CN101226994B - Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof - Google Patents

Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof Download PDF

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Publication number
CN101226994B
CN101226994B CN2008103001481A CN200810300148A CN101226994B CN 101226994 B CN101226994 B CN 101226994B CN 2008103001481 A CN2008103001481 A CN 2008103001481A CN 200810300148 A CN200810300148 A CN 200810300148A CN 101226994 B CN101226994 B CN 101226994B
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polymer
woven cloth
diaphragm
preparation
cloth increasing
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CN101226994A (en
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潘中来
邓正华
王璐
王凯
邓佳闽
李仁贵
杜鸿昌
高建东
索继栓
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Sichuan Technology Co., Ltd.
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CHENGDU ZHONGKE LAIFANG ENERGY TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/43—Acrylonitrile series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4309—Polyvinyl alcohol
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0218—Vinyl resin fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0245—Acrylic resin fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0254—Polyolefin fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0263—Polyamide fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/02—Dispersion
    • D06N2205/023—Emulsion, aqueous dispersion, latex
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/141—Hydrophilic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
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    • D06N2209/14—Properties of the materials having chemical properties
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    • D—TEXTILES; PAPER
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    • D06N2209/00—Properties of the materials
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    • D06N2209/1621—Water-soluble, water-dispersible
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a non-woven fabric enhanced micropore polymer diaphragm material for a non aqueous electrolyte battery energy accumulator and a method for preparation, which belongs to the manufacturing field of non aqueous electrolyte energy accumulators which are a battery and a capacitor. The non-woven fabric enhanced micropore polymer diaphragm is characterized in that the diaphragm comprises polymeric colloid emulsion which are copolymerized by 100 parts of water-soluble polymer, 30-500 parts of hydrophobic monomer, 0-200 parts of hydrophilic monomer and 1-5 parts of initiator. According to the 100 percent of the content of solids in polymer colloid emulsion, 0-100 percent of inorganic filler and 20-100 percent of plasticizer are added, obtained slurry is coated on the two surfaces of the non-woven fabric, and the non-woven fabric enhanced micropore polymer film is dried and obtained. The diaphragm has excellent heat resistance, excellent mechanical strength and low produce cost, is applied for a maintaining power, has higher safety and long cycle service life, and is friendly to the environment.

Description

Non-woven cloth increasing micropore polymer diaphragm and its production and use
Technical field
The present invention relates to be used for diaphragm material of energy storage device such as nonaqueous electrolyte battery and preparation method thereof, belong to energy storage devices such as battery, capacitor and make the field.
Background technology
Micropore polymer diaphragm is to make nonaqueous electrolyte energy storage device such as lithium ion battery, lithium metal secondary battery, one of three big materials that ultracapacitor etc. are indispensable, it should keep ionic conduction again the inside battery positive and negative electrode to be spaced from each other in energy storage device, so the employed material behavior of microporous polymer membranes, microcellular structure, physicochemical property are closely related to electrical property, fail safe and the cycle life of lithium ion battery.The used barrier film of commercial nonaqueous electrolyte energy storage device mainly is microporous polyolefin film, micropore polyvinylidene fluoride film and micropore polyolefin/poly-vinylidene-fluoride composite film.
Microporous polyolefin film comprises that polyethylene/polypropylene/polyethylene propylene composite membrane is to adopt machine two-way stretching (dry method) and the manufacturing of solvent extraction (wet method) technology.Because polyolefin belongs to non-polar material, the polar organic solvent compatibility of it and electrolyte solution is poor, in battery, only play both positive and negative polarity room machine buffer action, and electrolyte is not had affinity interaction, make electrolyte solution be present in the battery with free state, battery charging and discharging recycle in the process this free electrolyte inevitably with positive and negative pole material generation redox side reaction, electrolyte in the consuming cells, cause the battery lean solution, thereby make battery polarization increase, easily make lithium ion be reduced into lithium metal and produce the lithium depositing crystalline to generate Li dendrite, cause the barrier film diapirism.Dried district and Li dendrite that the battery lean solution produces easily make inside battery generation electrostatic breakdown and positive and negative direct short-circuit phenomenon, thereby cause lithium ion battery burning, explosion safety problem.The potential safety hazard of lithium ion battery has restricted its development space in big capacity, high-power power type application of power.
Kynoar (PVDF) and derivative thereof only just have film forming in the presence of plasticizer.The pvdf membrane that contains plasticizer is big from adhesive, and mechanical strength is low, and the technology poor operability can't be prepared into microporous polymer membranes separately.The preparation method of this class microporous polymer membranes adopts substantially the pvdf membrane of plasticizer-containing and battery plus-negative plate pole piece is made dried electric core by heat bonding, with an organic solvent extracts then, forms and the compound PVDF microporous polymer membranes of both positive and negative polarity.In order to solve PVDF microporous polymer membrane preparation technology difficult point, make it as the independent film forming of microporous polyolefin film, improve the operability that battery is made, PVDF solution is coated on the microporous polyolefin film, adopts solvent extraction or paraphase film forming legal system to be equipped with micropore polyolefin/poly-vinylidene-fluoride composite film then.
The major defect that microporous polyolefin film, micropore polyvinylidene fluoride film, micropore polyolefin/poly-vinylidene-fluoride composite film exist is that its thermal endurance is lower; when internal temperature of battery in case above 150 ℃; although polyolefin substrate produces fusing, micropore disappears; the both so-called fuse protection effect of blocking-up ionic conduction; but when owing to microporous polymer membranes fusing taking place; must be accompanied by and produce a large amount of volume contractions; membrane area shrinks and diminishes; thereby make inside battery might take place positive and negative between direct short-circuit, cause the battery security problem as phenomenons such as burning, blasts.
In order to overcome micropore polyolefin film heat resistance problem, be reduced in the shrinkage of high-temperature condition lower diaphragm plate, improve the fail safe of battery, the Degussa of Germany is that supporter has prepared inorganic ceramic perforated membrane (CN1735983A) with the high polymer non woven fabric, this non woven fabric support membrane has adopted a large amount of inorganic fillers, and these fillers are compound on the non woven fabric by the silane adhesive.This inoranic membrane can improve the thermal endurance of barrier film, reduces the shrinkage of high-temperature condition lower diaphragm plate.But this complex method is in diaphragm drying and use, because vibration, crooked, folding inevitably the dry linting phenomenon can occur, cause the diaphragm coating uneven, during battery charging and discharging, because the CURRENT DISTRIBUTION inequality, local voltage raises, and may cause the electric current punch-through.
In a word, press at present a kind of be used for lithium ion battery, lithium metal battery under higher temperature, should guarantee that barrier film has blocking effect to ionic conduction, and bigger variation does not take place in diaphragm size simultaneously, to guarantee that battery plus-negative plate has the good isolation effect each other, guarantee the fail safe of battery, have cheap microporous polymer membranes simultaneously again concurrently.
Show in the present inventor's research work (ZL01133737.0) in the past, adopt acrylonitrile monemer synthetic polyacrylonitrile colloid emulsion in EVA (ethylene-vinyl acetate copolymer) toluene solution, behind this polymeric colloid emulsion casting film-forming, can obtain the microporous polymer membranes that keeps the cohesion of polyacrylonitrile colloidal particle to constitute.This film (greater than 150 ℃) under higher temperature still can keep more stable physical dimension, bigger volume and area can not take place shrink.In addition, the polymer dielectric film that forms behind the absorbed electrolyte solution is in 70～90 ℃ of scopes of temperature, the fusion of EVA component, and ionic conduction capable of blocking makes it to become the dielectric film of no ionic conductance.Use the lithium ion battery of this film production to have excellent security reliability.In addition, since microporous polymer membranes in cyano group (CN) and ester group (COO-) electrolyte solution is had good compatibility, prepared lithium ion battery has good battery charging and discharging and cycle life.High security that this film had and good battery performance be owing to the specified particle microcellular structure of this film, chemical composition and character.But this film be with EVA as the binding agent between the polyacrylonitrile colloidal particle because EVA thermal softening temperature and mechanical strength are low, so the mechanical strength of this film is lower, makes at battery to have bigger difficulty on the operating procedure.In addition, use toluene as reaction medium in the synthetic preparation of polyacrylonitrile colloid, in film forming procedure, have bigger problem of environmental pollution.
