WO2017038628A1 - Batterie secondaire non aqueuse et procédé de fabrication de celle-ci - Google Patents

Batterie secondaire non aqueuse et procédé de fabrication de celle-ci Download PDF

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Publication number
WO2017038628A1
WO2017038628A1 PCT/JP2016/074829 JP2016074829W WO2017038628A1 WO 2017038628 A1 WO2017038628 A1 WO 2017038628A1 JP 2016074829 W JP2016074829 W JP 2016074829W WO 2017038628 A1 WO2017038628 A1 WO 2017038628A1
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positive electrode
secondary battery
mixture layer
negative electrode
electrode mixture
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PCT/JP2016/074829
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English (en)
Japanese (ja)
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映理 児島
丈主 加味根
上田　篤司
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日立マクセル株式会社
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/06—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinylidene chloride
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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 non-aqueous secondary battery excellent in charge / discharge characteristics at a large current and a method for producing the same.
  • Non-aqueous secondary batteries such as lithium ion secondary batteries are widely used as power sources for various portable devices because of their high voltage and high capacity.
  • medium-sized and large-sized tools such as power tools such as electric tools, electric vehicles, and electric bicycles has been spreading.
  • Non-aqueous secondary batteries are first widespread for consumer use, and at present, they are spreading for in-vehicle and industrial use. Under these circumstances, non-aqueous secondary batteries are desired to improve various battery characteristics.
  • Patent Document 1 uses a positive electrode using a specific lithium iron phosphate as a positive electrode active material and a negative electrode using amorphous carbon (amorphous carbon) such as soft carbon as a negative electrode active material.
  • amorphous carbon amorphous carbon
  • a lithium ion secondary battery has been proposed that has secured characteristics suitable for in-vehicle use.
  • non-aqueous secondary batteries in particular, considering application to in-vehicle and industrial applications, for example, it is required to have battery characteristics (high output characteristics) that can function well even when discharged with a large current. is assumed.
  • the positive electrode for a non-aqueous secondary battery was prepared by collecting a composition for forming a positive electrode mixture layer (a positive electrode mixture-containing composition) prepared by dispersing a positive electrode active material, a binder, a conductive additive and the like in a solvent. In general, it is manufactured by a method of forming a positive electrode mixture layer on the surface of the current collector through a process of applying the surface of the electric body and removing the solvent by drying.
  • a fluorine resin such as polyvinylidene fluoride is generally used for the binder for the positive electrode mixture layer.
  • lithium-containing composite oxides such as lithium iron phosphate, which are widely used as positive electrode active materials for non-aqueous secondary batteries, contain alkaline impurities because of their manufacturing method. For this reason, when such a positive electrode active material is formulated using a solvent containing water, the alkaline component of the impurity is easily eluted in the solvent, and a fluorine resin such as polyvinylidene fluoride as a binder is crosslinked. Cause.
  • the binder in the positive electrode mixture-containing composition when the binder in the positive electrode mixture-containing composition is cross-linked, the composition becomes a gel and loses fluidity, so that application to the current collector becomes difficult or impossible. Therefore, the positive electrode mixture-containing composition using a fluorine resin such as polyvinylidene fluoride as the binder must be used for forming the positive electrode mixture layer in a short time until the binder is crosslinked after the preparation. This tends to impair the productivity of the positive electrode for a non-aqueous secondary battery.
  • a fluorine resin such as polyvinylidene fluoride
  • the positive electrode active material having a high content of alkaline impurities tends to have a high water content, and in particular, when the surface is coated with a carbon material in order to improve the conductivity of the material, the water is adsorbed. It becomes easier and the water content is further increased. Therefore, when a positive electrode is produced using such a positive electrode active material and used as it is for producing a battery, a large amount of moisture is brought into the battery. In that case, the moisture contained in the positive electrode mixture reacts with a fluorine-containing inorganic lithium salt such as LiPF 6 used as the electrolyte of the non-aqueous electrolyte solution to generate hydrogen fluoride. For this reason, in a situation where the battery is left in a high temperature environment for a long time, the constituent materials of the electrode are deteriorated, and problems such as a decrease in capacity are likely to occur.
  • a fluorine-containing inorganic lithium salt such as LiPF 6 used as the electrolyte of the non-aqueous electroly
  • Patent Document 3 discloses that a phosphoric acid compound having a specific structure is added to the non-aqueous electrolyte, thereby suppressing the influence of moisture brought into the battery, load characteristics and high temperature. It has been proposed to improve the load characteristics after storage.
  • JP 2009-104983 A JP 2010-272272 A Japanese Patent Laid-Open No. 2001-319685
  • Patent Document 2 While the technique described in Patent Document 2 is effective in suppressing the cross-linking reaction of polyvinylidene fluoride that may be caused by an alkali component in the positive electrode active material and suppressing the gelation of the positive electrode mixture-containing composition, In order to improve rate characteristics and cycle characteristics using an active material with a specific surface area, the binder content is increased, and there is room for improvement in terms of improving charge / discharge characteristics at a large current.
  • An object of the present invention is to provide a non-aqueous secondary battery excellent in charge / discharge characteristics at a large current, and a method for producing the same, by preventing occurrence of problems associated with the positive electrode active material or moisture contained in the positive electrode.
  • One embodiment of the non-aqueous secondary battery of the present invention that can achieve the above object is a positive electrode having a positive electrode mixture layer containing a positive electrode active material, a binder, and a conductive additive on one or both sides of a current collector, A negative electrode having a negative electrode mixture layer containing a negative electrode active material and a binder on one side or both sides of a current collector, a separator, and a non-aqueous electrolyte containing a lithium salt and an organic solvent.
  • a positive electrode mixture layer containing a binder and a conductive additive on one or both sides of the current collector the positive electrode mixture layer containing an olivine type compound as the positive electrode active material, and the following general formula
  • the polymer (A) having a unit represented by (1) in the molecule is contained as the binder.
  • R 1 represents H or a methyl group
  • R 2 represents an alkyl group having 1 to 18 carbon atoms.
  • the non-aqueous electrolyte in the non-aqueous secondary battery preferably includes a phosphoric acid compound having a group represented by the following general formula (2) in the molecule.
