WO2011129410A1 - Composition de liant fluoré, mélange d'électrode pour batterie secondaire la comprenant, électrode pour batterie secondaire et batterie secondaire - Google Patents

Composition de liant fluoré, mélange d'électrode pour batterie secondaire la comprenant, électrode pour batterie secondaire et batterie secondaire Download PDF

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WO2011129410A1
WO2011129410A1 PCT/JP2011/059304 JP2011059304W WO2011129410A1 WO 2011129410 A1 WO2011129410 A1 WO 2011129410A1 JP 2011059304 W JP2011059304 W JP 2011059304W WO 2011129410 A1 WO2011129410 A1 WO 2011129410A1
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fluorine
binder composition
secondary battery
solvent
electrode
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PCT/JP2011/059304
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English (en)
Japanese (ja)
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丈裕 巨勢
中野　貴志
智行 藤田
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旭硝子株式会社
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Publication of WO2011129410A1 publication Critical patent/WO2011129410A1/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
    • 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
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 fluorine-containing binder composition, an electrode mixture for a secondary battery obtained using the same, an electrode for a secondary battery, and a secondary battery.
  • nonaqueous secondary batteries lithium or lithium alloys are used as negative electrodes
  • nonaqueous secondary batteries using an electrolyte-impregnated solid electrolyte lithium ion secondary batteries using a carbonaceous material as a negative electrode are attracting attention. .
  • Electrode fabrication technology is important for improving the energy density of this lithium ion secondary battery.
  • a negative electrode is fabricated using a carbonaceous material such as carbon or graphite as a negative electrode active material
  • the carbonaceous material is powdered together with a binder. It is obtained by dispersing in a solvent to prepare a negative electrode mixture, coating the negative electrode current collector, removing the solvent by drying, and rolling with a press or the like.
  • a positive electrode is prepared by pulverizing a lithium-containing oxide such as lithium cobaltate as a positive electrode active material and dispersing it in a solvent together with a conductive agent such as acetylene black and a binder. After applying to the body, the solvent is removed by drying and rolling.
  • polyvinylidene fluoride is generally used as a binder of this lithium ion secondary battery.
  • a positive electrode mixture prepared by mixing a lithium-containing oxide such as LiCoO 2 as a positive electrode active material and graphite as a conductive agent with polyvinylidene fluoride and dispersing it in N-methylpyrrolidone to form a slurry is used as a positive electrode of an aluminum foil.
  • the negative electrode mixture prepared by applying to the current collector, mixing with a carbonaceous material as the negative electrode active material and polyvinylidene fluoride and dispersing in N-methylpyrrolidone to form a slurry
  • a technique is disclosed in which an electrode sheet is processed by compression molding with a roller press machine after being applied to each other and dried (see Patent Document 1).
  • polyvinylidene fluoride tends to swell with respect to organic solvents of non-aqueous electrolytes such as propylene carbonate, ethylene carbonate, diethyl carbonate, or mixtures thereof used in lithium ion secondary batteries. For this reason, there is a problem that the adhesiveness with the metal foil as a current collector is deteriorated while the charge and discharge are repeated, and the battery performance is lowered.
  • the melting point of polyvinylidene fluoride is about 170 ° C., when the drying temperature is increased in order to increase the productivity, it reaches the vicinity of the melting point of the polymer, so that the polymer in the electrode mixture moves during drying. A phenomenon such as migration occurs.
  • the battery capacity is improved by using, as an electrode, an electrode obtained by adhering a mixed layer of an insoluble infusible substrate having a polyacene skeleton structure and a specific binder in the form of a metal foil.
  • the fluorine-containing polymer has an atomic ratio of fluorine atom / carbon atom of less than 1.5 and 0.75 or more.
  • what is specifically disclosed is only polyvinylidene fluoride.
  • the ethylene-4 fluoroethylene copolymer described in the publication is generally insoluble in an organic solvent and insoluble as a binder. It was considered appropriate.
  • TFE tetrafluoroethylene
  • An ETFE solution was obtained by using a dicarboxylic acid diester such as diisobutyl adipate as a solvent, but the dissolution temperature requires a high temperature of 230 ° C., 260 to 265 ° C., or 290 ° C. (Patent Document 3, Patent Document) 4, see Patent Document 5).
  • the present invention includes a secondary battery that has excellent adhesion between a battery active material and a current collector, has low electrode swelling with respect to an electrolyte solution at high temperatures, and can sufficiently exhibit productivity and practical performance. It aims at providing the fluorine binder composition, the electrode mixture for secondary batteries obtained using the same, the electrode for secondary batteries, and a secondary battery.
  • a solvent capable of dissolving the fluorine-containing copolymer at a temperature below the melting point of the fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene has not been known.
  • a solvent capable of dissolving the fluorine-containing copolymer at a temperature below the melting point of the fluorine copolymer was found, and the present invention was completed based on this finding.
  • the present invention provides a fluorine-containing binder composition, a method for producing the same, an electrode mixture for a secondary battery obtained by using the fluorine-containing binder composition, an electrode for a secondary battery, and a secondary battery having the following configuration: To do.
  • a binder comprising a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene, and the fluorine-containing copolymer can be dissolved at a temperature below the melting point of the fluorine-containing copolymer.