The present inventor on ZL01133737.0 improvement basis, a large amount of evidences, the polymer that changes film is formed the polymer latex precursor emulsion that also can synthesize the polar monomer that comprises acrylonitrile in aqueous medium.Microporous polymer membranes by this waterborne polymeric colloid emulsion preparation keeps the advantage of the polyacrylonitrile microporous polymer membranes that is prepared by toluene solvant except continuing, and has also improved the softening point temperature and the mechanical strength of microporous polymer membranes.As reaction medium, not having problem of environmental pollution with water in film-forming process, is a kind of production Technology of preparation microporous polymer membranes of clean environment firendly.Owing to contain hydrophilic radical in this microporous polymer membranes, this film is relatively more responsive to the ambient humidity influence.Under higher air humidity, the size of film can change to some extent, and this preparation to battery brings the difficulty of technology controlling and process.
Summary of the invention
First technical problem to be solved by this invention provides a kind of with the barrier film that be applicable to energy storage devices such as lithium ion battery, lithium metal secondary battery and ultracapacitor of nonaqueous electrolyte as the ionic conduction medium, i.e. non-woven cloth increasing micropore polymer film.This barrier film is on the microporous polymer membranes basis of ZL01133737.0 and the preparation of waterborne polymeric colloid emulsion, solved the defective of its existence, for energy storage devices such as lithium ion battery, lithium metal secondary battery, ultracapacitor provide a kind of have high-fire resistance more, higher mechanical strength and cheap microporous polymer membranes, this film is applied to energy storage device, has higher fail safe and longer recycles the life-span.
Technical scheme of the present invention:
Non-woven cloth increasing micropore polymer diaphragm provided by the invention is by 100 parts of water-soluble polymers, 30～500 parts of hydrophobic monomers, 0～200 part of hydrophilic monomer, 1～5 part of combined polymerization of initator obtains the polymer latex precursor emulsion, by polymer latex precursor emulsion solid content in 100%, the inorganic filler of adding 0～100% and 20～100% plasticizer, it is two-sided that the gained slurry is coated in nonwoven fabrics, and drying obtains the non-woven cloth increasing micropore polymer film.
Wherein, described nonwoven fabrics is selected from a kind of in the nonwoven fabrics that polyacrylonitrile, nylon, formal polyvinyl alcohol, polyester such as polyethylene terephthalate (PET), polyolefine fiber make.
Wherein, described water-soluble polymer is polyvinyl alcohol, polyethylene glycol oxide, PVP or PVP water solubility copolymer; Wherein, the polyvinyl alcohol degree of polymerization is 1700～2400, degree of hydrolysis 50～99; Polyethylene glycol oxide molecular weight 100,000 to 2,000,000; PVP or its water solubility copolymer molecular weight are 500 to 100,000, preferred 1～30,000.
Described hydrophobic monomer structural formula is: CH 2=CR 1R 2, wherein,
R 1=-H or-CH 3
R 2＝-C 6H 5、-OCOCH 3、-COOCH 3、-COOCH 2CH 3、-COOCH 2CH 2CH 2CH 3、-COOCH 2CH(CH 2CH 3)CH 2CH 2CH 2CH 3、-CN。Hydrophobic monomer is at least a in the above-mentioned hydrophobic monomer;
Described hydrophilic monomer structural formula is: CHR 3=CR 4R 5, wherein,
R 3=-H ,-CH 3Or-COOLi;
R 4=-H ,-CH 3Or-COOLi;
R 5＝-COOLi、-CH 2COOLi、-COO(CH 2) 6SO 3Li、-CONH 2、-CONHCH 3、
Figure G200810300148120080118D000031
-CONHCH 2CH 3、-CON(CH 3) 2、-CON(CH 2CH 3) 2。Hydrophilic monomer is at least a in the above-mentioned hydrophilic monomer;
Described initator is ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide or azo two NSC 18620s, or they and Na 2SO 3, FeSO 4The redox initiation system that constitutes.
Described plasticizer is at least a in propylene glycol, phenmethylol, n-butanol, isopropyl alcohol, diethyl phosphate, triethyl phosphate, trimethyl phosphate or the tributyl phosphate.
In order to improve the microporous polymer thermal endurance, the rigidity of porosity and film can add inorganic filler in the waterborne polymeric colloid emulsion.Superfine powder is adopted in inorganic filler usually, has higher specific surface area and stronger surface adsorption ability, helps the absorption of electrolyte and increases the disassociation of electrolytic salt and improve the ionic conductivity of film thus.Described inorganic filler is fume colloidal silica, alundum (Al, titanium dioxide, zirconium dioxide, magnesium oxide, calcium carbonate or glass fibre.
In order to improve the dispersiveness of inorganic filler in the polymer latex precursor emulsion, can add silane coupler, coupling agent can be 3-aminopropyltriethoxywerene werene, 2-amino-ethyl-3-aminocarbonyl propyl trimethoxy silane, 3-glycidyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyl three (2-methoxy (ethoxy)) base silane, and the addition of silane coupler is 0.5～5.0% of an inorganic filler weight.
In order to strengthen the purpose of non-woven cloth increasing micropore polymer membrane safety, can also add organic filler to strengthen the ionic conduction blocking characteristics of barrier film, battery operated temperature control make the battery of non-woven cloth increasing micropore polymer film continue to flow with the blocking-up cation, in case can be guaranteed the fail safe of battery 100～130 ℃ of scopes.Described organic filler is selected from least a in polyethylene powder, Tissuemat E powder, the OPE powder.In polymer latex precursor emulsion solid content is 100%, and the addition of organic filler is 5.0～20%.
Another one technical problem to be solved by this invention provides a kind of environment amenable non-woven cloth increasing micropore polymer membrane preparation technology, also can reduce the production cost of microporous polymer simultaneously, for the manufacturing of nonaqueous electrolyte energy storage device provides cheap at a low price, the microporous polymer membranes of excellent performance.
The method of the above-mentioned non-woven cloth increasing micropore polymer diaphragm of preparation provided by the invention may further comprise the steps:
The preparation of a, polymer latex precursor emulsion
With water-soluble polymer or (with) hydrophilic monomer and auxiliary agent add water, adds thermal agitation up to dissolving fully; Temperature of reactor is constant in desired reaction temperature 30-90 ℃, with hydrophobic monomer adopt once, the mode of gradation or dropping adds in the reactor, adds the initator polymerization reaction 4-35 hour, obtains the polymer latex precursor emulsion; Initator also can drip in course of reaction or gradation adds.
Also can add the effect that the auxiliary agent that is no more than 3 weight portions serves as emulsifying agent in the reaction, colloid emulsion is played certain stabilization.Described auxiliary agent is selected from dodecane sulfonate, dodecyl benzene sulfonate, vinylsulfonate.
The preparation of b, polymeric colloid slurry
By solid content 100%, add 0～100% inorganic filler and 20～100% plasticizer in the polymer latex precursor emulsion in the polymer latex precursor emulsion, dispersed with stirring is even, mills preferred 3～5 hours 2～10 hours.Slurry after milling again by＜200 purpose screen filtrations to remove the material of not fine ground larger particles.