  • X represents Si, Ge or Sn
  • R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine.
  • X represents Si, Ge or Sn
  • R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine.
  • the method for producing a non-aqueous secondary battery of the present invention capable of achieving the above object includes a positive electrode having a positive electrode mixture layer containing a positive electrode active material, a binder and a conductive auxiliary agent on one side or both sides of a current collector, A nonaqueous secondary battery comprising a negative electrode having a negative electrode mixture layer containing a negative electrode active material and a binder on one or both sides of a current collector, a separator, and a nonaqueous electrolyte containing a lithium salt and an organic solvent
  • a positive electrode having a water content of 500 to 3000 ppm in the positive electrode mixture layer and a nonaqueous electrolytic solution containing a phosphate compound having a group represented by the general formula (2) in the molecule are packaged. It is sealed inside the body.
  • the present invention it is possible to provide a non-aqueous secondary battery that is less prone to problems associated with moisture contained in the positive electrode active material or the positive electrode and has excellent charge / discharge characteristics at a large current, and a method for manufacturing the same.
  • the positive electrode (hereinafter simply referred to as “positive electrode”) according to the non-aqueous secondary battery of the present invention has a structure having a positive electrode mixture layer containing a positive electrode active material, a binder and a conductive additive on one side or both sides of a current collector.
  • positive electrode contains the polymer (A) which contains an olivine type compound as a positive electrode active material, and has the unit represented by the said General formula (1) in a molecule
  • the olivine type compound contains a lot of alkaline impurities as compared with a lithium-containing composite oxide such as lithium cobaltate. Therefore, when a composition (slurry) for forming a positive electrode mixture layer is prepared, Since the alkaline component of impurities elutes in the solvent (N-methyl-2-pyrrolidone, water, etc.) of the composition and crosslinks a fluororesin such as polyvinylidene fluoride (PVDF) as a binder, the composition over time The fluidity of the is reduced.
  • a fluororesin such as polyvinylidene fluoride (PVDF)
  • the polymer (A) that hardly causes a crosslinking reaction due to an alkaline impurity in the olivine type compound is used instead of PVDF.
  • the polymer (A) that hardly causes a crosslinking reaction due to an alkaline impurity in the olivine type compound is used instead of PVDF.
  • the group represented by the general formula (2) is combined with a positive electrode having a positive electrode mixture layer containing a large amount of water of 500 to 3000 ppm.
  • the phosphoric acid compound has a structure in which at least one of hydrogen atoms of phosphoric acid is substituted with a group represented by the general formula (2).
  • X is Si, Ge, or Sn.
  • a phosphoric acid silyl ester in which X is Si is preferably used.
  • R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. However, a methyl group or an ethyl group is more preferable.
  • R 3 , R 4, and R 5 may have some or all of their hydrogen atoms replaced with fluorine.
  • the group represented by the general formula (2) is particularly preferably a trimethylsilyl group.
  • the phosphoric acid compound only one of the hydrogen atoms possessed by phosphoric acid may be substituted with the group represented by the general formula (2). Two of them may be substituted with a group represented by the general formula (2), and all three hydrogen atoms of phosphoric acid may be substituted with a group represented by the general formula (2). However, it is more preferable that all three hydrogen atoms of phosphoric acid are substituted with the group represented by the general formula (2).
  • phosphoric acid (tris) trimethylsilyl is particularly preferable.
  • the moisture content of the positive electrode mixture layer is 500 ppm or more, preferably 1000 ppm or more, more preferably 1200 ppm or more, based on mass.
  • the water content of the positive electrode mixture layer may be 3000 ppm or less and 2500 ppm or less on a mass basis. Preferably, it is more preferably 2000 ppm or less.
  • the water content of the positive electrode mixture layer as used in the present specification can be determined by, for example, the following method.
  • a measurement sample positive electrode
  • a measurement sample positive electrode
  • the flowd nitrogen gas is introduced into the measurement cell of the Karl Fischer moisture meter, and the moisture content is measured.
  • the integrated value up to the end of titration is taken as the moisture content (the “moisture content” used as the standard for the calculation of “moisture content” described in the examples below) is a value determined by this method.
  • a value obtained by dividing the water content by the mass of the positive electrode mixture layer is referred to as “moisture content of the positive electrode mixture layer” in the present specification.
  • the moisture content is measured in a glove box having a dew point of ⁇ 70 ° C.
  • the moisture brought into the battery is mostly due to the positive electrode mixture layer, there are also those other than the positive electrode such as the negative electrode, the separator and the non-aqueous electrolyte, and these moisture are also contained in the non-aqueous electrolyte.
  • the phosphoric acid compound can contribute to the formation of an SEI film.
  • the water content of the entire battery including the moisture due to the configuration other than the positive electrode, to be within a preferable range for the SEI film formation by the phosphoric acid compound.
  • the SEI film of the phosphoric acid compound on the positive electrode is used.
  • the total amount of the non-aqueous electrolyte is preferably about 1000 ppm or more, more preferably 1500 ppm or more, and particularly preferably 1700 ppm or more, based on mass.
  • the water content of the entire battery is preferably 3500 ppm or less, more preferably 3000 ppm or less on a mass basis. It is especially preferable to set it as 2500 ppm or less.
  • moisture content of the entire battery is the measurement of the moisture content in the measurement of the moisture content when determining the moisture content of the positive electrode mixture layer, with the measurement sample as all the constituent materials of the battery with the battery container opened. And this is calculated
  • the olivine type compound exemplified as the positive electrode active material in the non-aqueous secondary battery of the present invention is typically represented by a chemical formula of LiM 1 PO 4 (M 1 : Co, Ni, Mn, Fe, etc.). However, it may contain one or more elements other than M 1 such as Al and Y as additive elements. Moreover, the olivine type compound contained in the positive electrode mixture layer may be only one kind of those not containing the above-mentioned additive elements or one containing the above-mentioned additive elements, or two or more kinds. May be.
  • the average particle size of the olivine type compound particles is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
  • the average particle size of the olivine-type compound particles becomes too large, the conductivity of the positive electrode mixture layer decreases and the charge / discharge characteristics decrease, so the average particle size is preferably 20 ⁇ m or less, It is more preferably 17 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the olivine type compound particles may be composed of primary particles, but when the secondary particles are aggregated primary particles having a particle diameter of about 10 to 100 nm, or a granulated body obtained by granulating the primary particles, Compared with primary particles having the same particle size, charge / discharge characteristics can be further improved, which is preferable.