  • a fluorine-containing binder composition comprising a solvent.
  • a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene can dissolve the fluorine-containing copolymer at a temperature lower than the melting point of the fluorine-containing copolymer.
  • a secondary battery electrode mixture comprising the fluorine-containing binder composition described in any one of [1] to [6] and a battery active material.
  • a thin film layer in which a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene is dispersed in a battery active material is formed on the current collector surface.
  • Secondary battery electrode [12] A secondary battery comprising the secondary battery electrode according to [10] or [11].
  • the secondary battery obtained by using the fluorine-containing binder composition of the present invention has a small swelling of the electrode with respect to the electrolyte even at high temperatures, and has a high binding property between the current collector of the electrode and the battery active material. Excellent discharge characteristics.
  • the fluorine-containing binder composition of the present invention has, as a binder, a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene (hereinafter sometimes simply referred to as “fluorinated copolymer”). And a solvent capable of dissolving the fluorinated copolymer at a temperature equal to or lower than the melting point of the fluorinated copolymer.
  • the fluorine-containing copolymer in the fluorine-containing binder composition of the present invention is not particularly limited as long as it is a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene.
  • a fluorinated copolymer include ETFE having a repeating unit based on ethylene and a repeating unit based on TFE as the main repeating unit in the copolymer.
  • the molar ratio of the repeating unit based on TFE / the repeating unit based on ethylene is preferably 70/30 to 30/70, more preferably 65/35 to 40/60, most preferably 60 / 40 to 40/60.
  • this composition ratio the swelling of the electrolytic solution with respect to the solvent at a high temperature is small, and when the current collector and the electrode are integrated, the electrode mixture containing the battery active material and the binder composition, and the current collector Good adhesion.
  • the fluorine-containing copolymer may contain a repeating unit based on another monomer in addition to the repeating unit based on ethylene and the repeating unit based on TFE.
  • the polyfluoroalkylethylenes are preferable because they can increase the toughness of ETFE and improve the resistance to electrode bending.
  • These comonomers may be used alone or in combination of two or more.
  • the other monomer include a monomer having an adhesive functional group in addition to the above-mentioned comonomer. If there is a functional group on the surface of the battery active material or current collector plate, the adhesive functional group reacts with the functional group on the surface of the battery active material or current collector to form a chemical bond, hydrogen bond, etc.
  • the battery active material or the current collector plate and the fluorine-containing copolymer are linked by having an interaction or the like.
  • Examples of such adhesive functional groups include a carboxyl group, a residue obtained by dehydration condensation of two carboxyl groups in one molecule (hereinafter referred to as a carboxylic acid anhydride group), an epoxy group, a hydroxyl group, an isocyanate group, and an ester group.
  • Preferred examples include amide group, aldehyde group, amino group, hydrolyzable silyl group, cyano group, carbon-carbon double bond, sulfonic acid group and ether group.
  • a carboxyl group, a carboxylic acid anhydride group, an epoxy group, a hydrolyzable silyl group, or a carbon-carbon double bond is preferable.
  • a compound having a carboxylic anhydride group is preferred in order to improve the adhesion to the current collector plate.
  • a monomer include itaconic anhydride, maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like.
  • Two or more different functional groups may exist in one molecule of the fluorine-containing copolymer, or two or more functional groups may exist in one molecule.
  • the content ratio of the repeating unit based on the other monomer is The amount is preferably 0.1 to 30 mol%, more preferably 0.1 to 25 mol%, still more preferably 0.1 to 20 mol%, and more preferably 0.1 to 15 mol%, based on all repeating units of the polymer. Is most preferred.
  • the upper limit may be 50 mol%, and repeating units based on other monomers may be contained.
  • the fluorine-containing copolymer used in the fluorine-containing binder composition of the present invention when the content of the repeating unit based on a comonomer other than TFE and ethylene is within this range, it is composed of only TFE and ethylene. Functions such as high solubility, water repellency, oil repellency, and adhesion to a substrate can be imparted without impairing the properties of ETFE.
  • the method for producing the fluorine-containing copolymer in the composition of the present invention include a method of copolymerizing ethylene, TFE, and other monomers optionally further contained by an ordinary polymerization method. .
  • the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like.
  • the fluorine-containing copolymer in the present invention those obtained as commercial items can also be used.
  • ETFE is manufactured by Asahi Glass Co., Ltd .: Fluon (registered trademark) ETFES series, Fluon (registered trademark) LM Series, Daikin Industries, Ltd .: NEOFLON (registered trademark), Dyneon Commercial products such as Dyeon (registered trademark) ETFE and DuPont: Tefzel (registered trademark) are available.
  • the melting point of the fluorine-containing copolymer in the fluorine-containing binder composition of the present invention is not particularly limited, but is preferably 130 ° C.
  • the fluorine-containing binder composition of the present invention can contain one of these fluorine-containing copolymers alone or two or more as a mixture.
  • the content of the fluorine-containing copolymer in the fluorine-containing binder composition of the present invention is not particularly limited, but is preferably 0.1 to 80% by mass, and preferably 0.5 to 50% by mass with respect to the total amount of the composition. % Is more preferable, and 1 to 40% by mass is most preferable. In particular, this range is preferable when an electrode mixture for a secondary battery or the like is obtained using the fluorine-containing binder composition of the present invention. When the content is in this range, the handleability in preparing the electrode mixture is excellent, and a homogeneous electrode can be obtained.
