WO2000049103A1 - A method for the adhesion of vinylidene fluoride resins to metal substrates, and an electrode structure and its method of production - Google Patents
A method for the adhesion of vinylidene fluoride resins to metal substrates, and an electrode structure and its method of production Download PDFInfo
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- WO2000049103A1 WO2000049103A1 PCT/EP1999/001272 EP9901272W WO0049103A1 WO 2000049103 A1 WO2000049103 A1 WO 2000049103A1 EP 9901272 W EP9901272 W EP 9901272W WO 0049103 A1 WO0049103 A1 WO 0049103A1
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- vinylidene fluoride
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- carboxylic acid
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- organic compound
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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
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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
-
- 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
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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
- 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
- C08L2666/28—Non-macromolecular organic substances
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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
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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
Definitions
- the present invention relates to a method for the adhesion/lamination of vinylidene fluoride resins and metals which are inherently non-adhesive thereto, and it 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.
- polyvinylidene fluoride and vinylidene fluoride copolymer resins are used as coating materials and for electrical/electronic components, steel pipe linings, chemical plant components and weather-resistant/stain-resistant films, etc.
- they since they have practically no adhesion properties in terms of other materials, they suffer from the problem of being difficult to modify or composite with other materials.
- Japanese Unexamined Patent Publication No. 50-41791 there is disclosed a method of grafting a carboxyl-group-containing fluoromonomer while irradiating with ionizing radiation but, in addition to the industrial difficulties of handling radiation, this method also has the problem of decomposition of the polymer main chains or of a crosslinking reaction occurring at the same time.
- this method in addition to the industrial difficulties of handling radiation, this method also has the problem of decomposition of the polymer main chains or of a crosslinking reaction occurring at the same time.
- the negative electrode active material there can be used as the negative electrode active material therein a carbonaceous material such as coke or graphite which undergoes lithium ion doping and un-doping (Japanese Unexamined Patent Publication No. 62-90863), and as the positive electrode active material there can be used transition metal oxides such as manganese oxide and vanadium pentoxide, transition metal sulphides such as iron sulphide and titanium sulphide, and composite compounds of these with lithium (e.g. lithium cobalt composite oxide, lithium cobalt nickel composite oxide and lithium manganese oxide), etc.
- transition metal oxides such as manganese oxide and vanadium pentoxide
- transition metal sulphides such as iron sulphide and titanium sulphide
- composite compounds of these with lithium e.g. lithium cobalt composite oxide, lithium cobalt nickel composite oxide and lithium manganese oxide
- the electrodes are obtained by mixing a solvent with the mixture obtained by adding a suitable quantity of a binding agent to the powder-form electrode active material, to produce a paste, which is then coated onto a current collector, and dried, followed by press-bonding.
- the binding agent employed in such secondary battery electrodes needs to have resistance to the organic solvent used in the electrolyte and resistance to the active species produced by the electrode reaction.
- PVDF resin is employed in most cases as a binding agent which satisfies these requirements.
- PVDF resin has inherently poor adhesion to metals and, in the case of both the negative and positive electrodes, the adhesive strength between the current collector and the active material is inadequate following the press-bonding of the active material to the current collector, so there has been the problem that the active material tends to separate away from the current collector and the cycling characteristics of the battery deteriorate.
- As a method for improving the bonding between the current collector and electrode active material there has been proposed roughening the current collector surface (Japanese Unexamined Patent Publication No.
- the present invention has the objective of offering a metal- adhesive vinylidene fluoride resin composition where metal adhesion is introduced by a simple method and without impairing the solvent resistance and mechanical and thermal properties inherently possessed by the vinylidene fluoride resin, and also of offering an electrode structure in which the adhesion between the electrode active material and the current collector is enhanced by using this composition as an electrode binding agent for batteries.
- the present inventors have found that a composition composed of three components, namely a vinylidene fluoride resin, an acrylic and/or methacrylic polymer having functional groups with bonding properties or affinity in respect of metals, and an organic compound with at least one functional group selected from the mercapto group, thioether group, carboxylic acid group and carboxylic acid anhydride group, at a specified compositional ratio, exhibits adhesion properties in respect of metal materials, and they have discovered that not only are such properties valuable in the production of composite materials comprising PVDF resins and metals, but they are also valuable in a binder used for stably fixing an electrode active material to the current collector.
