WO2003046026A1 - Groupe epoxy contenant un copolymere de fluorure de vinylidene, et composition de resine, structure d'electrode et element electrochimique non aqueux comprenant ce groupe - Google Patents

Groupe epoxy contenant un copolymere de fluorure de vinylidene, et composition de resine, structure d'electrode et element electrochimique non aqueux comprenant ce groupe Download PDF

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Publication number
WO2003046026A1
WO2003046026A1 PCT/JP2002/012266 JP0212266W WO03046026A1 WO 2003046026 A1 WO2003046026 A1 WO 2003046026A1 JP 0212266 W JP0212266 W JP 0212266W WO 03046026 A1 WO03046026 A1 WO 03046026A1
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WIPO (PCT)
Prior art keywords
vinylidene fluoride
electrode
epoxy group
copolymer
monomer
Prior art date
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PCT/JP2002/012266
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English (en)
Japanese (ja)
Inventor
Tomoaki Kawakami
Toshio Hosokawa
Takumi Katsurao
Original Assignee
Kureha Chemical Industry Company, Limited
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Publication date
Application filed by Kureha Chemical Industry Company, Limited filed Critical Kureha Chemical Industry Company, Limited
Priority to AU2002349709A priority Critical patent/AU2002349709A1/en
Publication of WO2003046026A1 publication Critical patent/WO2003046026A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a polyvinylidene fluoride copolymer and a resin composition which provides a cured product having good adhesion to a base material such as a metal containing the same and having excellent heat resistance and chemical resistance.
  • a resin composition is useful in the fields of binders, paints and the like.
  • the present invention provides an electrode structure for a non-aqueous electrochemical element containing such a vinylidene fluoride copolymer as a binder, and a non-aqueous system such as a secondary battery or an electric double layer capacitor including the electrode structure.
  • the present invention relates to an electrochemical device. .
  • Polyvinylidene fluoride resins have excellent chemical resistance, weather resistance, and stain resistance, and are used not only as various films or molding materials, but also as paints and binders. However, since polyvinylidene fluoride resin has low adhesive strength to a substrate such as a metal, improvement of the adhesive strength is desired.
  • Japanese Patent Application Laid-Open No. HEI 3-171909 discloses that (a) 50 to 98 mol of vinylidene fluoride, (b) 2 to 50 mol of tetrafluoroethylene, A fluorinated monomer selected from hexafluoropropylene or a mixture of at least two of these three monomers, and (c) a total of 100 moles per 100 moles of the fluorinated monomer.
  • Lil Dali glycidyl consists of units derived from an epoxidised Arirueteru like ether substantially as a solution in dimethylformamide of 2 5 D C at a concentration 1 g of Roh d 1 Disclosed is that a curable copolymer having an intrinsic viscosity of 0.03 to 0.4 d1 Zg is obtained by solution polymerization. These copolymers are soluble in solvents such as butyl acetate, isobutyl acetate, and ethyl acetate, and are crosslinked by mixing and heating with known curing agents such as melamine formaldehyde, polyamide, organic acids and their anhydrides. 'Discloses that it cures and can be used as a paint or varnish to form a coating that adheres well to metals, glass, wood, cement, plastics, etc.
  • copolymers are soluble in common solvents as described above, Those which do not perform the above are not applicable to the field where chemical resistance and heat resistance are required. In addition, even those that have been subjected to a curing treatment are required to be used in fields where high chemical resistance is required, such as when they are used as binders for manufacturing non-aqueous solvent-based lithium secondary batteries or electrodes for electric double layer capacities. It is still not enough in application.
  • the present applicant has conducted a study to obtain a vinylidene fluoride-based copolymer having improved adhesiveness to a base material such as a metal while utilizing the excellent properties of vinylidene fluoride resin.
  • polar monomers such as monoesters of unsaturated dibasic acids or copolymers with epoxidized aryl ethers such as Z and aryl glycidyl ether have improved adhesion and solvent resistance (Japanese Unexamined Patent Publications Nos. 6-172452 and 9-12639).
  • the thus obtained vinylidene fluoride-based copolymer was also used as a binder for producing electrodes of non-aqueous electrochemical elements which generate heat during use.
  • this thermal decomposition occurs more remarkably when an electrode is formed by blending a powdered carbon material or the like than a resin alone. It is also desired to further improve the adhesion to a current collecting base such as a metal.
  • Ru Rushito 3 ⁇ 4 to provide a process for producing vinylidene fluoride copolymer as described above 0