  • the average particle size in this case may be calculated based on the particle size of the secondary particles or the granulated body.
  • the average particle diameter is a number average particle diameter measured using a laser scattering particle size distribution analyzer (for example, “LA-920” manufactured by Horiba, Ltd.).
  • a method of firing a mixture of an organic material that becomes a carbon precursor and an olivine type compound; a surface of an olivine type compound while decomposing a gas that becomes a carbon precursor by a vapor deposition (CVD) method and a general coating method such as:
  • the amount of carbon when the olivine type compound is coated with the carbon material is 1 mass per 100 parts by mass of the olivine type compound from the viewpoint of improving the conductivity of the positive electrode and enabling a more efficient charge / discharge reaction. Part or more.
  • the amount of carbon on the surface of the olivine type compound is too large, carbon may become a barrier during the lithium ion insertion / desorption reaction, which may cause a reduction in load characteristics of the non-aqueous secondary battery, for example. Therefore, the amount of carbon when the olivine type compound is coated with the carbon material is preferably 5 parts by mass or less with respect to 100 parts by mass of the olivine type compound.
  • the particle diameter in the case where a carbon coating layer is provided on the surface of the olivine-type compound particle may be regarded as the particle diameter of the olivine-type compound particle for the sake of simplicity. Good.
  • the content of the polymer (A) in the positive electrode mixture layer is reduced to, for example, 7% by mass or less, more preferably 5% by mass or less.
  • the BET specific surface area of the positive electrode active material is 25 m. 2 / g or less is preferable, 15 m 2 / g or less is more preferable, 13 m 2 / g or less is particularly preferable, and 10 m 2 / g or less is most preferable.
  • the BET specific surface area of the positive electrode active material is preferably 5 m 2 / g or more, and 8 m 2 / g or more. More preferably.
  • the BET specific surface area is a value obtained by analyzing a gas adsorption amount measured by a gas adsorption method using nitrogen gas using the BET method.
  • positive electrode active material in which an olivine type compound is used as the positive electrode active material, other positive electrode active materials may be used together with the olivine type compound.
  • positive electrode active material include various lithium-containing composite oxides (lithium-containing composite oxides other than olivine type compounds) used in non-aqueous secondary batteries such as lithium ion secondary batteries.
  • the amount of the positive electrode active material other than the olivine type compound in the total amount of the positive electrode active material is preferably 30% by mass or less.
  • the positive electrode active material used in the positive electrode in which the positive electrode mixture layer has a water content of 500 to 3000 ppm includes lithium nickelate and a part of the nickel, other materials such as Co and Al.
  • the content of the positive electrode active material in the positive electrode mixture layer is preferably 85 to 98% by mass.
  • the unit represented by the general formula (1) is a unit derived from an acrylic ester or a methacrylic ester [hereinafter referred to as acrylic acid and methacrylic ester.
  • the acid may be collectively referred to as “(meth) acrylic acid”]
  • the polymer (A) is synthesized by polymerizing the (meth) acrylic acid ester.
  • the (meth) acrylate ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ( Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acryl
  • a monomer other than the (meth) acrylic acid ester may be used together with the (meth) acrylic acid ester.
  • the polymer is a copolymer having in the molecule also units derived from monomers other than (meth) acrylic acid ester.
  • Monomers that are polymerized with the (meth) acrylic acid ester include cyano group-containing monomers; aromatic vinyl compounds (styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrene, divinylbenzene, vinyltoluene, etc.); conjugated dienes Compounds (butadiene, isoprene, chloroprene, 2-chloro-1,3-butadiene, etc.); unsaturated carboxylic acids; and the like.
  • aromatic vinyl compounds styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrene, divinylbenzene, vinyltoluene, etc.
  • conjugated dienes Compounds butadiene, isoprene, chloroprene, 2-chloro-1,3-butadiene, etc.
  • unsaturated carboxylic acids and the like.
  • cyano group-containing monomer examples include unsaturated carboxylic acid nitriles such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide; 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, Cyanoalkyl esters of unsaturated carboxylic acid nitriles such as (meth) acrylic acid 3-cyanopropyl; and the like.
  • unsaturated carboxylic acid nitriles such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide
  • 2-cyanoethyl (meth) acrylate 2-cyanopropyl (meth) acrylate
  • Cyanoalkyl esters of unsaturated carboxylic acid nitriles such as (meth) acrylic acid 3-cyanopropyl; and the like.
  • unsaturated carboxylic acid examples include unsaturated carboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; Can be mentioned.
  • the proportion of (meth) acrylic acid ester in all monomers is preferably 5% by mass or more, and more preferably 8% by mass or more. Preferably, it is 10 mass% or more.
  • the ratio of the cyano group-containing monomer in all monomers is preferably 1 to 50% by mass, and more preferably 2 to 15% by mass. Further, when the above aromatic vinyl compound is used, the ratio of the aromatic vinyl compound in all monomers is preferably 20 to 50% by mass, and more preferably 30 to 45% by mass.
  • the ratio of the conjugated diene compound in all monomers is preferably 10 to 60% by mass, and more preferably 20 to 40% by mass.
  • the proportion of the unsaturated carboxylic acid in all monomers is preferably 1 to 10% by mass, and more preferably 2 to 7% by mass.
  • the polymer (A) is derived from a cyano group-containing monomer, an aromatic vinyl compound, a conjugated diene compound and an unsaturated carboxylic acid together with a (meth) acrylic acid ester. It is preferable to have a structural unit.
  • the positive electrode mixture layer may contain a binder other than the polymer (A) having a unit represented by the general formula (1) in the molecule as a binder.
  • a binder other than the polymer (A) having a unit represented by the general formula (1) in the molecule as a binder.
  • a resin such as PVDF that is easily gelled by an alkali component is used.
  • the binder used in addition to the polymer (A) include polyvinylidene fluoride (PVDF), vinylidene fluoride copolymer (PVDF-HFP, etc.), polyimide, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC). And acrylic resin.