  • the content of the solvent in the fluorine-containing binder composition of the present invention is not particularly limited, but the content of the solvent in the composition is preferably 20 to 99.9% by mass based on the total amount of the composition, 50 to 99.5% by mass is more preferable, and 60 to 99% by mass is most preferable. In particular, this range is preferable when an electrode mixture for a secondary battery or the like is obtained using the fluorine-containing binder composition of the present invention. When the content is in this range, the handleability in preparing the electrode mixture is excellent, and a homogeneous electrode can be obtained.
  • the solvent in the present invention is a solvent that can dissolve the fluorinated copolymer at a temperature lower than the melting point of the fluorinated copolymer.
  • the fluorine-containing copolymer can be dissolved at a temperature below the melting point of the fluorine-containing copolymer means that the fluorine-containing copolymer can be dissolved at all temperatures below the melting point of the fluorine-containing copolymer. Instead, it means that the fluorine-containing copolymer can be dissolved in at least a part of the temperature range below the melting point of the fluorine-containing copolymer.
  • the fluorine-containing binder composition of the present invention has a temperature range in which the composition exhibits a solution state at a temperature not higher than the melting point of the fluorine-containing copolymer.
  • the fluorine-containing binder composition of the present invention only needs to maintain a solution state in a certain temperature range below the melting point of the fluorine-containing copolymer, and does not necessarily need to be in a solution state at room temperature.
  • the solvent is preferably at least one selected from the group consisting of an aliphatic compound having at least one of a carbonyl group and a nitrile group, a fluorine-containing aromatic compound, a hydrofluoroalkyl ether, and a hydrofluorocarbon.
  • the amount by which the solvent can dissolve the fluorinated copolymer is more preferably 5% by mass or more, and most preferably 10% by mass or more.
  • the melting point of the solvent capable of dissolving the fluorine-containing copolymer is preferably 230 ° C. or less, more preferably 200 ° C. or less, and more preferably 180 ° C. or less. When the melting point is within this range, the handleability when dissolving the fluorine-containing copolymer is excellent.
  • the fluorine atom content in the solvent ((fluorine atom weight ⁇ number of fluorine atoms in the molecule) ⁇ 100 / molecular weight) is preferably 5 to 75% by mass, preferably 9 to 75% by mass. Is more preferable, and 12 to 75% by mass is most preferable. Within this range, the solubility of the fluorine-containing copolymer is excellent.
  • the vapor pressure of the solution is preferably at least within the range of the spontaneously generated pressure or less, and more preferably within the range of 3 MPa or less.
  • vapor pressure of the solution in the solution state of the fluorine-containing copolymer composition of the present invention is within this range, it can be easily carried out in actual work.
  • spontaneous generated pressure means a pressure that a mixture of a solvent and a fluorinated copolymer naturally exhibits in a closed container.
  • the boiling point of the solvent is preferably room temperature or higher, more preferably 50 ° C. or higher, and 80 ° C. or higher. Most preferred.
  • the upper limit of the boiling point of the solvent is not particularly limited, but is preferably 220 ° C. or lower from the viewpoint of easiness of drying.
  • the fluorine-containing aromatic compound examples include fluorine-containing benzonitrile, fluorine-containing benzoic acid and its ester, fluorine-containing polycyclic aromatic compound, fluorine-containing nitrobenzene, fluorine-containing phenyl alkyl alcohol, fluorine-containing phenol and its ester, fluorine-containing Aromatic ketone, fluorine-containing aromatic ether, fluorine-containing aromatic sulfonyl compound, fluorine-containing pyridine compound, fluorine-containing aromatic carbonate, perfluoroalkyl-substituted benzene, perfluorobenzene, polyfluoroalkyl ester of benzoic acid, polyfluoroalkyl of phthalic acid Examples include esters and aryl esters of trifluoromethanesulfonic acid.
  • the fluorine-containing aromatic compound is preferably a fluorine-containing aromatic compound having at least two or more fluorine atoms.
  • fluorine-containing aromatic compounds more preferred examples include pentafluorobenzonitrile, 2,3,4,5-tetrafluorobenzonitrile, 2,3,5,6-tetrafluorobenzonitrile, 2,4,5- Trifluorobenzonitrile, 2,4,6-trifluorobenzonitrile, 3,4,5-trifluorobenzonitrile, 2,3-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,5-difluorobenzonitrile 2,6-difluorobenzonitrile, 3,4-difluorobenzonitrile, 3,5-difluorobenzonitrile, 4-fluorobenzonitrile, 3,5-bis (trifluoromethyl) benzonitrile, 2- (trifluoromethyl ) Benzonitrile, 3- (trifluoromethyl) benzonitrile, 4- (Trifluoromethyl) benzonitrile, 2- (trifluoromethoxy) benzonitrile, 3- (trifluor
  • hydrofluoroalkyl ether capable of dissolving the fluorine-containing copolymer
  • hydrofluoroalkyl ether capable of dissolving the fluorine-containing copolymer
  • 1-ethoxy-1,1,2,2-tetrafluoroethane 1-ethoxy-1,1,2,3,3,3.
