WO1997027260A1 - Procede pour l'adherence de resines fluorees a des metaux - Google Patents

Procede pour l'adherence de resines fluorees a des metaux Download PDF

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Publication number
WO1997027260A1
WO1997027260A1 PCT/EP1997/000313 EP9700313W WO9727260A1 WO 1997027260 A1 WO1997027260 A1 WO 1997027260A1 EP 9700313 W EP9700313 W EP 9700313W WO 9727260 A1 WO9727260 A1 WO 9727260A1
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WIPO (PCT)
Prior art keywords
weight
metals
parts
composition
fluorinated
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PCT/EP1997/000313
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English (en)
Inventor
Yoshiyuki Miyaki
Kazuyoshi Ohashi
Kuniyuki Goto
Jérôme MAILLET
Yoshiyuki Shimonishi
Original Assignee
Elf Atochem S.A.
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Publication date
Priority claimed from JP8008610A external-priority patent/JPH09199134A/ja
Priority claimed from JP8008608A external-priority patent/JPH09199132A/ja
Priority claimed from JP8008611A external-priority patent/JPH09199130A/ja
Priority claimed from JP25846596A external-priority patent/JPH10102021A/ja
Application filed by Elf Atochem S.A. filed Critical Elf Atochem S.A.
Priority to JP09526547A priority Critical patent/JP2000507996A/ja
Priority to EP97901079A priority patent/EP0876439A1/fr
Priority to AU14448/97A priority patent/AU1444897A/en
Publication of WO1997027260A1 publication Critical patent/WO1997027260A1/fr

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • 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
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for the adhesion/lamination of fluorinated resins and metals which are inherently non-adhesive thereto, and the invention can be applied to steel pipe linings, chemical plant components, and binders for the electrodes of batteries, etc, where corrosion resistance, weathering resistance or chemical resistance is demanded
  • PVDF polyvinylidene fluoride
  • PMMA polymethyl methacrylate resin
  • the present invention has the objective of improving the adhesion of fluorinated resins to metal mate ⁇ als, and of offering a method for obtaining composite materials of metal materials and fluorinated resins MEANS FOR RESOLVING THE PROBLEM
  • a fluorinated composition comprising at least 2 of the 3 following components : (a) at least a PVDF resin, (b) at least a acrylic an/or methacrylic polymer having functional groups with bonding properties or affinity in respect of metals, (c) at least a vinylidene fluoride copoiymer resin exhibits good adhesion properties on metal materials, and they have discovered that such characteristics are effective in the production of composite materials comprising such compositions and metals.
  • the PVDF resins (a) referred to here can be selected from polyvinylidene fluoride homopolymers and have preferably a melt flow rate (MFR) of 0.01 to 300 g/10min at 230 °C under a load of 2.16 kg.
  • MFR melt flow rate
  • the vinylidene fluoride copolymers (c) are copolymers of vinylidene fluoride (VF2) and other monomer(s) which can copolymerize with VF2, and the percentage VF2 component in these copolymers should be from 50 to 95 wt%, more preferably from 75 to 95 wt%.
  • fluoro-monomers such as tetrafluoroethylene, hexafluoropropylene, tri-fluoroethylene and trifluorochloroethylene, etc, are preferred, and it is possible to use one or more of these.
  • the copolymers (c) have a room temperature flexural modulus of no more than 1.000 MPa and that they exhibit a breaking elongation of at least 50% and preferably a melt flow rate (MFR) at 230°C under a 2.16kg load in the range from 0.01 to 300g/10 min.
  • MFR melt flow rate
  • the fluorinated resins (a) and (c) may be obtained by the polymerization of vinylidene fluoride monomer or vinylidene fluoride monomer and other monomer(s) by the suspension polymerization method or emulsion polymerization method, etc,
  • the acrylic and/or methacrylic polymers (b) are polymers in which the chief component is an alkyl acrylate and/or alkyl methacrylate and which has, in the main chain, in the side chains or at the terminals, functional groups which exhibit bonding properties or affinity in terms of metals.
  • Such polymers there are the random copolymers, block copolymers and graft polymers produced by methods such as radical polymerization, ionic polymerization or co-ordination polymerization from at least one type of monomer selected from alkyl acrylates and alkyl methacrylates, plus monomer with a functional group which exhibits bonding properties or affinity in respect of metals.
  • acrylic and/or methacrylic polymer comprises the copoiymer of monomer with a carboxylic acid group or carboxylic acid anhydride group and an alkyl acrylate and/or alkyl methacrylate.
