comprise the steps:
1) copolymer emulsion with oleophylic monomer, hydrophilic monomer, monomer is dissolved in the solvent as the heat-resistant resin binding agent, preparation polymer bonding agent solution;
2) inorganic non-conductive insulating particle is joined in the above-mentioned polymer bonding agent solution, make coating fluid after disperseing;
3) scattered slurry is coated the single or double at the polyolefin-based end after, through the operation of dry solidification, and get final product.
Solvent is the solvent of good solvent with respect to heat-resistant resin preferably, namely uses the principle of similar compatibility to remove to seek suitable solvent, preferably has the solvent of similar polarity and solubility parameters to the heat-resistant resin binding agent.More preferably, this solvent has lower boiling characteristic simultaneously, is particularly conducive to like this dry solidification operation after the 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, preferably with the mixture of water and the ethanol solvent as the heat-resistant resin binding agent, more preferably separately with water as solvent.
The ratio of inorganic non-conductive insulating particle and heat-resistant resin binding agent can account for for inorganic non-conductive insulating particle the 60-95% of inorganic non-conductive insulating particle and heat-resistant resin binding agent gross weight, more preferably accounts for 75-95%.Solid content about the coating fluid (slurry) that includes heat-resistant resin binding agent and inorganic non-conductive insulating particle can be 10-50%, more preferably 20-45%.Dispersing apparatus about 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.Characteristics and requirement of the present invention for the wet type dispersion, the preferred method that adopts sand mill to disperse, this moment, suitable jitter time was 0.5-20 hour, after slurry disperses the size distribution of inorganic non-conductive insulating particle in 0.1～2.2 mu m range that meets claim of 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.Can adopt above one or more array configuration to be coated with among the present invention, as long as can realize slurry evenly coating on the polyethylene base material, be not particularly limited.
Preferably, the described polyolefin-based end is the ultrahigh molecular weight polyethylene(UHMWPE) barrier film, and its surface is through photochemical treatment.The described polyolefin-based end, in general, can adopt three layers of barrier film of polypropylene diaphragm, PP/PE/PP of dry process or the polyethylene barrier film of wet processing preparation, the present invention preferably adopts the polyethylene barrier film of wet processing preparation pore distribution is even because the wet method barrier film has, hole size evenly, even thickness, porosity and Gas permeability is good, puncture intensity and biaxial tensile strength advantages of higher.Preferred, the present invention adopts the ultrahigh molecular weight polyethylene(UHMWPE) barrier film of wet processing preparation, and this barrier film possesses outside all advantages of wet method barrier film, further improves on intensity and thermotolerance especially.
In addition, thickness and the porosity of the ultrahigh molecular weight polyethylene(UHMWPE) barrier film that adopts 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 carry out flexible choice according to the needs of composite microporous film of the present invention.
In addition, the ultrahigh molecular weight polyethylene(UHMWPE) substrate among the present invention, the 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 the polyolefin film printing, carry out chemistry or physical method and process, make its upper layer that forms polarity with the binding strength of raising with polarity printing ink.Usually, the 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 among the present invention is improved surface tension thereby reach, and improves wettability and fusible purpose.For example, using photosensitizers benzophenone pre-treatment polyethylene surface, is the uviolizing polyethylene surface of 184mm with wavelength, and it is crosslinked that its surface is occured, and benzophenone also can be sublimated and remove noresidue afterwards.
Composite microporous film of the present invention, its thermotolerance coating to the contact angle of water droplet less than 30 °.Contact angle is that a kind of of degree of wetting measures, 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, as can be known, the thermotolerance coating has excellent close electrolytic solution wettability equally.The electrolytic solution wettability that barrier film is good then can enlarge the contact area of barrier film and electrolytic solution, thereby increases ionic conductivity, improves charge-discharge performance and the capacity of battery.Testing method for the water droplet contact angle of refractory coating, can be enumerated as: deionized water is dropped in the refractory coating surface, then with the contact angle measurement test contact angle of water droplet is tested, can take to test many group panel datas, the method of averaging at last, thus refractory coating obtained to the contact angle of water droplet.
The base adhesion force of the thermotolerance coating among the present invention (sticking power between refractory coating and the base material) is greater than 120N/m, and force of cohesion (reactive force between the refractory coating molecule) is greater than 100N/m.Usually, if the thermotolerance coating can't form reliable bonding in the polyalkene diaphragm substrate, then in battery manufacturing procedure, barrier film dry linting problem can occur, cause the generation of defective products, such refractory layer can't 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 can be avoided the generation of the problems referred to above all greater than 100N/m.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 degree peeling strength test machines.
