Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • 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
  • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
  • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09J127/16—Homopolymers or copolymers of vinylidene fluoride
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • 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
• • 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
  • H01M10/058—Construction or manufacture
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • 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
  • C08F116/00—Homopolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F116/36—Homopolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a ketonic radical
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/32—Compounds containing nitrogen bound to oxygen
  • C08K5/33—Oximes
• • 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 binder. More specifically, the present invention relates to a binder, an electrode mixture using the binder, an electrode, and a non-aqueous electrolyte secondary battery.
• Vinylidene fluoride polymers mainly containing repeating units derived from vinylidene fluoride are widely used as binder resins for batteries such as lithium ion secondary batteries.
• the binder resin is used to adhere the active material to the current collector.
• the ternary positive electrode active material contains a large amount of base, deterioration of the binder composition containing the vinylidene fluoride polymer is likely to be promoted. Then, due to the deterioration, the slurry-like electrode mixture (hereinafter, also referred to as the electrode combination slurry) thickens and finally gels. It is difficult to apply the gelled electrode mixture slurry to the current collector. Therefore, in a battery using a ternary positive electrode active material, the electrode mixture is required to have higher gelation resistance.
• Patent Document 1 describes a binder composition containing a copolymer having a first structural unit derived from vinylidene fluoride and a structural unit having an isocyanate group or a structure having a structure that produces an isocyanate group when heated. Is described. It is described that the binder composition is difficult to gel even if it is stored for a long time.
• Patent Document 2 describes a conductive paste for a positive electrode of a lithium ion battery containing a dispersion resin, polyvinylidene fluoride, conductive carbon, a solvent, and a polymerization inhibitor. It is described that the paste has a high viscosity and gelation is suppressed.
• the present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a binder that suppresses gelation of an electrode mixture as compared with a conventional binder.
• the present inventors unexpectedly changed the electrode mixture by using a binder containing vinylidene fluoride polymer and oxime as the electrode mixture. Based on the finding that gelation can be suppressed, the present invention has been made.
• the binder according to one aspect of the present invention contains a vinylidene fluoride polymer containing 50 mol% or more of vinylidene fluoride units, and an oxime.
• the binder of the present embodiment contains a vinylidene fluoride polymer and an oxime.
• the binder according to the present embodiment is used as a binder for binding the electrode active material onto the current collector.
• the binder of the present embodiment can suppress gelation of the electrode mixture. That is, the binder of this embodiment has high gelation resistance. For example, when the viscosity of the electrode mixture immediately after preparation is higher than the viscosity, it can be determined that gelation is progressing.
• vinylene fluoride polymer refers to a homopolymer of vinylidene fluoride and a copolymer of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride. It contains any of (polymers).
• a known monomer can be appropriately selected.
• the copolymer contains vinylidene fluoride as a main constituent.
• the copolymer preferably contains the vinylidene fluoride unit in an amount of 50 mol% or more, preferably contains the vinylidene fluoride unit in an amount of 80 mol% or more, and may contain a vinylidene fluoride unit in an amount of 90 mol% or more. More preferred.
• the vinylidene fluoride polymer is a copolymer
• it is preferably a vinylidene fluoride polymer containing vinylidene fluoride as a main component and containing a structural unit represented by the following formula (3).
• R 4 is a carboxyl group substituted with a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms, and R 5 and R 6 are independent of each other. It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. From the viewpoint of the polymerization reaction, it is particularly desired that R4 and R5 are substituents having less steric hindrance, hydrogen or an alkyl group having 1 to 3 carbon atoms is preferable, and hydrogen or a methyl group is preferable.
• X is an atomic group having a single bond or a main chain composed of 1 to 20 atoms and having a molecular weight of 500 or less.
• the molecular weight in the atomic group is preferably 200 or less.
• the lower limit of the molecular weight in the atomic group is not particularly limited, but is usually 15.
• X Means the number of atoms in the skeleton of the chain connected by the smallest number of atoms.
• X may be branched by containing a functional group as a side chain.
• the side chain contained in X may be one or a plurality of side chains.
• the compound in the formula ( 3 ) has a structure in which the carboxyl group is directly bonded to the carbon atom bonded to R6.
• Examples of compounds having a structural unit represented by the formula (3) are acrylic acid (AA), methacrylic acid, 2-carboxyethyl acrylate (CEA), 2-carboxyethyl methacrylate, maleic acid monomethyl ester, and acryloyloxyethyl succinic acid.
• examples thereof include acid (AES), acrylicyloxypropylsuccinic acid (APS), methacrylicloyroxyethyl succinic acid, and methacrylicyloxypropylsuccinic acid.