  • alkyl (meth)acrylate are methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
  • the monomer with a carboxylic acid group or carboxylic acid anhydride group there are acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, alkenylsuccinic acid, acrylamido-glycolic acid, allyl 1 ,2- cyclohexanedicarboxylate and other such unsaturated carboxylic acids, and maleic anhydride, alkenylsuccinic anhydride and other such unsaturated carboxylic acid anhydrides, etc.
  • At least 50 wt%, and more desirably at least 70 wt%, of this acrylic and/or methacrylic polymer be composed of at least one type of monomer selected from acrylate and/or methacrylate esters.
  • the amount of the contained functional groups which exhibit bonding properties or affinity in respect of metals will preferably be from 0.01 to 2 mole per 1kg of the acrylic and/or methacrylic polymer.
  • this polymer component is a copoiymer of at least one monomer selected from acrylate and/or methacrylate esters and monomer having a carboxylic acid group or carboxylic acid anhydride group
  • the proportion of the monomer with a carboxylic acid group or carboxylic acid anhydride group will preferably be from 0.2 to 30 wt% of the said copoiymer, and more preferably from 1 to 20 wt%.
  • a constituent component there may also be included in the molecular chain, besides the above, vinyl monomer such as styrene or modified units such as imides, but the amount of these will not be more than 50 wt%, and preferably not more than 30 wt% of the said polymer.
  • the metal-adhesive composition contains (a), (b) and (c) components, it contains from 0.5 to 100 parts by weight of an acrylic and/or methacrylic polymer (b), from 1 to 200 parts by weight of vinylidene fluoride copoiymer resin (c) per 100 parts by weight of polyvinylidene fluoride resin (a).
  • the metal-adhesive composition of the present invention can be prepared by a solution process or melt process.
  • the aforesaid components (a), (b) and (c) may be dissolved in the prescribed proportions in a solvent such as N-methylpyrrolidone, N.N-dimethylformamide, tetrahydrofuran, dimethyl-acetamide, dimethylsulphoxide, hexamethylphosphoramide, tetramethylurea, acetone, methyl ethyl ketone or the like, at a temperature lower than the boiling point of the solvent used.
  • a solvent such as N-methylpyrrolidone, N.N-dimethylformamide, tetrahydrofuran, dimethyl-acetamide, dimethylsulphoxide, hexamethylphosphoramide, tetramethylurea, acetone, methyl ethyl ketone or the like.
  • production can be carried out by a conventional method, i-e.
  • the amount of the vinylidene fluoride copoiymer added per 100 parts by weight of the vinylidene fluoride resin is from 1 to 10 parts by weight, and preferably from 1 to 5 parts by weight, and, similarly, if the amount of the acrylic or methacrylic polymer is from 0.5 to 10 parts by weight, preferably from 1 to 5 parts by weight, then it is possible to improve the adhesion to metals without greatly altering the properties of the vinylidene fluoride resin. This method is especially effective where the adhesion process is a solution application method.
  • this fluorinated composition of the present invention can be employed as the adhesive agent when sticking fluorinated resins to metals.
  • the three component-composition is composed of 5 to 100 parts by weight of the acrylic or methacrylic polymer (b) with bonding properties or affinity in terms of metals and from 10 to 200 parts by weight of vinylidene fluoride copoiymer (c) per 100 parts by weight of PVDF resin (a).
  • the fluorinated composition with improved metal adhesion can be used as an adhesive agent when sticking a fluorinated resin to a metal, the said fluorinated resin does not necessarily have to be composed of the same fluorinated resin as fluorinated resin which constitutes the surface layer.
  • the fluorinated resin employed in the adhesive layer a resin having an appropriate melt flow rate (MFR), copoiymer composition and melting point, according to the adhesion/processing operation.
  • metal materials employed as the adhered base material in the present invention there are iron, stainless steel, aluminium, copper, nickel, titanium, lead, silver, chromium, and alloys of various kinds, etc, and the form thereof is not particularly restricted.
  • the metal-adhesive fluorinated composite materials obtained by this method consist of fluorinated resin such as an extrusion moulded article (film, sheet, plate, pipe, rod, profile extruded article, strand, monofilament, fibre, etc), injection moulded article or press moulded article, etc, part or the entire face of which comprises a layer of the aforesaid metal-adhesive composition, and it is not especially restricted.
  • Means for the preparation thereof include calendering, coextrusion, extrusion lamination, multi-layer injection, fluid immersion coating, dipping, spraying and coating the surface of a moulded body, etc.