  • Another object of the present invention is to provide a resin composition containing the above vinylidene fluoride copolymer, an electrode structure for a non-aqueous electrochemical element, further a non-aqueous electrochemical element, particularly a secondary battery and An electric double layer capacitor is provided.
  • the copolymer of vinylidene fluoride and a relatively small amount of an acrylic vinyl monomer having an epoxy group is surprisingly obtained from the above-described pinylidene fluoride and unsaturated divinylidene.
  • Polar monomers such as monoesters of basic acids, or di- and arylidaricydyl esters
  • epoxidized aryl ethers such as ter, not only exhibit significantly better copolymerization properties during suspension polymerization, but also exhibit improved heat stability and adhesion to substrates such as metals. It was also found that the properties were good.
  • the present invention firstly provides a copolymer of 100 mol of vinylidene fluoride monomer and 0.1 to 5.0 mol of an acrylic vinyl monomer containing at least an epoxy group. It is intended to provide a vinylide-based copolymer.
  • the method for producing a vinylidene fluoride copolymer of the present invention is characterized by producing the above-mentioned vinylidene fluoride copolymer by suspension polymerization using water as a dispersion medium.
  • the present invention relates to a resin composition obtained by dissolving the above vinylidene fluoride copolymer in an organic solvent, an electrode mixture composition obtained by adding a powdered electrode material to the resin composition, and further comprising the electrode mixture composition. It is intended to provide an electrode structure for a non-aqueous electrochemical element formed by coating a substance on a current collecting substrate and removing an organic solvent to form a porous electrode layer.
  • the present invention provides a non-aqueous solvent-based secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte disposed between the positive electrode and the negative electrode, wherein at least one of the positive electrode and the negative electrode comprises the above electrode structure
  • the present invention also provides an electric double layer capacity in which a non-aqueous electrolyte is disposed between a pair of the electrode structures.
  • FIG. 1 is a partially exploded perspective view of a non-aqueous solvent secondary battery that can be configured according to the present invention.
  • FIG. 2 is a partial cross-sectional view of an electrode structure used in the secondary battery.
  • FIG. 3 is a sectional view of an example of a non-aqueous solvent-based electric double layer capacity constructed according to the present invention. [Best Mode for Carrying Out the Invention]
  • the vinylidene fluoride copolymer of the present invention comprises at least 100 mol of vinylidene fluoride monomer and 0.1 to 5.0 mol, preferably 0.2 to 3.0 mol of epoxy group-containing acrylic vinyl monomer. 0 mol, consisting of a copolymer of If the amount of the epoxy group-containing acrylic vinyl monomer is less than 0.1 mol, the desired effect of improving the adhesiveness to a substrate such as a metal cannot be obtained. An improvement effect cannot be obtained, and the polymerization time for obtaining a vinylidene fluoride-based copolymer tends to be long.
  • the epoxy group-containing acrylic vinyl monomer used in the present invention is generally substituted or unsubstituted.
  • Glycidyl (meth) acrylate in this specification, the term “(meth) acrylate” is used as a term encompassing acrylate and methacrylate), and is a preferred specific example. Examples thereof include glycidyl (meth) acrylate, 2-methyldaricidyl (meth) acrylate, 2-ethyltilididyl (meth) acrylate, and 1-methylglycidyl (meth) acrylate.
  • Methacrylates are preferable to acrylates in view of providing a good thermal decomposition stability pinylidene fluoride copolymer, and among them, substituted, especially alkyl-substituted glycidyl methacrylate is preferable.
  • the vinylidene fluoride copolymer should have a melting point (DSC) of 150 to 180 ° C, more preferably 160 to 180 ° C.
  • DSC melting point
  • the melting point of a vinylidene fluoride-based copolymer decreases as the amount of the comonomer increases when the amount of the monomer (co-monomer) copolymerized with the vinylidene fluoride monomer is relatively small.
  • the higher the inherent viscosity of the vinylidene fluoride copolymer the better the solvent resistance and mechanical strength.
  • a copolymer having a large intrinsic viscosity has a low solubility in a solvent, so that the intrinsic viscosity in the above range is preferable.
  • the vinylidene fluoride copolymer of the present invention is characterized by having excellent heat resistance, and has a thermal decomposition onset temperature of at least 350 ° C in a nitrogen atmosphere, preferably at 380 ° C. Above, more preferably at least 400 ° C.
  • a third monomer can be added to obtain a pinylidene fluoride-based copolymer within a range not inconsistent with the object of the present invention. it can.