• the vinylidene fluoride polymer may have components of vinylidene fluoride and a compound other than the structural unit represented by the formula (3) as a constituent unit.
• Other such compounds include perfluoroalkyl vinyl ethers such as vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene (HFP), and perfluoromethyl vinyl ether; (meth).
• perfluoroalkyl vinyl ethers such as vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene (HFP), and perfluoromethyl vinyl ether; (meth).
• examples thereof include (meth) acrylate-based monomers having no COOH group at the terminal, such as glycidyl acrylate and methyl (meth) acrylate.
• the modification amount (structural unit represented by the formula (3) in the vinylidene fluoride polymer) is preferably 0.01 to 10 mol%, preferably 0.1 to 5 mol%. Is more preferable, and it is further preferable to have 0.2 to 1 mol%. Further, it is preferable to have 90 to 99.99 mol%, more preferably 95 to 99.90 mol%, and 99.00 to 99.80 mol% of the structural unit derived from vinylidene fluoride in the vinylidene fluoride polymer. It is more preferable to have it, and it is particularly preferable to have 99.50 to 99.80 mol%.
• the amount of vinylidene fluoride unit of the vinylidene fluoride polymer and the amount of the structural unit represented by the formula (3) can be determined by 1 H NMR spectrum or 19 F NMR spectrum of the copolymer, or by neutralization titration. ..
• vinylidene fluoride polymer As the vinylidene fluoride polymer, a commercially available one can be used. For example, KF # 7300, KF # 9100, KF # 9700, KF # 7500, KF # 9400, etc. manufactured by Kureha Corporation can be mentioned.
• the intrinsic viscosity of the vinylidene fluoride polymer used in the present embodiment is not particularly limited, but is preferably 0.5 to 5.0 dl / g, and is 1.0 dl / g or more and 4.5 dl / g or less. More preferably, it is more preferably 1.5 dl / g or more and 4.0 dl / g or less.
• the intrinsic viscosity is in the above range, it is preferable that the electrode can be easily manufactured without causing unevenness in the thickness of the electrode when the electrode mixture slurry is applied.
• Inherent viscosity ( ⁇ i) is calculated as follows, for example.
• a polymer solution is prepared by dissolving 80 mg of vinylidene fluoride polymer in 20 mL of N, N-dimethylformamide.
• the viscosity ⁇ of the produced polymer solution is measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C.
• the intrinsic viscosity ( ⁇ i ) is calculated from the following formula.
• ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0 )
• ⁇ 0 is the viscosity of N, N-dimethylformamide as a solvent
• C is the concentration of vinylidene fluoride polymer in the prepared polymer solution (0.4 g / dL).
• the polymerization method of the vinylidene fluoride polymer is not particularly limited, and a conventionally known polymerization method can be used.
• the polymerization method include suspension polymerization, emulsion polymerization, solution polymerization and the like. Among them, aqueous suspension polymerization or emulsion polymerization is preferable from the viewpoint of ease of post-treatment, and aqueous suspension polymerization is particularly preferable. preferable.
• Examples of the oxime include the compound represented by the formula (1).
• R 1 and R 2 are independently hydrogen atoms, aldehyde groups, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms. Select from a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, or a heterocyclic group having 3 to 13 carbon atoms.
• R 1 and R. 2 may be bonded to each other to form a ring with the carbon atom to which R 1 and R 2 are bonded.
• the number of carbon atoms of the alkyl group is 1 to 10, preferably 1 to 5, and more preferably 1 to 2.
• the alkenyl group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms.
• the carbon number of alkynyl is 2 to 10, preferably 2 to 6, and more preferably 2 to 4.
• the cycloalkyl group has 3 to 10 carbon atoms, preferably 3 to 7 carbon atoms, and more preferably 5 to 7 carbon atoms.
• the aryl group has 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms.
• the aralkyl group has 7 to 14 carbon atoms, preferably 7 to 11 carbon atoms, and more preferably 7 to 9 carbon atoms.
• the heterocyclic group has 3 to 13 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms.
• the ring when R 1 and R 2 are bonded to each other to form a ring together with the carbon atom to which R 1 and R 2 are bonded, the ring may be an aromatic ring or non-aromatic ring. It may be an aromatic ring. Further, the compound represented by the formula (1) may be a conjugated compound.
• the ring may be a 3- to 12-membered ring, preferably a 3- to 8-membered ring.
• the compound represented by HO-N R3 is preferable , where R3 is a cycloalkyl group having 3 to 8 carbon atoms.
