CN1213393A - Method for adhesion of fluorinated resins to metals - Google Patents
Method for adhesion of fluorinated resins to metals Download PDFInfo
- Publication number
- CN1213393A CN1213393A CN97193081A CN97193081A CN1213393A CN 1213393 A CN1213393 A CN 1213393A CN 97193081 A CN97193081 A CN 97193081A CN 97193081 A CN97193081 A CN 97193081A CN 1213393 A CN1213393 A CN 1213393A
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- weight
- metal
- electrode
- resin
- caking agent
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 63
- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- 150000002739 metals Chemical class 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 41
- 239000002033 PVDF binder Substances 0.000 claims abstract description 39
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
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- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000007769 metal material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
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- 238000012360 testing method Methods 0.000 description 16
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
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- 238000001125 extrusion Methods 0.000 description 9
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 6
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- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 2
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- 229920000098 polyolefin Polymers 0.000 description 2
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- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J127/00—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives 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 a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/16—Homopolymers or copolymers of vinylidene fluoride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- 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 objective of the present invention is to offer a method for improving the adhesion of fluorinated resins to metal materials, and for obtaining composite materials of metal materials and polyvinylidene fluoride resins. A metal-adhesive fluorinated composition can be used as an adhesive agent between the fluorinated resins and the metals or can replace the fluorinated resins.
Description
The present invention relates to a kind of method that bonding/lamination is not bonding fluoro-resin and metal that is used for itself, the present invention can be used for that needs are corrosion-resistant, the inner lining of steel pipe of weather or chemical stability, chemical plant's parts and as binding agent of battery electrode or the like.
As the fluoropolymer that can melt with the fabulous weathering resistance of having of moulding and chemical stability or the like, poly(vinylidene fluoride) (being abbreviated as PVDF later on) resin can be as coating material with as electricity/electronic unit, inner lining of steel pipe, chemical plant's parts and weather-proof/proof stress film or the like.But since it with other material in fact do not have cementability, so its existence be difficult to other material modification or compound problem.
Therefore, people attempted the mixing overcoming this shortcoming of other polymkeric substance and PVDF, but did not almost have polymkeric substance and PVDF to have cementability or consistency, and owing to disadvantageous effect of PVDF physicals or the like, its range of application is very limited.For instance, known polymethylmethacrylate (hereinafter being abbreviated as PMMA) is a kind of material (JP43-12012 and JP51-18197) that has excellent compatibility with PVDF, but the glass transition temp of PPMA is very high with comparing of PVDF, so these mixtures of material lack flexibility and they and metal and have relatively poor cementability.On the other hand, people also proposed with the mixture (JP57-8244) of polycarbonate, with the mixture (JP62-57448) with modified polyolefin of functional group and with mixture (JP2-308856) of pi or the like, relatively poor but these compositions lack the cementability of consistency and they and metal.In addition, also proposed and acrylate or the elastomeric mixture of methacrylic ester (JP4-218552), but do not known the adhesiveproperties of they and metal system.
The objective of the invention is to improve the cementability of fluoro-resin and metallic substance, and a kind of method that is used to obtain the matrix material of metallic substance and fluoro-resin is provided.
The inventor finds a kind of fluorinated composition, which comprises at least two kinds in following three kinds of compositions:
(a) at least a PVDF resin,
(b) at least a acrylic acid series and/or the metha crylic polymer that has the functional group of cementability or affinity with metal that have,
(c) at least a vinylidene fluoride copolymer resin
Said composition has good cementability on metallic substance, find that also these characteristics can prepare the matrix material of being made up of these compositions and metal effectively.
Said herein PVDF resin can be selected from the poly(vinylidene fluoride) homopolymer, and preferably it restrains/10 minutes in the melt flow rate (MFR) (MFR) under 2.16 kilograms of loads under 230 ℃ for 0.01-300.
Vinylidene fluoride copolymer (c) is vinylidene fluoride (VF
2) with other can with VF
2The monomeric multipolymer of copolymerization, and VF
2The per-cent of composition in these multipolymers should be 50-95 weight %, more preferably is 75-95 weight %.Other monomer as can copolymerization is preferably fluorochemical monomer, as tetrafluoroethylene, R 1216 acid system, trifluoro-ethylene and trifluorochloroethylene or the like, can adopt wherein one or more.The room temperature modulus in flexure of suitable is multipolymer (c) is no more than 1000MPa and they and has at least 50% extension at break, and preferably it is 0.01-300 gram/10 minutes in the melt flow rate (MFR) (MFR) under 2.16 kilograms of loads under 230 ℃.
Fluoro-resin (a) and (c) can interpolymerized vinylidene fluoride monomer or interpolymerized vinylidene fluoride monomer and other monomer polymerization be obtained by adopting suspension polymerization or emulsion polymerization etc.
Acrylic acid series and/or metha crylic polymer (b) are that wherein main component is that alkyl acrylate and/or alkyl methacrylate and it have the polymkeric substance that has the functional group of cementability or affinity with metal in main chain, side chain or end.As the example of this polymkeric substance, can be to have and to have random copolymers, segmented copolymer and the graftomer that the monomer of the functional group of cementability or affinity produces with metal by adding by at least a monomer that is selected from alkyl acrylate and alkyl methacrylate as radical polymerization, ionic polymerization or polycoordination.
As having the example of the functional group of cementability or affinity, hydroxy-acid group or carboxylic acid anhydride group, epoxide group (glycidyl), sulfydryl, sulfenyl, oxazolinyl, phenolic group, ester group and similar group thereof can be proposed with metal.