  • the proportion of the binder other than the polymer (A) having the unit represented by the general formula (1) in the molecule in the total binder contained in the positive electrode mixture layer may be 20% by mass or less. It is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably only the polymer (A).
  • the synthesis of the polymer (A), that is, the polymerization of the (meth) acrylic acid ester can be performed by an emulsion polymerization method.
  • the conditions at that time are not particularly limited, and may be the same as those usually employed in the emulsion polymerization of (meth) acrylic acid ester.
  • emulsifiers anionic surfactants, nonionic surfactants, amphoteric surfactants, etc.
  • polymerization initiators persulfates such as ammonium persulfate, hydroperoxides such as cumene hydroperoxide, polymerization initiators and (Meth) acrylic acid ester and other monomers used as needed are added to water to which a redox polymerization initiator combined with a reducing agent, etc.) is added, and 1 at a temperature of about 30 to 90 ° C. Polymerization may be performed for about 30 hours.
  • a copolymer of the (meth) acrylic acid ester and vinylidene fluoride or a mixture of the (meth) acrylic acid ester polymer and the vinylidene fluoride polymer (PVDF) as a binder.
  • PVDF vinylidene fluoride polymer
  • a composite obtained by polymerizing a (meth) acrylic acid ester in the presence of a polymer of vinylidene fluoride can also be used.
  • the (meth) acrylic acid ester is bonded to the vinylidene fluoride polymer molecule, and the polymerization proceeds, so that the copolymer [consists of units represented by the general formula (1).
  • a (meth) acrylic acid ester polymer is formed by the progress of homopolymerization of (meth) acrylic acid ester.
  • it can be a mixture of this and the polymer of vinylidene fluoride, but it is not certain which form it will take.
  • the polymerization of (meth) acrylic acid ester in the presence of the polymer of vinylidene fluoride can also be performed by an emulsion polymerization method.
  • the conditions at that time are not particularly limited, and for example, the synthesis conditions for the polymer (A) described above may be applied.
  • the unit which comprises a fluororesin is contained in a polymer (A) like the copolymer of (meth) acrylic acid ester and vinylidene fluoride
  • the proportion of the polymer (A) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Most preferably not.
  • the content of the polymer (A) in the positive electrode mixture layer is preferably 1% by mass or more, more preferably 1.5% by mass or more, and charging / discharging. In order to improve the characteristics, the content is preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less.
  • the total content of all binders in the positive electrode mixture layer is also preferably 1% by mass or more, more preferably 1.5% by mass or more, and preferably 7% by mass or less. It is more preferably 5% by mass or less, and particularly preferably 4% by mass or less. Therefore, when using another binder with the said polymer (A) for the binder of a positive mix layer, the ratio of binders other than the said polymer (A) in all the binders in a positive mix layer is the said suitable value. It is preferable that the total content of all the binders in the positive electrode mixture layer is adjusted so as to be the above-mentioned preferable value while limiting to be.
  • Conductive aids for the positive electrode mixture layer include natural graphite (such as flake graphite) and artificial graphite (graphite carbon material); acetylene black; ketjen black, channel black, furnace black, lamp black, thermal Carbon materials such as carbon black such as carbon black; carbon fibers (including carbon nanofibers); carbon nanotubes;
  • conductive aids it is preferable to use at least one of carbon nanotubes and carbon nanofibers and at least one of acetylene black and carbon black.
  • the olivine-type compound used as the positive electrode active material is a material having low conductivity.
  • particulate acetylene black or carbon Conductivity is ensured by black.
  • carbon nanotubes or carbon nanofibers having a fibrous form are used. Conductivity is ensured. Therefore, the conductivity in the positive electrode mixture layer can be better ensured by the combination of the conductive aids.
  • the average length of carbon nanotubes and carbon nanofibers is preferably 1 nm to 5 ⁇ m.
  • the average diameter of the carbon nanotube or carbon nanofiber is preferably 1 nm to 2 ⁇ m.
  • the average length and average diameter of the carbon nanotubes and carbon nanofibers used in the present specification are determined by using a transmission electron microscope (TEM such as “JEM series” manufactured by JEOL Ltd., “H-700H” manufactured by Hitachi, Ltd.), etc. Is measured from a photographed TEM image at 100 or 200 kV.
  • TEM images of 100 samples were taken at 20,000 to 40,000 magnification, and when viewing the average diameter at 200,000 to 400,000 magnification.
  • the length and diameter are measured one by one with a metal scale certified as No. 1, and the average is taken as the average length and average diameter.
  • graphite flaky graphite
  • graphite also contributes to ensuring the conductivity between these particles at a location where the distance between the positive electrode active material particles is relatively long, as in the case of carbon nanotubes and carbon nanofibers. Therefore, it is also preferable to use graphite together with at least one of acetylene black and carbon black as a conductive additive for the positive electrode mixture layer.
  • carbon nanotubes, carbon nanofibers and graphite and at least one of acetylene black and carbon black are used as a conductive additive
  • carbon nanotubes, carbon nanofibers and graphite in the positive electrode mixture layer are used.
  • the total amount (when only one of them is used) is preferably 0.1 to 5% by mass.
  • the total of acetylene black and carbon black in the positive electrode mixture layer is preferably 1 to 10% by mass.
  • the content of the conductive additive in the positive electrode mixture layer is preferably 1 to 10% by mass.
  • a positive electrode active material, a binder, and a conductive auxiliary agent are dispersed in a solvent such as water or an organic solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a positive electrode mixture-containing composition (however, , The binder may be dissolved in a solvent), and this may be applied to one or both sides of the current collector (however, if a coat layer is formed on the surface of the current collector as described later, the surface of the coat layer) ) And a method of forming a positive electrode mixture layer through a step of drying, that is, the production method of the present invention.
  • a solvent such as water or an organic solvent such as N-methyl-2-pyrrolidone (NMP)
  • NMP N-methyl-2-pyrrolidone
  • carboxymethyl cellulose CMC
  • PVP polyvinylpyrrolidone
  • a pressing process such as a calendar process may be performed.
  • the positive electrode current collector the same one as used for the positive electrode of a conventionally known non-aqueous secondary battery can be used.