The tensile strength of the MD of composite microporous film of the present invention and TD direction, heated 1 hour in the 150-180 ℃ of temperature range all greater than 120MPa, and the percent thermal shrinkage of MD and TD direction remains in the 1-5% scope.Known, the barrier film of wet processing manufacturing has intensity significantly better than the characteristics of dry method, and TD and MD tensile strength are more even, is 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, further improve on intensity and thermotolerance especially, the tensile strength of therefore having given the MD of composite microporous film of the present invention and TD direction is all greater than the feature of 120MPa.
Composite microporous film has in 150-180 ℃ of temperature range, heated 1 hour, the percent thermal shrinkage of MD and TD direction remains on the notable feature in the 1-5% scope, 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 short circuit has occured, short-circuited region can not continue to enlarge yet, thereby has guaranteed 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 ℃.The characteristics such as that described mineral filler has is high temperature resistant, density is little, hardness is low and water-intake rate is low, because the single or double in the substrate of composite microporous film has adhered to the coating that is formed by coating composition of the present invention, so that this composite microporous film not only has low closed pore temperature, high breaking temperature, its percent thermal shrinkage is little simultaneously, the characteristics such as refractory coating and base material bonding force are high, the refractory coating surface wettability is good, barrier film as lithium-ion secondary cell has better over-all properties, has reliable safety performance, and the 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 (such 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, adsorption theory according to one of cementation theory, there are all problems of adhere firmly in the above of at present known printing ink and tackiness agent, so usually, the thermotolerance coating also exists can't form in the polyalkene diaphragm substrate problem of reliable bonding, and then can cause refractory layer can't effectively bring into play the effect that suppresses thermal contraction.And thermotolerance coating base adhesion force of the present invention and force of cohesion can be avoided the generation of the problems referred to above all greater than 100N/m, 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 to the contact angle of water droplet less than 30 °, so that the thermotolerance coating has excellent close electrolytic solution wettability, the electrolytic solution wettability that barrier film is good, then can enlarge the contact area of barrier film and electrolytic solution, thereby the 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 ℃ of temperature range, heated 1 hour, the percent thermal shrinkage of MD and TD direction remains in the 1-5% scope, have excellent intensity and resistance toheat, can not cause the generation of internal short-circuit of battery.Even short circuit has occured, short-circuited region can not continue to enlarge yet, thereby has guaranteed the safety performance of battery.And TD and MD tensile strength are more even, are conducive to like this improve the safety performance of battery.
Embodiment
For the content among the present invention better is described, be described further below in conjunction with specific embodiment.
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) is the heat-resistant resin binding agent, as solvent, dissolving disperseed 1 hour under the room temperature with water.Then the ratio in 80 parts of glass powder (median size is 0.8 μ m), 20 parts of above-mentioned heat-resistant resin binder solutions joins in 100 parts of deionized waters, then passes through the sand mill dispersing and mixing 3 hours, thereby makes coating fluid.
The above-mentioned coating fluid that makes is coated in the line rod on two surfaces of ultrahigh molecular weight polyethylene(UHMWPE) basement membrane (be called for short UHMWPE, lower with) of 20 μ m, then carries out drying in blast dry oven, drying temperature is 50 ℃.Making the coated on both sides total thickness is that 6 μ m(are respectively 3 μ m) composite microporous film.
Above-mentioned prepared lithium-ion secondary cell sees Table 1 with the composite microporous film performance.
Embodiment 2
The difference of present embodiment and embodiment 1 is: the coating fluid that embodiment 1 makes is coated on the surface of UHMWPE basement membrane, then at 50 ℃ baking oven inner drying and get.Make the composite microporous film that the single face coat-thickness is 6 μ m.
Above-mentioned prepared lithium-ion secondary cell sees Table 1 with the composite microporous film performance.
Embodiment 3
The difference of 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 sees Table 1 with the composite microporous film performance.
Embodiment 4
The difference of present embodiment and embodiment 1 is: the ratio of component in the 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 sees Table 1 with the composite microporous film performance.
Embodiment 5
The difference of present embodiment and embodiment 1 is: kind and the ratio of heat-resistant resin binding agent 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, the N-DMAA: vinylformic acid=10:9:1), all the other are identical with embodiment 1.
Above-mentioned prepared lithium-ion secondary cell sees Table 1 with the composite microporous film performance.
Comparative Examples 1
The UHMWPE barrier film of selecting uncoated refractory coating as a comparison case 1.
The UHMWPE membrane properties sees Table 1.
Comparative Examples 2
This Comparative Examples is with the difference of embodiment 1: kind and the ratio of heat-resistant resin binding agent 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 Examples 3
This Comparative Examples 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 sees Table 1 with the composite microporous film performance.
The performance synopsis of the composite diaphragm of table 1: embodiment and Comparative Examples
Figure BDA00002444046900151
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 ℃, 1.0 hours.
3, the generation of expression test septation is curling, can't measure.
4, unit: N/m.
For a person skilled in the art, can make other various corresponding changes and distortion according to technical scheme described above and design, and these all changes and distortion should belong within the protection domain of claim of the present invention all.