- the present invention relates to a method for the adhesion of vinylidene fluoride resins to metal substrates which is characterized in that, when sticking a vinylidene fluoride resin to a metal substrate, vinylidene fluoride resin (a), at least one type of polymer (b) selected from acrylic and methacrylic polymers with functional groups which exhibit bonding properties or affinity in terms of metals, or an acrylic or methacrylic resin composition containing such polymer, and an organic compound (c) with at least one functional group selected from the mercapto group, thioether group, carboxylic acid group and carboxylic acid anhydride group, are added to and mixed with vinylidene fluoride resin (a).
- the vinylidene fluoride resin referred to here can be selected from vinylidene fluoride homopolymer and copolymers (vinylidene fluoride copolymers) of vinylidene fluoride with other monomers which can copolymerize with vinylidene fluoride, and these resins can be used on their own or as mixtures of two or more types.
- the vinylidene fluoride copolymers should have from 50 to 98 wt% vinylidene fluoride component in the copolymer, and more desirably from 75 to 96 wt%.
- Fluoromonomers such as tetrafluoroethylene, hexafluoropropylene, tri-fluoroethylene and trifluorochloroethylene, etc, are preferred as the other monomer copolymerizable with the vinylidene fluoride, and one or more than one of these can be used.
- the vinylidene fluoride copolymer has a vinylidene fluoride component content of 75 to 96 wt%, and has a flexural modulus at room temperature (23°C) of no more than 1000 MPa and a breaking elongation of at least 50 wt%.
- vinylidene fluoride resins are obtained by the polymerization of the vinylidene fluoride monomer and other monomer by a known suspension polymerization method or emulsion polymerization method, etc (literature example: "Fluororesin Handbook", Edited by Satogawa, Published by Nikkan Kogyo Shinbunsha 1990). Methods for the copolymerization of vinylidene fluoride monomer and other monomer are described in, for example, US Patent Nos 4,076,929 and 4,569,978, and in Japanese Unexamined Patent Publication No. 6-336510).
- the (a) component it is also possible to use a mixture of from 1 to 99 wt% vinylidene fluoride homopolymer and from 99 to 1 wt% vinylidene fluoride copolymer resin.
- Properties such as the resin flexibility and the solvent resistance can be varied according to the mixing ratio thereof (that is to say, by increasing the proportion of the vinylidene fluoride copolymer, the flexibility is increased, while, on the other hand, swelling by solvents is also increased) and there can be employed an optimal combination in accordance with the objectives.
- the acrylic or methacrylic polymer with functional groups which exhibit bonding properties or affinity in terms of metals which is used as component (b) in the present invention, is a polymer in which the chief component is an alkyl acrylate or alkyl methacrylate and which has at least in one position in the main chain, side chains or at chain ends, a functional group which exhibits 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.
- the functional groups possessed by the (b) component which exhibit bonding properties or affinity in respect of metals
- One example of an aforesaid acrylic or methacrylic polymer is the copolymer of at least one type of monomer selected from those with a carboxylic acid group or carboxylic acid anhydride group, and an alkyl acrylate and/or alkyl methacrylate.
- alkyl acrylate and alkyl methacrylate are methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, etc.
- 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-cyclohexanedi- carboxylate 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 from 70 wt% to 99 wt%, of this acrylic or methacrylic polymer be composed of at least one type of monomer selected from alkyl acrylates and alkyl methacrylates.
- 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 moles per 1 kg of the acrylic or methacrylic polymer.
- this polymer component is a copolymer of at least one monomer selected from alkyl acrylates and alkyl methacrylates 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 said copolymer, 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 be no more than 50 wt%, and preferably no more than 30 wt% of said polymer.
- Component (b) used in the present invention may also be a composition composed of an acrylic or methacrylic polymer which does not possess special functional groups and an aforesaid acrylic or methacrylic polymer having functional groups which show bonding properties or affinity in terms of metals.
- the (b) component is a polymer
- the organic compound with at least one functional group selected from the mercapto group, thioether group, carboxylic acid group and carboxylic acid anhydride group used as component (c) in the, present invention is a comparatively low molecular weight compound. Its molecular weight range is up to 5000, preferably up to 2000 and more preferably from 60 to 1000.