• the hydrogen atom of the cycloalkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms.
• Examples of the compound represented by the formula (1) include acetone oxime (acetoxime), 2-butanone oxime (methyl ethyl ketone oxime), methyl isopropyl ketone oxime, methyl tertiary butyl ketone oxime, jittery butyl ketone oxime, 2-pentanone oxime, 3.
• -Pentanone oxime 1-cyclohexyl-1-propanone oxime, acetaldoxime (acetaldehyde oxime), benzalxime (benzaldehyde oxime), acetophenone oxime, benzophenone oxime, 4-hydroxyacetophenone oxime, cyclopropanone oxime, cyclobutanone oxime , Cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanonone oxime, cyclodecanone oxime, cyclododecanone oxime, benzoquinone dioxime, benzoquinone monooxime, 2,3-butandion mono Examples thereof include oxime, acetamide oxime, 3-hydroxy-3-methyl-2-butanone oxime, ⁇ -benzoin oxime, 1,3-dihydroxyace
• R 1 and R 2 are independent of each other, a hydrogen atom, an aryl group having 6 to 18 carbon atoms, and an aldehyde. It is preferably selected from a group or an alkyl group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of these groups may be substituted with a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group and an amino group.
• R 1 and R 2 may be bonded to each other to form a ring together with the carbon atom to which R 1 and R 2 are bonded.
• Examples of the compound represented by the formula (1) which is a preferred embodiment, include acetone oxime, 2-butanone oxime, cyclohexanone oxime, acetaldehyde oxime, benzaldehyde oxime, 2,3-butanedione monooxime and the like.
• the compound represented by the formula (1) has R 1 and R 2 independently selected from alkyl groups having 1 to 10 carbon atoms. Is more preferable. Some or all of the hydrogen atoms in these groups may be substituted with substituents selected from alkyl, aryl, hydroxyl and amino groups having 1-10 carbon atoms, as well as R 1 and R. When 2 is an alkyl group, R 1 and R 2 may be bonded to each other to form a ring together with the carbon atom to which R 1 and R 2 are bonded. Examples of the compound represented by the formula (1), which is a more preferable embodiment, include acetone oxime, 2-butanone oxime, cyclohexanone oxime and the like.
• the compound represented by the formula (2) can be mentioned.
• R 7 and R 8 are independently hydrogen atoms, aldehyde groups, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms. Select from a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, or a heterocyclic group having 3 to 13 carbon atoms.
• R7 and R. 8 may be bonded to each other to form a ring with a carbon atom to which R 7 is bonded and a carbon atom to which R 8 is bonded.
• Examples of the compound represented by the formula (2) include dimethylglyoxime, methylethylglyoxime, diethylglyoxime, diphenylglioxime, and the like.
• the preferred embodiments of the substituents (R 7 and R 8 ) of the formula (2) are similar to those of the preferred substituents (R 1 and R 2 ) of the formula (1).
• Examples of the compound represented by the formula (2), which is a preferred embodiment, include dimethylglyoxime and the like.
• examples of the oxime include a polymer containing a hydroxyimine group (hereinafter, may be referred to as "oxime polymer”) or an oligomer containing a hydroxyimine group (hereinafter, may be referred to as "oxime oligomer”).
• oxime polymer a polymer containing a hydroxyimine group
• oxime oligomer an oligomer containing a hydroxyimine group
• the oxime polymer or oxime oligomer can be synthesized by polymerizing a monomer or oligomer containing a hydroxyimine group, or by reacting a polymer or oligomer having a ketone group with a hydroxyamine.
• the polymer having a ketone group as a skeleton include poly (methyl vinyl ketone), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketone. Examples thereof include ketones (PEEKK), polyetherketone etherketoneketones (PEKEKK), and the like.
• oxime polymers or oxime oligomers examples include poly (methylvinyl oxime) and the like.
• the above oxime may be used alone or in combination of two or more.
• 0.005 to 5 mmol of oxime is preferably contained, more preferably 0.1 to 5 mmol is contained, and 0.25 to 5 mmol is contained with respect to 1 g of the vinylidene fluoride polymer. It is more preferable that it is.
• 0.005 to 5 mmol of the hydroxyimine group contained in the oxime is preferably contained, and more preferably 0.1 to 5 mmol is contained, more preferably 0.25, with respect to 1 g of the vinylidene fluoride polymer. It is more preferably contained in an amount of up to 5 mmol.
• the form of the binder of this embodiment is not particularly limited, and may be powdery or liquid. Further, the binder may contain a solvent.