Claims (10)

1. the coating composition that is used for 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, and its heat decomposition temperature is greater than 250 ℃; Wherein, the weight ratio of oleophylic structural unit, hydrophilic-structure unit and structure of functional groups unit is 10～90:80～9:10～1.
2. the coating composition for lithium ion secondary battery membrane according to claim 1, it is characterized in that: described inorganic non-conductive insulating particle has following performance perameter: thermotolerance is greater than 400 ℃, and true density is less than 3g/cm 3, knoop hardness is less than 600kgf/mm 2, 100 ℃ of lower dry air 4.0h, the per unit volume water content is less than 5mg/cm 3
3. the coating composition for lithium ion secondary battery membrane according to claim 1 and 2, it is characterized in that: the oleophylic structural unit that the heat-resistant resin molecular chain comprises, hydrophilic-structure unit and structure of functional groups unit are transformed by oleophylic monomer, hydrophilic monomer and monomer respectively, wherein, oleophylic monomer, hydrophilic monomer and monomer's weight ratio is 10～90:80～9:10～1.
4. the coating composition for lithium ion secondary battery membrane according to claim 3, it is characterized in that: described oleophylic monomer is that carbonatoms is the acrylate of 4-20, and its glass transition temperature Tg is-70 ℃～120 ℃; Described hydrophilic monomer is no more than 8 acrylate derivative of carbonatoms, and it contains any one hydrophilic radical in carboxyl, hydroxyl or the 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 the amide group.
5. the coating composition for lithium ion secondary battery membrane according to claim 2, it is characterized in that: described inorganic non-conductive insulating particle is silicate compound.
6. the coating composition that is used for lithium ion secondary battery membrane of stating according to claim 5, it is characterized in that: described inorganic non-conductive insulating particle is glass powder; Median size is 0.8-1.5 μ m, and pore size distribution is 0.1-2.2 μ m.
7. the coating composition that is used for lithium ion secondary battery membrane of stating according to claim 1, it 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.
8. 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, form the thermotolerance coating after drying is solidified, finally obtain composite microporous film; It is characterized in that: described coating fluid comprises each described coating composition and solvent among the claim 1-7.
9. the manufacture method of lithium ion secondary battery membrane according to claim 8, it is characterized in that: the described polyolefin-based end is the ultrahigh molecular weight polyethylene(UHMWPE) barrier film, its surface is through photochemical treatment.
10. the manufacture method of lithium ion secondary battery membrane according to claim 8 is characterized in that: described thermotolerance coating to the contact angle of water droplet less than 30 oThe 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, heated 1 hour in 150-180 ℃ of temperature range all greater than 120MPa, and the percent thermal shrinkage of MD and TD direction remains in the 1-5% scope.
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 true CN102942831A (en) 2013-02-27
CN102942831B 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)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811702A (en) * 2014-02-12 2014-05-21 佛山市金辉高科光电材料有限公司 Novel ceramic coating polyolefin composite film and preparation method thereof
WO2014079177A1 (en) * 2012-11-21 2014-05-30 佛山市金辉高科光电材料有限公司 Coating composition for lithium ion secondary battery separator and method for manufacturing the separator
CN104505484A (en) * 2014-12-16 2015-04-08 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
CN106537643A (en) * 2014-07-11 2017-03-22 帝人株式会社 Separator roll and nonaqueous secondary battery
CN109082883A (en) * 2017-06-13 2018-12-25 中兴应用材料科技股份有限公司 Fireproof insulating composite film and manufacturing method thereof
CN109524601A (en) * 2018-10-16 2019-03-26 上海恩捷新材料科技有限公司 A kind of diaphragm of power lithium ion battery and preparation method thereof
CN109671893A (en) * 2017-10-17 2019-04-23 Sk新技术株式会社 For the diaphragm of secondary cell, its manufacturing method and including its lithium secondary battery
CN109841784A (en) * 2017-11-29 2019-06-04 Sk新技术株式会社 Composite diaphragm for secondary cell and the lithium secondary battery including it
WO2020142702A1 (en) 2019-01-04 2020-07-09 Celgard, Llc Battery separators that include a microporous membrane and a coating.
CN112952289A (en) * 2021-01-27 2021-06-11 江苏厚生新能源科技有限公司 High-performance lithium ion battery diaphragm and preparation method thereof
CN113416270A (en) * 2021-05-31 2021-09-21 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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102408243B1 (en) * 2014-06-26 2022-06-13 니폰 제온 가부시키가이샤 Laminate for nonaqueous secondary cell, method for producing same, and nonaqueous secondary cell
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
KR20200065814A (en) * 2018-11-30 2020-06-09 삼성에스디아이 주식회사 Separator for rechargeable lithium battery and rechargeable lithium battery including the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01267960A (en) * 1988-04-20 1989-10-25 Matsushita Electric Ind Co Ltd Hydrogen absorption alloy electrode and its manufacture
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 (2)