- a sulphur-containing compound with a mercapto group there is preferred an organic compound with a plurality (2 to 6) of mercapto groups in the molecule, or a mercapto carboxylic acid with at least one mercapto group and at least one carboxylic acid group, or a mercapto carboxylic acid ester with at least one mercapto group and at least one ester group, or a mercapto sulphide group with at least one mercapto group and at least one thiol group.
- organic compounds with a plurality of mercapto groups in the molecule there are ethanedithiol, 1 ,3- propanedithiol, hexanedithiol, penta-erythrithiol, dimercaptodiethyl ether, 1 ,8-dimercapto-3,6-dioxaoctane, and 1 ,5- or 2,7-dimercaptonaphthaiene, etc.
- mercapto-carboxylic acids there are thioglycolic acid and 3-mercaptopropionic acid.
- mercapto- carboxylic acid esters there are 2-ethylhexyl ⁇ -mercaptopropionate, 3- methoxybutyl ⁇ -mercaptopropionate, trimethylolpropane-tris( ⁇ -thio- propionate), pentaerythritetra(mercaptopropionate ester) and other such mercaptopropionic acid derivatives, 2-ethylhexyl thioglycolate, isooctyl thioglycolate, butyl thioglycolate, methoxybutyl thioglycolate, trimethylol- propanetris(thioglycolate) and other such thioglycolic acid derivatives.
- mercapto sulphides there are 2,2'-dimercaptodiethylsulphide and bis-(2-mercaptoethyl)sulphide.
- R denotes OR ⁇ , SR2 or NR1 R2 (where R1 and R2 are the same or different and represent hydrogen, an alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group or alkylaryl group), and M denotes hydrogen, an alkali metal or alkaline earth metal.
- the alkyl group here, there are the methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, octyl, nonyl, 2-ethylhexyl, dodecyl and octadecyl groups; as examples of the alkenyl group, there are the allyl and oleyl groups; as examples of the arylalkyl group, there are the benzyl, methylbenzyl, phenylethyl and phenyl-propyl groups; as examples of the ary
- the organic compound with a thioether group employed as the (c) component in the present invention desirably has at least one functional group selected from the carboxylic acid group, carboxylic acid anhydride group, ester group and amide group, as well as this thioether group.
- thioethers with a carboxylic acid group or carboxylic acid anhydride group there are 3,3'-thiodipropionic acid, carboxyethylthio- succinic acid, carboxyethylthiosuccinic anhydride and hydroxyethylthiopropionic acid.
- thioethers with an ester group there are dilauryl thiodipropionate, distearyl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate and di-dodecyl thiodipropionate.
- a thioether with an amide group there is hydroxyethylthio-propionamide.
- a thioethercarboxylic acid represented by the following formula 2, or anhydride thereof there is especially desirably used as the organic compound with a thioether group, a thioethercarboxylic acid represented by the following formula 2, or anhydride thereof,
- R3 and R4 are C2 to C20 hydrocarbon groups, and m and n are the same or different integer in the range 1 to 4), and still more preferably it is carboxyethyl-thiosuccinic acid or carboxyethylthiosuccinic anhydride.
- R 5 -S-R 6 -C O (3) (where R5 and RQ are C2 to C20 hydrocarbon groups), an example of which is hydroxyethylthiopropionamide.
- component (c) it is possible to use an organic compound with at least one functional group selected from carboxylic acid and carboxylic acid anhydride groups.
- carboxylic acid and carboxylic acid anhydride groups there are acetic acid, acrylic acid, formic acid, citric acid, oxalic acid, lactic acid, maleic acid, propionic acid, malonic acid and butyric acid, etc.
- the vinylidene fluoride resin composition with improved metal adhesion of the present invention contains, per 100 parts by weight of (a) vinylidene fluoride resin, from 0.5 to 50 parts by weight and more preferably from 1 to 20 parts by weight of (b) acrylic or methacrylic polymer with functional groups which exhibit bonding properties or affinity in terms of metals, and from 0.01 to 5 parts by weight and more preferably 0.03 to 1 part by weight of (c) an organic compound with at least one functional group selected from the mercapto group, thioether group, carboxylic acid group and carboxylic acid anhydride group.