  • the polyvinylidene fluoride resin used as the base material and the polyvinylidene resin used in the metal-adhesive composition may be the same or different.
  • the method of the present invention can be used for fluoro-coating materials employing fluorinated resin dissolved or dispersed in a solvent or for electric wire coating by means of fluorinated resin. Moreover, it can be used for the binders for the electrodes of lithium batteries, etc, and in such circumstances it is useful in improving the adhesion between the metal substrate (in the case of a battery, the current collector) and the electrode active material layer.
  • the method of the present invention for sticking fluorinated resins and particularly PVDF resins and/or VF2 copoiymer resins to metals can be employed in various products, and it is valuable in many fields such as structural components of equipment where chemical inactivity is demanded in the chemical, pharmaceutical and foodstuffs industries, and exterior building materials and industrial materials where weatherability over a prolonged period is required, and also for the binders for electrodes in lithium batteries, etc.
  • the lithium-ion batteries are an excellent solution because they are thin and lightweight, do not contain heavy metals than cause environmental problems and they provide higher energy density than existing nickel-cadmium, nickel-metal hydride, and lead-acid batteries.
  • the lithium-ion battery's laminate structure is generally as follows
  • the anode active substance can be made of any material which permits doping and releasing of lithium ions and is generally made of carbonaceous materials including cokes such as petroleum cokes and carbon cokes, carbon blacks such as acetylene black, graphite, fibrous carbon, activated carbon, carbon fibers and sintered articles obtained from organic high polymers by burning the organic high polymer in non-oxidation atmosphere Copper oxide or other electro-conductive materials also can be incorporated or added to the cathode active substance
  • the binder which must possess high resistance to solvents and chemicals is generally based on fluorinated resins, polyolefins, synthetic rubbers but fluorinated resins are preferred
  • the contents of fluorinated resins in the binder is preferably more than 90 wt%
  • the PVDF resins are preferably used and more particularly these ones with more than 75 wt% VF2 because of their high resistance to solvents and to active chemicals so as their high solubility in methylpyrolidone which is a common solvent of lithium-ion batteries
  • PVDF resins these ones consisting of mixtures of homopolymer of vinyl idenefluo ⁇ de and fluorinated copolymer(s), the contents of VF2 of the fluorinated copolymer(s) is 50 to 95 wt% and whose amount of homopolymer of viny denefluo ⁇ de in the mixture is 50 to 99 5 wt% are also preferred
  • An usual process for making the anode consists of mixing the carbonaceous material in powder form with a suitable amount of binder and is kneaded with a solvent to prepare a paste or slurry Then a collector (generally copper) is coated onto the paste and is then dried and compacted to obtain the anode
  • the lithium-ion battery cathode is generally made of lithium and oxide of transition metals as manganese oxide and vanadium oxide, sulfides of transition metals such as iron sulfide and titanium sulfide, or composite compounds between these substances as composite oxides of lithium and cobalt, composite oxides of lithium, cobalt and nickel, composite oxides of lithium and manganese
  • the cathode active substance can also be mixed with electroconductive substances (usually, carbon) and a suitable amount of binder and is kneaded with a solvent to prepare a paste which is then applied to a collector (generally an aluminum collector) and is then dried and compacted to obtain the cathode
  • the binders for cathodes can be the same than disclosed for the anodes and are preferably based on fluorinated resins.
  • the amount of binder is generally of 1 to 30 parts, preferably 3 to 15 parts by weight, with respect to 100 parts by weight of electrode active substance.
  • the present invention provides improved binders consisting of the above metal-adhesive compositions :
  • the electrode can be produced by the steps of kneading predetermined amounts of electrode active substance and binder in the presence of solvent to obtain a slurry, coating the resulting slurry onto a collector of an electrode and drying the slurry, optionally followed by press-molding.
  • the coated slurry is preferably subjected to heat-treatment at 60 to 250 °C, preferably 80 to 200 °C for 1 minute to 10 hours.
  • the resulting band-shaped electrode can be wound together with separator sheet to produce a spirally wound cylindrical electrode.
  • the solvent used to prepare the slurry to be coated on a metal collector can be water and/or an organic solvent as N-methylpyrolidone, N, N-dimethylformamide, tetrahydrofuran, dimethyl acetoamide, dimethyl sulfoxide, hexamethylsulfonamide, tetramethylurea, acetone and/or methylethyl ketone.
  • N-methylpyrolidone is preferably used.
  • a dispersant can also be used, and preferably an nonionic dispersant.