  • an aluminum foil having a thickness of 10 to 30 ⁇ m is preferable.
  • the positive electrode current collector is preferably a metal foil (such as an aluminum foil) having a plurality of through holes.
  • a metal foil such as an aluminum foil
  • the adhesion between the positive electrode mixture layer and the current collector is improved, and even if the battery is repeatedly charged and discharged, the positive electrode mixture layer and the current collector Since peeling becomes difficult to occur, the charge / discharge cycle characteristics of the battery are enhanced, and the conductivity in the positive electrode mixture layer is also improved.
  • the metal foil When a metal foil having a plurality of through holes is used for the positive electrode current collector, the metal foil is partially bonded to the main body of the metal foil without removing the metal in the part forming the through holes. It is more preferable to have a protrusion that is bent and raised from the flat surface of the metal foil. When a metal foil having such protrusions is used as a positive electrode current collector, the protrusion penetrates into the positive electrode mixture layer, and thus the adhesion between the positive electrode mixture layer and the current collector and the positive electrode mixture layer The conductivity of the is further improved.
  • the number of holes is preferably 5 to 30 per 1 cm 2 in a plan view of the current collector. Therefore, in the case of a positive electrode current collector made of a metal foil having a plurality of through-holes and the protrusions, the number of protrusions should be 5 to 30 per 1 cm 2 in plan view of the current collector. preferable.
  • the height of the protrusion is preferably 1 ⁇ 2 or less of the thickness of the positive electrode mixture layer formed on the side where the protrusion is provided.
  • the through holes and the protrusions may be regularly arranged or irregularly arranged, but are more preferably regularly arranged.
  • the positive electrode current collector is also preferably a metal foil (such as an aluminum foil) having a coating layer containing a carbon material on the surface. Also in this case, the adhesion between the positive electrode mixture layer and the positive electrode current collector is improved, and peeling of the positive electrode mixture layer and the current collector hardly occurs even when the battery is repeatedly charged and discharged. The charge / discharge cycle characteristics are enhanced, and the conductivity in the positive electrode mixture layer is also improved.
  • Examples of the carbon material contained in the coating layer include graphite (graphite carbon material) such as natural graphite (scaly graphite), artificial graphite; acetylene black; ketjen black, channel black, furnace black, lamp black, thermal black. Carbon black such as activated carbon; activated carbon; etc., and only one of these may be used, or two or more may be used in combination. Among these, activated carbon is more preferable because it can contribute to the capacity increase of the positive electrode.
  • the coat layer may contain a binder together with the carbon material.
  • a binder include various binders including a fluororesin such as PVDF and the polymer (A) exemplified above as a binder for a positive electrode mixture layer.
  • the carbon material content is preferably 40 to 95% by mass, and the binder content is preferably 5 to 60% by mass.
  • the thickness of the coat layer is preferably 0.1 to 5 ⁇ m.
  • the coating layer is a method in which a coating material containing a coating material prepared by dispersing and dissolving a carbon material and a binder in an organic solvent such as NMP or water is applied to the surface of a metal foil serving as a positive electrode current collector and dried. Etc. can be formed.
  • the thickness of the positive electrode mixture layer (when the positive electrode mixture layer is provided on both sides of the current collector, the thickness per side) is preferably 3 to 100 ⁇ m.
  • a lead body for electrical connection with other members in the battery may be formed on the positive electrode according to a conventional method.
  • the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution containing a lithium salt and an organic solvent, and the positive electrode may be the positive electrode of the above embodiment.
  • the positive electrode may be the positive electrode of the above embodiment.
  • a negative electrode mixture layer containing a negative electrode active material and a binder can be used on one or both sides of the current collector.
  • the negative electrode active material a conventionally known negative electrode active material used for the negative electrode of a non-aqueous secondary battery, that is, an active material capable of occluding and releasing lithium ions can be used.
  • a negative electrode active material include, for example, graphite (natural graphite; artificial graphite obtained by graphitizing graphitized carbon such as pyrolytic carbons, mesophase carbon microbeads, and carbon fibers at 2800 ° C.
  • the negative electrode only one type of the above illustrated negative electrode active materials may be used, or two or more types may be used in combination.
  • negative electrode active materials it is preferable to use at least one of graphitizable carbon (soft carbon) and non-graphitizable carbon (hard carbon).
  • Examples of the soft carbon include coke obtained by firing a pitch.
  • examples of the hard carbon include amorphous carbon obtained by low-temperature firing of furfuryl alcohol resin (PFA), polyparaphenylene (PPP), and phenol resin.
  • PFA furfuryl alcohol resin
  • PPP polyparaphenylene
  • phenol resin amorphous carbon obtained by low-temperature firing of furfuryl alcohol resin
  • Such a carbon material has a d 002 obtained by, for example, X-ray diffraction measurement of more than 0.340 nm (preferably 0.370 nm or more), preferably 0.400 nm or less.
  • graphite which is widely used as negative electrode active materials for batteries, the lithium ion accepting speed is faster, so by making these batteries with negative electrodes using negative electrode active materials, they are charged with a large current and per hour.
  • the amount of negative electrode active material other than soft carbon and hard carbon in the total amount of the negative electrode active material Is preferably 30% by weight or less. That is, the amount of soft carbon and hard carbon in the total amount of the negative electrode active material (when only one of them is used, it is the amount thereof, and when both are used together, it is the total amount thereof. The same applies hereinafter). Is preferably 70% by mass or more, and since only one of soft carbon and hard carbon may be used for the negative electrode active material, soft carbon and hard carbon in the total amount of the negative electrode active material The preferred upper limit of the amount is 100% by mass.
  • the negative electrode mixture layer contains a binder.
  • binder related to the negative electrode mixture layer include fluororesins such as PVDF, SBR, CMC, and acrylic resins.
  • acrylic resin examples include a copolymer of butyl acrylate and acrylic acid (a copolymer having a unit derived from butyl acrylate and a unit derived from acrylic acid in the molecule), and such a resin.
  • a copolymer of butyl acrylate and acrylic acid a copolymer having a unit derived from butyl acrylate and a unit derived from acrylic acid in the molecule
  • the binder of the negative electrode mixture layer By using such a binder, the heat resistance of the negative electrode can be improved, so that the storage characteristics of the battery in a high temperature environment can be further improved.
