WO2015064099A1 - Composition de bouillie pour électrode positive pour batterie rechargeable lithium-ion, électrode positive pour batterie rechargeable lithium-ion et batterie rechargeable lithium-ion - Google Patents

Composition de bouillie pour électrode positive pour batterie rechargeable lithium-ion, électrode positive pour batterie rechargeable lithium-ion et batterie rechargeable lithium-ion Download PDF

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Publication number
WO2015064099A1
WO2015064099A1 PCT/JP2014/005475 JP2014005475W WO2015064099A1 WO 2015064099 A1 WO2015064099 A1 WO 2015064099A1 JP 2014005475 W JP2014005475 W JP 2014005475W WO 2015064099 A1 WO2015064099 A1 WO 2015064099A1
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Prior art keywords
lithium ion
polymer
positive electrode
ion secondary
secondary battery
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PCT/JP2014/005475
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English (en)
Japanese (ja)
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智也 村瀬
拓己 杉本
郁哉 召田
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日本ゼオン株式会社
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Priority to JP2015544809A priority Critical patent/JP6369473B2/ja
Priority to KR1020167009212A priority patent/KR102264698B1/ko
Priority to CN201480055323.9A priority patent/CN105612641B/zh
Publication of WO2015064099A1 publication Critical patent/WO2015064099A1/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
    • H01M4/624—Electric conductive fillers
    • 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
    • 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
    • H01M4/62—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
    • 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 slurry composition for a positive electrode of a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
  • Lithium ion secondary batteries are small and light, have high energy density, and can be repeatedly charged and discharged, and are used in a wide range of applications. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of lithium ion secondary batteries. Specifically, to improve the performance of lithium ion secondary batteries, it is necessary to improve battery capacity, cycle characteristics, rate characteristics, etc., so battery members such as electrodes have been improved to improve battery capacity, cycle characteristics. In addition, improvement of the rate characteristics is being studied.
  • a positive electrode for a lithium ion secondary battery usually includes a current collector and an electrode mixture layer (positive electrode mixture layer) formed on the current collector.
  • the positive electrode mixture layer is formed, for example, by applying a slurry composition obtained by dispersing or dissolving a positive electrode active material, a conductive material, a binder, or the like in a dispersion medium on a current collector and drying it.
  • the amount and type of the positive electrode active material in the positive electrode mixture layer affect the battery capacity of the lithium ion secondary battery, and the amount and property of the conductive material in the positive electrode mixture layer affect the rate characteristics.
  • the amount and binding force of the binder in the positive electrode mixture layer affect the cycle characteristics and rate characteristics of the lithium ion secondary battery.
  • the positive electrode active material and the conductive material in the positive electrode mixture layer can be secured. It has been proposed to increase the amount and improve battery capacity and rate characteristics.
  • Patent Document 1 in a slurry composition for a positive electrode of a lithium ion secondary battery used for forming a positive electrode mixture layer, two fluorine-free polymers having different insoluble contents with respect to N-methylpyrrolidone, and fluorine It has been proposed that by using a binding material composed of a contained polymer, it is possible to increase the amount of the positive electrode active material and the conductive material in the positive electrode mixture layer while ensuring the binding property. And in patent document 1, by using the slurry composition for lithium ion secondary battery positive electrodes which contains two types of fluorine-free polymers and fluorine-containing polymer in a predetermined ratio as a binder, Battery capacity, cycle characteristics and rate characteristics are improved.
  • Patent Document 2 in a slurry composition for a positive electrode of a lithium ion secondary battery, a polymer having a specific composition having a 1-olefin unit and a (meth) acrylic acid alkyl ester unit, a fluorine-containing polymer, and N-methylpyrrolidone
  • a polymer having a specific composition having a 1-olefin unit and a (meth) acrylic acid alkyl ester unit, a fluorine-containing polymer, and N-methylpyrrolidone The amount of the positive electrode active material and the conductive material in the positive electrode mixture layer can be increased while ensuring the binding property by using a binder composed of a polymer having an insoluble content with respect to 50% by mass or more.
  • a binder composed of a polymer having an insoluble content with respect to 50% by mass or more.
  • Patent Document 2 a polymer having a specific composition having a 1-olefin unit and a (meth) acrylic acid alkyl ester unit, a fluorine-containing polymer, and a polymer having an insoluble content in N-methylpyrrolidone of 50% by mass or more.
  • the lithium ion secondary battery produced using the conventional lithium ion secondary battery positive electrode slurry composition still has room for improvement in terms of further improving battery performance, particularly cycle characteristics and rate characteristics. It was.
  • the conventional slurry composition for a lithium ion secondary battery positive electrode using the above-described binder is conductive in order to improve the rate characteristics of the lithium ion secondary battery.
  • the BET specific surface area of the material is increased to, for example, 400 m 2 / g or more, the conductive material tends to aggregate, the viscosity stability of the slurry composition is lowered, and the storage stability of the slurry composition is lowered. It became clear that there was a problem that the coatability on the body changed over time.
  • the present invention provides a slurry composition for a lithium ion secondary battery positive electrode that can further improve the performance of the lithium ion secondary battery, particularly the cycle characteristics and rate characteristics, and is excellent in viscosity stability.
  • a positive electrode for a lithium ion secondary battery that can further improve the performance of the lithium ion secondary battery, particularly the cycle characteristics and rate characteristics.
  • an object of the present invention is to provide a high-performance lithium ion secondary battery using the positive electrode for a lithium ion secondary battery.
  • the present inventors have intensively studied for the purpose of solving the above problems. Then, the present inventors include a slurry composition for a positive electrode of a lithium ion secondary battery including a conductive material having a predetermined BET specific surface area and including specific polymers X, Y, and Z as a binder at a predetermined ratio. It was found that the product has excellent viscosity stability and can sufficiently improve the cycle characteristics and rate characteristics of the lithium ion secondary battery, thereby completing the present invention.
  • the slurry composition for a lithium ion secondary battery positive electrode of the present invention comprises a positive electrode active material, a conductive material, a binder and an organic solvent.
  • the conductive material has a BET specific surface area of 400 m 2 / g or more
  • the binder comprises (1) a fluorine-containing polymer X and (2) a nitrile group-containing monomer unit of 10% by mass.
  • the ratio of the fluorine-containing polymer X is 50% by mass or more and 95% by mass or less.
  • the lithium ion secondary which uses predetermined polymer X, Y, Z as a binder, and made the ratio of the fluorine-containing polymer X in a binder 50 mass% or more and 95 mass% or less.
  • the slurry composition for a battery positive electrode is excellent in viscosity stability and can sufficiently improve cycle characteristics and rate characteristics of a lithium ion secondary battery.
  • the “BET specific surface area” is a BET specific surface area determined by a nitrogen adsorption method and can be measured in accordance with ASTM D3037-81.
  • the ratio (X / Y) of the content of the fluorine-containing polymer X to the content of the polymer Y is 9.5 on a mass basis. /0.5 to 5.5 / 4.5 is preferable.
  • X / Y is within the above range, the dispersibility and viscosity stability of the slurry composition can be sufficiently improved.
  • the binding property of the binder can be sufficiently secured, and the cycle characteristics and rate characteristics of the lithium ion secondary battery produced using the slurry composition can be improved. Further improvement can be achieved.
  • the ratio (X / Z) of the content of the fluorine-containing polymer X to the content of the polymer Z is 9.5 / on a mass basis. It is preferably 0.5 to 5.5 / 4.5. If X / Z is within the above range, the binding property of the binder can be sufficiently secured, and the cycle characteristics and rate characteristics of the lithium ion secondary battery produced using the slurry composition are further improved. Can be made.
  • the polymer Z preferably further includes an acidic group-containing monomer unit. If the polymer Z containing an acidic group-containing monomer unit is used, the binding property of the binder can be sufficiently increased, and the cycle characteristics of the lithium ion secondary battery produced using the slurry composition can be improved. This can be further improved.
  • the polymer Z contains the acidic group.
  • the monomer unit is preferably contained in an amount of 10% by mass to 30% by mass.
  • the polymer Y preferably has an insoluble content with respect to N-methylpyrrolidone of 5% by mass or less. If the polymer Y having an insoluble content with respect to N-methylpyrrolidone of 5% by mass or less is used, it is possible to suppress a decrease in viscosity stability of the slurry composition. Furthermore, in the slurry composition for a lithium ion secondary battery positive electrode of the present invention, the polymer Z preferably has an insoluble content with respect to N-methylpyrrolidone of 50% by mass or less.
  • the polymer Z having an insoluble content with respect to N-methylpyrrolidone of 50% by mass or less it is possible to suppress a decrease in viscosity stability of the slurry composition.