  • Example 2 Except for changing the proportions of Example 1 to 2 parts by weight of the
  • Example 5 Excepting that, as the acrylic polymer with functional groups which exhibit good bonding properties or affinity in respect of metals in Example 3, there was used a copoiymer of maleic anhydride, N-methyl-dimethylglutarimide, carboxylic-acid- containing monomer and methyl methacrylate (Paraloid® EXL4151 sold by Rohm and Haas), a solution of metal-adhesive composition was prepared in the same way as in Example 3. When the adhesive strength was measured in the same way as in Example 3, no peeling of the PVDF resin layer was noted and the adhesive strength was excellent.
  • Example 5 a copoiymer of maleic anhydride, N-methyl-dimethylglutarimide, carboxylic-acid- containing monomer and methyl methacrylate
  • Example 3 Excepting that, as the acrylic polymer with functional groups which exhibit bonding properties or affinity in respect of metals in Example 3, there was used polymethyl methacrylate to which epoxy-modified polymethyl methacrylate had been grafted (made by Toagosei Chemical Industry Co., Rezeda GP-301 ), a solution of metal-adhesive composition was prepared in the same way as in Example 3.
  • the cylinder temperatures of extruders A and B at this time were 170-240°C and 150-220°C respectively.
  • PVDF resin pellets Kynar ®710 100 parts by weight of PVDF resin pellets Kynar ®710) and 30 parts by weight of a copoiymer of maleic anhydride and methyl methacrylate (Sumipex TR sold by
  • Example 3 1000ml of N-methylpyrrolidone and a solution produced. Then, in the same way as in Example 3, a PVDF resin layer was formed on metal sheet. When the adhesion properties were evaluated by means of a cross-cut adhesion test in the same way as in Example 3, it was found that, in the case of copper sheet, about 80% of the PVDF layer, and in the case of the aluminium sheet, all of the PVDF layer separated away due to the cutting at spacings of 1 mm. Comparative Example 3
  • Example 7 A binder solution was made by dissolving 10 parts by weight of polyvinylidenefluoride Kynar®500 and 0.1 part by weight of a methacrylate copoiymer (MFR at 230 °C/3.8 kg : 2.4 g/10 min ) comprising 100 parts by weight of methylmethacrylate and 10 parts by weight of maleic anhydride in N- methylpyrolidone. Then, 90 parts by weight of coal pitch coke crushed in a ball mill as anode activ substance was added to the solution to obtain a slurry (paste).
  • MFR methacrylate copoiymer
  • a cathode was prepared as follows : 90 parts by weight of LiCo ⁇ 2 as cathode active substance, 6 parts of graphite as electro-conductive additive, 10 parts by weight of PVDF as binder and 0.1 part by weight of the above-mentioned methylmethacrylate-maleic anhydride copoiymer were mixed and dispersed in N-methylpyrolidone to obtain a slurry (paste).
  • the slurry was coated on both sides of an aluminum foil of thickness 20 ⁇ m, heated at 120 °C for 1 hour, dried under reduced pressure and then press-molded to obtain anode having a thickness of 170 ⁇ m and of width 20 mm.
  • a good adhesion between the electrodes and the collectors was noted : the collectors cannot be removed from the surface of the electrodes when peeled off with a cutter-knife.
  • the resulting cathode and anode were laminated alternately through a film of porous polypropyleneof thickness of 25 ⁇ m as separator to form a laminate of separator/cathode/separator/anode/separator which was wound up spirally to obtain a cylindrical electrode assembly.
  • the electrode assembly was packed in a stainless container into which an electrolyte was poured.
  • the electrolyte is 1 M solution of LiPF ⁇ dissolved in a equivolumic mixture of propylene carbonate and 1 , 2-dimethoxyethane.
  • a charge-discharge test was effected : the battery was charged with a current density of 30 mA / 1 g of carbon to 4.1 V and then was discharged with the same current to 2.5 V. The same charge-discharge operation was repeated to evaluate the capacity of discharge. The capacity of discharge after 100 cycles was 90 % of a value of 10th cycle.
  • Example 7 The procedure of Example 7 was repeated but and the methacrylate copoiymer was changed to a block copoiymer consisting of methymethacrylate block and a copoiymer block comprising methylmethacryate and acrylic acid (acrylic acid contents 5 % by weight) and as the PVDF type resin, a copoiymer of vinylidenefluoride and hexafluoropropylene sold by the applicant under Kynar ® 2800) was used to prepare both anode and cathode.
  • a copoiymer of vinylidenefluoride and hexafluoropropylene sold by the applicant under Kynar ® 2800
  • a cell was manufactured by the same method as Example 1 and the same charge-discharge test was effected.