The preparation of c, non-woven cloth increasing micropore polymer diaphragm
It is two-sided to use coating equipment evenly to be coated in nonwoven fabrics in the polymeric colloid slurry of above-mentioned preparation, is drying to obtain the non-woven cloth increasing micropore polymer film; Described nonwoven fabrics is selected from a kind of in the nonwoven fabrics that polyacrylonitrile, nylon, formal polyvinyl alcohol, polyester such as polyethylene terephthalate (PET), polyolefine fiber make.Wherein the nonwoven thickness of Cai Yonging is less than 50 μ m, and porosity is greater than 40%, and is preferred 50～70%, aperture size: 5～200 μ m, preferred 8～100 μ m.The area weight of nonwoven fabrics is less than 25g/m 2, preferred 10～20g/m 2
In order to improve the dispersiveness of inorganic filler in the polymer latex precursor emulsion, can add silane coupler, coupling agent can be 3-aminopropyltriethoxywerene werene, 2-amino-ethyl-3-aminocarbonyl propyl trimethoxy silane, 3-glycidyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyl three (2-methoxy (ethoxy)) base silane, and the addition of silane coupler is 0.5～5.0% of an inorganic filler weight.
In order to strengthen the purpose of non-woven cloth increasing micropore polymer membrane safety, can also add the ionic conduction blocking characteristics of organic filler-reinforced barrier film, battery operated temperature control make the battery of non-woven cloth increasing micropore polymer film continue to flow with the blocking-up cation, in case can be guaranteed the fail safe of battery 100～130 ℃ of scopes.Described organic filler is selected from least a in polyethylene powder, Tissuemat E powder, the OPE powder.
Further, the 3rd technical problem to be solved of the present invention provides the application of non-woven cloth increasing micropore polymer diaphragm in preparation lithium ion battery, ultracapacitor, battery/super electric capacity energy storage means.
The micropore polymer diaphragm that nonwoven fabrics provided by the invention strengthens adopt contain strong polar group (as-CN-,-COO-,-NH 2,-O-etc.) macromolecular compound is a material of main part, this material and nonaqueous electrolyte have good intermiscibility, can form polymer sol, simultaneously, the super solvent of its polar group and nonaqueous electrolyte can form the chemical association effect, make the electrolyte in the battery be solid-state properties, and can make barrier film keep good moisture state.Nonwoven fabrics strengthens the intensity of barrier film in microporous polymer membranes, increase flexibility, improves thermal endurance, reduces the influence that ambient humidity is changed diaphragm size because of the hydrophilic polymer component, improves the cell making process reliability and stability.The microporous polymer membranes that nonwoven fabrics therefore of the present invention strengthens has the operability of battery manufacturing preferably as the lithium ion battery with nonaqueous electrolyte barrier film, and given energy storage device good electrical properties such as battery, capacitor, higher security reliability and length recycle the life-span.
Embodiment
The following specifically describes the embodiment of non-woven cloth increasing micropore polymer diaphragm of the present invention.
What will indicate usually is, under identical porosity and the tortuosity situation, and the Kong Yueda of microporous polymer membranes, then the resistance that barrier film produced through electrolyte-impregnated is low more.The Gurley-number of microporous polymer membranes is the measuring of gas permeability of the porous septum done.With as O.besenhard described in " handbook of Battery Materials ", the ionic conductivity that can directly infer known architectures by the Gurley-number.It has been generally acknowledged that higher gas permeability (being less Gurley-number) can make the moistening barrier film of energy storage device electrolyte produce higher conductivity.But it is noted that especially little Gurley-number can show that also barrier film is defective, promptly have big hole in microporous polymer membranes, this big hole defect can cause internal short-circuit when energy storage device is worked.Very fast self discharge can take place with the reaction of danger in this energy storage device so, and very big electric current can appear in this moment, causes inner a large amount of heats that produce, under worst situation even the energy storage device of sealing is blasted.Owing to this reason, barrier film especially plays a decisive role to the fail safe of lithium ion battery, lithium metal secondary battery.Therefore microporous polymer membranes is to be worth the decisive member of concern energetically in the energy storage device.The scope that the Gurley-number is suitable is 5～200, the Gurley-number of prior art normally 10～50.For expression non-woven cloth increasing micropore polymer membrane micropore state more directly perceived, characterize barrier film gas permeability, conductivity in embodiments of the present invention and directly use the air penetrability of microporous polymer membranes as tolerance.
One, the preparation of waterborne polymeric colloid emulsion
The present invention is reaction medium with water, and hydrophobic monomer, hydrophilic monomer (if employing) in containing the solution of water-soluble polymer, obtain the polymer latex precursor emulsion by the combined polymerization of initator initiation grafting.
Concrete preparation method: a. adds water with water-soluble polymer, hydrophilic monomer (if employing), auxiliary agent, adds thermal agitation up to dissolving fully; B, temperature of reactor is constant in desired reaction temperature 30-90 ℃, with hydrophobic monomer adopt once, the mode of gradation or dropping adds in the reactor, adds the initator polymerization reaction 4-35 hour, is good with 5～20 hours, obtains the polymer latex precursor emulsion; Initator also can drip in course of reaction or gradation adds.Each raw material weight proportioning is in c, the polymeric colloid: 100 parts of water-soluble polymers, 0～200 part of hydrophilic monomer, 30～500 parts of hydrophobic monomers, 1～5 part of initator.Wherein, described water-soluble polymer is polyvinyl alcohol, PVP and water soluble copolymer thereof, polyethylene glycol oxide; The polyvinyl alcohol degree of polymerization is between 1700～2400, degree of hydrolysis 50～99.PVP and water soluble molecular weight of copolymer thereof are 500 to 100,000, preferred 1～30,000.Polyethylene glycol oxide molecular weight 100,000 to 2,000,000.
Wherein, described hydrophobicity (lipophile) monomer structure formula is: CH 2=CR 1R 2, wherein,
R 1=-H or-CH 3
R 2＝-C 6H 5、-OCOCH 3、-COOCH 3、-COOCH 2CH 3、
-COOCH 2CH 2CH 2CH 3、-COOCH 2CH(CH 2CH 3)CH 2CH 2CH 2CH 3、-CN。Hydrophobic monomer is that any or the mixing more than at least two kinds in the above-mentioned hydrophobic monomer used.
In order to improve barrier film, also can add hydrophilic monomer in the reaction to affinity of electrolyte etc.Described hydrophilic monomer structural formula is: CHR 3=CR 4R 5, wherein,
R 3=-H ,-CH 3Or-COOLi;
R 4=-H ,-CH 3Or-COOLi;
R 5＝-COOLi、-CH 2COOLi、-COO(CH 2) 6SO 3Li、-CONH 2、-CONHCH 3、
-CONHCH 2CH 3、-CON(CH 3) 2、-CON(CH 2CH 3) 2。Hydrophilic monomer is that any or the mixing more than at least two kinds in the above-mentioned hydrophilic monomer used.
Described initator is water soluble starters such as ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, azo two NSC 18620s or they and Na 2SO 3, FeSO 4Deng the redox initiation system that constitutes.
Also add the effect that the auxiliary agent be no more than 3 weight portions serves as emulsifying agent in the reaction, colloid emulsion is played certain stabilization, described auxiliary agent is selected from dodecane sulfonate, dodecyl benzene sulfonate, vinylsulfonate.
Two, the preparation of polymeric colloid slurry
In order to improve the microporous polymer thermal endurance, the rigidity of porosity and film can add the ultra-fine inorganic filler in the waterborne polymeric colloid emulsion.The ultra-fine inorganic filler has higher specific surface area and stronger surface adsorption ability, helps the absorption of electrolyte and increases the disassociation of electrolytic salt and improve the ionic conductivity of film thus.The preparation of waterborne polymeric gum size with above-mentioned synthetic waterborne polymeric colloid emulsion by solid content in 100%, the plasticizer that adds O～100% inorganic filler and 20～100%, be uniformly dispersed with homogenizer earlier, use ball mill or sand mill or agitating ball mill to mill then 2～10 hours, preferred 3～5 hours.Slurry after milling again by＜200 purpose screen filtrations to remove the material of not fine ground larger particles.
Described inorganic filler can be inorganic oxide such as fume colloidal silica, alundum (Al, titanium dioxide, zirconium dioxide, magnesium oxide, calcium carbonate, glass fibre etc. any.