  • the “insoluble content of the polymer with respect to N-methylpyrrolidone” can be measured using the measuring method described in the examples of the present specification.
  • the positive electrode for lithium ion secondary batteries of the present invention comprises a positive electrode mixture layer formed using any of the above-described slurry compositions for lithium ion secondary battery positive electrodes on a current collector. To do.
  • a positive electrode for a lithium ion secondary battery comprising a positive electrode mixture layer formed using the above-described slurry composition for a lithium ion secondary battery positive electrode is used, the cycle characteristics and rate characteristics of the lithium ion secondary battery are obtained. Can be sufficiently improved.
  • the lithium ion secondary battery of this invention is equipped with the positive electrode for lithium ion secondary batteries mentioned above, a negative electrode, electrolyte solution, and a separator, It is characterized by the above-mentioned.
  • the positive electrode for lithium ion secondary batteries described above is used, a high performance lithium ion secondary battery can be provided.
  • a slurry composition for a positive electrode of a lithium ion secondary battery that can further improve the performance of the lithium ion secondary battery, in particular, cycle characteristics and rate characteristics, and is excellent in viscosity stability. be able to.
  • the positive electrode for lithium ion secondary batteries which can further improve the performance of a lithium ion secondary battery, especially cycling characteristics and rate characteristics can be provided.
  • a high-performance lithium ion secondary battery can be provided.
  • the slurry composition for a lithium ion secondary battery positive electrode of the present invention is used when forming a positive electrode of a lithium ion secondary battery.
  • the positive electrode for lithium ion secondary batteries of this invention has the positive mix layer formed using the slurry composition for lithium ion secondary batteries positive electrodes of this invention, It is characterized by the above-mentioned.
  • the lithium ion secondary battery of the present invention is characterized by using the positive electrode for a lithium ion secondary battery of the present invention.
  • the slurry composition for a lithium ion secondary battery positive electrode of the present invention is a slurry composition using an organic solvent as a dispersion medium, and includes a positive electrode active material, a conductive material, a binder, and an organic solvent.
  • the slurry composition for lithium ion secondary battery positive electrodes of this invention uses the electrically conductive material whose BET specific surface area is 400 m ⁇ 2 > / g or more as an electrically conductive material.
  • the binder contains the polymers X, Y, and Z described in the following (1) to (3), and the weight in the binder is The ratio of the combined X is 50% by mass or more and 95% by mass or less.
  • (1) Fluorine-containing polymer X (2) Polymer Y containing 10% by mass or more and 50% by mass or less of a nitrile group-containing monomer unit (3) Polymer Z containing 50% by mass or more and 90% by mass or less of (meth) acrylic acid alkyl ester monomer unit
  • (meth) acryl means acryl and / or methacryl.
  • “including a monomer unit” means “a monomer-derived structural unit is contained in a polymer obtained by using the monomer”.
  • a well-known positive electrode active material can be used, without being specifically limited.
  • the positive electrode active material is not particularly limited, and lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium-containing nickel oxide (LiNiO 2 ), Co— Ni—Mn lithium-containing composite oxide, Ni—Mn—Al lithium-containing composite oxide, Ni—Co—Al lithium-containing composite oxide, olivine-type lithium iron phosphate (LiFePO 4 ), olivine-type manganese phosphate Lithium - rich spinel compound represented by lithium (LiMnPO 4 ), Li 1 + x Mn 2 ⁇ x O 4 (0 ⁇ X ⁇ 2), Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 , LiNi 0.5 Mn 1.5 O 4 or the
  • lithium as a positive electrode active material.
  • -Containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium-containing composite oxide, Ni—Co—Al lithium-containing composite oxide, Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 or LiNi 0.5 Mn 1.5 O 4 is preferably used.
  • the compounding quantity and particle size of a positive electrode active material are not specifically limited, It can be made to be the same as that of the positive electrode active material used conventionally.
  • the conductive material is for ensuring electrical contact between the positive electrode active materials.
  • the conductive material used in the slurry composition for a lithium ion secondary battery positive electrode of the present invention requires a BET specific surface area of 400 m 2 / g or more, and the BET specific surface area of the conductive material is 500 m 2 / g or more. It is preferably 600 m 2 / g or more, more preferably 700 m 2 / g or more, further preferably 3000 m 2 / g or less, and 2000 m 2 / g or less. More preferably, it is more preferably 1270 m 2 / g or less, particularly preferably 900 m 2 / g or less.
  • the BET specific surface area of the conductive material used is 400 m 2 / g or more, even if the blending amount of the conductive material is small, electrons can be easily transferred in the positive electrode mixture layer formed using the slurry composition. In addition, the rate characteristics of the lithium ion secondary battery can be improved. In addition, if the BET specific surface area of the conductive material used is 3000 m 2 / g or less, it is sufficiently suppressed that the dispersibility and viscosity stability of the slurry composition are lowered by using it together with the binder described later. be able to.
  • the conductive material is not particularly limited as long as it has the above-described BET specific surface area, and a known conductive material can be used.
  • a known conductive material can be used as the conductive material.
  • acetylene black, ketjen black (registered trademark) furnace black, graphite, carbon fiber, carbon flake, carbon ultrashort fiber (for example, carbon nanotube, vapor grown carbon fiber, etc.), etc.
  • Conductive carbon materials various metal fibers, foils and the like can be used.
  • acetylene black or ketjen black is preferably used as the conductive material from the viewpoint of sufficiently improving the rate characteristics while maintaining the battery capacity of the lithium ion secondary battery.
  • one type of conductive material having the above-described BET specific surface area may be used alone, or two or more types of conductive materials having different BET specific surface areas may be used as the BET of the conductive material after mixing. They may be used in combination so that the specific surface area is in the above-mentioned range.
  • the blending amount of the conductive material is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and 3.0 parts by mass or less per 100 parts by mass of the positive electrode active material. It is preferably 2.5 parts by mass or less, and more preferably 2.0 parts by mass or less. If the blending amount of the conductive material is too small, sufficient electrical contact between the positive electrode active materials cannot be ensured, and the rate characteristics of the lithium ion secondary battery may not be sufficiently improved. On the other hand, if the amount of the conductive material is too large, the viscosity stability of the lithium ion secondary battery positive electrode slurry composition may be lowered, and the density of the positive electrode mixture layer in the positive electrode for the lithium ion secondary battery may be low. The capacity of the lithium ion secondary battery may not be sufficiently increased.
  • the binder is a positive electrode manufactured by forming a positive electrode mixture layer on a current collector using the slurry composition for a positive electrode of the lithium ion secondary battery of the present invention, and the component contained in the positive electrode mixture layer is a positive electrode. It is a component that can be held so as not to be detached from the composite material layer. Generally, when the binder in the positive electrode mixture layer is immersed in the electrolytic solution, the positive electrode active material, the positive electrode active material and the conductive material, or between the conductive materials absorb the electrolytic solution and swell. To prevent the positive electrode active material and the like from falling off the current collector.
  • the binder used for the slurry composition for a lithium ion secondary battery positive electrode of the present invention needs to contain the following three types of polymers that can be dissolved or dispersed in an organic solvent as a dispersion medium in a predetermined ratio.
  • the binder is (1) Fluorine-containing polymer X, (2) Polymer Y containing 10% by mass or more and 50% by mass or less of a nitrile group-containing monomer unit, and (3) Polymer Z containing 50% by mass or more and 90% by mass or less of (meth) acrylic acid alkyl ester monomer unit, And the ratio of the fluorine-containing polymer X is required to be 50% by mass or more and 95% by mass or less when the polymer contained as the binder is 100% by mass.
  • the fluorine-containing polymer X, the polymer Y, and the polymer Z are used as the binder, and the ratio of the fluorine-containing polymer X in the binder is 50 to 95% by mass,
  • the cycle characteristics and rate characteristics of the lithium ion secondary battery produced using the slurry composition for the positive electrode of the lithium ion secondary battery of the invention can be sufficiently improved, and a conductive material having a large BET specific surface area is used. Even if it exists, the viscosity stability of a slurry composition can be made favorable.
  • the mechanism that can improve the viscosity stability of the slurry composition and the cycle characteristics and rate characteristics of the lithium ion secondary battery by using the binder described above is not clear, but the following It is inferred that That is, the fluorine-containing polymer X is not high in binding properties as compared with the polymer Z and the like, but exhibits the viscosity adjusting function of the slurry composition, and when the positive electrode mixture layer is formed, the positive electrode active layer is formed. It exists in the positive electrode mixture layer without covering the surface of the substance or conductive material.