  • the capacity of discharge after 100 cycles was 85 % of a value of 10th cycle.
  • Comparative Example 4 The same procedure as Example 7 was repeated but no methacrylate copoiymer was added to the slurry during the preparation of both anode and cathode.
  • a binder solution was made by dissolving 10 parts by weight of polyvinylidenefluoride Kynar ®500 and 0.3 parts by weight of a copoiymer of vinylidenefluoride and hexafluoropropylene (contents of hexafluoropropylene: 10 % by weight, a product of Elf Atochem, Kynar ⁇ 2820, MFR of 1.0 g/10 min at 230 °C under a load of 2.16 kg) in N-methylpyrolidone. Then, 90 parts by weight of coal pitch coke crushed in a ball mill as anode active substance was added to the solution to obtain a slurry (paste).
  • the slurry was coated on both sides of a copper foil of thickness 20 ⁇ m and whose surfaces have been roughened previously by Emery paper No. 1000, heated at 120 °C for 1 hour, dried under reduced pressure and then press-molded to obtain a cathode of thickness of 140 ⁇ m and of width 20 mm.
  • a cathode was prepared as follows: 90 parts by weight of LiCo ⁇ 2 as cathode active substance, 6 parts of graphite as electro-conductive additive and 10 parts by weight of the same PVDF and 0.3 % by weight of the same fluorinated copoiymer as binder were mixed and dispersed in N-methylpyrolidone to obtain a slurry (paste). The slurry was coated on both sides of the aluminum foil whose surface have been roughened previously by Emery paper No. 1000, heated at 120 °C for 1 hour, dried under reduced pressure and then press-molded to obtain anode of thickness 165 ⁇ m and of width 20 mm.
  • the resulting cathode and anode were laminated alternately through a film of porous polypropylene of thickness of 25 ⁇ m as separator to form a laminate of separator/cathode/separator/anode/separator which was wound spirally to obtain a cylindrical electrode assembly.
  • the electrode assembly was packed in a stainless container into which an electrolyte was poured.
  • the electrolyte is 1 M LiPF ⁇ solution dissolved in an equivolumic mixture of propylene carbonate and 1 , 2-dimethoxyethane.
  • the battery was charged with a current density of 30 mA / 1 g of carbon to 4.1 V and then was discharged with the same current to 2.5 V. The same charge-discharge operation was repeated to evaluate the capacity of discharge. The capacity of discharge after 100 cycles was 90 % of a value of 10th cycle. 13
  • Example 9 The procedure of Example 9 was repeated but the vinylidenefluonde copoiymer was changed to a copoiymer of vinylidenefluonde and tetrafluoroethylene (Kynar ® 2820, weight contents of tetrafluoroethylene 27 %, MFR of 3 g/10 mm at 230 °C under a load of 2 16 kg) to prepare an anode and a cathode
  • Example 9 A cell was manufactured by the same method as Example 9 and the same charge-discharge test was effected The capacity of discharge after 100 cycles was 85 % of a value of 10th cycle Comparative Example 5
  • Example 9 The procedure of Example 9 was repeated but no vinylidenefluonde copoiymer was- added to the slurry for electrodes No part of both collectors remains on both electrodes when peeled off with a cutter-knife
  • Example 11 A cell was manufactured by the same method as in Example 9 and the same charge-discharge test was effected After 100 cycles the capacity of discharge was 60 % of a value of 10th cycle Example 11
  • a binder solution was made by dissolving 10 parts by weight of PVDF Kynar 500, 0 1 part by weight of a methacrylate copoiymer (melt flow index of 2 4 g/10 mm at 230 °C under a load of 3 8 kg) comprising 100 parts by weight of methylmethacrylate and 10 parts by weight of maleic anhydride, and 0 1 part by weight of a copoiymer of vinylidenefluonde and hexafluoropropylene Kynar®2800 MFR of 0 2 g/10 mm at 230 °C under a load of 2 16 kg) in N-methylpyrolidone
  • 90 parts by weight of coal pitch coke crushed in a ball mill as anode active carrier was added to the solution to obtain a slurry (paste)