An example of aforesaid propylene acid system and/or metha crylic polymer comprises the monomer that has carboxylic acid group or carboxylic acid anhydride group and the multipolymer of alkyl acrylate and/or alkyl methacrylate.In this case, the specific examples of (methyl) alkyl acrylate is methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi and butyl methacrylate.In addition, as the monomeric specific examples that has carboxylic acid group or carboxylic acid anhydride group, can be vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, alkenyl succinic, acrylic acid series acyl ammonia-oxyacetic acid, 1,2-cyclohexane dicarboxylic acid allyl ester and other similar unsaturated carboxylic acid and maleic anhydride, alkenyl succinic anhydrides and other similar unsaturated carboxylic acid anhydrides or the like.
In addition, at least 50 weight % preferably more preferably are made up of at least a monomer that is selected from acrylate and/or methacrylic ester for this acrylic acid series of at least 70 weight % and/or metha crylic polymer.The content that has a functional group of cementability or affinity with metal is preferably the per kilogram acrylic acid series and/or metha crylic polymer has the 0.01-2 mole.When this component of polymer be at least a be selected from acrylate and/monomer of methacrylic ester and when having carboxylic acid group or carboxylic acid anhydride group's monomeric multipolymer, the monomeric ratio that has carboxylic acid group or carboxylic acid anhydride group is preferably the 0.2-30 weight % of said multipolymer, more preferably is 1-20 weight %.In addition, as a kind of moiety, except mentioned component, can also in molecular chain, contain vinyl monomer, unit as vinylbenzene or modification, as inferior acid amides, but the content of these compositions is no more than 50 weight % of the said polymer, and is preferably and is no more than 30 weight %.
When the composition with metal sticking contains the composition (a) and (b) and (c) time, per 100 parts of weight polyvinylidene fluoride resins (a), it contain 0.5-100 part weight percent acrylic acid system and/metha crylic polymer (b), 1-200 part weight vinylidene fluoride copolymer resin (c).
Of the present invention and composition metal sticking can prepare by solution method or method of fusion.Under the situation of solution method, can be under the temperature that is lower than used solution boiling point mentioned component (a) (b) and (c) be dissolved in solvent such as N-Methyl pyrrolidone, N with certain proportion, in dinethylformamide, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, tetramethyl-urea, acetone, methylethylketone or its analogue.Under the situation of method of fusion, can (b) He (c) produce as adopting mixing screw heating and mixing element (a) in certain proportion by conventional method.Here, can adopt conventional known method as fusing and blended method, as adopt Banbury mixing machine, rubber roll and list or duplex forcing machine etc., and normally by at 100-300 ℃, preferably in 150-260 ℃ (though also depending on said composition) fusing and mix and obtain this resin combination down.
In the present invention, if the add-on of vinylidene fluoride copolymer is per 100 parts of weight vinylidene fluoride resin 1-10 part weight, be preferably 1-5 part weight, and similarly, if the amount of acrylic acid series or metha crylic polymer is 0.5-10 part weight, be preferably 1-5 part weight, the performance that so just can need not to change greatly the vinylidene fluoride resin just can be improved the cementability with metal.When technique for sticking was a kind of solution cladding process, this method was effective especially.
In addition, this fluorinated composition of the present invention (its metal sticking performance is improved by aforesaid method) can be used as the caking agent use when bonding to fluoride resin on the metal.Particularly when technique for sticking is a kind of melting process, preferably this three components composition has the acrylic acid series of cementability or affinity or metha crylic polymer (b) and 10-200 part weight vinylidene fluoride polymer (c) by per 100 parts of weight PVDF resins (a) 5-100 part weight and metal and forms.
In the present invention, this fluorinated composition with improved metal sticking can be used as caking agent when bonding to fluoride resin on the metal, and said fluoride resin not necessarily will be made up of the fluoride resin identical with the fluoride resin that constitutes upper layer.As the fluoride resin that is used for this adhesive linkage, can select a kind of resin according to bonding/process operation with suitable melt flow rate (MFR) (MFR), multipolymer composition and fusing point.
As the example as the metallic substance of bonding base mateiral in the present invention can be iron, stainless steel, aluminium, copper, nickel, titanium, lead, silver, chromium and various alloys or the like, and its shape there is no particular limitation.
As above said, by the present invention, can improve the bonding of fluoride resin (with the material that contains fluoride resin) and metallic substance at an easy rate, and can obtain at an easy rate with metal sticking together fluoridize matrix material.The matrix material of fluoridizing with metal sticking of Huo Deing is made up of fluoride resin by this method, extrusion moulding product (film, sheet, plate, pipe, rod, special-shaped extruded product, silk, monofilament, fiber etc.) for example, injection moulded products or compression moulding goods etc., there is the above-mentioned composition with metal sticking of one deck on its part or whole surface, and there is no particular limitation for it, and its preparation means comprises calendering, coextrusion, extrudes lamination, the surface of multi-layer injection molding, fluid submergence coating, dipping, spraying and coating molding body or the like.Here, the polyvinylidene fluoride resin that is used as base mateiral can be identical with being used for this with the polyvinylidene fluoride resin of the composition of metal sticking, also can be different.
Method of the present invention can be dissolved or dispersed in fluoride resin in a kind of solvent to be used to be coated with the fluorine material by employing, perhaps is used for carrying out the electric wire coating by fluoride resin.In addition, it can also be used for caking agent as electrode of lithium cell or the like, and in this case, it can be used to improve the bond properties between metallic matrix (being the electric current grabber for battery) and the electrode active material layers.