  • the polymer Y containing 10 to 50% by mass of the nitrile group-containing monomer unit is excellent in binding properties, and has a good dispersibility of the conductive material by covering the surface of the conductive material. Improve the viscosity stability of the slurry composition.
  • the polymer Z containing 50 to 90% by mass of the (meth) acrylic acid alkyl ester monomer unit has excellent binding properties, and the surface of the positive electrode active material when the positive electrode mixture layer is formed. To protect the positive electrode active material and improve the battery life (cycle characteristics).
  • the ratio of the fluorine-containing polymer X to 50% by mass or more, it is possible to prevent the conductive material and the positive electrode active material from being excessively covered with the polymer Y and the polymer Z in the positive electrode mixture layer, and to prevent lithium ions
  • the rate characteristic of the secondary battery can be enhanced.
  • the ratio of the fluorine-containing polymer X 95 mass% or less and mix
  • the binder may contain other polymers other than the fluorine-containing polymer X, the polymer Y, and the polymer Z, but from the viewpoint of obtaining the above-described effects satisfactorily, the other in the binder.
  • the ratio of the polymer is preferably 10% by mass or less, and the binder is preferably composed only of the fluorine-containing polymer X, the polymer Y, and the polymer Z.
  • the fluorine-containing polymer X is a polymer containing a fluorine-containing monomer unit.
  • a fluorine-containing polymer X a homopolymer or copolymer of one or more fluorine-containing monomers, one or more fluorine-containing monomers and a monomer containing no fluorine ( Hereinafter, it is referred to as a “non-fluorine-containing monomer”).
  • the ratio of the fluorine-containing monomer unit in the fluorine-containing polymer X is usually 70% by mass or more, and preferably 80% by mass or more.
  • the ratio of the fluorine-free monomer unit in the fluorine-containing polymer X is usually 30% by mass or less, preferably 20% by mass or less.
  • examples of the fluorine-containing monomer that can form a fluorine-containing monomer unit include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinyl trifluoride chloride, vinyl fluoride, and perfluoroalkyl vinyl ether. It is done. Among these, as the fluorine-containing monomer, vinylidene fluoride is preferable.
  • fluorine-free monomer that can form a fluorine-free monomer unit
  • fluorine-free monomer examples include a fluorine-free monomer copolymerizable with the fluorine-containing monomer, such as ethylene, propylene, and 1-butene.
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene, chlorostyrene; unsaturated nitrile compounds such as (meth) acrylonitrile; methyl (meth) acrylate, ( (Meth) acrylic acid ester compounds such as (meth) butyl acrylate and (meth) acrylic acid 2-ethylhexyl; (meth) acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide Acrylamide compounds; (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid Vinyl compounds containing carboxyl groups such as maleic acid; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; amino such as dimethylaminoethy
  • the fluorine-containing polymer X is preferably a polymer using vinylidene fluoride as a fluorine-containing monomer and a polymer using vinyl fluoride as a fluorine-containing monomer.
  • a polymer using vinylidene is more preferable.
  • the fluorine-containing polymer X is preferably a homopolymer of vinylidene fluoride (polyvinylidene fluoride), a copolymer of vinylidene fluoride and hexafluoropropylene, or polyvinyl fluoride, and more preferably polyvinylidene fluoride.
  • the fluorine-containing polymer X mentioned above may be used individually by 1 type, and may use 2 or more types together.
  • the weight-average molecular weight in terms of polystyrene by gel permeation chromatography of the fluorine-containing polymer X is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000, Particularly preferred is 400,000 to 1,000,000.
  • the glass transition temperature (Tg) of the fluorine-containing polymer X is preferably 0 ° C. or lower, more preferably ⁇ 20 ° C. or lower, and particularly preferably ⁇ 30 ° C. or lower.
  • the lower limit of the Tg of the fluorine-containing polymer X is not particularly limited, but is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 40 ° C. or higher.
  • the melting point (Tm) of the fluorine-containing polymer X is preferably 190 ° C. or less, more preferably 150 to 180 ° C., and further preferably 160 to 170 ° C.
  • Tm of the fluorine-containing polymer X can be adjusted by changing the type of monomer used for the polymerization or controlling the polymerization temperature. In addition, Tm can be measured based on JIS K7121; 1987 using a differential scanning calorimeter.
  • the manufacturing method of the fluorine-containing polymer X mentioned above is not specifically limited, for example, any methods, such as solution polymerization method, suspension polymerization method, block polymerization method, and emulsion polymerization method, can be used.
  • the polymerization method addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization and the like can be used.
  • a polymerization initiator a known polymerization initiator can be used as a known polymerization initiator can be used.
  • the fluorine-containing polymer X is used in the state of a dispersion liquid or a dissolved solution dispersed in a dispersion medium.
  • the dispersion medium of the fluorine-containing polymer X is not particularly limited as long as the fluorine-containing polymer X can be uniformly dispersed or dissolved, and water or an organic solvent can be used, and an organic solvent can be used. preferable.
  • an organic solvent it does not specifically limit, The organic solvent used as a dispersion medium of a slurry composition can be used.
  • the polymer Y is a polymer containing 10% by mass or more and 50% by mass or less of a nitrile group-containing monomer unit.
  • examples of the polymer Y include a copolymer of one or more kinds of nitrile group-containing monomers and a monomer copolymerizable with the nitrile group-containing monomers.
  • the polymer Y is not particularly limited.
  • an acrylonitrile-butadiene copolymer (NBR) containing acrylonitrile units at a ratio of 10% by mass to 50% by mass is hydrogenated by a known method. The hydrogenated NBR can be used.
  • the polymer Y may have a monomer unit containing fluorine (fluorine-containing monomer unit), the proportion of the fluorine-containing monomer unit of the polymer Y is usually 40% by mass or less, Preferably it is 30 mass% or less, and the polymer Y is different from the fluorine-containing polymer X described above.
  • examples of the nitrile group-containing monomer capable of forming a nitrile group-containing monomer unit include ⁇ , ⁇ -ethylenically unsaturated nitrile monomers.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
  • the nitrile group-containing monomer is preferably acrylonitrile and methacrylonitrile, and more preferably acrylonitrile. These can be used alone or in combination of two or more.
  • the ratio of the nitrile group containing monomer unit in the polymer Y needs to be 10 mass% or more and 50 mass% or less, it is preferable that it is 15 mass% or more, and it is 40 mass% or less. It is preferable that it is 30 mass% or less. This is because if the ratio of the nitrile group-containing monomer unit is 10% by mass or more, the binding force of the binder containing the polymer Y can be sufficiently increased. Moreover, it is because the viscosity stability of a slurry composition can fully be improved if the ratio of a nitrile group containing monomer unit shall be 50 mass% or less.
  • the monomer copolymerizable with the nitrile group-containing monomer is not particularly limited, and is a polymerizable compound having a 1-olefin, a conjugated diene compound, a (meth) acrylic acid ester compound, or a hydrophilic group. Compound etc. are mentioned.
  • the monomer copolymerizable with the nitrile group-containing monomer it is preferable to use at least a 1-olefin or a conjugated diene compound. That is, the polymer Y preferably includes a monomer unit derived from 1-olefin or a monomer unit derived from a conjugated diene compound.
  • conjugated diene compound When a conjugated diene compound is used as a monomer copolymerizable with a nitrile group-containing monomer, the conjugated diene monomer unit derived from the conjugated diene compound present in the polymer is hydrogenated after polymerization. Also good. Moreover, these monomers can be used individually by 1 type or in combination of 2 or more types.
  • examples of the 1-olefin include ethylene, propylene, 1-butene and the like. Of these, ethylene is preferable as the 1-olefin.
  • conjugated diene compound examples include conjugated diene compounds having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Of these, 1,3-butadiene is preferred.
  • (meth) acrylic acid ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate.
  • Acrylic acid alkyl esters such as heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, a Methacrylic acid alkyl esters such as butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl me
  • the (meth) acrylic acid ester compound includes an alkyl group bonded to a non-carbonyl oxygen atom.
  • Acrylic acid alkyl ester having 4 to 10 carbon atoms is preferable, and among them, specifically, n-butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable. .
  • examples of the polymerizable compound having a hydrophilic group include a compound having a carboxylic acid group, a compound having a sulfonic acid group, a compound having a phosphoric acid group, and a compound having a hydroxyl group.
  • the hydrophilic group is preferably a carboxylic acid group or a sulfonic acid group, and more preferably a carboxylic acid group.
  • Examples of the compound having a carboxylic acid group include monocarboxylic acids and derivatives thereof, dicarboxylic acids and acid anhydrides, and derivatives thereof.
  • Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, ⁇ -diaminoacrylic acid, and the like.
  • Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, methylallyl maleate, diphenyl maleate, nonyl maleate, decyl maleate, dodecyl maleate And maleate esters such as octadecyl maleate and fluoroalkyl maleate.
  • the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
  • generates a carboxyl group by hydrolysis can also be used.
  • monoesters and diesters of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acids such as monobutyl itaconate and dibutyl itaconate.
  • Examples of the compound having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, ethyl (meth) acrylic acid-2-sulfonate, 2-acrylamido-2-methylpropane sulfone. Acid, 3-allyloxy-2-hydroxypropanesulfonic acid and the like.
  • “(meth) allyl” means allyl and / or methallyl.
  • Examples of the compound having a phosphoric acid group include 2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl (meth) acryloyloxyethyl phosphate.
  • “(meth) acryloyl” means acryloyl and / or methacryloyl.
  • Examples of the compound having a hydroxyl group include ethylenically unsaturated alcohols such as (meth) allyl alcohol, 3-buten-1-ol, 5-hexen-1-ol; 2-hydroxyethyl acrylate, 2-hydroxy acrylate Ethylenic unsaturation such as propyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl maleate, di-4-hydroxybutyl maleate, di-2-hydroxypropyl itaconate Alkanol esters of carboxylic acids; general formula CH 2 ⁇ CR 1 —COO— (C n H 2n O) m —H, wherein m is an integer from 2 to 9, n is an integer from 2 to 4, and R 1 is 2-hydroxyethyl-esters of polyalkylene glycols represented by hydrogen or methyl groups) and (meth) acrylic acid; Mono (meth) acrylic acid esters of dihydroxy esters of dicarboxylic acids such as
  • the polymer Y is a monomer unit derived from 1-olefin and a monomer unit derived from a conjugated diene compound hydrogenated after polymerization (that is, a hydrogenated conjugated diene monomer unit).
  • the total proportion of the monomer unit derived from 1-olefin and the hydrogenated conjugated diene monomer unit in the polymer Y is preferably 40% by mass or more, and 50% by mass. % Or more, more preferably 55% by weight or more, further preferably 90% by weight or less, more preferably 80% by weight or less, and further preferably 75% by weight or less. It is preferably 70% by mass or less.
  • the dispersibility and viscosity stability of the slurry composition can be sufficiently improved. This is because the rate characteristics of the lithium ion secondary battery can be further improved. Further, if the total ratio of the monomer unit derived from 1-olefin and the hydrogenated conjugated diene monomer unit is 90% by mass or less, the viscosity stability of the slurry composition can be secured. This is because it is possible to suppress a reduction in the binding force of the binder containing the polymer Y.
  • the polymer Y is a monomer unit derived from a conjugated diene compound that is not hydrogenated after polymerization, a monomer unit derived from a (meth) acrylate compound, or a single unit derived from a polymerizable compound having a hydrophilic group.
  • the total ratio of the monomer units is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. . If the total proportion of these monomer units is 40% by mass or less, it is possible to suppress the decrease in the viscosity stability of the slurry composition while improving the binding force of the binder containing the polymer Y. Because you can.
  • the ratio is preferably 10% by mass or less, and more preferably 5% by mass or less. It is because it can fully suppress that the viscosity stability of a slurry composition falls if the ratio of the monomer unit derived from the polymerizable compound which has a carboxylic acid group is 10 mass% or less.
  • the polymer Y preferably has an insoluble content with respect to N-methylpyrrolidone (hereinafter sometimes referred to as “NMP insoluble content”) of 5% by mass or less. This is because if the NMP insoluble content is 5% by mass or less, the generation of aggregates in the slurry composition can be suppressed, and the viscosity stability of the slurry composition can be improved.
  • the amount of NMP insoluble in the polymer Y can be adjusted by changing the type and amount of the monomer used for the polymerization of the polymer Y and the polymerization conditions. For example, the content of the nitrile group in the polymer Y is included. If the proportion of monomer units is increased, the amount of NMP insoluble matter can be reduced. Further, the amount of NMP insoluble matter can be reduced by not using a crosslinkable monomer having a functional group capable of crosslinking after polymerization.
  • the weight average molecular weight of the polymer Y in terms of polystyrene by gel permeation chromatography is preferably 10,000 to 700,000, more preferably 50,000 to 500,000, particularly preferably 100,000 to 300,000.
  • the positive electrode can be made flexible and the viscosity of the slurry composition can be easily adjusted.
  • the glass transition temperature (Tg) of the polymer Y is preferably 25 ° C. or less, more preferably 15 ° C. or less, and particularly preferably 0 ° C. or less.
  • the lower limit of Tg of the polymer Y is not particularly limited, but is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45 ° C. or higher, and particularly preferably ⁇ 40 ° C. or higher.
  • Tg of the polymer Y can be adjusted by changing the kind of monomer used for superposition
  • the polymer Y described above can be produced and used in the same manner as the fluorine-containing polymer X.
  • the polymer Z is a polymer containing 50% by mass or more and 90% by mass or less of (meth) acrylic acid alkyl ester monomer units. Specifically, the polymer Z is a copolymer of one or more kinds of (meth) acrylic acid alkyl ester monomers and a monomer copolymerizable with the (meth) acrylic acid alkyl ester monomers. Coalescence is mentioned. In addition, although the polymer Z may have a fluorine-containing monomer unit, the ratio of the fluorine-containing monomer unit of the polymer Z is usually 40% by mass or less, preferably 30% by mass or less, The polymer Z is different from the fluorine-containing polymer X described above.
  • the (meth) acrylic acid alkyl ester monomer that can form a (meth) acrylic acid alkyl ester monomer unit a (meth) acrylic acid ester compound that can be used for the polymerization of the polymer Y described above and Similar ones can be used.
  • a (meth) acrylic acid alkyl ester monomer of the polymer Z an acrylic acid alkyl ester is preferable. From the viewpoint of increasing the binding force of the binder containing the polymer Z, n-butyl acrylate, 2-Ethylhexyl acrylate is more preferred.
  • These (meth) acrylic acid alkyl ester monomers can be used alone or in combination of two or more.
  • the ratio of the (meth) acrylic-acid alkylester monomer unit in the polymer Z needs to be 50 mass% or more and 90 mass% or less, It is preferable that it is 55 mass% or more, and 80 mass% or less. It is preferable that it is 75 mass% or less, and it is still more preferable that it is 70 mass% or less. This is because if the ratio of the (meth) acrylic acid alkyl ester monomer unit is 50% by mass or more, the binding force of the binder containing the polymer Z can be sufficiently increased. Moreover, it is because it can suppress that a cycling characteristic falls if the ratio of a (meth) acrylic-acid alkylester monomer unit shall be 90 mass% or less.
  • the monomer copolymerizable with the (meth) acrylic acid alkyl ester monomer is not particularly limited, and is a monomer having an acidic group (acidic group-containing monomer) or a nitrile group-containing monomer. Examples thereof include a monomer, a crosslinkable monomer, an aromatic vinyl monomer, and an ethylenically unsaturated carboxylic acid amide monomer. And as a monomer copolymerizable with a (meth) acrylic-acid alkylester monomer, it is preferable to use the monomer which has an acidic group at least. That is, the polymer Z preferably includes a monomer unit having an acidic group (an acidic group-containing monomer unit). In addition, these monomers can be used individually by 1 type or in combination of 2 or more types.
  • the monomer having an acidic group is not particularly limited, and a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, and a monomer having a phosphoric acid group may be used. it can. From the viewpoint of effectively balancing the improvement of the binding force of the binder containing the polymer Z and the improvement of the cycle characteristics of the lithium ion secondary battery, the monomer having an acidic group may be a carboxylic acid.
  • a monomer having a group and a monomer having a sulfonic acid group it is preferable to use a monomer having a carboxylic acid group and a monomer having a sulfonic acid group in combination.
  • the same compounds as those having a carboxylic acid group that can be used for the polymerization of the polymer Y described above can be used.
  • a monocarboxylic acid as the monomer having a carboxylic acid group from the viewpoint of expressing good dispersibility in the slurry composition using the binder containing the polymer Z. More preferred are acrylic acid and methacrylic acid, and particularly preferred is methacrylic acid.
  • Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, (meth) acryl sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-hydroxy.
  • Examples thereof include propanesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • the monomer having a sulfonic acid group is 2-acrylamido-2-hydroxypropane.
  • a sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid is preferably used, and 2-acrylamido-2-methylpropanesulfonic acid is more preferably used.
  • Examples of the monomer having a phosphoric acid group include (meth) acrylic acid-3-chloro-2-phosphate, (meth) acrylic acid-2-ethyl phosphate, 3-allyloxy-2-hydroxypropane phosphoric acid, etc. Is mentioned.