  • a third monomer include a vinylidene fluoride obtained by copolymerizing a fluorine-based monomer copolymerizable with vinylidene fluoride or a hydrocarbon-based monomer such as ethylene or propylene. The solubility of the copolymer in a solvent can be controlled.
  • Fluorinated monomers copolymerizable with vinylidene fluoride include vinyl fluoride, trifluoroethylene, chlorofluoroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoropropylene. And low alkyl vinyl ethers. Two or more third monomers can be used in combination. However, the amount of the third monomer used is preferably kept within a range in which the melting point and the inherent viscosity described above are satisfied in the obtained vinylidene fluoride-based copolymer, and more specifically, It is preferable to keep the amount to 5 mol or less, more preferably 4 mol or less, per 100 mol of the vinylidene fluoride monomer.
  • the above-mentioned pinylidene fluoride copolymer of the present invention can be produced by a method such as suspension polymerization, emulsion polymerization, and solution polymerization.
  • aqueous suspension polymerization and emulsion polymerization are preferable, and aqueous suspension polymerization is particularly preferable, in view of the solvent resistance of the obtained copolymer and ease of post-treatment.
  • a suspending agent such as methylcellulose, methoxylated methylcellulose, propoxylated methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyethylene oxide, or gelatin is added to water. And added in the range of 0.05 to 1.0% by weight, preferably 0.010. 4% by weight.
  • polymerization initiator examples include diisopropylperoxydicarbonate, dinormal propylpropoxydicarbonate, dinormal heptafluoropropylperoxydica monocarbonate, isobutyryl peroxide, di ( Fluoroacyl peroxide and di (perfluoroacyl) peroxide can be used.
  • the amount is 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the total amount of monomers.
  • a chain transfer agent such as ethyl acetate, methyl acetate, acetone, ethanol, n-propanol, acetoaldehyde, propyl aldehyde, ethyl propionate, carbon tetrachloride, etc.
  • the amount used is usually from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, based on the total amount of the monomers.
  • the total charged amount of the monomers is 1: 1 to 1:10, preferably 1: 2 to 1: 5, by weight ratio of the total amount of monomers to water, and the polymerization is carried out at a temperature of 10 to 50. For 100 to 100 hours.
  • the vinylidene fluoride copolymer of the present invention can be easily produced.
  • the vinylidene fluoride-based copolymer of the present invention By dissolving, for example, 100 parts by weight of the vinylidene fluoride-based copolymer of the present invention in 500 to 200 parts by weight of an organic solvent, it can be suitably used as a paint, a lining material, a binder, or the like.
  • the resin composition of the present invention to be used is obtained.
  • the solvent N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like, which dissolve the vinylidene fluoride polymer well, are suitable.
  • the epoxy group-containing vinylidene fluoride copolymer of the present invention is coexistent with (meth) Due to the presence of the acrylate group, the epoxy group itself has the curability of the epoxy group, but if necessary, for example, 0.3 to 3.0 mol of a curing agent is further mixed with respect to 1 mol of the epoxy group to paint, It can also be used as a binder or the like.
  • amines eg, ethylenetriamine, triethylenetetramine, ethylenediamine, tetraethyleneamine
  • acid anhydrides phthalic anhydride, succinic acid
  • Acid anhydrides and low molecular weight curing agents such as glycidyl ether amine adducts.
  • the vinylidene fluoride copolymer of the present invention has a small average particle diameter of 100,000 or less, particularly 50 to 350 im, in order to enable rapid dissolution in the solvent. It is also desirable to use it.
  • the resin composition of the present invention thus obtained is applied to a substrate such as a metal, and then evaporated and, if necessary, cross-linked and cured, to thereby improve the adhesiveness to the substrate, the chemical resistance, and the electrolyte resistance. Produces excellent coatings.
  • the resin composition of the present invention is suitably used as a binder, paint, or lining agent which is required to have adhesion to a substrate such as a metal and solvent resistance and chemical resistance. It has extremely good suitability as a binder for electrode production of non-aqueous electrochemical elements with strong odor. Therefore, this application will be described in more detail.
  • FIG. 1 is a partially exploded perspective view of a lithium secondary battery as an example of a secondary battery that is a nonaqueous electrochemical device of the present invention.
  • this secondary battery is basically a battery in which a separator 3 composed of a microporous film of a polymer substance such as polypropylene or polyethylene impregnated with an electrolyte is arranged and stacked between the positive electrode 1 and the negative electrode 2.