Of the present invention being used for fluoride resin, particularly the method for PVDF resin and/or VF2 copolymer resin and metal sticking can be used in the various products, it all is valuable in multiple field, for example in chemical industry, medicine and foodstuffs industry, need in the chemically inert equipment as structure unit and at the exterior building material and the Industrial materials of the long-time weathering resistance of needs, can also be as caking agent of electrode of lithium cell or the like.
Concerning the electrode production process of lithium ion battery, it can be used to strengthen bonding between the metallic matrix of electric current grabber and the electrode active material layers.
At portable electronic product (honeycomb electricity works, pagers, personal digital assistance, be used for device that person-to-person communication serves, portable or portable box terminal computer, electronic game, protruding stupefied register etc.) with electric vehicle has heavy body and long-life small rechargeable battery requirements amount is very big.Lithium ion battery (LIB) is because they are thin and in light weight, do not contain the heavy metal that can cause environmental problem and they have higher energy density than existing nickel-cadmium, nickel-metal hydrides and lead-acid cell, thereby is a kind of fabulous solution.
The laminar structure of lithium-ion battery is following said usually:
-metal grabber
-lithium-metal oxide based positive electrode or negative electrode
-ionogen
-carbon back negative potential or anode
-metal grabber
This anode active material can be made by any material that can mix and discharge lithium ion, and this material is made by carbonaceous material usually, comprises coke, as petroleum coke and charcoal coke.Carbon black is as acetylene black, graphite, fibrous carbon, gac, carbon fiber and the sintered article that made by organic high molecular polymer by organic high molecular polymer is burnt in nonoxidizing atmosphere.Can in this cathode active material, mix or add cupric oxide or other electro-conductive material.
The caking agent that must have high good solubility-resistence and anti-chemical reagent is usually based on fluoro-resin, polyolefine, synthetic rubber, and still, fluoride resin is preferred.The content of fluoride resin is preferably more than 90 weight % in the caking agent.
Preferably adopt the PVDF resin, particularly have those of the above VF2 of 75% weight, this is because they have high-resistance to solvent with to active agent, thereby they highly dissolve in the methylpyrroline ketone, and methylpyrroline ketone is solvent commonly used in the lithium ion battery.In the PVDF resin, by foraflon with fluoridize in the fluorinated copolymers that the mixture of copolymerization forms, the content of VF2 is 50-95 weight %, and the content of foraflon is that those resins of 50-99.5 weight % are preferred in the mixture.
Thereby being used to prepare a kind of ordinary method of anodic comprises pulverous carbonaceous material being mixed with the caking agent of proper amt and mediating with a kind of solvent and prepares a kind of slurry or slip.Then grabber (being generally copper) is coated to be dried then on this slurry and compacting to obtain anode.
The lithium-ion cell cathode is usually by sulfide such as the iron sulphide and the titanium sulfide of lithium and transition metal oxide such as manganese oxide and vanadium oxide, transition metal, the perhaps composite oxides of the complex chemical compound of these materials such as lithium and cobalt, the composite oxides of lithium, cobalt and nickel, the composite oxides of lithium and manganese are made.This cathode active material can also mix with the conducting material (normally carbon) and the caking agent of proper amt, and mediate with a kind of solvent, thereby make a kind of slurry, then this slurry is coated to (normally a kind of aluminium grabber) on the grabber, then long-term drying and compacting are to obtain negative electrode.
Be used for negative electrode caking agent can be used for the identical of negative electrode and preferably based on fluoride resin.
For these two kinds of electrodes, the amount of caking agent is generally electrode active material 1-30 part of relative 100 parts of weight, preferably 3-15 part weight.
But as above said, the fluoride resin that itself has a relatively poor cementability with metal (electrode (active substance+caking agent)) is easy to and is used for two kinds of electrodes, promptly negative electrode and anodic grabber separately, thereby the life-span of battery is descended.Thereby the JP5-6766 proposition makes the surface irregularity of grabber increase the bonding effect of fluoride resin.But common this technology can not obtain sufficient cementability.
The invention provides a kind of by the above-mentioned caking agent that has the composition of cementability (metal-acdhesive) to form to metal:
1/ it only contain (a) and (b), amount (b) is the 0.2-20 weight % of composition total weight,
2/ it only contain (a) and (c), amount (c) is the 0.5-50 weight % of total composition,
3/ it only contain (a) and (b) and (c), amount (b) is the 0.5-20 weight % of total composition, amount (c) is 0.5-50 weight %.
Obtain a kind of slip by electrode active material and the caking agent of in the presence of solvent, mediating predetermined amount, the slip that is obtained is coated on the grabber of electrode and step this slip is dry and that randomly carry out extrusion forming subsequently, can forms electrode.Institute's coat slurry is preferably under 60-250 ℃, more preferably 80-200 ℃ of following thermal treatment 1 minute-10 hours.The strip electrode that is obtained can be intertwined with the separator sheet material, produces the cylindrical electrode that a kind of spiral twines.
Being used for preparing the solvent that is coated in the slip on the metal grabber can be water and/or organic solvent such as N-methylpyrroline ketone, N, dinethylformamide, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), hexamethyl sulphonamide amine, tetramethyl-urea, acetone and/or methylethylketone.In these solvents, preferably adopt methylpyrroline ketone.Can also adopt a kind of dispersion agent if desired, preferably a kind of non-ionic dispersing agent.