  • the acidic group of the monomer having an acidic group described above may be in the form of an alkali metal salt or an ammonium salt.
  • the nitrile group-containing monomer the same nitrile group-containing monomers that can be used for the polymerization of the polymer Y described above can be used.
  • acrylonitrile and methacrylonitrile are preferable as the nitrile group-containing monomer from the viewpoint of improving the strength of the positive electrode by improving the adhesion between the positive electrode mixture layer and the current collector, and acrylonitrile is more preferable. .
  • the crosslinkable monomer a monomer containing an epoxy group, a monomer containing a carbon-carbon double bond and an epoxy group, a monomer containing a halogen atom and an epoxy group, N-methylol
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, pt-butylstyrene, vinyltoluene, chlorostyrene and the like.
  • examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N, N-dimethylacrylamide and the like.
  • the proportion of the monomer unit having an acidic group in the polymer Z is preferably 10% by mass or more, and 13% by mass. More preferably, it is more preferably 15% by mass or more, preferably 30% by mass or less, more preferably 27% by mass or less, and further preferably 25% by mass or less. . If the ratio of the monomer unit having an acidic group is 10% by mass or more, the binding force of the binder containing the polymer Z and the cycle characteristics of the lithium ion secondary battery can be sufficiently improved. It is.
  • the ratio of the monomer unit having an acidic group is 30% by mass or less, the generation of aggregates in the slurry composition is suppressed, and the viscosity stability of the slurry composition is improved. Because it can.
  • the polymer Z has both a monomer unit having a carboxylic acid group and a monomer unit having a sulfonic acid group as a monomer unit having an acidic group, the sulfonic acid group in the polymer Z
  • the ratio of the ratio of the monomer unit having a carboxylic acid group to the ratio of the monomer unit having a carboxylic acid group is 99 by mass ratio. / 1 to 85/15 is preferable.
  • the ratio of the nitrile group-containing monomer unit in the polymer Z is preferably 5% by mass or more, and preferably 10% by mass or more. Is more preferably 15% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. This is because when the ratio of the nitrile group-containing monomer unit is within this range, the adhesion between the positive electrode mixture layer and the current collector can be improved, and the strength of the resulting positive electrode can be improved.
  • the total proportion of these monomer units is 30
  • the content is preferably at most mass%, more preferably at most 25 mass%. This is because if the total proportion of these monomer units is 30% by mass or less, the binding force of the binder containing the polymer Z can be sufficiently improved.
  • the polymer Z preferably has an insoluble content with respect to N-methylpyrrolidone (NMP insoluble content) of 50% by mass or less, more preferably 30% by mass or less, and preferably 20% by mass or less. Further preferred. This is because when the NMP insoluble content is 50% by mass or less, the generation of aggregates in the slurry composition can be suppressed, and the viscosity stability of the slurry composition can be improved.
  • NMP insoluble content of the polymer Z can be adjusted by changing the type and amount of the monomer used for the polymerization of the polymer Z and the polymerization conditions. For example, the nitrile group-containing content in the polymer Z If the proportion of monomer units is increased, the amount of NMP insoluble matter can be reduced.
  • the weight average molecular weight of the polymer Z in terms of polystyrene by gel permeation chromatography is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,000,000, particularly preferably. 100,000 to 500,000.
  • the positive electrode can be flexible, and the viscosity of the slurry composition can be easily adjusted.
  • the glass transition temperature (Tg) of the polymer Z is preferably 50 ° C. or lower, more preferably 10 ° C. or lower.
  • the lower limit of Tg of the polymer Z is not particularly limited, but is preferably ⁇ 50 ° C. or higher.
  • Tg of the polymer Z can be adjusted by changing the kind of monomer used for superposition
  • the polymer Z mentioned above can be manufactured and used similarly to the fluorine-containing polymer X and the polymer Y.
  • the binder used in the slurry composition for a lithium ion secondary battery positive electrode of the present invention requires that the ratio of the fluorine-containing polymer X be 50% by mass or more and 95% by mass or less,
  • the proportion of the fluorine-containing polymer X is preferably 60% by mass or more, more preferably 67% by mass or more, further preferably 70% by mass or more, and preferably 90% by mass or less. More preferably, it is 85 mass% or less. It is because the rate characteristic of a lithium ion secondary battery can be improved if the ratio of the fluorine-containing polymer X is 50 mass% or more. Moreover, if the ratio of the fluorine-containing polymer X is 95% by mass or less, the viscosity stability of the slurry composition and the cycle characteristics of the lithium ion secondary battery can be improved.
  • the content of the fluorine-containing polymer X is such that the mass ratio X / Y with respect to the content of the polymer Y is 9.5 / 0.5 to 5.5 / 4.5.
  • the amount is preferably 9.5 / 0.5 to 6.5 / 3.5, more preferably 9.5 / 0.5 to 7.5 / 2.5. preferable.
  • X / Y is 9.5 / 0.5 or less, the dispersibility and viscosity stability of the slurry composition can be sufficiently improved, and the binding property of the binder can be sufficiently ensured. This is because the cycle characteristics of the ion secondary battery can be further improved. Further, if X / Y is 5.5 / 4.5 or more, the rate characteristics of the lithium ion secondary battery can be sufficiently improved.
  • the content of the fluorine-containing polymer X is such that the mass ratio X / Z with respect to the content of the polymer Z is 9.5 / 0.5 to 5.5 / 4.5.
  • the amount is preferably 9.5 / 0.5 to 6.5 / 3.5, more preferably 9.5 / 0.5 to 7.5 / 2.5. preferable. This is because if X / Z is 9.5 / 0.5 or less, the binding property of the binder can be sufficiently secured, and the cycle characteristics of the lithium ion secondary battery can be further improved. Further, if X / Z is 5.5 / 4.5 or more, the rate characteristics of the lithium ion secondary battery can be sufficiently improved.
  • the content of the polymer Y is preferably such that the mass ratio Y / Z is 1/9 to 9/1 with respect to the content of the polymer Z and is 2/8 to 8/2. More preferably, the amount is 3/7 to 7/3.
  • the content of the polymer Y is low, the viscosity stability of the slurry composition may be reduced.
  • the content of the polymer Z is low, the binding property of the binder is reduced, and the lithium ion secondary battery This is because the cycle characteristics may be degraded.
  • the ratio (X / Y / Z) is preferably 50 to 95 / 0.5 to 45 / 0.5 to 45 on a mass basis, and preferably 60 to 90 / 0.4 to 36 / 0.4 to 36. More preferred is 65 to 85 / 0.35 to 31.5 / 0.35 to 31.5.
  • the amount of the binder is preferably 0.5 parts by mass or more per 100 parts by mass of the positive electrode active material, and 1.0 part by mass. More preferably, it is 2.5 parts by mass or less, and more preferably 2.0 parts by mass or less. If the blending amount of the binder is too small, the viscosity stability of the slurry composition may not be secured, and the binding force cannot be secured sufficiently, and the cycle characteristics of the lithium ion secondary battery are sufficiently improved. It may not be possible to On the other hand, if the amount of the binder is too large, the rate characteristics of the lithium ion secondary battery may be deteriorated.
  • the compounding amount of the fluorine-containing polymer X is preferably 0.25 parts by mass or more, more preferably 0.5 parts by mass or more per 100 parts by mass of the positive electrode active material, and 1.0 part by mass. More preferably, it is preferably 2.475 parts by mass or less, more preferably 1.9 parts by mass or less, and further preferably 1.25 parts by mass or less. This is because if the amount of the fluorine-containing polymer X is too small, the rate characteristics of the lithium ion secondary battery may not be sufficiently improved. Moreover, it is because there exists a possibility that the viscosity stability of a slurry composition and the cycling characteristics of a lithium ion secondary battery cannot fully be improved when there are too many compounding quantities of the fluorine-containing polymer X.
  • the blending amount of the polymer Y is preferably 0.025 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.1 parts by mass or more per 100 parts by mass of the positive electrode active material. More preferably, it is preferably 1.25 parts by mass or less, more preferably 1.0 part by mass or less, and further preferably 0.25 part by mass or less. This is because if the blending amount of the polymer Y is too small, the viscosity stability of the slurry composition and the binding property of the binder may not be sufficiently ensured. Moreover, when there are too many compounding quantities of the polymer Y, there exists a possibility that the rate characteristic of a lithium ion secondary battery may fall.