In order to improve the dispersiveness of inorganic filler in the polymer latex precursor emulsion, can add silane coupler, coupling agent can be 3-aminopropyltriethoxywerene werene, 2-amino-ethyl-3-aminocarbonyl propyl trimethoxy silane, 3-glycidyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyl three (2-methoxy (ethoxy)) base silane, and the addition of silane coupler is 0.5～5.0% of an inorganic filler weight.
In order to strengthen the purpose of non-woven cloth increasing micropore polymer membrane safety, can also add the ionic conduction blocking characteristics of organic filler-reinforced barrier film, battery operated temperature control make the battery of non-woven cloth increasing micropore polymer film continue to flow with the blocking-up cation, in case can be guaranteed the fail safe of battery 100～130 ℃ of scopes.Described micron order organic filler can be micronized polyethylene wax, oxidized petroleum waves powder, micronized polyethylene wax powder any.In polymer latex precursor emulsion solid content 100%, the addition of organic filler is 5.0～20%.
Described plasticizer can be that any or the mixing more than at least two kinds such as propylene glycol, phenmethylol, n-butanol, isopropyl alcohol, diethyl phosphate, triethyl phosphate, trimethyl phosphate, tributyl phosphate are used.
Three, the preparation of non-woven cloth increasing micropore polymer film
Usually by the synthetic polymeric material of hydrophilic monomer, it is big mostly to present fragility, and poor toughness is to shortcomings such as ambient humidity sensitivities.For overcoming these shortcomings, the present invention selects the supporter of flexible nonwoven fabrics as the waterborne polymeric colloid, and preparing with the nonwoven fabrics is the microporous polymer membranes of supporter.Its preparation method: with the waterborne polymeric gum size or the waterborne polymeric colloid emulsion of above-mentioned preparation, it is two-sided that the employing coating equipment evenly is coated in nonwoven fabrics, by the drying tunnel heat drying, volatilization moisture and plasticizer can obtain non-woven cloth increasing micropore polymer film of the present invention then.
Wherein, described nonwoven fabrics is selected from a kind of in the nonwoven fabrics that polyacrylonitrile, nylon, formal polyvinyl alcohol, polyester such as polyethylene terephthalate (PET), polyolefine fiber make.Selected nonwoven fabrics, its thickness be less than 50 μ m, and porosity is greater than 40%, and be preferred 50～70%, aperture size: 5～200 μ m, preferred 8～100 μ m.The area weight of nonwoven fabrics is less than 25g/m 2, preferred 10～20g/m 2
Waterborne polymeric gum size of the present invention can by print, suppress, be pressed into, that the equipment of coating method such as roller coat, blade coating, brushing, dip-coating, spraying, curtain coating, sloping flow coat is coated in nonwoven fabrics with it is two-sided, wherein waterborne polymeric may also may be in the nonwoven fabrics in nonwoven surface.
The dry heat mode of non-woven cloth increasing micropore polymer film of the present invention can be by the air of heating, infrared radiation or the drying means commonly used by prior art.
Below mode by specific embodiment the present invention is further described, but do not represent the present invention to implement in the following manner.
The preparation of embodiment 1 non-woven cloth increasing micropore polymer film of the present invention
Synthesizing of first step polymer latex precursor emulsion
In the present embodiment, carry out graft copolymerization with hydrophilic macromolecule polyvinyl alcohol (PVA) 1750 and lipophile monomer vinylacetate (VAC)/ethyl acrylate (EA)/acrylonitrile (AN) at aqueous phase, make the waterborne polymeric colloid emulsion that is used for lithium battery diaphragm, its copolymerization consists of PVA: VAC: EA: AN=10: 2: 2: 5 (weight ratios, down together), copolymer content is 17%, and product is the White-opalescent emulsion.
The concrete method for making of this polymer latex precursor emulsion is: in the four-hole reaction vessel of band condensed water, add 1000g distilled water and 100g polyvinyl alcohol (PVA) 1750, reactor is warmed up to 75 ℃, stirring and dissolving, rotating speed are 100 rev/mins, after 3 hours, when material is transparence, can be considered dissolving and finish, close heating, naturally cool to 55 ℃.The lipophile monomer vinylacetate (VAC) of disposable adding 40g and 1: 1 blend of ethyl acrylate (EA), dispersed with stirring 10 minutes, add 0.5g water-based initator Ammonium Persulfate 98.5 (aps), after about 20 minutes, it is light blue that material is, transfer white emulsus after 30 minutes to, copolyreaction 2 hours obtains reaction intermediate.
Above-mentioned reactant liquor and 50g lipophile monomer acrylonitrile (AN) mixed disperse, add 1.5g initator Ammonium Persulfate 98.5 (aps) and 0.5g faintly acid vinyl sulfonic acid lithium (SVSLi) carries out emulsion polymerisation, the reaction time is 10 hours, promptly gets the polymer latex precursor emulsion.
The second step slurry is equipped with
The polymer latex precursor emulsion that makes adds zirconium dioxide filler and the 160g phenmethylol plasticizer of 19g, ball milling 5 hours.T=20.6 ℃, measure slurry viscosity under the RH=64% ambient temperature: T slurry=35 ℃, viscosity=2500mpas;
The 3rd step applied
With pair roller extrusion (the about 2m/min of belt speed) above-mentioned slurry is applied to thick about 24 μ m and the heavy 17g/m of face 2The PET nonwoven fabrics on, the drying tunnel of hot blast by the defined temperature and infrared radiation volatilization moisture and plasticizer immediately.All use same procedure in the experiment below or equipment applies.Obtaining thickness at last, to be about 25 μ m average pore sizes be the microporous polymer membranes of 400～600nm.
Prepared film gas permeation rate is about 20 (S/in 2100ml1.22KPa), this unit is meant that at pressure be under the 1.22Kpa condition, sees through the required time (following examples are identical) of 100ml air per square inch on the area.
The preparation of embodiment 2 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
Reactions steps is substantially with embodiment 1, and difference is, lipophile monomer ethyl acrylate (EA) is changed to the good acrylamide of hydrophily, and its copolymerization consists of PVA: VAC: AM: AN=10: 2: 1: 8.
The concrete method for making of this polymer emulsion is: all monomers adopt disposable feeding mode to add, and material concentration is adjusted to about in the of 13%, directly adds initator, and reaction in 12 hours finishes, and promptly gets the polymer latex precursor emulsion.
The second step slurry is equipped with
The filled share of institute is identical with embodiment 1, and material is titanium dioxide and phenmethylol, ball milling 5 hours.
The 3rd step applied
With embodiment 1, prepared film gas permeation rate is about 40 (S/in 2100ml1.22KPa).
The preparation of embodiment 3 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
In the present embodiment, add lipophile monomer styrene (St)/butyl acrylate (Ba)/acrylonitrile (AN) in the PVP aqueous solution and carry out ternary polymerization at aqueous phase, its copolymerization consists of PVA: St: Ba: AN=10: 2: 4: 2 (weight ratios, down together), copolymer content is 15%.
This polymer emulsion adopts step-by-step polymerization: in the four-hole reaction vessel of band condensed water, add 1000g distilled water and PVP, reactor is warmed up to 90 degree, when stirring and dissolving is transparence to material.Add styrene (St) monomer and 2g ammonium persulfate initiator, reacted 20 hours, the look emulsion that bleaches adds butyl acrylate (Ba), continues reaction 2 hours.In above-mentioned reactant liquor, add the 20g acrylonitrile monemer again, and add the 1.5g initator and continue polymerization 12 hours, promptly get the polymer latex precursor emulsion.
The second step slurry is equipped with
The polymer latex precursor emulsion that makes adds 15% silica filler and 100% tributyl phosphate plasticizer, ball milling 5 hours.Regulate slurry viscosity=2500mpas;
The 3rd step applied
With embodiment 1, prepared film gas permeation rate is about 15 (S/in 2100ml1.22KPa).