To explain the present invention by embodiment below, but the present invention is not subjected to any qualification of said embodiment.
Embodiment 1
With 100 parts of weight by Kynar
The 710 PVDF resin granular materials of forming (are sold by the applicant, 170 ℃ of fusing points, MFR=12 under 230 ℃/2.16 kilograms loads gram/10 minutes), 30 parts of weight is wherein introduced wherein polymethylmethacrylate (SumipexTR is made by Sumitomo Chemical Co.) and 70 parts of sour system/vinylidene fluoride copolymer (Kynar of weight R 1216 with maleic anhydride as the multipolymer composition
2800, sell the MFR=6 gram under 230 ℃/12.5 kilograms loads/10 minutes, 142 ℃ of fusing points by the applicant) join in the mixing tank, through mixing, can be set in 170-240 ℃ duplex forcing machine with temperature cylinder and make pellet by these three kinds of compositions.
The about 0.2 millimeter film (A) of the thickness that utilization adopts simple helix forcing machines to make by these pellets, the Kynar that makes separately
710 films (B) (thickness is 0.3 millimeter) and the about 1 millimeter steel plate (C) of thickness, with these materials with the order of B/A/C stack then under 180 ℃, with about 10 kilograms per centimeter
2Peak pressure pressurize.After being cooled to room temperature, be that 23 ℃ steel plate utilizes the tension test machine with tear 2 centimetres wide B/A layer of the speed of 100 mm/min from temperature.When this power was measured, bonding strength was 2.0 kilograms per centimeter.
Embodiment 2
Prepare the composition grain of being made up of three kinds of components in the mode identical with embodiment 1, its difference is the ratio among the embodiment 1 is become per 100 parts of weight Kynar
710 have 2 parts of weight SumipexTR and 5 parts of weight Kynar 2800.When the bonding strength measured in the mode identical with embodiment between steel plate and the PVDF resin layer, it is 310 gram per centimeters.
Embodiment 3
100 parts of weight PVDF toners (are sold with Kynr 310F by the applicant, 160 ℃ of fusing points, MFR=1.2 under 230 ℃/12.5 kilograms loads gram/10 minutes), 1 part of weight SumipexTR and 1 part of weight Kynar 2800 join in 1000 milliliters of N-methylpyrroline ketone, by obtaining a kind of uniform solution in 24 hours at 30 ℃ of following stir abouts.
This solution is coated on the copper coin and aluminium sheet of 1 mm thick, these plates carry out degreasing with toluene, and are then that this solution is following dry 2 hours at 120 ℃.About 50 microns of the thickness of PVDF resin layer.When with this PVDF resin layer of cut-space of 1 millimeter and carry out crosscut adhesive test (based on Nippon Standard JIS K5400,6.15) and the band stripping test, in any test, all do not see the separation of PVDF resin layer.
Embodiment 4
Prepare the solution that metal is had the composition of cementability in the mode identical with embodiment 3, its difference is to adopt maleic anhydride, N-methyl-dimethyl-penten imide, contain the monomer of carboxylic acid and the multipolymer of methyl methacrylate (Paraloid EL4151 is sold by Rohm and Haas company) as having the acrylic acid polymer that has the functional group of good bonding performance or affinity with metal among the embodiment 3.When measuring bonding strength, do not see peeling off and the bonding strength excellence of PVDF resin layer in the mode identical with embodiment 3.
Embodiment 5
Prepare the solution that metal is had the composition of cementability in the mode identical with embodiment 3, its difference is to adopt have been used through epoxide modified polymethylmethacrylate grafted polymethylmethacrylate (Rezeda GP-301 is sold by Toagosei chemical industrial company) as having the acrylic acid polymer that has the functional group of good bonding performance or affinity with metal among the embodiment 3.
When measuring bonding strength, do not see peeling off and the bonding strength excellence of PVDF resin layer in the mode identical with embodiment 3.
Embodiment 6
Employing is used to obtain double-deck thermoplastic structure's the coextrusion machine that is made of co-extrusion head and the two forcing machines that are used to provide molten resin, and (forcing machine A has and adds pressure ratio is 3.5 and the screw machine of L/D=15, forcing machine B have add pressure ratio be 4 and the screw machine of L/D=20), by extruding the PVDF resin among the forcing machine A (by the applicant with Kynar
740 sell), extrude the bonding composition that obtains by embodiment 1 by forcing machine B, produce the composite membrane that contains 0.3mmPVDF resin layer and 0.1mm adhesive linkage thus.Forcing machine A and B temperature cylinder at this moment is respectively 170-240 ℃ and 150-220 ℃.
When with and embodiment 1 same way as when measuring the film obtained and the adhesiveproperties between the steel plate, it is 1.9 kilograms per centimeter.
The comparative example 1
With 100 parts of weight PVDF resin particles (by Kynar
710 that form, 30 parts of weight maleic anhydrides and methyl methacrylate (Sumipex TR, make by Sumitomo Chemical Co.) join in the mixing tank, through mixing, can be set in 170-240 ℃ duplex forcing machine with temperature cylinder and make the film that thickness is about 0.1mm.
As the Kynar that utilizes this film and make separately with aforesaid method
When 710 films (thickness is 0.3 millimeter) were measured bonding strength with steel plate, its value was for being no more than 1 kilograms per centimeter.