  • the slurry was coated on both sides of a copper foil of thickness 20 ⁇ m, heated at 120 °C for 1 hour, dried under reduced pressure and then press-molded to obtain an anode
  • a cathode was prepared as follows 90 parts by weight of L1C0O2 as cathode active substance, 6 parts of graphite as electro-conductive additive, 10 parts by weight of PVDF, 0 1 part by weight of the above-mentioned methacrylate copoiymer and 0 1 part by weight of the above copoiymer of vinylidenefluonde and hexafluoropropylene as binder were mixed and dispersed in N-methylpyrolidone to obtain a slurry (paste) The slurry was coated on both sides of an aluminum foil of thickness 20 ⁇ m, heated at 120 °C for 1 hour, dried under reduced pressure and then press-molded to obtain an anode of thickness 175 ⁇ m and of width 20 mm
  • the resulting cathode and anode were laminated alternately through a film of porous polypropylene of thickness 25 ⁇ m as separator to form a laminate of separator/cathode/separator/anode/separator which was wound up spirally to obtain a cylindrical electrode assembly
  • the electrode assembly was packed in a stainless container into which an electrolyte was poured
  • the electrolyte is 1 M solution of LiPF ⁇ dissolved in an equivolumic mixture of propylene carbonate and 1 , 2-dimethoxyethane
  • Example 11 The procedure of Example 11 was repeated but the methacrylate copoiymer was replaced to a block copoiymer consisting of methyl methacrylate block and a copoiymer block comprising methylmethacrylate and acrylic acid (weight contents of acrylic acid . 5 %) and the fluorinated copoiymer was replaced by a copoiymer of vinylidenefluonde and tetrafluoroethylene (weight contents of tetrafluoroethylene 27 %, MFR of 3 g/10 mm at 230 °C under a load of 2.16 kg) to prepare an anode and a cathode.
  • a copoiymer of vinylidenefluonde and tetrafluoroethylene weight contents of tetrafluoroethylene 27 %, MFR of 3 g/10 mm at 230 °C under a load of 2.16 kg
  • Example 11 A cell was manufactured by the same method as Example 11 and the same charge-discharge test was effected The capacity of discharge after 100 cycles was 92 % of a value of 10th cycle Comparative Example 6
  • Example 2 The same procedure as Example 1 was repeated but the methacrylate copoiymer and the fluorinated copolymere were not added to the slurry in preparation of both anode and cathode

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention a pour objet un procédé simple permettant d'améliorer l'adhérence de résines fluorées à des matériaux métalliques, et d'obtenir des matériaux composites de matériaux métalliques et de résines de polyfluorure de vinylidène. Il est possible d'utiliser une composition fluorée adhérant aux métaux comme agent adhésif entre des résines fluorées et des métaux ou à la place des résines fluorées.
PCT/EP1997/000313 1996-01-22 1997-01-22 Procede pour l'adherence de resines fluorees a des metaux WO1997027260A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP09526547A JP2000507996A (ja) 1997-01-22 1997-01-22 フッ化樹脂の金属材料への接着方法
EP97901079A EP0876439A1 (fr) 1996-01-22 1997-01-22 Procede pour l'adherence de resines fluorees a des metaux
AU14448/97A AU1444897A (en) 1996-01-22 1997-01-22 Method for the adhesion of fluorinated resins to metals

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP8/8610 1996-01-22
JP8/8608 1996-01-22
JP8008610A JPH09199134A (ja) 1996-01-22 1996-01-22 電極およびそれを使用した二次電池
JP8/8611 1996-01-22
JP8008608A JPH09199132A (ja) 1996-01-22 1996-01-22 電極およびそれを使用した二次電池
JP8008611A JPH09199130A (ja) 1996-01-22 1996-01-22 電極およびそれを使用した二次電池
JP8/258465 1996-09-30
JP25846596A JPH10102021A (ja) 1996-09-30 1996-09-30 ポリフッ化ビニリデン樹脂の金属材料への接着方法および金属接着性組成物

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WO1997027260A1 true WO1997027260A1 (fr) 1997-07-31

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EP (1) EP0876439A1 (fr)
KR (1) KR19990081865A (fr)
CN (1) CN1213393A (fr)
AU (1) AU1444897A (fr)