The preparation of embodiment 4 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
Be vinyl pyrrolidone (NVP) with polyvinyl alcohol 1799 (PVA), hydrophilic monomer in the present embodiment; The lipophile monomer is butyl acrylate (Ba) and acrylonitrile (AN), and its copolymerization consists of PVA: NVP: Ba: AN=10: 2: 4: 5 (weight ratio).
This polymer latex precursor emulsion adopts the one-step method polymerization and gets, and monomer, initator drop into simultaneously, and initator is selected oxidation-reduction system ammonium sulfite-potassium peroxydisulfate for use, and reaction temperature is 50 ℃, and the reaction time still is 12 hours.Obtain the polymer latex precursor emulsion.
The second step slurry is equipped with
The silica filler and the 100% triethyl phosphate plasticizer of usefulness 2% coupling agent treatment of the polymer latex precursor emulsion adding 15% that makes.Regulate slurry viscosity to 2500mpas.
The 3rd step applied
With embodiment 1, prepared film gas permeation rate is about 56 (S/in 2100ml1.22KPa).
The preparation of embodiment 5 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
Present embodiment is with PVA, and hydrophilic monomer is the acrylic acid lithium salts, and lipophile monomer acrylonitrile (AN) is made the waterborne polymeric colloid emulsion that is used for lithium battery diaphragm in the aqueous phase polymerization, and its copolymerization consists of PVA: MAALi: AN=10: 2: 5 (weight ratio).
The concrete method for making of this polymer latex precursor emulsion is: 90 ℃ of complete dissolve polyvinyl alcohols 1788, treat that temperature is reduced to 50 ℃ after, disposable adding acrylates and acrylonitrile monemer, the same precedent of polymerization, 12 hours time, polymerization finishes.
The second step slurry is equipped with
The polymer latex precursor emulsion that makes adds 30% alundum (Al filler and 120% triethyl phosphate plasticizer, in order to improve the adhesiveness of barrier film and BOPP base material, has added OPE powder 35%.Ball milling 5 hours is regulated slurry viscosity to 2500mpas.
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 12 (S/in 2100ml1.22KPa).
The preparation of embodiment 6 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
Be that vinyltriethoxysilane coupling agent (151)/acrylonitrile (AN) is in the aqueous phase glycerol polymerization with polyvinyl alcohol 1799 (PVA), hydrophobic monomer in the present embodiment, make aqueous polymer emulsion, its copolymerization consists of PVA: 151: AN=10: 4: 5 (weight ratio).
The concrete method for making of this polymer latex precursor emulsion is: in the four-hole reaction vessel of band condensed water, add 1000g distilled water and 100g hydrophilic monomer polyvinyl alcohol (PVA) 1799, be heated to 90 ℃, be transparence to material.Add vinyltriethoxysilane (151) 40g and acrylonitrile (AN) 50g initator Ammonium Persulfate 98.5 1.9g, graft copolymerization 12 hours.Obtain the polymer latex precursor emulsion.
The second step slurry is equipped with
Add the silica filler that triethyl phosphate disperses at polymer emulsion, concrete amount is: 20% silica filler and 100% triethyl phosphate plasticizer.Add 30% alkali-free glass fibre then, this glass fibre is used 500 ℃ of high temperature roasts of Muffle furnace in advance, natural cold standby in the stove.Blend ball milling 5 hours is regulated slurry viscosity to 2500mpas.
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 30 (S/in 2100ml1.22KPa).
The preparation of embodiment 7 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
Carry out copolymerization with hydrophilic monomer acrylamide (AM), lipophile monomer vinylacetate (VAC)/ethyl acrylate (EA) and lipophile monomer acrylonitrile (AN) at aqueous phase in the present embodiment, make the polymer latex precursor emulsion, its copolymerization consists of AM: (VAC+EA): AN=2: 3: 3 (weight ratios, down together), copolymer content is 17%.
The concrete method for making of this polymer emulsion is: in the four-hole reaction vessel of band condensed water, add 100 parts of distilled water and 5 parts of hydrophily acrylamides (AM) monomer, stirring and dissolving, rotating speed is 100 rev/mins, when material is transparence in the reactor, can be considered dissolving finishes, gradation or once add 7.5 parts-lipophile monomer vinylacetate (VAC) and ethyl acrylate (EA) blend, dispersed with stirring 10 minutes, add 1 part of water-based initator Ammonium Persulfate 98.5 (aps), 0.5 part conditioning agent, copolyreaction 2 hours obtains reaction intermediate.
Above-mentioned reactant liquor and 7.5 parts of lipophile monomer acrylonitrile (AN) are mixed disperse, add 0.5 part of initator and 0.2 part of faintly acid vinyl sulfonic acid lithium (svsLi) carries out emulsion polymerisation, the reaction time is 10 hours, promptly gets the polymer latex precursor emulsion.
The second step slurry is equipped with embodiment 1
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 25 (S/in 2100ml1.22KPa).
The preparation of embodiment 8 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
Reactions steps is substantially with embodiment 1, difference is, lipophile monomer vinylacetate (VAC) and ethyl acrylate (EA) blend are changed to 2.5 parts of hydrophily methacrylic acids (MAA), 5 parts of lipophile monomer acrylonitrile (AN), faintly acid vinyl sulfonic acid lithium are changed to highly acid dodecyl sodium sulfonate lithium (DsLi) emulsion polymerisation.Its copolymerization consists of AM: MAA: AN=2: 1: 2, copolymer content was 11%, the product translucent glue that is white in color.
The second step slurry is equipped with embodiment 3
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 40 (S/in 2100ml1.22KPa).
The preparation of embodiment 9 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
In the reactor of band condensed water, add 100 parts of distilled water, 2 parts of hydrophilic monomer acrylic acid and 8 parts of acrylamides earlier, be warmed up to 60 ℃ of stirring and dissolving, add 4 parts of lipophile monomer styrenes (BA) then, emulsifying agent dodecyl sodium sulfonate lithium (DsLi), 0.6 part of stabilizer polyvinyl alcohol (PVA1788), initator is the OR agent: 0.1 part of ammonium sulfite-sodium peroxydisulfate, 2 hours time
Above-mentioned reactant liquor and 16 parts of lipophile monomer acrylonitrile (AN) carry out emulsion polymerisation, and the reaction time is 12 hours.Its copolymerization consists of AM: MAA: BA: AN=2: 0.5: 1: 4, copolymer content was 17%.
The second step slurry is equipped with embodiment 4
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 20 (S/in 2100ml1.22KPa).
The preparation of embodiment 10 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
In the four-hole reactor of band condensed water, add 100 parts of distilled water and 10 hydrophilic monomer polyvinyl alcohol 1788, be warmed up to 80 ℃ of stirring and dissolving of solution temperature, concentration is 10%.
Treat to dissolve fully back (being transparence), cool to 50 ℃ of reaction temperatures.Add the lipophile mix monomer: 8 parts of 2 parts in acrylic acid and vinylacetates; logical nitrogen protection, 0.3 part of Ammonium Persulfate 98.5 of disposable adding and 0.1 part of conditioning agent adopt slow dropping mode to introduce 10 parts of the 3rd monomer acrylonitrile (AN); graft copolymerization obtained the polymer latex precursor emulsion more than 10 hours.
The second step slurry is equipped with embodiment 1
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 35 (S/in 2100ml1.22KPa).
The preparation of example 11 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
100 parts distilled water is put into four-hole boiling flask, and water-bath is heated to 80 ℃, adds 15 parts of PVA particles, keep temperature to solution to clarify, add glacial acetic acid and regulate pH value, add 1 part formaldehyde or butyraldehyde again to acid, reacted 3～5 hours, and added highly basic then and regulate the pH value to neutral.Maintain the temperature at 70 ℃, add 3 parts tributyl phosphate, after stirring a period of time, add 0.6 part APS, slowly drip 15 parts of lipophile monomer A N again, in 3～5 hours, dropwise.After becoming milky Deng solution, the reaction time is 12 hours.Both obtained concentration and be 33% polymer emulsion.