* 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
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01267960A (en) * 1988-04-20 1989-10-25 Matsushita Electric Ind Co Ltd Hydrogen absorption alloy electrode and its manufacture
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

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014079177A1 (en) * 2012-11-21 2014-05-30 佛山市金辉高科光电材料有限公司 Coating composition for lithium ion secondary battery separator and method for manufacturing the separator
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
CN103811702A (en) * 2014-02-12 2014-05-21 佛山市金辉高科光电材料有限公司 Novel ceramic coating polyolefin composite film and preparation method thereof
CN106537643A (en) * 2014-07-11 2017-03-22 帝人株式会社 Separator roll and nonaqueous secondary battery
CN106537643B (en) * 2014-07-11 2019-10-25 帝人株式会社 Membrane coil and non-aqueous secondary battery
CN104505484A (en) * 2014-12-16 2015-04-08 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
CN109082883A (en) * 2017-06-13 2018-12-25 中兴应用材料科技股份有限公司 Fireproof insulating composite film and manufacturing method thereof
CN109671893A (en) * 2017-10-17 2019-04-23 Sk新技术株式会社 For the diaphragm of secondary cell, its manufacturing method and including its lithium secondary battery
CN109841784B (en) * 2017-11-29 2023-03-10 Sk新技术株式会社 Composite separator for secondary battery and lithium secondary battery including the same
CN109841784A (en) * 2017-11-29 2019-06-04 Sk新技术株式会社 Composite diaphragm for secondary cell and the lithium secondary battery including it
CN109524601A (en) * 2018-10-16 2019-03-26 上海恩捷新材料科技有限公司 A kind of diaphragm of power lithium ion battery and preparation method thereof
WO2020142702A1 (en) 2019-01-04 2020-07-09 Celgard, Llc Battery separators that include a microporous membrane and a coating.
CN112952289A (en) * 2021-01-27 2021-06-11 江苏厚生新能源科技有限公司 High-performance lithium ion battery diaphragm and preparation method thereof
CN113416270A (en) * 2021-05-31 2021-09-21 珠海辰玉新材料科技有限公司 Polymer and preparation method and application 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

Also Published As

Publication number Publication date
WO2014079177A1 (en) 2014-05-30
CN102942831B (en) 2014-10-29

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
CN106252565B (en) A kind of lithium ion battery separator and preparation method thereof of composite coated processing
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
JP6872932B2 (en) Separator for power storage device
CN108281592A (en) A kind of heat safe composite battery separator film and preparation method thereof
CN106784534A (en) The preparation method of PVDF and its copolymer ceramic coating membrane
CN105633326B (en) Aromatic polyamide composite diaphragm
JP6739320B2 (en) Storage device separator
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
WO2012165580A1 (en) Multilayer porous film, separator for batteries, and battery
CN108305972A (en) A kind of ceramic-coated separator and preparation method and application
CN104638217A (en) Modified composite diaphragm and method for preparing diaphragm
CN104183805B (en) A kind of preparation method of ceramic-coated separator
CN102148344B (en) Preparation method of lithium ion battery diaphragm
WO2013075524A1 (en) Porous multi-layer separating film for lithium ion secondary battery and method for manufacturing same
CN105552285B (en) A kind of ceramic-coated separator and preparation method thereof and the application in lithium ion battery
CN106898720B (en) Lithium ion battery diaphragm and preparation method thereof
CN104993084A (en) Biomass nanocrystal coated polyolefin lithium ion battery diaphragm and production method thereof
WO2022114228A1 (en) Separator for power storage device, and power storage device including same
CN109509855A (en) A kind of aramid fiber ceramic diaphragm and its preparation method and application
WO2021042928A1 (en) Polymer battery diaphragm having interpenetrating network structure, and preparation method therefor
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
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.

TR01 Transfer of patent right
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.