  • the blending amount of the polymer Z is preferably 0.025 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.1 parts by mass or more per 100 parts by mass of the positive electrode active material. More preferably, it is preferably 1.25 parts by mass or less, more preferably 1.0 part by mass or less, and further preferably 0.25 part by mass or less. If the blending amount of the polymer Z is too small, the binding property of the binder cannot be sufficiently secured, and the cycle characteristics of the lithium ion secondary battery may be deteriorated. Moreover, it is because there exists a possibility that the rate characteristic of a lithium ion secondary battery may fall when there are too many compounding quantities of the polymer Z. FIG.
  • organic solvent used in the slurry composition for a lithium ion secondary battery positive electrode of the present invention for example, an organic solvent having a polarity capable of dissolving or dispersing the above-described fluorine-containing polymer X, polymer Y, and polymer Z is used. be able to.
  • organic solvent acetonitrile, N-methylpyrrolidone, acetylpyridine, cyclopentanone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, methylformamide, methyl ethyl ketone, furfural, ethylenediamine, or the like may be used. It can.
  • N-methylpyrrolidone is most preferable as the organic solvent from the viewpoints of ease of handling, safety, and ease of synthesis.
  • these organic solvents may be used independently and may mix and use 2 or more types.
  • the slurry composition for a lithium ion secondary battery positive electrode of the present invention includes, for example, a viscosity modifier, a reinforcing material, an antioxidant, an electrolyte additive having a function of suppressing decomposition of the electrolyte, and the like. It may contain components. As these other components, known ones can be used.
  • the slurry composition for a lithium ion secondary battery positive electrode of the present invention can be prepared by dissolving or dispersing each of the above components in an organic solvent as a dispersion medium.
  • a known mixer such as a ball mill, sand mill, bead mill, pigment disperser, cracker, ultrasonic disperser, homogenizer, planetary mixer, fill mix, etc. Can do.
  • the positive electrode for lithium ion secondary batteries of the present invention can be produced using the slurry composition for positive electrodes of lithium ion secondary batteries of the present invention.
  • the positive electrode for a lithium ion secondary battery of the present invention includes a current collector and a positive electrode mixture layer formed on the current collector.
  • the positive electrode mixture layer includes at least a positive electrode active material, a BET A conductive material having a specific surface area of 400 m 2 / g or more and a binder containing a fluorine-containing polymer X, a polymer Y, and a polymer Z are included.
  • the positive electrode active material, the conductive material, and the binder contained in the positive electrode mixture layer are those contained in the slurry composition for a lithium ion secondary battery positive electrode of the present invention.
  • the preferred abundance ratio of is the same as the preferred abundance ratio of each component in the slurry composition for the positive electrode of the lithium ion secondary battery of the present invention.
  • the positive electrode compound material layer is formed using the slurry composition for lithium ion secondary battery positive electrodes of this invention mentioned above, the positive electrode for lithium ion secondary batteries of this invention is a lithium ion secondary battery. Cycle characteristics and rate characteristics can be sufficiently improved.
  • the manufacturing method of the positive electrode for lithium ion secondary batteries of this invention is not specifically limited, The process (application
  • the positive electrode for a lithium ion secondary battery of the present invention is prepared by dry granulating the slurry composition for a lithium ion secondary battery positive electrode described above to prepare composite particles, and using the composite particles, a positive electrode is formed on a current collector. It can also be manufactured by a method of forming a composite material layer.
  • a method for applying the slurry composition for a lithium ion secondary battery positive electrode on the current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the slurry composition for a lithium ion secondary battery positive electrode may be applied to only one surface of the current collector or may be applied to both surfaces. The thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the positive electrode mixture layer obtained by drying.
  • the current collector on which the slurry composition for the positive electrode of the lithium ion secondary battery is applied a material having electrical conductivity and electrochemical durability is used.
  • a current collector made of aluminum or an aluminum alloy can be used as the current collector.
  • aluminum and an aluminum alloy may be used in combination, or different types of aluminum alloys may be used in combination.
  • Aluminum and aluminum alloys are excellent current collector materials because they have heat resistance and are electrochemically stable.
  • the method for drying the positive electrode slurry composition for the lithium ion secondary battery on the current collector is not particularly limited, and a known method can be used. For example, drying with warm air, hot air, low-humidity air, vacuum drying, infrared rays And a drying method by irradiation with electron beam or the like.
  • a positive electrode mixture layer is formed on the current collector, and the lithium ion provided with the current collector and the positive electrode mixture layer A positive electrode for a secondary battery can be obtained.
  • the positive electrode mixture layer may be subjected to pressure treatment using a die press or a roll press. By the pressure treatment, the adhesion between the positive electrode mixture layer and the current collector can be improved. Furthermore, when the positive electrode mixture layer contains a curable polymer, the polymer is preferably cured after the positive electrode mixture layer is formed.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator, and the positive electrode for a lithium ion secondary battery of the present invention is used as the positive electrode. And since the lithium ion secondary battery of this invention uses the positive electrode for lithium ion secondary batteries of this invention, it is excellent in cycling characteristics and rate characteristics, and is high performance.
  • a negative electrode of a lithium ion secondary battery a known negative electrode used as a negative electrode for a lithium ion secondary battery can be used.
  • the negative electrode for example, a negative electrode made of a thin plate of metallic lithium or a negative electrode formed by forming a negative electrode mixture layer on a current collector can be used.
  • a collector what consists of metal materials, such as iron, copper, aluminum, nickel, stainless steel, titanium, a tantalum, gold
  • the negative electrode mixture layer a layer containing a negative electrode active material and a binder can be used.
  • the binder is not particularly limited, and any known material can be used.
  • an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used as the supporting electrolyte.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable, and LiPF 6 is particularly preferable because it is easily dissolved in a solvent and exhibits a high degree of dissociation.
  • electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
  • carbonates because they have a high dielectric constant and a wide stable potential region, and it is more preferable to use a mixture of ethylene carbonate and ethyl methyl carbonate.
  • concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate. For example, it is preferably 0.5 to 15% by mass, more preferably 2 to 13% by mass, and 5 to 10% by mass. Is more preferable.
  • known additives such as fluoroethylene carbonate and ethyl methyl sulfone may be added to the electrolytic solution.
  • the separator is not particularly limited, and for example, those described in JP 2012-204303 A can be used. Among these, the film thickness of the entire separator can be reduced, thereby increasing the ratio of the electrode active material in the secondary battery and increasing the capacity per volume.
  • a microporous film made of a resin such as polyethylene, polypropylene, polybutene, or polyvinyl chloride is preferable.
  • a positive electrode and a negative electrode are overlapped via a separator, and this is wound into a battery container according to the battery shape as necessary, and placed in the battery container. It can manufacture by inject
  • an overcurrent prevention element such as a fuse or a PTC element, an expanded metal, a lead plate, etc. may be provided as necessary.
  • the shape of the secondary battery may be any of, for example, a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, and a flat shape.
  • NMP insoluble content A N-methylpyrrolidone solution of the polymer (solid content concentration: 8%) was poured into a Teflon (registered trademark) petri dish so that the thickness after drying was 100 ⁇ m to form a film.
  • the obtained film was punched into a circle having a diameter of 16 mm, and the weight was measured (weight is assumed to be “A”).
  • the punched film was immersed in 20 ml of N-methylpyrrolidone (NMP) and stored at 60 ° C. for 72 hours. Thereafter, the NMP solution in which the film was immersed was filtered through an 80-mesh sieve (the weight of the sieve before filtration was “B”) and dried.
  • the slurry composition whose viscosity was measured was stirred (rotational speed: 60 rpm) for 24 hours with a planetary mixer.
  • viscosity ⁇ 1 at a temperature of 25 ° C. and a rotation speed of 60 rpm was measured again using a B-type viscometer.
  • the viscosity retention ratio ⁇ ( ⁇ 1 / ⁇ 0) ⁇ 100% was calculated, and the viscosity stability of the slurry composition was evaluated according to the following criteria. It shows that the viscosity stability of a slurry composition is excellent, so that the value of a viscosity retention rate is large.
  • Viscosity retention is 80% or more
  • B Viscosity retention is 70% or more and less than 80%
  • C Viscosity retention is less than 70% ⁇ peel strength>
  • the positive electrode after the roll press on which the positive electrode mixture layer was formed was cut into a rectangle having a width of 1.0 cm and a length of 10 cm to obtain a test piece. Then, a cellophane tape was attached to the surface of the test piece on the positive electrode mixture layer side. At this time, the cellophane tape defined in JIS Z1522 was used. Then, the stress when the test piece was peeled from the one end side toward the other end side at a speed of 50 mm / min with the cellophane tape fixed to the test stand was measured.
  • the measurement was performed 10 times, the average value of the stress was determined, and this was taken as the peel strength (N / m), and evaluated according to the following criteria. It shows that the adhesiveness of the positive mix layer with respect to a collector is excellent, so that peel strength is large.