• the solvent may be a non-aqueous solvent or water. Examples of the non-aqueous solvent include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, triethylphosphate, and trimethylphos.
• Examples thereof include fate, acetone, ethyl acetate, n-butyl acetate, n-butanol, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and cyclohexanone. Two or more kinds of these solvents may be mixed and used.
• the electrode mixture of the present embodiment contains the above binder and the active material.
• the electrode mixture may contain a conductive auxiliary agent, a non-aqueous solvent, a pigment dispersant, a dispersion stabilizer and the like.
• the electrode mixture can be an electrode mixture for the positive electrode or an electrode mixture for the negative electrode by changing the type of the active material or the like according to the type of the current collector to be applied. Since the vinylidene fluoride polymer generally has excellent oxidation resistance, it is preferable to use the electrode mixture of the present embodiment as an electrode mixture for a positive electrode.
• Lithium metal oxide is typically used as the positive electrode active material.
• the positive electrode active material may contain, for example, impurities and additives in addition to the lithium metal oxide. Further, the types of impurities and additives contained in the positive electrode active material are not particularly limited.
• lithium metal oxide examples include LiMnO 2 , LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 1), LiNi x Coy Mn 1-x-y O. 2 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), LiNi x Coy Al 1-x-y O 2 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), LiFePO 4 and the like can be mentioned.
• the lithium metal oxide contains Ni in that the capacity of the secondary battery can be increased by increasing the capacity density. Further, it is preferable that the lithium metal oxide contains Co or the like in addition to Ni in that the crystal structure change in the charge / discharge process is suppressed and stable cycle characteristics are exhibited.
• Preferred lithium metal oxides include lithium metal oxides (ternary lithium metal oxides) represented by the following formula (4).
• the ternary lithium metal oxide is particularly preferably used as the electrode active material in the present embodiment because it has a high charging potential and excellent cycle characteristics.
• preferable lithium metal oxides are Li 1.00 Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM523), Li 1.00 Ni 0.6 Co 0.2 Mn 0.2 O 2 (NCM622), Li 1.00 Ni 0.83 Co 0.12 Mn 0.05 O 2 (NCM811), and Li 1.00 Ni 0.85 Co 0.15 Al 0.05 O 2 (NCA811). be able to.
• These preferable lithium metal oxides have a pH of 10.5 or more when extracted with water. The extraction is at room temperature (25 ° C.) by the extraction method specified in JIS K 5101-16.2.
• the electrode active material is placed in ultrapure water having an amount of 50 times the weight of the electrode active material, and the solution is stirred with a magnetic stirrer at a rotation speed of 600 rpm for 10 minutes. Obtained by measuring pH using a pH meter MODEL: F-21 manufactured by Horiba Seisakusho Co., Ltd.
• the electrode mixture slurry containing the positive electrode active material having a pH of at least 10.5 or higher in the water contains a large amount of base in the slurry, so that the electrode mixture tends to deteriorate. As a result, thickening of the electrode mixture slurry is likely to occur. In order to suppress the thickening of the electrode mixture slurry, it is necessary to remove the base by washing the positive electrode active material with water. However, since the electrode mixture of the present embodiment contains oxime, thickening of the electrode mixture slurry (gelation of the electrode mixture) is suppressed even if a positive electrode active material containing a large amount of base is used. Therefore, since the electrode mixture of the present embodiment contains oxime, it is not necessary to wash the positive electrode active material with water.
• the negative electrode active material conventionally known materials such as carbon materials, metal / alloy materials, and metal oxides can be used.
• a carbon material is preferable from the viewpoint of further increasing the energy density of the battery, and examples of the carbon material include artificial graphite, natural graphite, non-graphitizable carbon, and easily graphitized carbon.
• the electrode mixture preferably contains 0.2 to 15 parts by mass of the vinylidene fluoride polymer, preferably 0.5 to 10 parts by mass. Is more preferable.
• 0.01 to 10 mmol of oxime is preferably contained, more preferably 0.2 to 10 mmol is contained, and 0.5 to 10 mmol is contained with respect to 100 g of the active material. Is more preferable. Further, it is preferable that 0.01 to 10 mmol of the hydroxyimine group contained in the oxime is contained in 100 g of the active material, more preferably 0.2 to 10 mmol is contained, and 0.5 to 10 mmol is contained. Is more preferable.
• the conductive auxiliary agent may be added for the purpose of improving the conductivity of the electrode mixture layer when an active material having low electron conductivity such as LiCoO 2 is used.
• the conductive auxiliary agent for example, carbonaceous substances such as carbon black, carbon nanotubes, graphite fine powder and graphite fiber, and metal fine powder or metal fiber such as nickel and aluminum can be used.