- the vinylidene fluoride resin in particular in the case where the adhesion process is a solution application method, it is preferred that the vinylidene fluoride resin contain from 1 to - 15 wt% vinylidene fluoride copolymer, and per 100 parts by weight of the vinylidene fluoride resin there is desirably added from 0.5 to 10 parts by weight and more preferably 1 to 5 parts by weight of the (b) component acrylic or methacrylic polymer, and from 0.03 to 1 part by weight of the (c) component organic compound.
- the vinylidene fluoride resin composition with metal adhesion improved by the above method can be used as an adhesive agent when sticking a vinylidene fluoride resin to a metal.
- the vinylidene fluoride resin used in the adhesive agent need not necessarily be composed of the same resin as the vinylidene fluoride resin which forms the surface layer.
- the metal-adhesive composition of the present invention is produced by a solution process 'or melt process.
- the aforesaid three components (a), (b) and (c) may be dissolved in the prescribed proportions in a solvent such as N-methylpyrrolidone, N,N-dimethylformamide, tetrahydro-furan, dimethylacetamide, dimethylsulphoxide, hexamethyl-phosphoramide, 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, tetrahydro-furan, dimethylacetamide, dimethylsulphoxide, hexamethyl-phosphoramide, tetramethylurea, acetone, methyl ethyl ketone or the like
- production can be carried out by a conventional method of heating and mixing the three components (a), (b) and (c) in the prescribed proportions using a screw mixing machine.
- a screw mixing machine e.g., a screw mixing machine
- conventionally-known methods can be used for the method of melting and mixing, such as a Banbury mixer, rubber mill or single or twin-screw extruder, etc, and normally the resin composition is obtained by melting and mixing at 100 to 300°C and preferably, although it will also depend on the composition, 150 to 260°C.
- metal materials employed as the adhesion substrate in the present invention 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 composite materials obtained by this method can have various forms such as film, sheet, plate, pipe, rod, strand, monofilament or fibre, and the means of production thereof include calendering, extrusion lamination, multilayer injection, fluid immersion coating, dipping, spray coating and melt-pressing, etc.
- the method of the present invention can also be employed for fluoro-coating materials using vinylidene fluoride resin dissolved or dispersed in a solvent, and for electric wire coating by means of vinylidene fluoride resin.
- the method of the present invention for the adhesion of polyvinylidene fluoride resin to a metal substrate can also be applied to the production of a battery electrode structure where an electrode constitutional material layer comprising at least electrode active material and binder is formed on the surface of a current collector and, in this way, the adhesion between the electrode active material and the current collector is improved, so that not only is it possible to prevent the dropping away of electrode active material from the current collector during battery production, but it is also possible to obtain an electrode for a battery of finally improved cycle characteristics.
- this is useful in an electrode binder for non-aqueous type secondary batteries such as lithium ion secondary batteries.
- the electrode current collector there may be used a metal foil, metal mesh or three-dimensional porous body, etc, but it is preferred that the metal employed in the current collector be a metal which cannot readily alloy with lithium, in particular, iron, nickel, cobalt, copper, aluminium, titanium, vanadium, chromium and manganese, employed on their own or as alloys thereof.
- the negative electrode active material should be a material which can undergo doping and undoping by lithium ions.
- examples of such materials are coke materials like petroleum- based or carbon-based coke, acetylene black or other such carbon black, graphite, glassy carbon, active carbon, carbon fibre and carbonaceous materials such as fired organic polymers obtained by the firing of organic high polymers in a non-oxidizing atmosphere.
- copper oxide may also sometimes be added thereto.
- positive electrode active materials there are the aforementioned generally-used materials and there are no particular restrictions.
- An electro-conductor may also be added thereto.
- a heat treatment is desirably carried out at from 60 to 250°C, more preferably from 80 to 200°C, for from 1 minute to 10 hours, according to the particular requirements.
- electrical conductivity conferring agents and other additives may also be added to the electrode constitutional material layer.
- organic solvents such as N- methylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethyl sulphoxide, hexamethylphosphoramide, tetra- methylurea, acetone and methyl ethyl ketone, or water, either on their own or as mixtures thereof.
- N-methylpyrrolidone is especially desirably used.