  • Hexafluoropropane 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) propane, 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) pentane and the like.
  • 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) pentane is preferable.
  • hydrofluorocarbons capable of dissolving the fluorinated copolymer include HFC-c447ef (1,1,2,2,3,3,4-heptafluorocyclopentane), 1H, 1H, 1H, 2H, 2H. -Perfluorodecane and the like.
  • HFC-c447ef (1,1,2,2,3,3,4-heptafluorocyclopentane) is preferable.
  • the molecular structure of the aliphatic compound having at least one of a carbonyl group and a nitrile group is not particularly limited.
  • the carbon skeleton may be linear, branched or cyclic, and constitutes a main chain or a side chain.
  • Etheric oxygen may be present between the carbon-carbon bonds, and some of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom such as a fluorine atom. These may be used alone or in combination of two or more.
  • examples of the aliphatic compound having a carbonyl group include cyclic ketones having 3 to 10 carbon atoms, ketones such as chain ketones, chain esters and glycols. One or more selected from the group consisting of esters such as monoesters and carbonates is preferred.
  • the number of carbonyl groups is preferably 1 or 2.
  • aliphatic compound having one or more carbonyl groups in the present invention include the following compounds.
  • the cyclic ketone include cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-ethylcyclohexanone, 2,6-dimethylcyclohexanone, 3,3,5-trimethylcyclohexanone, 4-tert-butylcyclohexanone, Cycloheptanone, isophorone, (-)-Fencon.
  • chain ketone examples include acetone, methyl ethyl ketone, 2-pentanone, methyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, 2-nonanone, diisobutyl ketone, 2-decanone and diisopropyl ketone.
  • chain ester examples include ethyl formate, isopentyl formate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, cyclohexyl acetate, 2-ethylhexyl acetate, ethyl butyrate, butyl butyrate, pentyl butyrate Bis (2,2,2-trifluoroethyl) adipate, methyl cyclohexanecarboxylate, 2,2,2-trifluoroethyl cyclohexanecarboxylate, ethyl perfluoropropionate, ethyl perfluorobutanoate, ethyl perfluoropentanoate, 2 , 2,3,3,4,4,5,5-octafluoropentanoic acid ethyl, perfluor
  • Monoesters of the above glycols include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 1-methoxy-2-acetoxypropane, 1-ethoxy-2-acetoxypropane, 3-methoxybutyl acetate 3-methoxy-3-methylbutyl acetate.
  • Examples of the carbonate include bis (2,2,3,3-tetrafluoropropyl) carbonate, bis (2,2,2-trifluoroethyl) carbonate, and diethyl carbonate.
  • the aliphatic compound having a nitrile group is an aliphatic nitrile having one or more nitrile groups, and the number of nitrile groups is one or two. Is preferred.
  • Specific examples of the aliphatic nitriles that can dissolve the fluorine-containing copolymer include butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, capronitrile, isocapronitrile, heptanenitrile, octanenitrile, nonanenitrile, decane. Nitrile etc.
  • butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, capronitrile, isocapronitrile, heptanenitrile, or octanenitrile is preferable.
  • dissolve a fluorine-containing copolymer may be used individually by 1 type, and may use 2 or more types together.
  • a solvent that does not dissolve or swell the fluorine-containing copolymer up to the melting point of the fluorine-containing copolymer or the boiling point of the solvent is defined as a non-solvent.
  • a non-solvent may be contained in the fluorine-containing copolymer solution as long as the solubility of the fluorine-containing copolymer is not impaired.
  • the solvent capable of dissolving the fluorinated copolymer in the present invention is more preferably in a specific range having the polarity of the solvent.
  • the solvent that satisfies the above conditions is preferably a solvent that is defined as a solvent having a certain range of polarity based on Hansen solubility parameters.
  • the Hansen solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of a dispersion term ⁇ d, a polar term ⁇ p, and a hydrogen bond term ⁇ h, and representing it in a three-dimensional space.
  • the dispersion term ⁇ d indicates the effect due to the dispersion force
  • the polar term ⁇ p indicates the effect due to the force between the dipoles
  • the hydrogen bond term ⁇ h indicates the effect due to the hydrogen bond force.
  • Hansen solubility parameter The definition and calculation of the Hansen solubility parameter is described in CharlesCM. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007).
  • the Hansen solubility parameter can be easily estimated by using the computer software Hansen Solubility Parameters in Practice (HSPiP).
  • HSPiP Hansen Solubility Parameters in Practice
  • the Hansen solubility parameter of a particular polymer can be determined by conducting a test to measure the solubility of a sample of the polymer in a number of different solvents for which the Hansen solubility parameter has been established. Specifically, among the solvents used in the solubility test, all the three-dimensional points of the solvent in which the polymer is dissolved are encapsulated inside the sphere, and the non-dissolved solvent points are outside the sphere ( The solubility sphere) is found, and the center coordinate of the sphere is used as the Hansen solubility parameter of the polymer.
  • the point indicated by the coordinates is the polymer. If it is encapsulated inside the solubility sphere, the solvent is considered to dissolve the polymer. On the other hand, if the coordinate point is outside the solubility sphere of the polymer, it is considered that this solvent cannot dissolve the polymer.