The second step slurry is equipped with embodiment 3
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 60 (S/in 2100ml1.22KPa).
The preparation of example 12 non-woven cloth increasing micropore polymer films of the present invention
In four-hole boiling flask, add 100 distilled water, the PVA particle that adds 8 parts, be heated to the solution clarification, the lipophile monomer propylene hydrocarbon gradation of 4 parts hydrophilic monomer acrylic acid and 8 parts is joined in the solution, drip 0.1 part peroxide initiator again, maintain the temperature at 55 ℃, the reaction time is 12 hours, has both obtained concentration and be 20% polymer latex precursor emulsion.
The second step slurry is equipped with embodiment 1
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 15 (S/in 2100ml1.22KPa).
The preparation of embodiment 13 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
125.0g acrylamide (AM) stirring and dissolving in 1800.0ml water, adds 75.0ml vinylacetate (VAC) and 15.0ml isopropyl alcohol (IPA), 60 ℃ of logical N 2Behind the deoxygenation 40min, add initiator ammonium persulfate (AP) 2.0g, system viscosity increases gradually, reacts to drip 125.0ml acrylonitrile (AN) after about 40min becomes milky, and copolymerization obtains the polymer latex precursor emulsion.
The second step slurry is equipped with
The polymer latex precursor emulsion that makes adds 30% alundum (Al filler and 120% triethyl phosphate plasticizer, adds 35% Tissuemat E powder.Ball milling 5 hours is regulated slurry viscosity to 2500mpas.
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 38 (S/in 2100ml1.22KPa).
The preparation of embodiment 14 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
50.0gAM stirring and dissolving in 725.0ml water, adds 40.0ml VAC, 15.0ml IPA and 127.0ml triethyl phosphate (TEP), 60 ℃ of logical N 2Behind the deoxygenation 40min, add initiator A P 0.8g, system viscosity increases gradually, reacts about 3.0h and becomes milky, and Dropwise 5 0.0ml AN copolymerization gets the polymer latex precursor emulsion then;
The second step copolymerization gets the polymer latex precursor emulsion through being cooled to room temperature, promptly can be used for applying nonwoven fabrics and prepares microporous polymer membranes.
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 12 (S/in 2100ml1.22KPa).
The preparation of embodiment 15 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
20.0g the AM stirring and dissolving in 400.0ml water, adds 11.2g methacrylic acid lithium, 5.0ml IPA, 50.0ml TEP and 30.0ml VAC, 60 ℃ of logical N 2Behind the deoxygenation 40min, add initiator A P 0.5g, system viscosity increases gradually, drips residue 40.0ml VAC behind the 1.0h, and copolymerization obtains the polymer latex precursor emulsion.
The second step slurry is equipped with embodiment 14
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 10 (S/in 2100ml1.22KPa).
The preparation of embodiment 16 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
25.0g the AM stirring and dissolving in 400.0ml water, adds 10.0ml butyl acrylate (BA) and 1.0ml IPA, 60 ℃ of logical N 2Behind the deoxygenation 30min, add initiator A P 0.5g, system viscosity increases gradually, reacts to drip 30.0ml AN after about 20min becomes milky, and copolymerization obtains the polymer latex precursor emulsion.
The second step slurry is equipped with embodiment 3
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 30 (S/in 2100ml1.22KPa).
The preparation of embodiment 17 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
25.0g the AM stirring and dissolving in 400.0ml water, adds 6.6ml VAC, 3.3ml BA and 1.0ml IPA, 60 ℃ of logical N 2Behind the deoxygenation 50min, add initiator A P 0.5g, system viscosity increases gradually, reacts about 15min and becomes blue back dropping 30.0ml AN, and copolymerization gets the polymer latex precursor emulsion.
The second step slurry is equipped with
The alundum (Al filler and the 120% propylene glycol plasticizer of adding 30% add 20% Tissuemat E powder in the polymer latex precursor emulsion that makes.Ball milling 5 hours is regulated slurry viscosity to 2500mpas.
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is 42 (S/in 2100ml1.22KPa).
The preparation of embodiment 18 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
25.0g the AM stirring and dissolving in 400.0ml water, adds 1.8g methacrylic acid lithium, 10.0ml BA and 1.0ml IPA, 60 ℃ of logical N 2Behind the deoxygenation 50min, add initiator A P 0.5g, system viscosity increases gradually, reacts about 15min and becomes blue back dropping 30.0ml AN, and copolymerization obtains the polymer latex precursor emulsion.
The second step slurry is equipped with
The polymer latex precursor emulsion that makes adds 30% titanium dioxide filler and 120% phenmethylol plasticizer.Ball milling 5 hours is regulated slurry viscosity to 2500mpas.
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of this embodiment is about 31 (S/in 2100ml1.22KPa).
The preparation of embodiment 19 non-woven cloth increasing micropore polymer films of the present invention
Synthesizing of first step polymer latex precursor emulsion
23.0g the AM stirring and dissolving in 300.0ml water, adds 15.0ml VAC and 4.0ml IPA, 60 ℃ of logical N 2Behind the deoxygenation 30min, add initiator A P 0.3g, reaction system viscosity increases gradually, becomes the 20ml aqueous solution that drips 46.0ml AN and 2.0g methacrylic acid lithium after the white respectively, and copolymerization obtains the polymer latex precursor emulsion.
The second step slurry is equipped with embodiment 1
The 3rd step applied
With embodiment 1, the prepared film gas permeation rate of present embodiment is about 35 (S/in 2100ml1.22KPa).
Test example 1: the thermal endurance of non-woven cloth increasing micropore polymer film of the present invention
The shrinkage of various barrier film different temperatures sees Table 1, shows that non-woven cloth increasing micropore polymer film of the present invention presents good thermal endurance than existing P P and PE microporous polymer membranes.
The shrinkage of the various barrier film different temperatures of table 1.
Figure G200810300148120080118D000161
Annotate: every kind of temperature all is vacuum treatment 2 hours, and the film of each embodiment, PP and PE film thickness are about 25 μ m.
Table 1 is the non-woven cloth increasing micropore polymer film shrinkage at various temperatures of part embodiment.Its shrinkage of non-woven cloth increasing micropore polymer film of the present invention is not more than 1.5% under temperature is 170 ℃, and commodity PP and PE microporous polymer membranes have melted under this temperature, non-woven cloth increasing micropore polymer film of the present invention presents good thermal endurance, and this is very favourable to the fail safe that improves battery.Simultaneously, non-woven cloth increasing micropore polymer diaphragm of the present invention is also insensitive to ambient humidity, even under higher air humidity, and the dimensionally stable of film.
Test example 2: non-woven cloth increasing micropore polymer film of the present invention recycle performance
To be assembled into lithium ion battery by the non-woven cloth increasing micropore polymer film of embodiment 6 preparations, this battery is by LiMn 2O 4Positive electrode, graphite cathode material and constitute by the electrolyte that the LiPF6 of ethylene carbonate/diethyl carbonate forms.This battery carries out the DOD100% charge and discharge cycles under the 1C condition, experiment shows through 1000 its capacity that circulate to also have more than 80% of initial volume of passenger traffic, and its internal resistance of cell increases less than 10%.With the lithium ion battery of commodity microporous polypropylene membrane assembling under the same conditions, 400 times its capacity of circulation back only is about 75% of an initial volume of passenger traffic as a comparison, and the internal resistance of cell increases more than 35%.
Test example 3: non-woven cloth increasing micropore polymer film of the present invention recycle performance
To be assembled into lithium ion battery by the non-woven cloth increasing micropore polymer film of embodiment 15 preparations, this battery is by LiCoO 2Positive electrode, graphite cathode material and by the LiPF of ethylene carbonate/diethyl carbonate 6The electrolyte of forming constitutes.This battery carries out the DOD100% charge and discharge cycles under the 1C condition, experiment shows through 1000 its capacity that circulate to also have more than 85% of initial volume of passenger traffic, and its internal resistance of cell increases less than 10%.