- a dispersing agent may be added. In such circumstances, a nonionic dispersing agent is preferably used.
- the amount of binder (total of (a) and (b) components) added to the electrode active material is preferably from 1 to 50 parts by weight and more preferably from 3 to 40 parts by weight per 100 parts by weight of the electrode active material. The optimum amount thereof added will vary with the battery and the electrode form.
- the respective proportions of the (a), (b) and (c) components are as stated above.
- the preferred (a) component vinylidene fluoride resin will vary with the properties demanded of the battery or electrode, and selection is made from vinylidene fluoride homopolymer, the aforesaid vinylidene fluoride copolymers, and mixtures of from 1 to 99 wt% vinylidene fluoride homopolymer and from 99 to 1 wt% vinylidene fluoride co-polymer.
- a vinylidene fluoride copolymer such as a copolymer of vinylidene fluoride and hexafluoropropylene, or a mixture of such vinylidene fluoride copolymer and vinylidene fluoride homopolymer is desirably used.
- vinylidene fluoride homopolymer is desirably used.
- the method of the present invention is effective in enhancing the adhesion between current collector and electrode active material.
- the swelling in terms of the carbonate solvents normally used in a lithium battery is about the same as that for vinylidene fluoride homopolymer, but the flexibility is improved when compared to vinylidene fluoride homopolymer, so such a mixture is preferably employed in a liquid type lithium battery.
- the negative electrode structure and positive electrode structure produced as described abovg are arranged with a liquid-permeable separator (for example polyethylene or polypropylene porous film) disposed between them, and then by impregnating this with a non-aqueous type electrolyte, there is formed a non-aqueous type secondary battery.
- a liquid-permeable separator for example polyethylene or polypropylene porous film
- a cylindrical secondary battery can be obtained by winding, in the form of a roll (a helical shape), a laminate comprising the negative electrode structure with an active layer formed on both faces/separator/positive electrode structure with an active layer formed on both faces/separator, then introducing the structure thus obtained into a metal casing with a bottom, connecting the negative electrode to the negative electrode terminal and the positive electrode to the positive electrode terminal, and impregnating with electrolyte, after which the casing is sealed.
- the electrolyte liquid employed here in the case of a lithium ion secondary battery for example, there is employed a lithium salt as the electrolyte dissolved in a non-aqueous organic solvent at a concentration of about 1 M.
- a lithium salt there are LiPF ⁇ , UCIO4, LiBF , LiAsF6, USO3CF3 and Li[(SO2CF3)2N], etc.
- the non-aqueous organic solvent there can be employed propylene carbonate, ethylene carbonate, 1 ,2-dimethoxyethane, 1 ,2- diethoxyethane, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, etc, either on their own or as mixtures of two or more.
- NMP N- methylp ⁇ rrolidone
- a solution (S-3) formed by dissolving 87 g of Kynar 301 F which is a vinylidene fluoride homopolymer produced by Elf Atochem (MFR at 230°C under a 2.16 kg load 0.03 g/10 min), 10 g of the copolymer of vinylidene fluoride and hexafluoropropylene, Kynar 2801 , described in Example 2, 3 g of Sumipex TR described in Example 1 and 0.1 g of 2,4,6- trimercapto-1 ,3,5-triazine in 900g of NMP, was applied onto 1 mm thickness aluminium sheet and copper sheet and left for 1 hour at 120°C, after which drying was carried out under reduced pressure.
- a solution (S-4) was prepared by dissolving 48 g of Kynar 301 F, 48 g of the copolymer of vinylidene fluoride and hexafluoropropylene, Kynar 2801 , described in Example 2, 4 g of the Sumipex TR described in Example 1 and 0.6 g of 2,4,6-trimercapto-1 ,3,5-triazine in 900g of NMP.
- the residual adhering percentage was 100% for both the aluminium and copper sheets.
- the residual adhering percentage was 100% for both the aluminium and copper sheets.
- NMP solution (S-5) was prepared in the same way as in Example 3, excepting that the 2,4,6-trimercapto-1 ,3,5-triazine was replaced by 3-mercaptopropionic acid.
- the residual adhering percentage was 100% for both the aluminium and copper sheets.
- the residual adhering percentage was 95% for the aluminium sheet and 100% for the copper sheet.