  • the power generating element has a structure in which it is housed in a bottomed metal casing 5 forming a negative electrode terminal 5a.
  • the negative electrode is electrically connected to the negative electrode terminal, and after the gasket 6 and the safety valve 7 are arranged on the top, the positive electrode 8a is electrically connected to the positive electrode 1 at the convex portion.
  • the top plate 8 is arranged, and the top rim 5b of the casing 5 is caulked to form a structure in which the whole is sealed.
  • the electrode structure 10 constituting the positive electrode 1 or the negative electrode 2 is made of metal foil such as iron, stainless steel, steel, aluminum, nickel, titanium, copper, or the like. It is composed of a metal net or the like, and has a thickness of 5 to 100 / xm, and in the case of a small scale, for example, has a thickness of 5 to 20 m.
  • the electrode mixture layers 12a and 12b having a thickness of 10 to 100111 are formed on both surfaces.
  • the electrode mixture layers 12a and 12b are made of an electrode mixture forming composition comprising an active material as a powdered electrode material, a binder, and a conductive material such as carbon added as necessary. It was formed by applying and bonding to 11.
  • a carbonaceous substance such as graphite, activated carbon, or a phenol resin or pitch obtained by firing and carbonizing is preferable as the active material.
  • active material such as, force first pump rack, graphite powder or fiber
  • carbonaceous materials such as, fine powder of metal such as nickel and aluminum, or fibers.
  • the binder does not contribute to the charge / discharge capacity of the battery at all, it is necessary to minimize the amount of the binder used, and it is required that the binder retains the active material even in a small amount and has excellent adhesion to the current collector. Is done. Also, since binders are usually electrically insulating, increasing their use increases the internal resistance of the battery. From this point of view, it is required that the pinda perform its function with as little usage as possible.
  • the amount of the binder is very small and is not more than 30% by weight based on the whole electrode mixture. With such a small amount of the binder, the binder cannot completely fill the gap between the fine components such as the active material and / or the conductive material or the gap between the fine component and the current collector in the electrode mixture. In the case of paints and lining materials that contain fillers such as pigments, there are almost no problems with retaining the fillers because the binder uses a large amount of binder that is sufficient to completely fill the gaps between the fillers. Does not occur. However, in the case of a binder for an electrode, as described above, the amount of the binder used is extremely small, and a binder that retains the active material well even in a small amount and has excellent adhesiveness to the current collector is required.
  • the nonaqueous electrolyte is impregnated in the separator 3, ethylene carbonate, propylene carbonate, dimethoxyethane E Tan, tetrahydrofuran, ⁇ over butyrolactone L i C 1_Rei strong solvent having dissolve force for polymers such as 4, L i PF for 6, L i BF 4 solution of electrolytes or the like is used, the binder, a long period of time be immersed in these solvents, and a binder Solvent resistance that does not significantly reduce the function of the solvent is required.
  • the resin composition of the present invention is used as a binder for producing a thin-film electrode structure 10 for a battery, the following is preferred.
  • the epoxy group-containing vinylidene fluoride copolymer of the present invention and a curing agent added as necessary are dissolved in an organic solvent to obtain the above-described resin composition of the present invention.
  • an active material and a conductive agent are further added to this resin composition, and the mixture is slurried to form an electrode forming composition, for example, a metal foil or metal net having a thickness of about 5 to 20 m.
  • the electrode is uniformly coated on the current collector, dried, and heated and pressed to form an electrode mixture layer as thin as, for example, about 10 Oim on the current collector to form a thin-film electrode.
  • the solvent is evaporated, and the resin is cross-linked and hardened as necessary to ensure strong adhesion to the current collector and the fine filler.
  • the fine components in the electrode forming composition (active material and The ratio of the conductive agent) to the vinylidene fluoride-based copolymer is usually about 80:20 to 98: 2 by weight, and retains fine components, adheres to the current collector, and conducts the electrode. Determined in consideration of gender.
  • FIG. 3 is a cross-section of a single-cell electric double layer capacity as an example.
  • a separator 23 is sandwiched between a pair of polarizable electrodes 20a and 20b, each of which corresponds to an example of the electrode structure of the present invention.