• Non-aqueous solvent As the non-aqueous solvent, those exemplified as the non-aqueous solvent that can be contained in the above-mentioned binder can be used, and examples thereof include N-methylpyrrolidone (NMP) and the like. Further, the non-aqueous solvent may be used alone or in combination of two or more.
• NMP N-methylpyrrolidone
• the electrode mixture of the present embodiment may contain components other than the above-mentioned components.
• examples of other components include pigment dispersants such as polyvinylpyrrolidone.
• the electrode mixture according to the present embodiment may be, for example, a binder containing a vinylidene fluoride polymer and an oxime, and an active material may be mixed so as to form a uniform slurry, and the order of mixing is not particularly limited.
• an electrode active material or the like may be added before the solvent is added to the binder.
• the electrode active material may be added to the binder, then the solvent may be added, and the mixture may be stirred and mixed to obtain an electrode mixture.
• the electrode active material may be dispersed in a solvent, a binder may be added thereto, and the mixture may be stirred and mixed to obtain an electrode mixture.
• the electrode active material may be added to a binder containing a solvent as the binder and mixed with stirring to obtain an electrode mixture.
• It can also be prepared by mixing an oxime and an active substance and then mixing a vinylidene fluoride polymer.
• the electrode according to the present embodiment includes an electrode mixture layer formed from the electrode mixture on the current collector.
• the "electrode” in the present specification and the like means a battery electrode in which an electrode mixture layer formed from the electrode mixture of the present embodiment is formed on a current collector.
• the current collector is the base material of the electrode and is a terminal for extracting electricity.
• Examples of the material of the current collector include iron, stainless steel, steel, copper, aluminum, nickel, titanium and the like.
• the shape of the current collector is preferably foil or net.
• the current collector is preferably aluminum foil.
• the thickness of the current collector is preferably 5 ⁇ m to 100 ⁇ m, more preferably 5 to 20 ⁇ m.
• the electrode mixture layer is a layer obtained by applying the above-mentioned electrode mixture to a current collector and drying it.
• a method for applying the electrode mixture a method known in the art can be used, and a method using a bar coater, a die coater, a comma coater, or the like can be mentioned.
• the drying temperature for forming the electrode mixture layer is preferably 50 ° C to 170 ° C, more preferably 50 ° C to 150 ° C.
• the electrode mixture layer may be formed on both sides of the current collector, or may be formed on only one of the surfaces.
• the thickness of the electrode mixture layer is usually 20 to 600 ⁇ m, preferably 20 to 350 ⁇ m per one side. Further, the electrode mixture layer may be pressed to increase the density.
• the basis weight of the electrode mixture layer is usually 20 to 700 g / m 2 , preferably 30 to 500 g / m 2 .
• the electrode becomes a positive electrode when an electrode mixture layer for a positive electrode is obtained, and a negative electrode when an electrode mixture layer for a negative electrode is obtained. It becomes.
• the electrode according to this embodiment can be used as a positive electrode of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, for example.
• Non-water electrolyte secondary battery The non-aqueous electrolyte secondary battery of the present embodiment includes the above electrodes.
• the other members of the non-aqueous electrolyte secondary battery are not particularly limited, and for example, conventionally used members can be used.
• Examples of the method for manufacturing a non-aqueous electrolyte secondary battery include a method in which a negative electrode layer and a positive electrode layer are overlapped with each other via a separator, placed in a battery container, and an electrolytic solution is injected into the battery container to seal the battery.
• this production method at least a part of the vinylidene fluoride polymer contained in the electrode mixture is melted and adhered to the separator by hot pressing after injecting the electrode solution.
• the binder according to the present embodiment contains a vinylidene fluoride polymer containing 50 mol% or more of vinylidene fluoride units and an oxime.
• R 1 and R 2 are independently hydrogen atoms, aldehyde groups, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkynyl groups having 2 to 10 carbon atoms.
• Selected, some or all of the hydrogen atoms of these groups may be substituted with substituents selected from alkyl, aryl, hydroxyl and amino groups having 1-10 carbon atoms, with R1 . It may be bonded to R 2 to form a ring together with the carbon atom to which R 1 and R 2 are bonded, and in formula (2), R 7 and R 8 are independently hydrogen atoms, respectively.
• Alkyl group alkyl group having 1 to 10 carbon atoms, alkyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, cycloalkenyl group having 3 to 10 carbon atoms, It is selected from an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, or a heterocyclic group having 3 to 13 carbon atoms, and some or all of the hydrogen atoms of these groups have 1 to 10 carbon atoms.