  • the negative electrode mixture layer may contain a conductive additive.
  • a conductive support agent which concerns on a positive mix layer can be used for the conductive support agent which concerns on a negative mix layer.
  • the negative electrode is prepared by, for example, preparing a negative electrode mixture-containing composition by dispersing a negative electrode active material, a binder, and a conductive auxiliary agent used as necessary in a solvent such as water or an organic solvent such as NMP.
  • the binder may be dissolved in a solvent), which can be produced by a method in which the binder is applied to one or both sides of the current collector and dried to form a negative electrode mixture layer. Further, after the formation of the negative electrode mixture layer, for example, in order to adjust the density of the negative electrode mixture layer, press treatment such as calendaring may be performed.
  • the current collector for the negative electrode copper or nickel foil, punching metal, mesh, expanded metal, or the like can be used, but copper foil is usually used.
  • the upper limit of the thickness is preferably 30 ⁇ m, and the lower limit of the thickness is 5 ⁇ m to ensure mechanical strength. Is desirable.
  • the content of the negative electrode active material (the total amount when a plurality of types of negative electrode active materials are used) is preferably 90 to 98% by mass, and the binder content is 2 to 2%. It is preferable that it is 10 mass%.
  • the content of the conductive aid in the active material layer is preferably 2 to 10% by mass.
  • the thickness of the negative electrode mixture layer (when the negative electrode mixture layer is provided on both sides of the current collector, the thickness per side) is preferably 20 to 100 ⁇ m.
  • the density of the negative electrode mixture layer is preferably 1.5 g / cm 3 or less from the viewpoint of further increasing the lithium ion receiving speed in the negative electrode, and the battery is provided with a certain amount of the negative electrode active material to secure the battery. From the viewpoint of increasing the capacity, it is preferably 0.9 g / cm 3 or more.
  • the density of the negative electrode mixture layer in the present specification is a value measured by the following method.
  • the negative electrode is cut into a predetermined area, the mass is measured using an electronic balance having a minimum scale of 0.1 mg, and the mass of the negative electrode mixture layer is calculated by subtracting the mass of the current collector.
  • the total thickness of the negative electrode was measured at 10 points with a micrometer having a minimum scale of 1 ⁇ m, and the volume of the negative electrode mixture layer was calculated from the average value obtained by subtracting the thickness of the current collector from these measured values and the area. To do. Then, the density of the negative electrode mixture layer is calculated by dividing the mass of the negative electrode mixture layer by the volume.
  • a lead body for electrical connection with other members in the battery may be formed according to a conventional method.
  • the negative electrode and the positive electrode include, for example, a laminated body (laminated electrode body) stacked with a separator interposed therebetween, or a wound body obtained by further winding this laminated body in a spiral shape ( Used in the form of a wound electrode body).
  • the separator preferably has a property (that is, a shutdown function) that closes the pores at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower).
  • a property that is, a shutdown function
  • Separator used in non-aqueous secondary batteries for example, a microporous membrane made of polyolefin such as polyethylene (PE) or polypropylene (PP) can be used.
  • the microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be.
  • non-aqueous electrolyte solution related to the non-aqueous secondary battery a solution containing a lithium salt and an organic solvent and dissolving the lithium salt in the organic solvent is used.
  • numerator is used.
  • the content of the phosphoric acid compound having in the molecule thereof the group represented by the general formula (2) in the non-aqueous electrolyte is 0.5 mass from the viewpoint of ensuring the above-mentioned effects better. % Or more, and more preferably 1% by mass or more.
  • the content of the phosphoric acid compound having a group represented by the general formula (2) in the molecule is preferably 7% by mass or less, more preferably 5% by mass or less, and 3% by mass or less. More preferably.
  • lithium salt examples include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (FSO 2 ) 2 [LiFSI], LiN (CF 3 SO 2 ) 2 [LiTFSI], LiN (C 2 F 5 SO 2 ) 2 , or an organic lithium salt such as lithium bisoxalate borate (LiBOB);
  • inorganic lithium salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2
  • a fluorine-containing inorganic lithium salt such as LiPF 6 alone or another inorganic lithium salt such as LiClO 4 or lithium bisoxalate is used as the lithium salt.
  • a positive electrode with an organic lithium salt such as borate (LiBOB) and a positive electrode mixture layer containing a large amount of moisture, hydrogen fluoride is generated by reaction with the moisture of the positive electrode, and the phosphorus The formation of the SEI film derived from the acid compound can be efficiently advanced.
  • organic solvent examples include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; chain esters such as methyl propionate; ⁇ -butyrolactone, ⁇ Cyclic esters such as lactones having a substituent at the position; chain ethers such as dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme; cyclic ethers such as dioxane, tetrahydrofuran and 2-methyltetrahydrofuran; Nitriles such as acetonitrile, propionitrile, methoxypropionitrile; sulfites such as ethylene glycol sulfite; These can be used as a mixture of two or more. In order to obtain a battery having better characteristics, it is
  • lactones having a substituent at the ⁇ -position are also preferable to use as the organic solvent. Since the lactone having a substituent at the ⁇ -position has a high boiling point of 150 ° C. or higher, it is difficult to volatilize even when the battery is placed in a high temperature environment, and the composition of the non-aqueous electrolyte changes and the outer body swells. Therefore, a battery having higher heat resistance and excellent storage characteristics at high temperatures can be configured.
  • high-boiling solvents having a boiling point of 150 ° C. or higher are known, but generally high-boiling solvents have low permeability to polyolefin separators, In order to increase the permeability of the non-aqueous electrolyte to the separator, it is necessary to use another solvent (generally having a low boiling point).
  • lactones having a substituent at the ⁇ -position have good permeability to polyolefin separators, by using a non-aqueous electrolyte using this, for example, without impairing the load characteristics of the battery, Heat resistance can be improved.
  • the lactone having a substituent at the ⁇ -position is preferably, for example, a 5-membered ring (having 4 carbon atoms constituting the ring).
  • the ⁇ -position substituent of the lactone may be one or two.