- NMP solution (S-6) was prepared in the same way as in Example 3, excepting that the 2,4,6-trimercapto-1 ,3,5-triazine was replaced by carboxyethylthiosuccinic anhydride.
- the residual adhering percentage of polymer coating layer was 100% for both the aluminium and copper sheets.
- the residual adhering percentage was 100% for both the aluminium and copper sheets.
- NMP solution (S-7) was prepared in the same way as in Example 3 excepting that, as the acrylic polymer with functional groups having bonding properties or affinity in terms of metals, there was used a copolymer comprising maleic anhydride, N-methyldimethylglutarimide, monomer containing carboxylic acid, and methyl methacrylate (Paraloid EXL4151 , produced by Rohm and Haas).
- a copolymer comprising maleic anhydride, N-methyldimethylglutarimide, monomer containing carboxylic acid, and methyl methacrylate (Paraloid EXL4151 , produced by Rohm and Haas).
- the residual adhering percentage of polymer coating layer was 100% for both the aluminium and copper sheets, and in the tape peeling test too, the residual adhering percentage was 100% for both the aluminium and copper sheets.
- NMP solution (S-8) was prepared in the same way as in Example 3 excepting that, as an acrylic polymer with functional groups having bonding properties or affinity in terms of metals, there was employed an epoxy-modified polymethyl methacrylate grafted polymethyl methacrylate (Rezeda GP-301 , Toagosei Chemical Industry Co.).
- an epoxy-modified polymethyl methacrylate grafted polymethyl methacrylate (Rezeda GP-301 , Toagosei Chemical Industry Co.).
- the residual adhering percentage of polymer coating layer was 100% for both the aluminium and copper sheets and, in the tape peeling test too, the residual adhering percentage was 100% for both the aluminium and copper sheets.
- a negative electrode active material support 100 g of coal pitch coke which had been pulverized in a ball mill was dispersed in 100 g of NMP solution (S-1 ) obtained in Example 1 , to produce a slurry (paste). This slurry was coated onto one face of copper foil of thickness 20 ⁇ m as the current collector, then dried for 15 minutes at 130°C, to produce an electrode structure of thickness 1 10 ⁇ m and width 20 mm (to be used as a negative electrode). Adhesive tape was affixed to the electrode active layer on this electrode surface, and when the adhesive strength between current collector and electrode active layer was measured, by means of a tensile tester, it was 185 g/cm.
- An electrode structure was prepared in the same way as in
- Example 9 except that there was used S-2 obtained in Example 2 as the NMP solution in Example 9.
- the adhesive strength between the current collector and the electrode active layer was 190 g/cm, and in the other tests too good adhesion was confirmed.
- An electrode structure was prepared in the same way as in
- Example 9 except that there was used S-3 obtained in Example 3 as the NMP solution in Example 9.
- the adhesive strength between the current collector and the electrode active layer was 300 g/cm, and in the other tests too good adhesion was confirmed.
- the residual percentage of adhering polymer coated layer was less than 20% for both the aluminium and copper sheets.
- the polymer layer completely separated away.
- the degree of swelling by ethylene carbonate was measured by the same method as in Example 1 using polymer which had separated away from the metal sheets, it was 23%.
- the residual percentage of adhering polymer coated layer was 100% for both the aluminium and copper sheets but, in the tape peeling test, the residual adhering percentage was about 50% on the aluminium sheet and about 80% on the copper sheet.
- the degree of swelling by ethylene carbonate of the polymer layer, measured by the same method as in Example 1 was 24%.
- the residual percentage of adhering polymer coated layer was about 70% on the aluminium sheet and about 90% on the copper sheet but, in the tape peeling test, the residual adhering percentage was about 30% on the aluminium sheet and about 50% on the copper sheet.
- the degree of swelling by ethylene carbonate of the polymer layer, measured by the same method as in Example 1 was 23%.
- the residual percentage of adhering polymer coated layer was 100% for both the aluminium and copper sheets whereas, in the tape peeling test, the residual adhering percentage was about 70% on the aluminium sheet and about 90% on the copper sheet.
- the degree of swelling by ethylene carbonate of the polymer layer, measured by the same method as in Example 1 was 42%.