• R 7 and R 8 are bonded to each other, and the carbon atom to which R 7 is bonded and R 8 are bonded. May form a ring with the carbon atom to which it is bonded.
• R 1 and R 2 are independently hydrogen atoms, an aryl group having 6 to 18 carbon atoms, an aldehyde group or an alkyl having 1 to 10 carbon atoms. Selected from the groups, some or all of the hydrogen atoms of these groups may be substituted with substituents selected from alkyl, aryl, hydroxyl and amino groups having 1-10 carbon atoms.
• R 1 and R 2 may be bonded to each other to form a ring together with the carbon atom to which R 1 and R 2 are bonded, in the above formula (2).
• R 7 and R 8 are independently selected from a hydrogen atom, an aryl group having 6 to 18 carbon atoms, an aldehyde group or an alkyl group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms of these groups. May be substituted with a substituent selected from an alkyl group, an aryl group, a hydroxyl group and an amino group having 1 to 10 carbon atoms, and when R 7 and R 8 are alkyl groups, R 7 and R 8 are used. May be bonded to each other to form a ring with the carbon atom to which R 7 is bonded and the carbon atom to which R 8 is bonded.
• R 1 and R 2 are independently selected from alkyl groups having 1 to 10 carbon atoms, and R 1 and R 2 are alkyl groups.
• R 1 and R 2 may be bonded to each other to form a ring together with the carbon atom to which R 1 and R 2 are bonded, and in the above formula (2), R 7 and R 8 are independent of each other.
• R 7 and R 8 are independent of each other.
• R 7 and R 8 are bonded to each other, and the carbon to which R 7 is bonded is bonded.
• a ring may be formed with an atom and a carbon atom to which R8 is bonded.
• the vinylidene fluoride polymer may be a vinylidene fluoride polymer containing a structural unit derived from the compound represented by the following formula (3).
• R 4 is a carboxyl group substituted with a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms, and R 5 and R 6 are independent of each other. It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is a single bond or an atomic group having a main chain consisting of 1 to 20 atoms and having a molecular weight of 500 or less.
• the active material is a lithium metal oxide represented by the following formula (4), and the pH of the water when the lithium metal oxide is extracted with water is It is preferably 10.5 or more.
• LiNi x Coy M z O 2 ... (4) (In the formula (4), M is Mn or Al, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1).
• the content of the oxime is preferably 0.01 to 10 mmol with respect to 100 g of the active material.
• the electrode according to the present embodiment is provided with an electrode mixture layer formed from the electrode mixture on the current collector.
• the non-aqueous electrolyte secondary battery according to this embodiment includes the electrode.
• VDF / APS copolymer a vinylidene fluoride copolymer containing a polar group.
• APS was added in a total amount of 4.0 g, including the amount initially added.
• a 2 wt% APS aqueous solution was continuously supplied to the reaction vessel under the condition that the pressure was kept constant during the polymerization.
• the obtained polymer slurry was dehydrated and dried to obtain a vinylidene fluoride copolymer (VDF / HFP / APS copolymer).
• APS was added in a total amount of 3.66 g, including the amount initially added.
• Example 1 Preparation of electrode mixture NCA811 was used as the electrode active material. Carbon black (SP: SuperP® manufactured by Timcal Japan, average particle size: 40 nm, specific surface area: 60 m 2 / g) was added to NCA811 as a conductive auxiliary agent, and powder mixing was performed.
• Carbon black SP: SuperP® manufactured by Timcal Japan, average particle size: 40 nm, specific surface area: 60 m 2 / g
• the VDF / APS copolymer and acetone oxime obtained in Preparation Example 1 were dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") to prepare a binder solution.
• NMP N-methyl-2-pyrrolidone
• the binder solution contains 6 wt% vinylidene fluoride polymer and 0.34 mmol of acetone oxime with respect to 1 g of the vinylidene fluoride polymer.
• the amount of hydroxyimino groups contained in acetone oxime with respect to 1 g of the vinylidene fluoride polymer was 0.34 mmol.
• the binder solution was added in two portions to the mixture of NCA811 and carbon black, and kneaded. Specifically, a binder solution was added so that the solid content concentration was 81.5 wt%, and primary kneading was performed at 2000 rpm for 2.5 minutes. Next, the remaining binder solution was added to adjust the solid content concentration to 75 wt%, and secondary kneading was performed at 2000 rpm for 3 minutes to obtain an electrode mixture.