  • the substituent examples include a hydrocarbon group and a halogen group (fluoro group, chloro group, bromo group, iodo group) and the like.
  • a hydrocarbon group an alkyl group, an aryl group, etc. are preferable, and it is preferable that the carbon number is 1 or more and 15 or less (more preferably 6 or less).
  • the substituent is a hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like are more preferable.
  • lactones having a substituent at the ⁇ -position include ⁇ -methyl- ⁇ -butyrolactone, ⁇ -ethyl- ⁇ -butyrolactone, ⁇ -propyl- ⁇ -butyrolactone, ⁇ -butyl- ⁇ -butyrolactone, ⁇ -phenyl - ⁇ -butyrolactone, ⁇ -fluoro- ⁇ -butyrolactone, ⁇ -chloro- ⁇ -butyrolactone, ⁇ -bromo- ⁇ -butyrolactone, ⁇ -iodo- ⁇ -butyrolactone, ⁇ , ⁇ -dimethyl- ⁇ -butyrolactone, ⁇ , ⁇ -Diethyl- ⁇ -butyrolactone, ⁇ , ⁇ -diphenyl- ⁇ -butyrolactone, ⁇ -ethyl- ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -phenyl- ⁇ -butyrolactone, ⁇ , ⁇ ,
  • lactones having a substituent at the ⁇ -position are used in the organic solvent, only lactones having a substituent at the ⁇ -position may be used, but when other organic solvents are used together, 150 ° C or higher It is preferable to use a high-boiling solvent having a boiling point (ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane, trimethyl phosphate, triethyl phosphate, etc.).
  • a high-boiling solvent having a boiling point ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane, trimethyl phosphate, triethyl phosphate, etc.
  • the ratio in the total organic solvent in the nonaqueous electrolytic solution is preferably 30 to 100% by volume.
  • the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.6 to 1.8 mol / L, and more preferably 0.9 to 1.6 mol / L.
  • vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, biphenyl, fluorobenzene are added to the non-aqueous electrolyte.
  • Additives such as t-butylbenzene and halogen-substituted cyclic carbonates (4-fluoro-1,3-dioxolan-2-one etc.) can also be added as appropriate.
  • a gel (gel electrolyte) obtained by adding a gelling agent such as a known polymer to the non-aqueous electrolyte may be used.
  • non-aqueous secondary battery examples include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can, an aluminum can, or the like as an outer can, or a coin shape. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
  • Example 1 Synthesis of binder for positive electrode mixture layer> A latex in which PVDF is dispersed in water (the amount of PVDF is 40% by mass) is placed in a reaction vessel (the amount of PVDF is 20 parts by mass), and water: 150 parts by mass is added thereto, and the reaction vessel is filled with nitrogen. Replaced.
  • emulsifier ether sulfate type emulsifier: dispersion having a solid content of 25% by mass
  • 2 parts by mass as solid content
  • methyl methacrylate 20 parts by mass
  • 2-ethylhexyl acrylate 10 parts by mass
  • butyl acrylate 25 parts by mass
  • acrylonitrile 20 parts by mass
  • acrylic acid 5 parts by mass
  • the temperature inside the reaction vessel was started, and when the internal temperature reached 50 ° C., 0.5 parts by mass of ammonium persulfate and 0.1 part by mass of sodium sulfite were added to the reaction vessel. Subsequently, when the temperature in the reaction vessel reaches 60 ° C., dropping of the emulsion into the reaction vessel is started, and the total amount of the emulsion is reduced to 2 while maintaining the temperature in the reaction vessel at 60 ° C. Added over time. Then, the binder for the positive electrode mixture layer containing the polymer (A) having the unit represented by the general formula (1) in the molecule by polymerizing for 2 hours while maintaining the inside of the reaction vessel at 60 ° C. (B1) was synthesized.
  • olivine-type lithium iron phosphate LiFePO 4 , average particle diameter 13 ⁇ m, BET specific surface area: 9 m 2 / g
  • a carbon material 89 parts by mass
  • acetylene black as a conductive auxiliary agent: 3.5 parts by mass and 1.5 parts by mass of graphite
  • binder B1 3.3 parts by mass
  • polyvinylpyrrolidone disersing agent
  • CMC thickening agent
  • the olivine-type lithium iron phosphate whose surface is coated with a carbon material is obtained by mixing iron phosphate, lithium phosphate and sucrose, and firing at 800 ° C. in nitrogen gas.
  • the amount of carbon covering the surface was 2.3 parts by mass with respect to 100 parts by mass of lithium iron phosphate.
  • This positive electrode mixture-containing composition was applied to one side of an aluminum foil (current collector) having a thickness of 15 ⁇ m and dried to obtain a positive electrode having a positive electrode mixture layer having a thickness of 5 ⁇ m on one side of the current collector. .
  • the negative electrode active material-containing composition was prepared by mixing 96 parts by mass of soft carbon as the negative electrode active material, 2 parts by mass of SBR, 2 parts by mass of CMC, and water. This negative electrode mixture-containing composition was applied to one side of a 10 ⁇ m thick copper foil (current collector) and dried to obtain a negative electrode having a negative electrode mixture layer having a thickness of 6 ⁇ m on one side of the current collector. .
  • the density of the negative electrode mixture layer was 1.0 g / cm 3 .
  • a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 2.
  • ⁇ Battery assembly> The positive electrode and the negative electrode are overlapped via a separator (a separator made of microporous polyethylene film, thickness 16 ⁇ m, opening ratio 50%) to form a laminated electrode body, which is inserted into an aluminum laminate film exterior body, and this exterior After injecting the non-aqueous electrolyte into the body, the outer package was sealed to produce a laminated non-aqueous secondary battery having the cross-sectional structure shown in FIG. 2 with the appearance shown in FIG.
  • a separator a separator made of microporous polyethylene film, thickness 16 ⁇ m, opening ratio 50%
  • FIG. 1 is a plan view schematically showing a non-aqueous secondary battery
  • FIG. 2 is a cross-sectional view taken along the line II of FIG.
  • the nonaqueous secondary battery 1 includes a laminated electrode body formed by laminating a positive electrode 5 and a negative electrode 6 via a separator 7 in a laminated film outer package 2 constituted by two laminated films, and a nonaqueous electrolytic solution. (Not shown) is accommodated, and the laminate film outer package 2 is sealed by heat-sealing the upper and lower laminate films at the outer peripheral portion thereof.