  • the Hansen solubility parameter is based on diisopropyl ketone, which is a solvent capable of dissolving the fluorine-containing copolymer contained in the binder composition at a temperature below its melting point. It is preferable to use a solvent group at a certain distance from the coordinates (15.7, 5.7, 4.3) as a preferred solvent.
  • R which is a value based on the Hansen solubility parameter represented by the following formula (1), was used as a solubility index for the fluorinated copolymer.
  • R 4 ⁇ ( ⁇ d ⁇ 15.7) 2 + ( ⁇ p ⁇ 5.7) 2 + ( ⁇ h ⁇ 4.3) 2 (1)
  • ⁇ d, ⁇ p and ⁇ h are Hansen solubility.
  • the dispersion term, the polar term, and the hydrogen bonding term in the parameters are shown, and the unit is (MPa) 1/2 .)
  • the solvent used in the present invention preferably has a solubility index (R) calculated by the above formula (1) of less than 40 and less than 30 using Hansen solubility parameter coordinates ( ⁇ d, ⁇ p, ⁇ h) of the solvent. More preferably, it is particularly preferably less than 20.
  • R solubility index
  • a solvent having a Hansen solubility parameter in which R represented by the above formula (1) falls within this range has high affinity with the fluorine-containing copolymer and high solubility of the fluorine-containing copolymer. When dispersed, it can be stably dispersed as fine particles.
  • the value of R calculated based on the Hansen solubility parameter by the above formula (1), whether it is a solvent composed of one compound or a mixed solvent of two or more compounds, It can be used as a dissolution index of ETFE.
  • a mixed solvent an average Hansen solubility parameter based on the mixing ratio (volume ratio) of the solvent to be used is obtained, and the solubility index (R) can be calculated using the Hansen solubility parameter.
  • the fluorine-containing binder composition of the present invention is a fluorine-containing binder composition comprising a binder comprising a fluorine-containing copolymer and a solvent capable of dissolving the fluorine-containing copolymer at a temperature below the melting point of the fluorine-containing copolymer. It is preferably a fluorine-containing binder composition obtained through a step of dissolving the fluorine-containing copolymer in a solvent.
  • the fluorine-containing copolymer contained in the binder composition may be contained in a dissolved state, or may be contained in a state where the fluorine-containing copolymer is precipitated and dispersed from a solution dissolved in a solvent. .
  • the fluorinated copolymer becomes fine particles.
  • the fluorine-containing binder composition of the present invention exhibits fluidity near room temperature.
  • the vicinity of room temperature is about 10 to 40 ° C., preferably about 15 to 30 ° C.
  • the production method of the present invention for producing the fluorine-containing binder composition of the present invention will be described below.
  • a method for producing the fluorine-containing binder composition of the present invention a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene is obtained at a temperature below the melting point of the fluorine-containing copolymer.
  • a method for producing a fluorine-containing binder composition having a step of dissolving in a solvent (hereinafter sometimes referred to as “dissolution step”) is preferred.
  • the temperature at which the fluorine-containing copolymer is dissolved in the solvent is more preferably 30 ° C. or lower than the melting point of the fluorine-containing copolymer used.
  • the temperature of the step of dissolving in the solvent is preferably 245 ° C. or lower, which is 30 ° C. lower than 275 ° C.
  • the temperature at which the fluorine-containing copolymer is dissolved in the solvent is more preferably 230 ° C. or less, and particularly preferably 200 ° C. or less.
  • 0 degreeC is preferable and 20 degreeC is more preferable. If it is this temperature range, a fluorine-containing copolymer will fully melt
  • conditions other than temperature are not particularly limited, and it is usually preferable to carry out under normal pressure.
  • the boiling point is lower than the temperature of the dissolving step depending on the type of the fluorinated copolymer or the solvent, at least the pressure generated spontaneously in the pressure vessel, preferably 3 MPa or less, more preferably 2 MPa or less, more preferably 1 MPa or less.
  • dissolution can be implemented on about 0.01-1 Mpa conditions.
  • the dissolution time depends on the content of the fluorine-containing copolymer in the composition of the present invention, the shape of the fluorine-containing copolymer, and the like.
  • the shape of the fluorine-containing copolymer to be used is preferably in the form of a powder in terms of work efficiency for shortening the dissolution time. Is also possible.
  • the dissolution means in the dissolution step is not special and may be a general method.
  • the necessary amount of each component to be blended in the composition is weighed, and these components are uniformly mixed at a temperature not higher than the melting point of the fluorine-containing copolymer to be used, preferably at a temperature of 0 to 230 ° C.
  • What is necessary is just to dissolve a polymer in a solvent such as the carbonyl group-containing aliphatic compound, using a general stirring mixer such as a homomixer, a Henschel mixer, a Banbury mixer, a pressure kneader, a single screw or a twin screw extruder. From the viewpoint of efficiency, it is preferable to carry out the dissolution.
  • an apparatus such as an autoclave with a stirrer is used, and the shape of the stirring blade is a marine propeller blade, paddle blade, anchor blade, turbine blade, or the like.
  • the fluorine-containing copolymer may be used as it is dissolved in a solvent, or may be used as a dispersion in which the fluorine-containing copolymer is dispersed in a solvent.
  • a dispersion it is preferable to pass through a step of precipitation from a solution in which the fluorine-containing copolymer is dissolved in a solvent (hereinafter sometimes referred to as “precipitation step”).