- An electrode structure was produced in the same way as in Example 9, excepting that S-9 obtained in Comparative Example 1 was used as the NMP solution in Example 9.
- the adhesive strength between the current collector and the electrode active layer was a low value of 35 g/cm. Further, in the roll winding test based on a cylinder of diameter 1 mm, separation of the electrode active layer was noted, and in the immersion test in ethylene carbonate at 60°C, considerable separation of the electrode active layer occurred.
- An electrode structure was produced in the same way as in Example 9, excepting that S-10 obtained in Comparative Example 2 was used as the NMP solution in Example 9.
- the value of the adhesive strength between the current collector and the electrode active layer was not very high, at 70 g/cm.
- separation of the electrode active layer was noted, and in the immersion test in ethylene carbonate at 60°C, considerable separation of the electrode active layer occurred.
- An electrode structure was produced in the same way as in
- Example 9 excepting that S-1 1 obtained in Comparative Example 3 was used as the NMP solution in Example 9.
- the value of the adhesive strength between the current collector and the electrode active layer was not all that high, at 76 g/cm.
- separation of electrode active layer was noted, albeit slight, and in the immersion test in ethylene carbonate at 60°C, some separation of the electrode active la ⁇ er occurred.
- Example 9 An electrode structure was produced in the same way as in Example 9, excepting that S-12 obtained in Comparative Example 4 was used as the NMP solution in Example 9.
- the value of the adhesive strength between the current collector and the electrode active layer was not all that high, at 80 g/cm.
- some separation of electrode active layer was noted, albeit slight, and in the immersion test in ethylene carbonate at
- Example 9 An electrode structure was produced in the same way as in Example 9, excepting that S-13 obtained in Comparative Example 5 was used as the NMP solution in Example 9.
- the value of the adhesive strength between the current collector and the electrode active layer was rather high, at 210 g/cm but did not reach the value achieved in Example 1 1 employing solution S-3.
- the stability was inadequate in the electrode structure production when compared to Example 1 1 .
- the present invention it becomes possible to obtain a metal-adhesive vinylidene fluoride resin composition by a simple method and without impairing the solvent resistance or the mechanical or thermal properties inherently possessed by a vinylidene fluoride resin.
- the metal-adhesive vinylidene fluoride resin composition of the present invention is used as a binder for battery electrodes, it becomes possible to produce an electrode structure with high adhesive strength between the electrode active material and current collector. In this way, not only is it possible to prevent separation of the electrode active material and the current collector at the time of battery production, but a secondary battery is obtained which does not show a deterioration in the discharge capacity due to repeated charging and discharging.
- the method of the present invention is particularly valuable for non-aqueous secondary batteries such as lithium ion secondary batteries, etc.
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- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99908950A EP1157074A1 (en) | 1999-02-18 | 1999-02-18 | A method for the adhesion of vinylidene fluoride resins to metal substrates, and an electrode structure and its method of production |
KR1020017010535A KR20010108237A (en) | 1998-02-17 | 1999-02-18 | A method for the adhesion of vinylidene fluoride resins to metal substrates, and an electrode structure and its method of production |
AU28359/99A AU2835999A (en) | 1999-02-18 | 1999-02-18 | A method for the adhesion of vinylidene fluoride resins to metal substrates, andan electrode structure and its method of production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10034755A JPH11228902A (en) | 1998-02-17 | 1998-02-17 | Method to adhere vinylidene fluoride resin to metalic base material, electrode structure and its preparation |
Publications (1)
Publication Number | Publication Date |