  • C Peel strength is less than 10 N / m ⁇ Rate characteristics> About 10 cells of the produced lithium ion secondary battery, a charge / discharge cycle of charging to 4.2 V with a constant current of 0.2 C and discharging to 3.0 V with a constant current of 0.2 C under the condition of a temperature of 25 ° C., Under the condition of a temperature of 25 ° C., a charge / discharge cycle of charging to 4.2 V with a constant current of 0.2 C and discharging to 3.0 V with a constant current of 1.0 C was performed.
  • the charge / discharge rate characteristic is 80% or more
  • D: The charge / discharge rate characteristic is less than 70% ⁇ cycle characteristic ( High potential cycle characteristics) > With respect to 10 cells of the produced lithium ion secondary battery, an operation of charging at 600 mA until the battery voltage reached 4.4 V under conditions of a temperature of 25 ° C. and discharging until the battery voltage reached 3 V at 600 mA were repeated 100 times. Then, the ratio of the 100th discharge capacity (average value) to the first discharge capacity (average value) (charge / discharge capacity retention rate (100th discharge capacity / first discharge capacity) ⁇ 100%) was determined.
  • Example 1 ⁇ Preparation of fluorine-containing polymer X1> A solution in which polyvinylidene fluoride (fluorine-containing polymer X1) was dissolved in NMP was prepared.
  • ⁇ Preparation of polymer Y1> In an autoclave equipped with a stirrer, 240 parts of ion exchange water, 25 parts by mass of acrylonitrile (AN) as a nitrile group-containing monomer, and 60 parts by mass of butadiene (BD) as a monomer copolymerizable with the nitrile group-containing monomer And 15 parts by weight of butyl acrylate (BA), 0.3 part of potassium persulfate as a polymerization initiator, 1.6 parts of sodium lauryl sulfate as an emulsifier, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator, After stirring and replacing the interior with nitrogen, polymerization was carried out by heating at 70 ° C
  • first-stage hydrogenation reaction the hydrogenation reaction
  • the autoclave was returned to atmospheric pressure, and further, 25 mg of palladium acetate was dissolved in 60 ml of water added with 4 times moles of nitric acid with respect to Pd as a hydrogenation reaction catalyst. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours.
  • LiCoO 2 lithium cobaltate LCO
  • Ketjen black Lion Corporation, EC300J, special oil furnace carbon powder, number average particle size of 40 nm, BET as the
  • the resulting slurry composition had a solid content concentration of 81 mass% and a viscosity of 5100 mPa ⁇ s. And the dispersibility and viscosity stability of the obtained slurry composition were evaluated. The results are shown in Table 1.
  • ⁇ Preparation of negative electrode for lithium ion secondary battery> A mixture of 90 parts of spherical artificial graphite (volume average particle diameter: 12 ⁇ m) and 10 parts of SiO x (volume average particle diameter: 10 ⁇ m) as the negative electrode active material, and an aqueous dispersion of styrene-butadiene polymer as the binder An amount of 1 part, 1 part of carboxymethylcellulose as a thickener, and an appropriate amount of water as a dispersion medium were stirred in a planetary mixer to prepare a slurry composition for a lithium ion secondary battery negative electrode. Next, a copper foil having a thickness of 15 ⁇ m was prepared as a current collector.
  • the said slurry composition for lithium ion secondary battery negative electrodes was apply
  • the negative electrode original fabric was obtained by heat-processing at 150 degreeC for 2 hours.
  • This negative electrode original fabric was rolled with a roll press to produce a sheet-like negative electrode comprising a negative electrode mixture layer having a density of 1.8 g / cm 3 and a copper foil. And the sheet-like negative electrode was cut
  • the produced positive electrode for a lithium ion secondary battery and the negative electrode for a lithium ion secondary battery were wound using a core having a diameter of 20 mm with a separator (a polypropylene microporous film having a thickness of 20 ⁇ m) interposed therebetween to obtain a wound body. Obtained.
  • the obtained wound body was compressed from one direction until the thickness became 4.5 mm at a speed of 10 mm / second.
  • the wound body after compression had an elliptical shape in plan view, and the ratio of the major axis to the minor axis (major axis / minor axis) was 7.7.
  • 2% by volume of vinylene carbonate was added as an additive.
  • the compressed winding body was accommodated in the predetermined aluminum laminate case with 3.2 g of non-aqueous electrolyte. After connecting the nickel lead wire connected to the negative electrode for the lithium ion secondary battery and the aluminum lead wire connected to the positive electrode for the lithium ion secondary battery to a predetermined location, the case opening is sealed with heat, and the lithium ion A secondary battery was obtained.
  • This lithium ion secondary battery is a pouch having a width of 35 mm, a height of 48 mm, and a thickness of 5 mm, and the nominal capacity of the battery is 700 mAh.
  • the obtained lithium ion secondary battery was evaluated for rate characteristics and cycle characteristics. The results are shown in Table 1.
  • Example 2 A slurry for a lithium ion secondary battery positive electrode in the same manner as in Example 1 except that the blending amount of the conductive material at the time of preparing the slurry composition for a lithium ion secondary battery positive electrode was changed to 1.0 part and 2.0 parts, respectively.
  • a composition, a positive electrode for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced and evaluated. The results are shown in Table 1.
  • the conductive materials used in preparing the slurry composition for the lithium ion secondary battery positive electrode were acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., AB35, Denka black powder, number average particle size 35 nm, BET specific surface area 68 m 2 / g), respectively.
  • Ketjen black (Lion, EC300J, special oil furnace carbon powder, number average particle size 40 nm, BET specific surface area 800 m 2 / g) mixture (BET specific surface area 600 m 2 / g), ketjen black (Lion Slurry composition for positive electrode of lithium ion secondary battery, positive electrode for lithium ion secondary battery in the same manner as in Example 1 except that EC600J, number average particle diameter 40 nm, BET specific surface area 1270 m 2 / g) was changed. Manufactured and evaluated negative electrodes for lithium ion secondary batteries and lithium ion secondary batteries It became. The results are shown in Table 1.
  • Example 6 A slurry composition for a lithium ion secondary battery positive electrode, lithium ion in the same manner as in Example 1, except that the amount of the polymer used in preparing the slurry composition for a lithium ion secondary battery positive electrode was changed as shown in Table 1.
  • a positive electrode for a secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery were manufactured and evaluated. The results are shown in Table 1.
  • Example 9 A slurry composition for a positive electrode of a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, lithium, and the like, except that the polymer Y2 prepared as follows was used instead of the polymer Y1
  • An anode for an ion secondary battery and a lithium ion secondary battery were manufactured and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of polymer Y2> The polymer Y2 was treated in the same manner as the polymer Y1, except that the amount of acrylonitrile (AN) was 15 parts by mass, the amount of butadiene (BD) was 75 parts by mass, and the amount of butyl acrylate (BA) was 10 parts by mass. Prepared.
  • the NMP insoluble content of the polymer Y2 was 15% by mass.
  • Example 10 A slurry composition for a lithium ion secondary battery positive electrode, a positive electrode for a lithium ion secondary battery, lithium, and the like, except that the polymer Y3 prepared as follows was used instead of the polymer Y1 An anode for an ion secondary battery and a lithium ion secondary battery were manufactured and evaluated. The results are shown in Table 1.
  • Example 11 A slurry composition for a positive electrode of a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, lithium, and the like, except that the polymer Z2 prepared as follows was used instead of the polymer Z1
  • An anode for an ion secondary battery and a lithium ion secondary battery were manufactured and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of polymer Z2> A polymer Z2 was prepared in the same manner as the polymer Z1, except that the amount of 2-ethylhexyl acrylate (2EHA) was 54.5 parts by mass and the amount of methacrylic acid (MAA) was 25 parts by mass. In addition, the NMP insoluble content of the polymer Z2 was 4% by mass.
  • Example 12 A slurry composition for a positive electrode of a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, lithium, and the like, except that the polymer Z3 prepared as follows was used instead of the polymer Z1
  • An anode for an ion secondary battery and a lithium ion secondary battery were manufactured and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of polymer Z3> The same as the polymer Z1, except that the amount of 2-ethylhexyl acrylate (2EHA) was 69.5 parts by mass, the amount of methacrylic acid (MAA) was 15 parts by mass, and the amount of acrylonitrile (AN) was 15 parts by mass.
  • a polymer Z3 was prepared.
  • the NMP insoluble content of the polymer Z3 was 13% by mass.