  • precipitation step By passing through the precipitation step, the binder made of the fluorine-containing copolymer is finely dispersed in the composition, and the binding property can be improved.
  • the average particle size of the fine particles of the fluorine-containing copolymer in the obtained binder composition is preferably in the range of 0.005 to 2 ⁇ m as an average particle size measured by a small angle X-ray scattering method at 20 ° C. 0.005 to 1 ⁇ m is more preferable.
  • Secondary batteries to which the fluorine-containing binder composition of the present invention is applied include, for example, lithium batteries such as lithium ion batteries, lithium polymer batteries, and lithium primary batteries as non-aqueous secondary batteries, and nickel-hydrogen batteries as aqueous secondary batteries. Is mentioned.
  • a secondary battery to which the fluorine-containing binder composition of the present invention is applied usually includes a positive electrode, a negative electrode, a separator, and an electrolytic solution.
  • the positive electrode include a positive electrode obtained by applying and drying a positive electrode mixture composed of a positive electrode active material, a binder composition, and a conductive agent added as necessary on a positive electrode current collector.
  • the negative electrode include a negative electrode obtained by applying and drying a negative electrode mixture composed of a negative electrode active material and a binder composition on a negative electrode current collector.
  • the secondary battery electrode of the present invention can be obtained.
  • lithium metal, a lithium alloy such as a lithium aluminum alloy, or the like can be used as a counter electrode.
  • cell active substance used in the present invention is not particularly limited, for example, a positive electrode active as the material MnO 2, V 2 O 5, V metal oxides such as 6 O 13 of the lithium battery and other, TiS 2, MoS 2, FeS, etc. And metal complex sulfides such as LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 , and lithium mixed metal oxides containing transition metals such as Ni, Mn, Fe, and Ti.
  • the negative electrode active material include carbonaceous materials such as coke, graphite, mesophase pitch spherules, polymer carbides such as phenol resin and polyparaphenylene, vapor-phase-generated carbon fibers, and carbon fibers.
  • nickel hydroxide in which nickel hydroxide or cobalt oxide is combined is preferably used, and nickel-based or titanium-based hydrogen storage alloy is preferably used for the negative electrode.
  • the current collector in the present invention is not particularly limited as long as it is made of a conductive material, but in general, a metal foil such as aluminum, nickel, stainless steel, copper, a metal net, a metal porous body, etc.
  • a metal foil such as aluminum, nickel, stainless steel, copper, a metal net, a metal porous body, etc.
  • aluminum is preferably used as the positive electrode current collector
  • copper is preferably used as the negative electrode current collector.
  • Nickel foil or nickel foam is used for the positive electrode current collector of the nickel metal hydride battery.
  • the thickness of the current collector is preferably 1 to 100 ⁇ m. If it is less than 1 ⁇ m, the durability of the battery is insufficient and the reliability of the battery may be lowered. On the other hand, if it exceeds 100 ⁇ m, the mass of the battery increases.
  • the electrode for a secondary battery of the present invention can be obtained by applying the electrode mixture for a secondary battery of the present invention to a current collector, drying it, and forming it to a desired thickness by pressing as necessary.
  • a method for applying the electrode mixture for a secondary battery of the present invention to a current collector various application methods may be mentioned, for example, a method using an application tool such as a doctor blade.
  • the coating temperature is not particularly limited, but is preferably 0 to 150 ° C., and more preferably 5 to 80 ° C. from the viewpoint of operability. Drying can be performed using various dryers, and examples thereof include a heating vacuum dryer.
  • the drying temperature is not particularly limited, but is usually preferably room temperature to 250 ° C, particularly preferably 80 to 250 ° C. By heating in this temperature range, the fluorine-containing copolymer is partially dissolved and homogenized.
  • a pressing method a mold press, a roll press or the like can be used.
  • the electrode mixture for secondary batteries of the present invention contains a fluorine-containing binder composition and a battery active material.
  • the content of the fluorine-containing binder composition is not particularly limited, but the binder composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the battery active material, 1-8 parts by mass is more preferable. If the amount is less than 0.1 parts by mass, the strength of the electrode becomes weak, and the adhesion strength between the electrode and the current collector becomes weak. If the amount is more than 20 parts by mass, the battery may be significantly overvoltage.
  • the content of the binder is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the battery active material.
  • the electrode mixture for secondary batteries of the present invention can be produced by mixing the fluorine-containing binder composition and the battery active material by various mixing methods.
  • the thickness of the coating layer of the electrode mixture for secondary batteries of the present invention is preferably 0.5 to 2000 ⁇ m, more preferably 1 to 1000 ⁇ m, and particularly preferably 10 to 500 ⁇ m after drying.
  • the thickness of the coating layer of the electrode mixture for secondary batteries of the present invention is as thin as 200 ⁇ m or less, and even when the thickness is thinner as 150 ⁇ m or less, the uniform thickness with less surface irregularities
  • the secondary battery electrode mixture coating layer can be formed on the surface of the current collector.
  • the electrode for secondary batteries of this invention which formed the thin film layer in which the fluorine-containing copolymer was disperse
  • the electrode for a secondary battery of the present invention can be used for a battery having any shape such as a cylindrical shape, a sheet shape, and a square shape.