The comparative example 2
With 100 parts of weight PVDF toner (Kynar
301F) be dissolved in 1000 milliliters of N-methylpyrroline ketone and form a kind of solution.Then, in the mode identical, on metal sheet, form the PVDF resin layer with embodiment 3.When adopting the crosscut adhesive test to estimate adhesiveproperties by the mode identical with embodiment 3, for copper coin, have an appointment the 80%PVDF layer with for all PVDF layers of aluminium sheet owing to separating with the 1mm cut-space.
The comparative example 3
With 100 parts of weight Kynar
301F and 1 part of weight Sumipex TR are dissolved in 1000 milliliters of N-methylpyrroline ketone, form a kind of solution.Then, in the mode identical, on aluminium sheet, form the PVDF resin layer with embodiment 3.When measuring bonding strength, find that about 80%PVDF layer is not peeled off in the crosscut test, and in the band stripping test, all PVDF layers have separated all.
Embodiment 7
By with 10 parts of weight poly(vinylidene fluoride)-Kynar
The alkylmethacrylate polymer (the MRF=2.4 gram/minute under 230 ℃/3.8 kilograms) that 500 and 0.1 parts of weight contains 100 parts of weight methacrylic acid methyl esters and 10 parts of weight maleic anhydrides is dissolved in the N-methylpyrroline ketone.Then, the coal tar carbon that adds the fragmentation in ball mill of 90 parts of weight in this solution obtains a kind of slip (slurry) as anode active material.It is on 20 microns the Copper Foil two sides that this slip is coated in thickness, and 120 ℃ of heating 1 hour down, drying under reduced pressure extrusion forming then obtains thickness and be 140 microns and width and be 20 millimeters negative electrode.
The preparation process of negative electrode is as follows:
With 90 parts of weight LiCoO
2As cathode active material, 6 parts of weight graphite are as conductive additive, and 10 parts of weight PVDF mix as caking agent and the 0.1 part of above-mentioned methyl methacrylate of weight-copolymer-maleic anhydride and are dispersed in the N-methylpyrroline ketone to obtain a kind of slurry.It is on 20 microns the aluminium foil two sides that this slurry is coated in thickness, and 120 ℃ of heating 1 hour down, drying under reduced pressure extrusion forming then obtains thickness and be the anode of 170 microns and 20 millimeters.
Can see and have good cementability between electrode and the grabber: when peeling off with cutters, grabber can not take off from electrode surface.
With the negative electrode that obtained and anode is that 25 microns porous polypropylene acid mesentery is stacked in together as spacer by thickness alternately, thereby form the interlayer material of separator/cathode/separator/anode/separator, its spiral is twined, obtain a kind of cylindrical electrode subassembly.Again with galvanized wire with after separately electrode is connected, this electrode assembly is packaged in the stainless steel vessel, to wherein pouring ionogen into.This ionogen is LiPF
6Being dissolved in isopyknic propylene carbonate acid is ester and 1, the 1M solution in the 2-glycol dimethyl ether mixture.
Charge-discharge test: this battery is charged to 4.1V with the current density that 30mA/1 restrains carbon, with identical electric current it is discharged to 2.5V then.Repeat identical charging-discharge operation process, to estimate discharge capability.At 100 later discharge capabilities of circulation is 90% of the 10th circulation time numerical value.
Embodiment 8
Repeat the process of embodiment 7, but change into alkylmethacrylate polymer by the methyl methacrylate block and comprise the segmented copolymer that the copolymer block of methyl methacrylate and vinylformic acid (acrylic acid content is 5% weight) is formed, and adopt the multipolymer that vinylidene fluoride and R 1216 acid is (by the applicant with Kynar
2800 sell) prepare anode and negative electrode as the PVDF resin.
Find between electrode and the grabber have good bonding: when peeling off with cutters, grabber can not take off from electrode surface.
Prepare battery and carry out identical charging-discharge test with the method identical with embodiment 1.100 times the later charging ability of circulation is 85% of the 10th circulation time numerical value.
The comparative example 4
In the process of preparation anode and negative electrode, repeat the process identical and still in slip, do not add alkylmethacrylate polymer with embodiment 7.
When peeling off, there is not grabber partly to be retained on the electrode with cutters.
Adopt the method identical with embodiment 7 to prepare battery and carry out identical charging-discharge test after circulating for 100 times, the ability of discharge is 50% of the 10th circulation time numerical value.
Embodiment 9
By with 10 parts of weight poly(vinylidene fluoride)-Kynar
(content of R 1216 acid system is 10% weight to the multipolymer of 500 and 0.3 parts of weight vinylidene fluorides and R 1216 acid system, the product of Elf Atochem, Kynar
2800, the MRF=1.0 gram under 230 ℃ and 2.16 kilograms of loads/10 minutes) be dissolved in the N-methylpyrroline ketone.Then, the coal tar carbon that adds the fragmentation in ball mill of 90 parts of weight in this solution obtains a kind of slip (slurry) as anode active material.It is on 20 microns Copper Foil (roughly ground with Emery paper No.1000 in advance on its surface) two sides that this slip is coated in thickness, heated 1 hour down at 120 ℃, drying under reduced pressure is extrusion forming then, obtains thickness and be 140 microns and width and be 20 millimeters negative electrode.
The preparation process of negative electrode is as follows: with 90 parts of weight LiCoO
2As cathode active material, 6 parts of weight graphite are as conductive additive, and 10 parts of identical PVDF of weight mix as caking agent with 0.3 part of identical fluorinated copolymers of weight and are dispersed in the N-methylpyrroline ketone to obtain a kind of slurry.It is on 20 microns aluminium foil (roughly ground with Emery paper No.1000 in advance on its surface) two sides that this slurry is coated in thickness, and 120 ℃ of heating 1 hour down, drying under reduced pressure extrusion forming then obtains thickness and be the anode of 165 microns and 20 millimeters.