• the weight ratio of the electrode active material, carbon black, and VDF / APS copolymer (electrode active material: carbon black: VDF / APS copolymer) in the obtained electrode mixture was 100: 2: 2. ..
• Example 2 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that the amount of acetone oxime in the binder solution was 0.17 mmol with respect to 1 g of the vinylidene fluoride polymer. At this time, the amount of hydroxyimino groups contained in acetoxime with respect to 1 g of the vinylidene fluoride polymer was 0.17 mmol.
• Example 3 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that the amount of acetone oxime in the binder solution was 0.84 mmol with respect to 1 g of the vinylidene fluoride polymer. At this time, the amount of hydroxyimino groups contained in acetoxime with respect to 1 g of the vinylidene fluoride polymer was 0.84 mmol.
• Example 4 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that the amount of acetone oxime in the binder solution was 0.09 mmol with respect to 1 g of the vinylidene fluoride polymer. At this time, the amount of hydroxyimino groups contained in acetoxime with respect to 1 g of the vinylidene fluoride polymer was 0.09 mmol.
• Example 5 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to 2-butanone oxime. At this time, the amount of hydroxyimino groups contained in 2-butanone oxime with respect to 1 g of the vinylidene fluoride polymer was 0.34 mmol.
• Example 6 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to cyclohexanone oxime. At this time, the amount of the hydroxyimino group contained in cyclohexanone oxime with respect to 1 g of the vinylidene fluoride polymer was 0.34 mmol.
• Example 7 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to acetaldehyde oxime. At this time, the amount of the hydroxyimino group contained in acetaldehyde oxime with respect to 1 g of the vinylidene fluoride polymer was 0.34 mmol.
• Example 8 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to benzaldehyde oxime. At this time, the amount of the hydroxyimino group contained in the benzaldehyde oxime with respect to 1 g of the vinylidene fluoride polymer was 0.34 mmol.
• Example 9 Preparation of electrode mixture An electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to 2,3-butanedione monooxime. At this time, the amount of the hydroxyimino group contained in 2,3-butanedione monooxime with respect to 1 g of the vinylidene fluoride polymer was 0.34 mmol.
• Example 10 Preparation of electrode mixture The electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to dimethylglyoxime. At this time, the amount of hydroxyimine groups contained in dimethylglyoxime with respect to 1 g of the vinylidene fluoride polymer was 0.67 mol.
• Example 11 Preparation of electrode mixture
• the electrode is the same as in Example 1 except that the VDF / APS copolymer obtained in Preparation Example 1 is a homopolymer KF # 7300 (manufactured by Kureha Corporation). A mixture was prepared.
• Example 12 Preparation of electrode mixture Same as in Example 3 except that the VDF / APS copolymer obtained in Preparation Example 1 was used as the VDF / HFP / APS copolymer obtained in Preparation Example 2. An electrode mixture was prepared in.
• Example 13 Preparation of electrode mixture
• the electrodes are the same as in Example 1 except that the VDF / APS copolymer obtained in Preparation Example 1 was used as the VDF / MMM copolymer obtained in Preparation Example 4. A mixture was prepared.
• Example 14 Preparation of electrode mixture
• the electrodes are the same as in Example 1 except that the VDF / APS copolymer obtained in Preparation Example 1 was used as the VDF / AA copolymer obtained in Preparation Example 3. A mixture was prepared.
• Example 15 Preparation of electrode mixture The acetone oxime was changed to poly (methyl vinyl oxime), and the poly (methyl vinyl oxime) contained in the binder solution was added to poly (methyl vinyl oxime) with respect to 1 g of the vinylidene fluoride polymer. ) Has an amount of hydroxyimine group of 0.34 mmol, and an electrode mixture was prepared in the same manner as in Example 11.
• Electrode Combination The electrode combination was prepared in the same manner as in Example 1 except that acetone oxime was changed to 3,5-dimethylpyrazole.
• Electrode Combination The electrode mixture was prepared in the same manner as in Example 1 except that acetone oxime was changed to the isocyanate compound MOI-BP (manufactured by Showa Denko KK).
• MOI-BP is 2- [0- (1'-methylpropanolamino) carboxyamino] ethylmethacrylate.
• the pH of the electrode active material was the pH of water when the electrode active material was extracted with water at room temperature (25 ° C.).
• the electrode active material was extracted into water by the extraction method specified in JIS K 5101-16.2. Specifically, the electrode active material is put into ultrapure water having an amount of 50 times the weight of the electrode active material, stirred with a magnetic stirrer at a rotation speed of 600 rpm for 10 minutes, and the solution is pHed by Horiba Seisakusho Co., Ltd.