  • a stainless steel can 5 filled with a non-aqueous electrolyte solution 26 through a packing 27.
  • the non-aqueous electrolyte 26 is impregnated in the separator 23, and is disposed between the pair of polarizable electrodes 20a and 20b.
  • the pair of polarizable electrodes 20a and 20b are respectively provided on one surface of current collecting substrates 21a and 21b similar to the current collecting substrate 11 shown in FIG.
  • Each of the electrode mixture layers 22a and 22b is formed by using the pinylidene fluoride-based copolymer of the present invention as a binder, for example, about 0.5 to 15% by weight. And more preferably 2 to 10% by weight, the remainder being powdered electrode material, preferably a palm-spray system having a specific surface area of about 500 to 300 m 2 / g, phenol.
  • a quaternary phosphonium salt or a quaternary ammonium salt such as (C 2 H 5 ) 4 NBF 4 is used as an electrolyte.
  • a solution dissolved in a solvent similar to the secondary battery solvent described above is used.
  • the binder forming the electrode mixture layer is required to have good adhesiveness with the current collecting base, electrolyte resistance and heat resistance, which is required in non-aqueous secondary batteries. This is exactly the same as the case described above, and the epoxy group-containing vinylidene fluoride copolymer of the present invention is suitably used.
  • the polymer slurry After completion of the polymerization, the polymer slurry is dehydrated, washed with water and dehydrated, and then dried at 80 ° C for 20 hours to obtain a powdery resin A corresponding to the epoxy group-containing vinylidene fluoride copolymer of the present invention.
  • the yield was about 80% by weight.
  • Resin A had an inherent viscosity (logarithmic viscosity at 30 ° C. of a solution in N, N-dimethylformamide with a resin concentration of 4 g / l) of 1.50 dlZg.
  • thermogravimetric analysis (using METTLER “TC10A”), which was heated at a temperature of 30 ° C. to 10 ° C./min in a nitrogen atmosphere and a weight change was observed.
  • Thermal decomposition onset temperature (weight loss onset temperature) was 425 ° C.
  • the above-mentioned electrode mixture composition A is uniformly applied on a 10-thick copper foil (area 10 OmmX 20 Omm) so that a dry film thickness becomes about 100, and dried at 130 ° C for 25 minutes to obtain The electrode structure A of the invention was obtained.
  • the electrode structure A was subjected to a thermogravimetric analysis in the same manner as the resin composition A. As a result, a pyrolysis onset temperature of 400 ° C was shown.
  • the above-mentioned electrode structure A separately formed in the same manner was immersed in propylene-based monoponate at 60 ° C. for 5 days.
  • the adhesive strength between the electrode layer and the copper foil before and after immersion was measured by a 180 ° peel test according to JIS K6845. As a result, the peel strength before and after immersion was 6 ⁇ O g / mm and 3.0 g / mm, respectively.
  • Comparative Resin D composed of a VDF / MMM copolymer, which was evaluated in the same manner as Resin A of Example 1.
  • the polymer slurry was dehydrated, washed with water, dehydrated, and dried at 80 ° C for 20 hours to obtain a comparative resin E composed of a VDF / AGE copolymer. evaluated.
  • Comparative Resin F composed of the VDF / AGEZMM M copolymer, which was evaluated in the same manner as in Resin A of Example 1.
  • the binder for non-aqueous electrochemical elements shows good adhesiveness to a substrate such as a metal, and shows improved heat stability.
  • Group-containing vinylidene fluoride copolymer having excellent suitability for use as well as a method for efficiently producing the same, a resin composition containing the pinylidene fluoride copolymer as a binder, an electrode structure and a non-aqueous resin An electrochemical device is provided.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Cette invention se rapporte à un groupe époxy contenant un copolymère de fluorure de vinylidène, se caractérisant en ce qu'il possède un copolymère de fluorure de vinylidène comme constituant primaire et une petite quantité d'un groupe époxy contenant un monomère acrylique, à un procédé pour produire ce copolymère de fluorure de vinylidène, consistant à effectuer une polymérisation de suspension dans un milieu de dispersion aqueux; à une composition comprenant ce copolymère de fluorure de vinylidène; ainsi qu'à un élément électrochimique non aqueux comprenant ce copolymère. Ce groupe époxy comprenant un copolymère de fluorure de vinylidène possède une bonne adhérence à des substrats, par exemple en métal, et également une excellente résistance thermique et il est par conséquent parfaitement approprié comme liant à utiliser dans une électrode d'éléments électrochimiques non aqueux, tels que des piles secondaires, des condensateurs à double couche électrique et similaires.
PCT/JP2002/012266 2001-11-26 2002-11-25 Groupe epoxy contenant un copolymere de fluorure de vinylidene, et composition de resine, structure d'electrode et element electrochimique non aqueux comprenant ce groupe WO2003046026A1 (fr)