Can see and have good cementability between electrode and the grabber: when peeling off with cutters, grabber can not take off from electrode surface.
With the negative electrode that obtained and anode is that 25 microns porous polypropylene acid mesentery is stacked in together as spacer by thickness alternately, thereby form the interlayer material of separator/cathode/separator/anode/separator, its spiral is twined, obtain a kind of cylindrical electrode subassembly.Again with galvanized wire with after separately electrode is connected, this electrode assembly is packaged in the stainless steel vessel, to wherein pouring ionogen into.This ionogen is LiPF
6Being dissolved in isopyknic propylene carbonate acid is ester and 1, the 1M solution in the 2-glycol dimethyl ether mixture.
Charge-discharge test: this battery is charged to 4.1V with the current density that 30mA/1 restrains carbon, with identical electric current it is discharged to 2.5V then.Repeat identical charging-discharge operation process, to estimate discharge capability.At 100 later discharge capabilities of circulation is 90% of the 10th circulation time numerical value.
Embodiment 10
Repeat the process of embodiment 9, but vinylidene fluoride copolymer is changed into the multipolymer (Kynar of vinylidene fluoride and tetrafluoroethylene
2820, the content of tetrafluoroethylene is 27%, and the MFR under 230 ℃ and 2.16 kilograms of loads is 3 grams/10 minutes), with preparation anode and negative electrode.
Find between electrode and the grabber have good bonding: when peeling off with cutters, grabber can not take off from electrode surface.
Prepare battery and carry out identical charging-discharge test with the method identical with embodiment 9.100 times the later charging ability of circulation is 85% of the 10th circulation time numerical value.
The comparative example 5
Repeat the process of embodiment 9, but vinylidene fluoride copolymer is not joined the slip that is used for electrode.
When peeling off, there is not the grabber part to stay on the electrode surface with cutters.
Prepare battery and carry out identical charging-discharge test with the method identical with embodiment 9.100 times the later charging ability of circulation is 60% of the 10th circulation time numerical value.
Embodiment 11
By with 10 parts of weight PVDF-Kynar
500, the multipolymer (Kynar of the alkylmethacrylate polymer (the MRF=2.4 gram under 230 ℃/3.8 kilograms/10 minutes) formed by 100 parts of weight methacrylic acid methyl esters and 10 parts of weight maleic anhydrides of 0.1 part of weight and 0.1 part of weight vinylidene fluoride and R 1216 acid system
2800, the MFR=0.2 gram under 230 ℃ and 2.16 kilograms of loads/10 minutes) be dissolved in the N-methylpyrroline ketone.Then, the coal tar carbon that adds the fragmentation in ball mill of 90 parts of weight in this solution obtains a kind of slip (slurry) as anode active material.It is on 20 microns the Copper Foil two sides that this slip is coated in thickness, and 120 ℃ of heating 1 hour down, drying under reduced pressure extrusion forming then obtains thickness and be 145 microns and width and be 20 millimeters negative electrode.
The preparation process of negative electrode is as follows: with 90 parts of weight LiCoO
2As cathode active material, 6 parts of weight graphite are as conductive additive, and the multipolymer of 10 parts of weight PVDF and 0.1 part of above-mentioned methylmethacrylate copolymer of weight and 0.1 part of above-mentioned vinylidene fluoride of weight and R 1216 acid system mixes as caking agent and is dispersed in the N-methylpyrroline ketone to obtain a kind of slurry.It is on 20 microns the aluminium foil two sides that this slurry is coated in thickness, and 120 ℃ of heating 1 hour down, drying under reduced pressure extrusion forming then obtains thickness and be the anode of 175 microns and 20 millimeters.
Can see have between electrode and the grabber good bonding: when peeling off with cutters, grabber can not take off from electrode surface.
With the negative electrode that obtained and anode is that 25 microns porous polypropylene acid mesentery is stacked in together as spacer by thickness alternately, thereby form the interlayer material of separator/cathode/separator/anode/separator, its spiral is twined, obtain a kind of cylindrical electrode subassembly.Again with galvanized wire with after separately electrode is connected, this electrode assembly is packaged in the stainless steel vessel, to wherein pouring ionogen into.This ionogen is LiPF
6Be dissolved in isopyknic propylene carbonate acid and be the 1M solution in ester and 1, the 2 glycol dimethyl ether mixture.
Charge-discharge test: this battery is charged to 4.1V with the current density that 30mA/1 restrains carbon, with identical electric current it is discharged to 2.5V then.Repeat identical charging-discharge operation process, to estimate discharge capability.At 100 later discharge capabilities of circulation is 95% of the 10th circulation time numerical value.
Embodiment 12
Repeat the process of embodiment 11, but use the segmented copolymer of forming by methyl methacrylate block and the copolymer block (acrylic acid content is 5%) formed by methyl methacrylate and vinylformic acid to replace alkylmethacrylate polymer and (content of tetrafluoroethylene is 27% with the multipolymer of vinylidene fluoride copolymer and tetrafluoroethylene, MFR under 230 ℃ and 2.16 kilograms of loads is 3 grams/10 minutes) replace fluorinated copolymers, with preparation anode and negative electrode.