Test example 4: non-woven cloth increasing micropore polymer film of the present invention recycle performance
To be assembled into lithium ion battery by the non-woven cloth increasing micropore polymer film of embodiment 15 preparations, this battery is by LiFePO 4Positive electrode, graphite cathode material and by the LiPF of ethylene carbonate/diethyl carbonate 6The electrolyte of forming constitutes.This battery carries out the DODl00% charge and discharge cycles under the 1C condition, experiment shows through 2000 its capacity that circulate to also have more than 80% of initial volume of passenger traffic, and its internal resistance of cell increases less than 20%.
Why the lithium ion battery that non-woven cloth increasing micropore polymer film of the present invention is assembled into has long circulation life and less battery polarization, and this is owing to the microporous polymer membranes that strengthens with nonwoven fabrics, adopt contain strong polar group (as-CN ,-COO-,-NH 2,-O-etc.) macromolecular compound is a material of main part, this material and nonaqueous electrolyte have good intermiscibility, can form polymer sol, simultaneously, the super solvent of its polar group and nonaqueous electrolyte can form the chemical association effect, make the electrolyte in the battery be solid-state properties, and can make barrier film keep good moisture state.

Claims (9)

1. non-woven cloth increasing micropore polymer diaphragm, it is characterized in that: it is by 100 parts of water-soluble polymers, 30～500 parts of hydrophobic monomers, 0～200 part of hydrophilic monomer, 1～5 part of combined polymerization of initator obtains the polymer latex precursor emulsion; By solid content 100% in the polymer latex precursor emulsion, the inorganic filler of adding 0～100% and 20～100% plasticizer, it is two-sided that the gained slurry is coated in nonwoven fabrics, and drying obtains the non-woven cloth increasing micropore polymer film;
Wherein, described nonwoven fabrics is selected from a kind of in the nonwoven fabrics that polyacrylonitrile, nylon, formal polyvinyl alcohol, polyester, polyolefine fiber make;
Described water-soluble polymer is polyvinyl alcohol, polyethylene glycol oxide, PVP or PVP water solubility copolymer; Wherein, the polyvinyl alcohol degree of polymerization is 1700～2400, degree of hydrolysis 50～99; Polyethylene glycol oxide molecular weight 100,000 to 2,000,000; PVP or its water solubility copolymer, molecular weight are 500 to 100,000;
Described hydrophobic monomer structural formula is: CH 2=CR 1R 2, wherein, R 1=-H or-CH 3
R 2=-C 6H 5,-OCOCH 3,-COOCH 3,-COOCH 2CH 3,-COOCH 2CH 2CH 2CH 3,-COOCH 2CH (CH 2CH 3) CH 2CH 2CH 2CH 3Or-CN; Hydrophobic monomer is at least a in the above-mentioned hydrophobic monomer;
Described hydrophilic monomer structural formula is: CHR 3=CR 4R 5, wherein,
R 3=-H ,-CH 3Or-COOLi;
R 4=-H ,-CH 3Or-COOLi;
R 5=-COOLi ,-CH 2COOLi ,-COO (CH 2) 6SO 3Li ,-CONH 2,-CONHCH 3,
Figure FDA0000019900720000011
-CONHCH 2CH 3,-CON (CH 3) 2Or-CON (CH 2CH 3) 2Hydrophilic monomer is at least a in the above-mentioned hydrophilic monomer;
Described initator is ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide or azo two NSC 18620s; Or they and Na 2SO 3Or FeSO 4The redox initiation system that constitutes;
Described inorganic filler is white carbon, alundum (Al, titanium dioxide, zirconium dioxide, magnesium oxide, calcium carbonate or glass fibre;
Described plasticizer is at least a in propylene glycol, phenmethylol, n-butanol, isopropyl alcohol, diethyl phosphate, triethyl phosphate, trimethyl phosphate, the tributyl phosphate.
2. non-woven cloth increasing micropore polymer diaphragm according to claim 1, it is characterized in that: when adding inorganic filler, also add silane coupler, the addition of silane coupler is 0.5～5.0% of an inorganic filler weight, and described silane coupler is 3-aminopropyltriethoxywerene werene, 2-amino-ethyl-3-aminocarbonyl propyl trimethoxy silane, 3-glycidyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyl three (2-methoxy (ethoxy)) base silane.
3. non-woven cloth increasing micropore polymer diaphragm according to claim 1 is characterized in that: also add organic filler, described organic filler is selected from least a in polyethylene powder, Tissuemat E powder, the OPE powder.
4. prepare the method for the described non-woven cloth increasing micropore polymer diaphragm of claim 1, it is characterized in that: may further comprise the steps:
The preparation of a, polymer latex precursor emulsion:
With 100 parts of water-soluble polymers, hydrophilic monomer adds water for 0～200 part, adds thermal agitation up to dissolving fully; Temperature of reactor is constant in 30 ℃-90 ℃, with 30～500 parts of employings of hydrophobic monomer once, the mode of gradation or dropping adds in the reactor, adds 1～5 part of initator polymerization reaction 4-35 hour, obtains the polymer latex precursor emulsion;
The preparation of b, polymeric colloid slurry:
In the polymer latex precursor emulsion by solid content 100%, add 0～100% inorganic filler and 20～100% plasticizer in the polymer latex precursor emulsion, dispersed with stirring is even, milled 2～10 hours, the slurry after milling again by＜200 purpose screen filtrations to remove the material of not fine ground larger particles;
The preparation of c, non-woven cloth increasing micropore polymer diaphragm:
It is two-sided that the waterborne polymeric gum size of above-mentioned preparation evenly is coated in nonwoven fabrics, is drying to obtain the non-woven cloth increasing micropore polymer film; Described nonwoven fabrics is selected from a kind of in the nonwoven fabrics that polyacrylonitrile, nylon, formal polyvinyl alcohol, polyester, polyolefine fiber make, wherein nonwoven thickness is less than 50 μ m, porosity is greater than 40%, and aperture size: 5～200 μ m, the area weight of nonwoven fabrics is less than 25g/m 2
5. according to the described method for preparing non-woven cloth increasing micropore polymer diaphragm of claim 4, it is characterized in that: a step also adds the auxiliary agent that is no more than 3 weight portions, and described auxiliary agent is selected from dodecane sulfonate, dodecyl benzene sulfonate, the vinylsulfonate at least a; Initator drips in course of reaction or gradation adds.
6. according to the described method for preparing non-woven cloth increasing micropore polymer diaphragm of claim 4, it is characterized in that: when a step polymerization reaction, add silane coupler or prepare in the gum size process, add silane coupler simultaneously with inorganic filler in the b step; The addition of silane coupler is 0.5～5.0% of an inorganic filler weight, and described silane coupler is selected from least a in 3-aminopropyltriethoxywerene werene, 2-amino-ethyl-3-aminocarbonyl propyl trimethoxy silane, 3-glycidyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane or vinyl three (2-methoxy (ethoxy)) base silane.
7. according to the described method for preparing non-woven cloth increasing micropore polymer diaphragm of claim 4, it is characterized in that: described nonwoven fabrics porosity is 50～70%, aperture size 8～100 μ m, and the area weight of nonwoven fabrics is 10～20g/m 2
8. according to the described method for preparing non-woven cloth increasing micropore polymer diaphragm of claim 4, it is characterized in that: in polymer latex precursor emulsion solid content 100%, the b step is also added the organic filler of 5.0-20%, and organic filler is selected from least a in polyethylene powder, Tissuemat E powder, the OPE powder.
9. the application of each described non-woven cloth increasing micropore polymer diaphragm of claim 1～3 in preparation lithium ion battery, ultracapacitor or battery/super electric capacity energy storage means spare.