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AU2002349709A AU2002349709A1 (en) 2001-11-26 2002-11-25 Epoxy group containing vinylidene fluoride copolymer, and resin composition, electrode structure and non-aqueous electrochemical element comprising the same

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JP2001-358897 2001-11-26
JP2001358897A JP2003155313A (ja) 2001-11-26 2001-11-26 エポキシ基含有フッ化ビニリデン系共重合体、これを含有する樹脂組成物、電極構造体および非水系電気化学素子

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Cited By (1)

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WO2014097618A1 (fr) * 2012-12-19 2014-06-26 パナソニック株式会社 Solvant non aqueux pour dispositifs accumulateurs d'électricité, solution d'électrolyte non aqueux, dispositif accumulateur d'électricité utilisant la solution d'électrolyte non aqueux et accumulateur au lithium

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JP2005310747A (ja) * 2004-03-23 2005-11-04 Kureha Chem Ind Co Ltd 非水系電気化学素子電極形成用バインダー、電極合剤、電極構造体および電気化学素子
JP4887653B2 (ja) * 2005-03-25 2012-02-29 日本ゼオン株式会社 非水電解質二次電池電極用バインダー、バインダー組成物、電極用組成物、ならびに電極
US9034997B2 (en) 2010-05-27 2015-05-19 Showa Denko K.K. Fluorine and epoxy group-containing copolymer, and method for producing same
JP2015513799A (ja) * 2012-02-22 2015-05-14 セルドン テクノロジーズ，インコーポレーテッド 電極及び用途
JP6380808B2 (ja) * 2015-05-19 2018-08-29 トヨタ自動車株式会社 二次電池用電極の製造方法
WO2018092676A1 (fr) * 2016-11-15 2018-05-24 株式会社クレハ Mélange d'électrodes, procédé de production de mélange d'électrodes, corps de structure d'électrode, procédé de production de corps de structure d'électrode et batterie secondaire
JP7014639B2 (ja) 2018-02-28 2022-02-01 株式会社クレハ フッ化ビニリデンポリマー、バインダー組成物、電極合剤、電極及び非水電解質二次電池、並びに電極合剤の製造方法
JP7060986B2 (ja) 2018-03-15 2022-04-27 株式会社クレハ バインダー組成物、非水電解質二次電池用電極を製造するための合剤、非水電解質二次電池用の電極および非水電解質二次電池

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JPH11246631A (ja) * 1998-03-04 1999-09-14 Kanto Denka Kogyo Co Ltd 硬化性含フッ素共重合体及びその製造方法

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JPS61218612A (ja) * 1985-03-25 1986-09-29 Daikin Ind Ltd メツキ治具
JPH03213336A (ja) * 1990-01-19 1991-09-18 Mitsubishi Petrochem Co Ltd 多層積層体
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JPH11246631A (ja) * 1998-03-04 1999-09-14 Kanto Denka Kogyo Co Ltd 硬化性含フッ素共重合体及びその製造方法

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* Cited by examiner, † Cited by third party
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WO2014097618A1 (fr) * 2012-12-19 2014-06-26 パナソニック株式会社 Solvant non aqueux pour dispositifs accumulateurs d'électricité, solution d'électrolyte non aqueux, dispositif accumulateur d'électricité utilisant la solution d'électrolyte non aqueux et accumulateur au lithium

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