  • the nonaqueous secondary battery which uses the electrode of this invention for a positive electrode and / or a negative electrode, and is accommodated in a case with a nonaqueous electrolyte solution through a separator between a positive electrode and a negative electrode has high reliability also at high temperature.
  • a microporous polymer film is used, and the material is nylon resin, polyester resin, cellulose acetate resin, nitrocellulose resin, polysulfone resin, polyacrylonitrile resin, polyvinylidene fluoride resin, tetrafluoroethylene resin. Tetrafluoroethylene-ethylene copolymer resin, polypropylene resin, polyethylene resin and the like.
  • a non-aqueous electrolyte is used.
  • the solvent for the non-aqueous electrolyte include aprotic organic solvents such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, and diethoxyethane.
  • the electrolyte include lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 5 , CF 3 SO 3 Li, and (CF 3 SO 2 ) 2 NLi.
  • Adhesion peel strength
  • An electrode produced by applying an electrode mixture on a current collector was cut into a strip shape having a width of 2 cm and a length of 10 cm, and fixed with the coating surface of the electrode mixture facing up.
  • Cellophane tape was affixed to the coating surface of the electrode mixture, and the strength (N) when the tape was peeled in the 90 ° C. direction at a speed of 10 mm / min was measured five times, and the average value was taken as the peel strength. It shows that it is excellent in adhesiveness (binding property), so that this value is large.
  • Electrolytic solution resistance As an electrolytic solution resistance, the swelling property of the electrode with respect to the solvent of a non-aqueous electrolyte solution was evaluated.
  • the longer the time the smaller the swellability and the better the electrolyte resistance.
  • the counter electrode was prepared by pressing a lithium metal foil against a copper net, with a porous polyethylene separator (25 ⁇ m) interposed therebetween, and the electrolyte solution 1M LiPF6 in ethyl methyl carbonate-ethylene carbonate (volume ratio 3 1), the overvoltage was measured at 70 ° C., and the discharge capacity at the 30th charge / discharge cycle was determined as the capacity retention rate with respect to the initial discharge capacity.
  • a fluorine-containing binder composition 2 in which ETFE2 was dispersed was obtained in the same manner as in Production Example 1 except that the heating temperature was changed to 160 ° C. Also in this case, as in Production Example 1, when heated to 160 ° C. with stirring, it was visually confirmed that there was no insoluble matter, and it was confirmed that the solution was in a transparent and uniform solution state.
  • Example 1 As a positive electrode active material, 95 parts by mass of LiCoO 2 having an average particle diameter of 8 ⁇ m and 5 parts by mass of acetylene black were premixed, and then 100 parts by mass of the fluorine-containing binder composition 1 was added and mixed for 20 minutes in a ball mill. Agent 1 was obtained.
  • the positive electrode mixture 1 was applied to a 15 ⁇ m thick aluminum foil (current collector) with a roughened surface so that the thickness after drying with a doctor blade was 120 ⁇ m at room temperature, followed by heat drying at 170 ° C. After being dried in a machine and vacuum-dried at 120 ° C. for 12 hours, it was rolled to a thickness of 70 ⁇ m using a roll press machine, cut into 1.5 cm ⁇ 2.0 cm, and used as the positive electrode 1. .
  • the evaluation results are shown in Table 1.
  • Example 2 A positive electrode mixture 2 was obtained in the same manner as in Example 1, except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 2. Moreover, using the positive electrode mixture 2, the positive electrode 2 was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 3 A positive electrode mixture 3 was obtained in the same manner as in Example 1 except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 3. Moreover, using the positive electrode mixture 3, the positive electrode 3 was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 4 A positive electrode mixture 4 was obtained in the same manner as in Example 1 except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 4. Further, using the positive electrode mixture 4, the positive electrode 4 was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 5 A positive electrode mixture 5 was obtained in the same manner as in Example 1, except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 5. Further, using the positive electrode mixture 5, the positive electrode 5 was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 6 A positive electrode mixture 6 was obtained in the same manner as in Example 1 except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 6. Moreover, the positive electrode mixture 6 was used, and the positive electrode 6 was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • Example 7 A positive electrode mixture 7 was obtained in the same manner as in Example 1 except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 7. Moreover, the positive electrode mixture 7 was used, and the positive electrode 7 was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • Example 8 A positive electrode mixture 8 was obtained in the same manner as in Example 1, except that the fluorine-containing binder composition 1 was replaced with the fluorine-containing binder composition 8. Moreover, the positive electrode 8 was obtained in the same manner as in Example 8 by using the positive electrode mixture 8. The evaluation results are shown in Table 2.
  • Example 9 As a negative electrode active material, 95 parts by mass of artificial graphite powder and 5 parts by mass of acetylene black were premixed, and then 100 parts by mass of fluorinated binder composition 1 was added and mixed for 20 minutes in a ball mill to obtain a negative electrode mixture. It was. The mixture was applied to a 20 ⁇ m thick copper foil (current collector) with a roughened surface so that the thickness after drying with a doctor blade was 100 ⁇ m at room temperature. Then, after vacuum drying at 120 ° C. for 12 hours, it was rolled to a thickness of 70 ⁇ m using a roll press, cut into 1.5 cm ⁇ 2.0 cm, and used as negative electrode 1. The evaluation results are shown in Table 3.