  • Example 13 A slurry composition for a positive electrode of a lithium ion secondary battery, a positive electrode for a lithium ion secondary battery, lithium, and the like, except that the polymer Z4 prepared as follows was used instead of the polymer Z1
  • An anode for an ion secondary battery and a lithium ion secondary battery were manufactured and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of polymer Z4> The same as polymer Z1 except that the amount of 2-ethylhexyl acrylate (2EHA) was 79.5 parts by mass, the amount of methacrylic acid (MAA) was 10 parts by mass, and the amount of acrylonitrile (AN) was 10 parts by mass.
  • a polymer Z4 was prepared.
  • the NMP insoluble content of the polymer Z4 was 20% by mass.
  • the conductive material used in preparing the slurry composition for the lithium ion secondary battery positive electrode was acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., AB35, Denka Black powder, number average particle size 35 nm, BET specific surface area 68 m 2 / g) and kettle.
  • Example 2 Except for changing to a mixture (BET specific surface area 350 m 2 / g) with Chain Black (Lion Corporation, EC300J, special oil furnace carbon powder, number average particle size 40 nm, BET specific surface area 800 m 2 / g)
  • a slurry composition for a lithium ion secondary battery positive electrode, a positive electrode for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery were produced and evaluated. The results are shown in Table 2.
  • the dispersibility and viscosity stability of the slurry composition, as well as the cycle characteristics and rate characteristics of the lithium ion secondary battery are of high dimensions. It can be seen that it can be arranged side by side. Also, from Examples 1 and 4 to 5 in Table 1, by adjusting the BET specific surface area of the conductive material, the dispersibility and viscosity stability of the slurry composition, and the cycle characteristics and rate characteristics of the lithium ion secondary battery It can be seen that can be juxtaposed in a high dimension.
  • Examples 1 and 6 to 8 in Table 1 by adjusting the blending ratio of the polymer, the dispersibility and viscosity stability of the slurry composition, and the cycle characteristics and rate characteristics of the lithium ion secondary battery can be obtained. It can be seen that they can be juxtaposed in a higher dimension. Also, from Examples 1 and 9 to 13 in Table 1, by adjusting the composition of the polymer, the dispersibility and viscosity stability of the slurry composition, and the cycle characteristics and rate characteristics of the lithium ion secondary battery are improved. It can be seen that they can be arranged side by side.
  • a slurry composition for a positive electrode of a lithium ion secondary battery that can further improve the performance of the lithium ion secondary battery, in particular, cycle characteristics and rate characteristics, and is excellent in viscosity stability. be able to.
  • the positive electrode for lithium ion secondary batteries which can further improve the performance of a lithium ion secondary battery, especially cycling characteristics and rate characteristics can be provided.
  • a high-performance lithium ion secondary battery can be provided.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

　L'invention porte sur une composition de bouillie pour électrode positive pour batterie rechargeable lithium-ion, qui possède une excellente visco-stabilité, et grâce à laquelle il est possible d'améliorer les performances d'une batterie rechargeable lithium-ion, en particulier les caractéristiques de cycle et les caractéristiques de vitesse. Cette bouillie pour électrode positive pour batterie rechargeable lithium-ion contient un matériau actif d'électrode positive, un matériau électroconducteur, un liant et un solvant organique. La zone de surface spécifique BET du matériau électroconducteur est au moins de 400 m2/g, le liant contient (1) un polymère contenant du fluor (X), (2) un polymère (Y) contenant 10-50 % en masse d'unités de monomère contenant un groupe de nitrile, et (3) un polymère (Z) contenant 50-90 % en masse d'unités de monomère d'ester alkylique d'acide (méth)acrylique, et le contenu de polymère contenant du fluor (X) dans le liant est de 50-95 % en masse.
PCT/JP2014/005475 2013-10-31 2014-10-29 Composition de bouillie pour électrode positive pour batterie rechargeable lithium-ion, électrode positive pour batterie rechargeable lithium-ion et batterie rechargeable lithium-ion WO2015064099A1 (fr)

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KR1020167009212A KR102264698B1 (ko) 2013-10-31 2014-10-29 리튬 이온 이차전지 정극용 슬러리 조성물, 리튬 이온 이차전지용 정극 및 리튬 이온 이차전지
CN201480055323.9A CN105612641B (zh) 2013-10-31 2014-10-29 锂离子二次电池正极用浆料组合物、锂离子二次电池用正极及锂离子二次电池

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WO2020004145A1 (fr) 2018-06-29 2020-01-02 日本ゼオン株式会社 Composition de liant pour électrode de batterie secondaire non aqueuse, composition de bouillie pour électrode de batterie secondaire non aqueuse et procédé de production de celle-ci, électrode pour batterie secondaire non aqueuse et batterie secondaire non aqueuse
WO2021065187A1 (fr) 2019-09-30 2021-04-08 日本ゼオン株式会社 Composition de liant pour batterie secondaire non aqueuse et son procédé d'évaluation, composition de bouillie pour couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle pour batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse et batterie secondaire non aqueuse
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JP7192774B2 (ja) * 2017-09-15 2022-12-20 日本ゼオン株式会社 電気化学素子電極用スラリー組成物、電気化学素子用電極、電気化学素子、および電気化学素子電極用スラリー組成物の製造方法
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WO2017029813A1 (fr) * 2015-08-20 2017-02-23 日本ゼオン株式会社 Composition de liant pour batteries rechargeables à électrolyte non aqueux, composition pour couches fonctionnelles de batteries rechargeables à électrolyte non aqueux, couche fonctionnelle pour batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux
WO2018020117A1 (fr) * 2016-07-26 2018-02-01 Hutchinson Anode pour cellule de batterie lithium-ion, son procede de fabrication et la batterie l'incorporant
FR3054728A1 (fr) * 2016-07-26 2018-02-02 Hutchinson Anode pour cellule de batterie lithium-ion, son procede de fabrication et cette batterie l'incorporant
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AU2018297321B2 (en) * 2017-07-07 2021-06-10 Ppg Industries Ohio, Inc. Electrode slurry composition for lithium ion electrical storage devices
JP7248644B2 (ja) 2017-07-07 2023-03-29 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド リチウムイオン蓄電装置用の電極用スラリー組成物
AU2018297321B9 (en) * 2017-07-07 2021-10-07 Ppg Industries Ohio, Inc. Electrode slurry composition for lithium ion electrical storage devices
WO2019010405A1 (fr) * 2017-07-07 2019-01-10 Ppg Industries Ohio, Inc. Composition de suspension d'électrode pour dispositifs de stockage d'électricité aux ions de lithium
JP2020527829A (ja) * 2017-07-07 2020-09-10 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． リチウムイオン蓄電装置用の電極用スラリー組成物
WO2020004526A1 (fr) 2018-06-29 2020-01-02 日本ゼオン株式会社 Composition de liant pour électrode de batterie secondaire non aqueuse, composition de bouillie pour électrode de batterie secondaire non aqueuse et son procédé de production, électrode de batterie secondaire non aqueuse et batterie secondaire non aqueuse
WO2020004145A1 (fr) 2018-06-29 2020-01-02 日本ゼオン株式会社 Composition de liant pour électrode de batterie secondaire non aqueuse, composition de bouillie pour électrode de batterie secondaire non aqueuse et procédé de production de celle-ci, électrode pour batterie secondaire non aqueuse et batterie secondaire non aqueuse
KR20210023860A (ko) 2018-06-29 2021-03-04 니폰 제온 가부시키가이샤 비수계 이차 전지 전극용 바인더 조성물, 비수계 이차 전지 전극용 슬러리 조성물 및 그 제조 방법, 비수계 이차 전지용 전극, 그리고 비수계 이차 전지
KR20210021975A (ko) 2018-06-29 2021-03-02 니폰 제온 가부시키가이샤 비수계 이차 전지 전극용 바인더 조성물, 비수계 이차 전지 전극용 슬러리 조성물 및 그 제조 방법, 비수계 이차 전지용 전극, 그리고 비수계 이차 전지
US11929507B2 (en) 2018-06-29 2024-03-12 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode and method of producing same, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
US11976147B2 (en) 2018-06-29 2024-05-07 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode and method of producing same, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
WO2021065187A1 (fr) 2019-09-30 2021-04-08 日本ゼオン株式会社 Composition de liant pour batterie secondaire non aqueuse et son procédé d'évaluation, composition de bouillie pour couche fonctionnelle de batterie secondaire non aqueuse, couche fonctionnelle pour batterie secondaire non aqueuse, élément de batterie pour batterie secondaire non aqueuse et batterie secondaire non aqueuse

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JP6369473B2 (ja) 2018-08-08
KR20160082503A (ko) 2016-07-08

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