• the pH was measured using the meter MODEL: F-21. When NCA811 was extracted with water, the pH after extraction was 11.5.
• ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0 )
• ⁇ 0 is the viscosity of N, N-dimethylformamide as a solvent
• C is the concentration of vinylidene fluoride polymer in the prepared polymer solution (0.4 g / dL).
• the amount of the structural unit derived from vinylidene fluoride of the polymer and the amount of the structural unit derived from the comonomer were calculated from the 1 H NMR spectrum. Specifically, it was calculated based on the integrated intensities of the signals mainly derived from comonomer and the signals observed at 2.24 ppm and 2.87 ppm mainly derived from vinylidene fluoride.
• the amount of the structural unit containing the structure derived from acrylic acid in the polymer is neutralized and titrated using an aqueous sodium hydroxide solution of 0.03 mol / L. Asked by. More specifically, 0.3 g of the polymer was dissolved in 9.7 g of acetone at about 80 ° C., and then 3 g of pure water was added to prepare a titration solution. Phenolphthalein was used as an indicator, and neutralization titration was performed using a 0.03 mol / L sodium hydroxide aqueous solution at room temperature.
• Electrode Mixture The electrode mixture obtained in Examples and Comparative Examples was stored at 40 ° C. in a nitrogen atmosphere for a predetermined time (24 hours or 168 hours). Then, the measurement was carried out at 25 ° C. and a shear rate of 2s -1 using an E-type viscometer. The viscosity was measured by charging the slurry (electrode mixture) into the measuring device, waiting for 60 seconds, and then rotating the rotor. Further, the value 300 seconds after the start of rotation of the rotor was taken as the slurry viscosity. The slurry viscosity of the electrode mixture immediately after preparation was taken as the initial slurry viscosity.
• Table 1 shows the materials used to prepare the electrode mixture of Examples and Comparative Examples.
• VDF / comonomer indicates the ratio (weight ratio) of VDF / the ratio (weight ratio) of VDF in the vinylidene fluoride polymer.
• Examples 12 and 6 show the ratio of VDF (weight ratio) / the ratio of HFP which is a comonomer (weight ratio) / the ratio of APS which is a conomer (weight ratio) in the vinylidene fluoride polymer.
• MMM indicates monomethyl maleate.
• the isocyanate compound of Comparative Example 5 is 2- [0- (1'-methylpropyridenamino) carboxyamino] ethylmethacrylate.
• the amount of hydroxyimino groups is the amount of hydroxyimine groups (mmol / g vinylidene fluoride polymer) contained in oxime with respect to 1 g of vinylidene fluoride polymer in the binder.
• Table 2 shows the evaluation results of the electrode mixture of Examples and Comparative Examples. For the electrode mixture of Examples 12 to 14 and Comparative Examples 1 to 8, the slurry viscosity after storage for 168 hours was not measured.
• the slurry viscosity of the electrode mixture of Examples 1 to 15 using the binder containing oxime was lower than the initial slurry viscosity after storage for 24 hours.
• the slurry viscosity after storage for 24 hours was higher than the initial slurry viscosity. From this, it was found that the electrode mixture of Examples 1 to 15 had high gelation resistance.
• the electrode mixture of Examples 1, 3, 5, 6, 10 and 11 has a slurry viscosity after storage for 168 hours, which is lower than the initial slurry viscosity, and has excellent gelation resistance. I understood.
• the present invention can be used for a lithium ion secondary battery.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Electrochemistry (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (8)

Applications Claiming Priority (2)

Publications (1)

Family

ID=80353127

Family Applications (1)

Country Status (6)

Cited By (2)

Citations (5)

Family Cites Families (15)

• 2021
  • 2021-07-01 CN CN202311591968.1A patent/CN117894986A/zh active Pending
  • 2021-07-01 JP JP2022545492A patent/JP7523551B2/ja active Active
  • 2021-07-01 CN CN202311591965.8A patent/CN117866554A/zh active Pending
  • 2021-07-01 KR KR1020237006052A patent/KR102837860B1/ko active Active
  • 2021-07-01 US US18/042,686 patent/US20230335741A1/en active Pending
  • 2021-07-01 WO PCT/JP2021/024890 patent/WO2022044538A1/ja not_active Ceased
  • 2021-07-01 CN CN202180058360.5A patent/CN116057120A/zh active Pending
  • 2021-07-01 EP EP21860968.3A patent/EP4206273A4/en active Pending
• 2024
  • 2024-03-22 JP JP2024046615A patent/JP2024071493A/ja active Pending

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events