Find between electrode and the grabber have good bonding: when peeling off with cutters, grabber can not take off from electrode surface.
Prepare battery and carry out identical charging-discharge test with the method identical with embodiment 11.100 times the later charging ability of circulation is 92% of the 10th circulation time numerical value.
The comparative example 6
Repeat the process of embodiment 1, but in the process of preparation anode and negative electrode, in slip, do not add alkylmethacrylate polymer and fluorinated copolymers.
When peeling off, there is not grabber to be retained on the electrode surface with cutters.
Prepare battery and carry out identical charging-discharge test with the method identical with embodiment 11.100 times the later charging ability of circulation is 50% of the 10th circulation time numerical value.
Claims (9)
1. one kind has the fluorinated composition of cementability to metal, which comprises at least two kinds in following three kinds of compositions:
(a) at least a PVDF resin,
(b) at least a acrylic acid series and/or the metha crylic polymer that has the functional group of cementability or affinity with metal that have,
(c) at least a vinylidene fluoride copolymer resin.
2. according to the composition of claim 1, per 100 parts of weight polyvinylidene fluoride resins (a), it contains 0.5-100 part weight percent acrylic acid system and/or metha crylic polymer (b), 1-200 part weight vinylidene fluoride copolymer resin (c).
3. be used for method that metal and fluoride resin are bonded together, it is characterized in that adopting claim 1 or 2 said compositions as the caking agent between this fluoride resin and the metal.
4. be used for method that metal and fluoride resin are bonded together, it is characterized in that adopting claim 1 or 2 said any compositions to replace being coated to fluoride resin on the metal.
5. the electrode binder of making by the said composition of claim 1, it only contains (a) and (b), and amount (b) is the 0.5-20 weight % of this caking agent gross weight.
6. the electrode binder of making by the said composition of claim 1, it only contains (a) and (c), and amount (c) is the 0.5-50 weight % of this caking agent gross weight.
7. the electrode binder of making by claim 1 or 2 said compositions, it only contains (a) and (b) and (c), and amount (b) is the 0.5-20 weight % of this caking agent gross weight, and amount (c) is the 0.5-50 weight % of this caking agent gross weight.
8. the electrode that contains the metal grabber that is coated on the electrode, said electrode contain active substance and according to any caking agent of claim 5-7.
9. contain at least a store battery and/or battery, preferably a kind of lithium one ion accumulator and/or battery as the electrode that claim 8 limited.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8610/96 | 1996-01-22 | ||
| JP8008611A JPH09199130A (en) | 1996-01-22 | 1996-01-22 | Electrode and secondary battery using it |
| JP8008610A JPH09199134A (en) | 1996-01-22 | 1996-01-22 | Electrode and secondary battery using it |
| JP8008608A JPH09199132A (en) | 1996-01-22 | 1996-01-22 | Electrode and secondary battery using it |
| JP8611/96 | 1996-01-22 | ||
| JP8608/96 | 1996-01-22 | ||
| JP258465/96 | 1996-09-30 | ||
| JP25846596A JPH10102021A (en) | 1996-09-30 | 1996-09-30 | Bonding of polyvinylidene fluoride resin to metal material and metal bonding composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1213393A true CN1213393A (en) | 1999-04-07 |
Family
ID=27454985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97193081A Pending CN1213393A (en) | 1996-01-22 | 1997-01-22 | Method for adhesion of fluorinated resins to metals |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0876439A1 (en) |
| KR (1) | KR19990081865A (en) |
| CN (1) | CN1213393A (en) |
| AU (1) | AU1444897A (en) |
| CA (1) | CA2243354A1 (en) |
| WO (1) | WO1997027260A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120210C (en) * | 2000-06-08 | 2003-09-03 | 华南理工大学 | Adhesive for lithium ion cell |
| CN100452486C (en) * | 2002-07-24 | 2009-01-14 | 索尼公司 | Cathode and battery including same |
| CN102318108A (en) * | 2009-02-12 | 2012-01-11 | 大金工业株式会社 | Electrode mixture slurry for lithium secondary batteries, and electrode and lithium secondary battery that use said slurry |
| CN104685673A (en) * | 2012-10-10 | 2015-06-03 | 日本瑞翁株式会社 | Method for producing positive electrode for secondary battery, secondary battery, and method for producing stack for secondary battery |
| CN106459644A (en) * | 2014-04-01 | 2017-02-22 | Ppg工业俄亥俄公司 | Electrode binder composition for lithium ion electrical storage devices |
| CN106910861A (en) * | 2015-12-23 | 2017-06-30 | 三星Sdi株式会社 | Dividing plate for rechargeable battery and the lithium rechargeable battery including the dividing plate |
| CN106941149A (en) * | 2016-01-04 | 2017-07-11 | 宁德新能源科技有限公司 | Lithium ion battery and its anode pole piece |