  • Example 2 A positive electrode mixture was obtained in the same manner as in Example 1, except that an N-methylpyrrolidone solution of polyvinylidene fluoride (polyvinylidene fluoride concentration: 5% by mass) was used instead of the fluorine-containing binder composition 1. A positive electrode 4 was obtained. The evaluation results are shown in Table 2.
  • Example 3 A negative electrode mixture was obtained in the same manner as in Example 9, except that an N-methylpyrrolidone solution of polyvinylidene fluoride (polyvinylidene fluoride concentration: 5% by mass) was used instead of the fluorine-containing binder composition 1. A negative electrode 2 was obtained. The evaluation results are shown in Table 3.
  • the electrode of the present invention has a high peel strength between a thin film layer in which a fluorine-containing copolymer having a repeating unit based on ethylene and a repeating unit based on tetrafluoroethylene is dispersed in the battery active material, and adhesion.
  • the peel strength can be 0.2 N or more, preferably 0.25 N or more, and more preferably 0.3 N or more.
  • the time until peeling can be 120 minutes or more, preferably 160 minutes or more, more preferably 190 minutes or more, and still more preferably It can be 220 minutes or longer.
  • the electrode of the present invention can have a capacity retention as charge / discharge characteristics of 90% or more, preferably 92% or more, and more preferably in a secondary battery made using the electrode. Can be 94% or more.
  • the fluorine-containing binder composition of the present invention can be used as a secondary battery, and can be used as various binder compositions for primary batteries, electric double layer capacitors and the like.
  • the electrode mixture for secondary batteries and the electrode for secondary batteries obtained using the fluorine-containing binder composition of the present invention have low swelling with respect to the electrolyte even at high temperatures, and the current collector and active material of the electrode It can be used for a secondary battery having high mutual binding properties and excellent charge / discharge characteristics.

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  • Electrochemistry (AREA)
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Abstract

L'invention porte sur : une composition de liant fluoré qui peut conférer une excellente adhérence entre un matériau actif de batterie et un collecteur de courant, peut réduire le degré de gonflement d'une électrode dans une solution électrolytique à température élevée, et peut présenter un comportement pratique de celle-ci de façon satisfaisante; sur un mélange d'électrode pour batterie secondaire, qui est produit à l'aide de la composition; une électrode pour batterie secondaire; et sur une batterie secondaire. L'invention décrit spécifiquement : une composition de liant fluoré qui comprend un liant comprenant un copolymère fluoré ayant une unité de répétition dérivée de l'éthylène et une unité de répétition dérivée du tétrafluoroéthylène et un solvant capable de dissoudre le copolymère fluoré à une température inférieure ou égale au point de fusion du copolymère fluoré; un mélange d'électrode pour batterie secondaire, qui est produit à l'aide de la composition; une électrode pour batterie secondaire; et une batterie secondaire.
PCT/JP2011/059304 2010-04-16 2011-04-14 Composition de liant fluoré, mélange d'électrode pour batterie secondaire la comprenant, électrode pour batterie secondaire et batterie secondaire WO2011129410A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019164937A (ja) * 2018-03-20 2019-09-26 宇部興産株式会社 非水電解液およびそれを用いた蓄電デバイス

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Publication number Priority date Publication date Assignee Title
JPS50138047A (fr) * 1974-04-23 1975-11-04
JPH06510086A (ja) * 1991-08-29 1994-11-10 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー テトラフルオロエチレン重合体の溶解方法並びに該方法によって得られる溶液を含んでなる組成物
JPH08321309A (ja) * 1995-05-23 1996-12-03 Kazuo Tagawa 非水系二次電池電極
JPH09106808A (ja) * 1995-10-09 1997-04-22 Nippon Telegr & Teleph Corp <Ntt> リチウム二次電池
JPH10233217A (ja) * 1996-12-16 1998-09-02 Daikin Ind Ltd 非水電解液二次電池用結着剤およびそれを用いた電池電極合剤
JP2004039569A (ja) * 2002-07-05 2004-02-05 Daikin Ind Ltd 電極用添加剤

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50138047A (fr) * 1974-04-23 1975-11-04
JPH06510086A (ja) * 1991-08-29 1994-11-10 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー テトラフルオロエチレン重合体の溶解方法並びに該方法によって得られる溶液を含んでなる組成物
JPH08321309A (ja) * 1995-05-23 1996-12-03 Kazuo Tagawa 非水系二次電池電極
JPH09106808A (ja) * 1995-10-09 1997-04-22 Nippon Telegr & Teleph Corp <Ntt> リチウム二次電池
JPH10233217A (ja) * 1996-12-16 1998-09-02 Daikin Ind Ltd 非水電解液二次電池用結着剤およびそれを用いた電池電極合剤
JP2004039569A (ja) * 2002-07-05 2004-02-05 Daikin Ind Ltd 電極用添加剤

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019164937A (ja) * 2018-03-20 2019-09-26 宇部興産株式会社 非水電解液およびそれを用いた蓄電デバイス
JP7105077B2 (ja) 2018-03-20 2022-07-22 Ｍｕアイオニックソリューションズ株式会社 非水電解液およびそれを用いた蓄電デバイス

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