CA (1) CA2243354A1 (fr)
WO (1) WO1997027260A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997049777A2 (fr) * 1996-06-26 1997-12-31 Elf Atochem S.A. Compositions de poly(fluorure de vinylidene) ayant des proprietes d'adhesion a un metal
EP0859417A2 (fr) * 1997-02-12 1998-08-19 Mitsubishi Denki Kabushiki Kaisha Adhésif pour batterie, batterie utilisant cet adhésif et procédé de fabricaiton d'une telle batterie
EP1138698A1 (fr) * 2000-03-31 2001-10-04 Atofina Structure comprenant un primaire fluoré et électrode à base de cette structure
WO2002006406A2 (fr) * 2000-07-19 2002-01-24 Atofina Surfaces metalliques revêtues de polymeres fluores
WO2002006355A2 (fr) * 2000-07-18 2002-01-24 Atofina Composition de resine adhesive de type fluoree
WO2002073720A2 (fr) * 2001-02-20 2002-09-19 Atofina Composition de liant
US6753478B2 (en) 2000-03-16 2004-06-22 Tyco Electronics Uk Limited Electrical wire insulation
EP2533335A1 (fr) * 2011-06-06 2012-12-12 JSR Corporation Composition de liant pour électrodes positives
WO2015153583A1 (fr) * 2014-04-01 2015-10-08 Ppg Industries Ohio, Inc. Composition de liant d'électrode pour dispositifs de stockage électrique au lithium-ion
US9711796B2 (en) 2014-01-10 2017-07-18 Samsung Sdi Co., Ltd. Binder composition for secondary battery, cathode and lithium battery including the binder composition
US9899681B2 (en) 2012-06-27 2018-02-20 Toyo Aluminium Kabushiki Kaisha Positive electrode for secondary batteries, secondary battery, and method for producing positive electrode for secondary batteries
US10109863B2 (en) 2013-09-24 2018-10-23 Samsung Sdi Co., Ltd. Composite binder composition for secondary battery, cathode and lithium battery containing the binder composition
US10717890B2 (en) 2015-11-24 2020-07-21 Arkema France Binder containing polyvinylidene fluoride capable of fixing to a metal and associated lithium-ion battery electrode
EP4336595A1 (fr) 2022-09-09 2024-03-13 Arkema France Liant pour électrode comprenant du poly(fluorure de vinylidène) et un polymère hydrophile

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CN1120210C (zh) * 2000-06-08 2003-09-03 华南理工大学 锂离子电池胶粘剂
JP3661945B2 (ja) * 2002-07-24 2005-06-22 ソニー株式会社 二次電池用正極およびそれを備えた二次電池
JP5625917B2 (ja) * 2009-02-12 2014-11-19 ダイキン工業株式会社 リチウム二次電池の電極合剤用スラリー、該スラリーを用いた電極およびリチウム二次電池
PL2908364T3 (pl) * 2012-10-10 2018-08-31 Zeon Corporation Sposób wytwarzania elektrody dodatniej dla akumulatora elektrycznego, akumulator elektryczny i sposób wytwarzania zespołu w postaci stosu dla akumulatora elektrycznego
KR20170075490A (ko) * 2015-12-23 2017-07-03 삼성에스디아이 주식회사 이차 전지용 세퍼레이터 및 이를 포함하는 리튬 이차 전지
CN113725398A (zh) * 2016-01-04 2021-11-30 宁德新能源科技有限公司 锂离子电池及其正极极片
CN108618633A (zh) * 2017-03-15 2018-10-09 佛山市顺德区美的电热电器制造有限公司 炊具及其制备方法
CN109351793B (zh) * 2018-12-03 2024-03-15 北京恩力动力科技有限公司 一种电池极片制造系统

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DE2022279A1 (de) * 1969-05-06 1970-11-19 Daikin Ind Ltd Thermostabilisierte Vinylidenfluoridmassen
JPH03213336A (ja) * 1990-01-19 1991-09-18 Mitsubishi Petrochem Co Ltd 多層積層体
EP0601754A1 (fr) * 1992-12-02 1994-06-15 Kureha Kagaku Kogyo Kabushiki Kaisha Copolymère de fluorure de vinylidène, et composition liante contenant de copolymère pour pile secondaire de type solvant non-aqueux
JPH0888385A (ja) * 1994-09-20 1996-04-02 Fuji Electric Corp Res & Dev Ltd 薄膜太陽電池

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DE2022279A1 (de) * 1969-05-06 1970-11-19 Daikin Ind Ltd Thermostabilisierte Vinylidenfluoridmassen
JPH03213336A (ja) * 1990-01-19 1991-09-18 Mitsubishi Petrochem Co Ltd 多層積層体
EP0601754A1 (fr) * 1992-12-02 1994-06-15 Kureha Kagaku Kogyo Kabushiki Kaisha Copolymère de fluorure de vinylidène, et composition liante contenant de copolymère pour pile secondaire de type solvant non-aqueux
JPH0888385A (ja) * 1994-09-20 1996-04-02 Fuji Electric Corp Res & Dev Ltd 薄膜太陽電池

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Title
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DATABASE WPI Derwent World Patents Index; AN 96-227546 *