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Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101226994B (en) * 2007-12-21 2010-06-30 成都中科来方能源科技有限公司 Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof
AT507533B1 (en) 2008-11-14 2010-08-15 Herbert Karl Fuchs DEVICE FOR CONVERTING HEAT ENERGY TO ELECTRICAL ENERGY
CN101434708B (en) 2008-12-19 2012-01-11 成都中科来方能源科技有限公司 Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof
CN101843389B (en) * 2010-05-25 2012-02-01 杭州三信织造有限公司 Degradable fastening tape and manufacturing method thereof
CN102412377B (en) * 2010-09-24 2015-08-26 比亚迪股份有限公司 A kind of barrier film and preparation method thereof, a kind of lithium ion battery
CN102487132A (en) * 2010-12-01 2012-06-06 徐亮良 Battery diaphragm
DE102011017105A1 (en) * 2011-04-14 2012-10-18 Li-Tec Battery Gmbh Lithium-ion battery with high voltage
CN102306725B (en) * 2011-08-04 2016-08-03 东莞新能源科技有限公司 A kind of lithium ion battery
CN102360950B (en) * 2011-09-14 2017-03-15 中国第一汽车股份有限公司 A kind of barrier film for flexible solid-state supercapacitor and preparation method thereof
TWI452755B (en) * 2011-12-29 2014-09-11 Ind Tech Res Inst Separators and method of fabricating the same
CN103515560A (en) * 2012-06-20 2014-01-15 万向电动汽车有限公司 Flexibly-packaged high-power lithium ion power battery
CN102856583A (en) * 2012-10-11 2013-01-02 山东天阳新能源有限公司 Cylindrical coil core explosion-proof lithium ion battery and processing method
CN102856582A (en) * 2012-10-11 2013-01-02 山东天阳新能源有限公司 Square cell of lithium manganate aluminum shell and preparation method
CN103199209B (en) * 2013-04-01 2015-09-02 中国海诚工程科技股份有限公司 There is lithium ion battery nonwoven fabrics ceramic diaphragm and the technique of excellent closed pore performance
CN103555119B (en) * 2013-11-01 2016-03-23 中国海诚工程科技股份有限公司 Polyalkene diaphragm coating, improved polyalkene diaphragm and preparation thereof
CN103613710B (en) * 2013-11-12 2016-01-06 南京彤天广元高分子材料有限公司 A kind of preparation method of thermoplastic polymer water dispersion
CN104140502B (en) * 2013-11-14 2016-12-07 上海泛能新材料科技有限公司 A kind of lithium ion battery separator binding agent, preparation method and use the barrier film of this binding agent
CN105830252A (en) * 2014-03-18 2016-08-03 积水化学工业株式会社 Heat resistant synthetic resin microporous film, method for manufacturing same, nonaqueous electrolyte secondary cell separator, and nonaqueous electrolyte secondary cell
CN105098121B (en) * 2014-04-16 2018-05-29 宁德时代新能源科技股份有限公司 Diaphragm, preparation method thereof and lithium ion battery using diaphragm
CN104088154A (en) * 2014-06-25 2014-10-08 中国第一汽车股份有限公司 Composite modification method of non-woven fabric diaphragm
CN104086869B (en) * 2014-07-01 2016-05-11 安徽江威精密制造有限公司 A kind of strengthening and toughening capacitor film filler special and preparation method thereof
CN104124418B (en) * 2014-07-25 2016-03-02 佛山市盈博莱科技有限公司 A kind of lithium ion battery separator and preparation method thereof
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WO2016193000A1 (en) 2015-06-02 2016-12-08 Evonik Degussa Gmbh Coating composition containing aluminum oxide and method for coating separators therewith
CN105199137B (en) * 2015-09-08 2018-03-16 哈尔滨工业大学 A kind of preparation method of porous composite polymer electrolyte membrane material
CN105990037A (en) * 2016-01-27 2016-10-05 安徽旭峰电容器有限公司 Enhanced nonwoven electrostatic spinning fiber membrane composite separator material
GB201609320D0 (en) * 2016-05-26 2016-07-13 Johnson Matthey Fuel Cells Ltd Membrane and process
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EP3707180B1 (en) * 2018-07-04 2021-05-05 Wacker Chemie AG Water soluble copolymers
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KR102504187B1 (en) * 2021-09-29 2023-03-02 주식회사 한솔케미칼 Copolymer for separator and secondary battery using thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5368614A (en) * 1994-03-21 1994-11-29 Hughes Aircraft Company Preparation of polymer-impregnated battery separator material and cell made therewith
US5478677A (en) * 1993-09-13 1995-12-26 Daramic, Inc. Composite gauntlet/separator
CN1428363A (en) * 2001-12-25 2003-07-09 成都茵地乐电源科技有限公司 Nano-pore polymer electrolyte film and its preparation method
CN1680482A (en) * 2005-02-04 2005-10-12 武汉大学 Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60130052A (en) * 1983-12-15 1985-07-11 Furukawa Electric Co Ltd:The Separator for alkaline battery
JPS60136161A (en) * 1983-12-26 1985-07-19 Japan Vilene Co Ltd Separator for lithium battery
US4741979A (en) * 1986-05-19 1988-05-03 Eastman Kodak Company Battery separator assembly
JP3598186B2 (en) * 1996-12-16 2004-12-08 リチャージャブル バッテリー インダストリーズ コーポレーション Separator, secondary battery employing the same, and method of manufacturing the same
JP4318233B2 (en) * 1998-06-15 2009-08-19 アオイ電子株式会社 Lithium secondary battery and manufacturing method thereof
JP3850654B2 (en) * 2000-10-19 2006-11-29 株式会社トクヤマ Manufacturing method of redox flow battery diaphragm
US6967232B2 (en) * 2001-10-04 2005-11-22 Dainichiseika Color & Chemicals Mfg., Co., Ltd. High-molecular gelling agent precursor for electrolyte
DE10238941B4 (en) 2002-08-24 2013-03-28 Evonik Degussa Gmbh Electric separator, process for its manufacture and use in lithium high-performance batteries and a battery having the separator
JP2006057019A (en) * 2004-08-20 2006-03-02 Nippon Synthetic Chem Ind Co Ltd:The Aqueous acrylic copolymer emulsion, redispersible acrylic copolymer emulsion powder and method for producing the same
JP2006100512A (en) * 2004-09-29 2006-04-13 Teijin Ltd Separator for capacitor and capacitor
US20060216584A1 (en) * 2005-03-24 2006-09-28 Michael Cheiky Oxidation resistant electrolyte absorber
CN1967906A (en) * 2005-11-14 2007-05-23 天津科技大学 Method for preparing gelatin membrane by radiation grafting method
KR100723391B1 (en) * 2006-01-13 2007-05-30 삼성에스디아이 주식회사 Polymer electrolytic membrane , and fuel cell employing the same
JP5403857B2 (en) * 2006-05-18 2014-01-29 日立マクセル株式会社 Battery separator, method for producing the same, and lithium secondary battery
CN100467504C (en) * 2006-12-01 2009-03-11 华南师范大学 Preparing method and application of polymer gel electrolyte for lithium ion cell
CN101226994B (en) * 2007-12-21 2010-06-30 成都中科来方能源科技有限公司 Non-woven cloth increasing micropore polymer diaphragm and usage as well as preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5478677A (en) * 1993-09-13 1995-12-26 Daramic, Inc. Composite gauntlet/separator
US5368614A (en) * 1994-03-21 1994-11-29 Hughes Aircraft Company Preparation of polymer-impregnated battery separator material and cell made therewith
CN1428363A (en) * 2001-12-25 2003-07-09 成都茵地乐电源科技有限公司 Nano-pore polymer electrolyte film and its preparation method
CN1680482A (en) * 2005-02-04 2005-10-12 武汉大学 Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2005-129535A 2005.05.19

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