| CN108618633A (en) * | 2017-03-15 | 2018-10-09 | 佛山市顺德区美的电热电器制造有限公司 | cooker and preparation method thereof |
| CN109351793A (en) * | 2018-12-03 | 2019-02-19 | 恩力能源科技有限公司 | Battery pole piece extrusion device and battery pole piece manufacturing system |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3438797A (en) * | 1996-06-26 | 1998-01-14 | Elf Atochem S.A. | Metal-adhesive polyvinylidene fluoride compositions |
| JPH10289732A (en) * | 1997-02-12 | 1998-10-27 | Mitsubishi Electric Corp | Battery adhesive and battery using the same |
| GB0006333D0 (en) | 2000-03-16 | 2000-05-03 | Raychem Ltd | Electrical wire insulation |
| FR2807212A1 (en) * | 2000-03-31 | 2001-10-05 | Atofina | STRUCTURE COMPRISING A FLUORINE PRIMER AND ELECTRODE BASED ON SAID STRUCTURE |
| JP2002030263A (en) * | 2000-07-18 | 2002-01-31 | Atofina Japan Kk | Fluorine-based adhesive resin composition |
| FR2811999B1 (en) * | 2000-07-19 | 2002-12-13 | Atofina | METAL SURFACES COATED WITH FLUORINATED POLYMERS |
| JP2002246029A (en) * | 2001-02-20 | 2002-08-30 | Atofina Japan Kk | Binder composition |
| JP4849286B1 (en) | 2011-06-06 | 2012-01-11 | Ｊｓｒ株式会社 | Positive electrode binder composition |
| JP6495009B2 (en) | 2012-06-27 | 2019-04-03 | 東洋アルミニウム株式会社 | Secondary battery positive electrode, secondary battery, and method for producing secondary battery positive electrode |
| KR101739299B1 (en) | 2013-09-24 | 2017-06-08 | 삼성에스디아이 주식회사 | Composite binder composition for secondary battery, cathode and lithium battery containing the binder |
| KR102234295B1 (en) | 2014-01-10 | 2021-03-31 | 삼성에스디아이 주식회사 | Composite binder composition for secondary battery, cathode and lithium battery containing the binder |
| FR3044012B1 (en) | 2015-11-24 | 2019-04-05 | Arkema France | BINDER FOR ATTACHING MATERIAL CONTAINING VINYLIDENE POLYFLUORIDE TO A METAL - ELECTRODE FOR LITHIUM ION BATTERY |
| EP4336595A1 (en) | 2022-09-09 | 2024-03-13 | Arkema France | Binder for electrode comprising poly(vinylidene fluoride) and a hydrophilic polymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1313701A (en) * | 1969-05-06 | 1973-04-18 | Daikin Ind Ltd | Thermo-stable composition of vinylidene fluoride polymer |
| JPH03213336A (en) * | 1990-01-19 | 1991-09-18 | Mitsubishi Petrochem Co Ltd | Multilayered laminate |
| JP3121943B2 (en) * | 1992-12-02 | 2001-01-09 | 呉羽化学工業株式会社 | Vinylidene fluoride copolymer |
| JPH0888385A (en) * | 1994-09-20 | 1996-04-02 | Fuji Electric Corp Res & Dev Ltd | Thin film solar battery |
-
1997
- 1997-01-22 KR KR1019980705576A patent/KR19990081865A/en not_active Application Discontinuation
- 1997-01-22 CA CA002243354A patent/CA2243354A1/en not_active Abandoned
- 1997-01-22 CN CN97193081A patent/CN1213393A/en active Pending
- 1997-01-22 WO PCT/EP1997/000313 patent/WO1997027260A1/en not_active Application Discontinuation
- 1997-01-22 AU AU14448/97A patent/AU1444897A/en not_active Abandoned
- 1997-01-22 EP EP97901079A patent/EP0876439A1/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1120210C (en) * | 2000-06-08 | 2003-09-03 | 华南理工大学 | Adhesive for lithium ion cell |
| CN100452486C (en) * | 2002-07-24 | 2009-01-14 | 索尼公司 | Cathode and battery including same |
| CN102318108A (en) * | 2009-02-12 | 2012-01-11 | 大金工业株式会社 | Electrode mixture slurry for lithium secondary batteries, and electrode and lithium secondary battery that use said slurry |
| CN104685673A (en) * | 2012-10-10 | 2015-06-03 | 日本瑞翁株式会社 | Method for producing positive electrode for secondary battery, secondary battery, and method for producing stack for secondary battery |
| CN104685673B (en) * | 2012-10-10 | 2017-09-22 | 日本瑞翁株式会社 | The manufacture method of the manufacture method of anode of secondary cell, secondary cell and secondary cell laminated body |
| CN106459644A (en) * | 2014-04-01 | 2017-02-22 | Ppg工业俄亥俄公司 | Electrode binder composition for lithium ion electrical storage devices |
| CN106459644B (en) * | 2014-04-01 | 2019-09-10 | Ppg工业俄亥俄公司 | Electrode adhesive composition for lithium ion storage device |
| CN106910861A (en) * | 2015-12-23 | 2017-06-30 | 三星Sdi株式会社 | Dividing plate for rechargeable battery and the lithium rechargeable battery including the dividing plate |
| CN106941149A (en) * | 2016-01-04 | 2017-07-11 | 宁德新能源科技有限公司 | Lithium ion battery and its anode pole piece |
| CN108618633A (en) * | 2017-03-15 | 2018-10-09 | 佛山市顺德区美的电热电器制造有限公司 | cooker and preparation method thereof |
| CN109351793A (en) * | 2018-12-03 | 2019-02-19 | 恩力能源科技有限公司 | Battery pole piece extrusion device and battery pole piece manufacturing system |
| CN109351793B (en) * | 2018-12-03 | 2024-03-15 | 北京恩力动力科技有限公司 | Battery pole piece manufacturing system |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990081865A (en) | 1999-11-15 |
| CA2243354A1 (en) | 1997-07-31 |
| AU1444897A (en) | 1997-08-20 |
| EP0876439A1 (en) | 1998-11-11 |
| WO1997027260A1 (en) | 1997-07-31 |
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