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997049777A3 (fr) * 1996-06-26 1998-05-07 Atochem Elf Sa Compositions de poly(fluorure de vinylidene) ayant des proprietes d'adhesion a un metal
WO1997049777A2 (fr) * 1996-06-26 1997-12-31 Elf Atochem S.A. Compositions de poly(fluorure de vinylidene) ayant des proprietes d'adhesion a un metal
EP0859417A3 (fr) * 1997-02-12 2003-05-02 Mitsubishi Denki Kabushiki Kaisha Adhésif pour batterie, batterie utilisant cet adhésif et procédé de fabricaiton d'une telle batterie
EP0859417A2 (fr) * 1997-02-12 1998-08-19 Mitsubishi Denki Kabushiki Kaisha Adhésif pour batterie, batterie utilisant cet adhésif et procédé de fabricaiton d'une telle batterie
US6753478B2 (en) 2000-03-16 2004-06-22 Tyco Electronics Uk Limited Electrical wire insulation
EP1138698A1 (fr) * 2000-03-31 2001-10-04 Atofina Structure comprenant un primaire fluoré et électrode à base de cette structure
FR2807212A1 (fr) * 2000-03-31 2001-10-05 Atofina Structure comprenant un primaire fluore et electrode a base de cette structure
SG100663A1 (en) * 2000-03-31 2003-12-26 Atofina Structure comprising a fluoro primer and electrode based on this structure
WO2002006355A2 (fr) * 2000-07-18 2002-01-24 Atofina Composition de resine adhesive de type fluoree
WO2002006355A3 (fr) * 2000-07-18 2002-05-16 Atofina Composition de resine adhesive de type fluoree
FR2811999A1 (fr) * 2000-07-19 2002-01-25 Atofina Surfaces metalliques revetues de polymeres fluores
WO2002006406A3 (fr) * 2000-07-19 2002-05-23 Atofina Surfaces metalliques revêtues de polymeres fluores
WO2002006406A2 (fr) * 2000-07-19 2002-01-24 Atofina Surfaces metalliques revêtues de polymeres fluores
US6773815B2 (en) 2000-07-19 2004-08-10 Atofina Metal surfaces coated with fluorinated polymers
WO2002073720A2 (fr) * 2001-02-20 2002-09-19 Atofina Composition de liant
WO2002073720A3 (fr) * 2001-02-20 2003-05-01 Atofina Composition de liant
EP2533335A1 (fr) * 2011-06-06 2012-12-12 JSR Corporation Composition de liant pour électrodes positives
US8513349B2 (en) 2011-06-06 2013-08-20 Jsr Corporation Binder composition for positive electrodes
US9899681B2 (en) 2012-06-27 2018-02-20 Toyo Aluminium Kabushiki Kaisha Positive electrode for secondary batteries, secondary battery, and method for producing positive electrode for secondary batteries
US10109863B2 (en) 2013-09-24 2018-10-23 Samsung Sdi Co., Ltd. Composite binder composition for secondary battery, cathode and lithium battery containing the binder composition
US9711796B2 (en) 2014-01-10 2017-07-18 Samsung Sdi Co., Ltd. Binder composition for secondary battery, cathode and lithium battery including the binder composition
US9385374B2 (en) 2014-04-01 2016-07-05 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
US10033043B2 (en) 2014-04-01 2018-07-24 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
WO2015153583A1 (fr) * 2014-04-01 2015-10-08 Ppg Industries Ohio, Inc. Composition de liant d'électrode pour dispositifs de stockage électrique au lithium-ion
US10964949B2 (en) 2014-04-01 2021-03-30 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
US11817586B2 (en) 2014-04-01 2023-11-14 Ppg Industries Ohio, Inc. Electrode binder composition for lithium ion electrical storage devices
US10717890B2 (en) 2015-11-24 2020-07-21 Arkema France Binder containing polyvinylidene fluoride capable of fixing to a metal and associated lithium-ion battery electrode
EP4336595A1 (fr) 2022-09-09 2024-03-13 Arkema France Liant pour électrode comprenant du poly(fluorure de vinylidène) et un polymère hydrophile
WO2024052543A1 (fr) 2022-09-09 2024-03-14 Arkema France Liant pour electrode comprenant du poly (fluorure de vinylidene) et un polymere hydrophile

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CN1213393A (zh) 1999-04-07
EP0876439A1 (fr) 1998-11-11
AU1444897A (en) 1997-08-20
CA2243354A1 (fr) 1997-07-31
KR19990081865A (ko) 1999-11-15

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