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WO2000049103A1 true WO2000049103A1 (en) | 2000-08-24 |
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ID=12423144
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PCT/EP1999/001272 WO2000049103A1 (en) | 1998-02-17 | 1999-02-18 | A method for the adhesion of vinylidene fluoride resins to metal substrates, and an electrode structure and its method of production |
Country Status (3)
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JP (1) | JPH11228902A (en) |
KR (1) | KR20010108237A (en) |
WO (1) | WO2000049103A1 (en) |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01149880A (en) * | 1987-12-08 | 1989-06-12 | Showa Denko Kk | Primer composition |
JPH03213336A (en) * | 1990-01-19 | 1991-09-18 | Mitsubishi Petrochem Co Ltd | Multilayered laminate |
EP0601754A1 (en) * | 1992-12-02 | 1994-06-15 | Kureha Kagaku Kogyo Kabushiki Kaisha | Vinylidene fluoride copolymer, and binder composition containing the copolymer for non-aqueous solvent type secondary battery |
JPH0982314A (en) * | 1995-09-11 | 1997-03-28 | Elf Atochem Japan Kk | Battery electrode and manufacture thereof |
JPH0982311A (en) * | 1995-09-11 | 1997-03-28 | Elf Atochem Japan Kk | Battery electrode and manufacture thereof |
WO1997027003A1 (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem S.A. | Method for the adhesion of fluorinated resins to metals |
WO1997032347A1 (en) * | 1996-02-27 | 1997-09-04 | Elf Atochem S.A. | Binders for electrodes and their production method |
WO1997049777A2 (en) * | 1996-06-26 | 1997-12-31 | Elf Atochem S.A. | Metal-adhesive polyvinylidene fluoride compositions |
-
1998
- 1998-02-17 JP JP10034755A patent/JPH11228902A/en active Pending
-
1999
- 1999-02-18 KR KR1020017010535A patent/KR20010108237A/en not_active Application Discontinuation
- 1999-02-18 WO PCT/EP1999/001272 patent/WO2000049103A1/en not_active Application Discontinuation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01149880A (en) * | 1987-12-08 | 1989-06-12 | Showa Denko Kk | Primer composition |
JPH03213336A (en) * | 1990-01-19 | 1991-09-18 | Mitsubishi Petrochem Co Ltd | Multilayered laminate |
EP0601754A1 (en) * | 1992-12-02 | 1994-06-15 | Kureha Kagaku Kogyo Kabushiki Kaisha | Vinylidene fluoride copolymer, and binder composition containing the copolymer for non-aqueous solvent type secondary battery |
JPH06172452A (en) * | 1992-12-02 | 1994-06-21 | Kureha Chem Ind Co Ltd | Vinylidene fluoride-based copolymer |
JPH0982314A (en) * | 1995-09-11 | 1997-03-28 | Elf Atochem Japan Kk | Battery electrode and manufacture thereof |
JPH0982311A (en) * | 1995-09-11 | 1997-03-28 | Elf Atochem Japan Kk | Battery electrode and manufacture thereof |
WO1997027003A1 (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem S.A. | Method for the adhesion of fluorinated resins to metals |
WO1997032347A1 (en) * | 1996-02-27 | 1997-09-04 | Elf Atochem S.A. | Binders for electrodes and their production method |
WO1997049777A2 (en) * | 1996-06-26 | 1997-12-31 | Elf Atochem S.A. | Metal-adhesive polyvinylidene fluoride compositions |
Non-Patent Citations (9)
Title |
---|
CHEMICAL ABSTRACTS, vol. 127, no. 2, 14 July 1997, Columbus, Ohio, US; abstract no. 21007, MYAKI, YOSHIYUKI ET AL: "Lithium secondary battery electrodes and their manufacture" XP002106364 * |
CHEMICAL ABSTRACTS, vol. 127, no. 2, 14 July 1997, Columbus, Ohio, US; abstract no. 21009, MIYAKI, YOSHIYUKI ET ALL: "Lithium secondary batterie electrode and their manufacture" XP002106363 * |
DATABASE WPI Section Ch Week 8929, Derwent World Patents Index; Class A14, AN 89-211558, XP002106367 * |
DATABASE WPI Section Ch Week 9144, Derwent World Patents Index; Class A14, AN 91-320650, XP002106368 * |
DATABASE WPI Section Ch Week 9723, Derwent World Patents Index; Class E19, AN 97-250897, XP002106365 * |
DATABASE WPI Section Ch Week 9723, Derwent World Patents Index; Class L03, AN 97-250894, XP002106366 * |
PATENT ABSTRACTS OF JAPAN vol. 013, no. 414 (C - 635) 13 September 1989 (1989-09-13) * |
PATENT ABSTRACTS OF JAPAN vol. 015, no. 491 (M - 1190) 12 December 1991 (1991-12-12) * |
PATENT ABSTRACTS OF JAPAN vol. 097, no. 007 31 July 1997 (1997-07-31) * |
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KR20010108237A (en) | 2001-12-07 |
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