  • each layer constituting the laminate film outer package 2 and each layer of the positive electrode 5 and the negative electrode 6 are not shown separately in order to prevent the drawing from becoming complicated.
  • the positive electrode 5 is connected to the positive electrode external terminal 3 in the battery 1 through a lead body.
  • the negative electrode 6 is also connected to the negative electrode external terminal 4 in the battery 1 through a lead body. is doing.
  • the positive electrode external terminal 3 and the negative electrode external terminal 4 are drawn out to the outside of the laminate film exterior body 2 so that they can be connected to an external device or the like.
  • Example 2 A positive electrode was produced in the same manner as in Example 1, except that the binder of the positive electrode was changed to 3.0 parts by mass the same as that produced in Example 1 and 0.3 parts by mass of PVDF manufactured by Kureha Corporation. A laminated nonaqueous secondary battery was produced in the same manner as in Example 1 except that this positive electrode was used.
  • Example 3 A positive electrode current collector was prepared in the same manner as in Example 1 except that the positive electrode current collector was changed to an aluminum foil having a plurality of through-holes. A water secondary battery was produced.
  • the aluminum foil used for the positive electrode current collector had 10 holes per 1 cm 2 area in plan view of the foil and a hole diameter of 80 ⁇ m.
  • Example 4 A positive electrode was produced in the same manner as in Example 1 except that a coating layer having a thickness of 3 ⁇ m per side was formed on both sides of an aluminum foil as a positive electrode current collector before forming a positive electrode mixture layer.
  • a laminated nonaqueous secondary battery was produced in the same manner as in Example 1 except that the positive electrode was used.
  • the said coating layer on a positive electrode electrical power collector is a coating liquid which mixed the water dispersion containing acetylene black: 59 mass parts, acrylic resin: 40 mass parts as a binder, and PVP: 1 mass part as a dispersing agent. Formed using.
  • Example 5 Implementation was conducted except that the conductive assistant for the positive electrode was changed to acetylene black: 2.5 parts by mass, graphite: 1.5 parts by mass, and carbon nanotubes (average length 2 ⁇ m, average diameter 10 nm): 1 part by mass.
  • a positive electrode was produced in the same manner as in Example 1, and a laminated nonaqueous secondary battery was produced in the same manner as in Example 1 except that this positive electrode was used.
  • Example 6 The non-aqueous electrolyte was changed to one prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a solvent in which ethylene carbonate, diethyl carbonate and ⁇ -methyl- ⁇ -butyrolactone were mixed at a volume ratio of 30:20:50.
  • a laminated nonaqueous secondary battery was produced in the same manner as in Example 1 except that.
  • Example 7 A negative electrode was produced in the same manner as in Example 1 except that the negative electrode active material was changed to natural graphite, and a laminated nonaqueous secondary battery was produced in the same manner as in Example 1 except that this negative electrode was used.
  • Comparative Example 1 A laminate type nonaqueous secondary battery was produced in the same manner as in Example 1 except that the binder of the positive electrode mixture layer was changed to PVDF at the time of producing the positive electrode.
  • rated capacity (1C) was measured on condition of the following. First, constant current charging is performed at a constant current of 0.1 mA / cm 2 until it reaches 3.85 V, and then constant voltage charging is performed at a constant voltage of 3.85 V until the current value decreases to 0.01 mA / cm 2. went.
  • Each battery after charging was discharged at a constant current of 0.1 mA / cm 2 until the battery voltage became 1.5 V, and the discharge capacity (mAh) at that time was defined as the rated capacity (1 C) of each battery.
  • the voltage drop at each current value: ⁇ V and the current value at that time: I were plotted on the vertical and horizontal axes, respectively, to determine the resistance value (DCR) of each battery during discharge.
  • each battery was discharged until the charging depth reached 0% under the same conditions as in the rated capacity measurement, and predetermined current values [2C (20 mA), 5C (50 mA), 20C (200 mA), and 40 C (400 mA) were obtained. )] was measured for a voltage increase when charged for 10 seconds.
  • the voltage rise at each current value: ⁇ V and the current value at that time: I were plotted on the vertical and horizontal axes, respectively, to determine the resistance value (DCR) for charging each battery.
  • a negative electrode containing soft carbon as a negative electrode active material and having a negative electrode mixture layer having an appropriate density, lithium iron phosphate as a positive electrode active material, and a specific binder The non-aqueous secondary batteries of Examples 1 to 6 having a positive electrode that has a low DCR in both charging and discharging and a large current compared to the battery of Comparative Example 1 using PVDF as the positive electrode binder. Even in the case of discharge, good output characteristics were exhibited.
  • the battery of Example 7 using natural graphite as the negative electrode active material showed better charge / discharge characteristics than Comparative Example 1, but when charged at a current value of 40 C, lithium ions to the negative electrode Insertion could not catch up, and lithium dendrite was deposited on the negative electrode surface, which penetrated the separator to the positive electrode, causing a short circuit. Therefore, it was found that soft carbon and hard carbon are more suitable than graphite as the negative electrode active material of the non-aqueous secondary battery of the present invention.
  • Example 8 Preparation of positive electrode> The same positive electrode mixture-containing composition as that prepared in Example 1 was applied to both sides of an aluminum foil (current collector) having a thickness of 15 ⁇ m, and vacuum-dried at 120 ° C. for 12 hours to obtain both sides of the aluminum foil. A positive electrode mixture layer was formed on the substrate, pressed, and cut into a predetermined size to obtain a strip-like positive electrode.
  • the thickness of the positive electrode mixture layer of the obtained positive electrode was 41 ⁇ m.
  • FIG. 3 is a plan view schematically showing the battery positive electrode (however, in order to facilitate understanding of the structure of the positive electrode, the size of the positive electrode shown in FIG. 3 does not necessarily match the actual one).
  • the positive electrode 10 has a tab portion 13 punched out so that a part of the exposed portion of the positive electrode current collector 12 protrudes, and the shape of the forming portion of the positive electrode mixture layer 11 is a substantially rectangular shape with four corners curved.
  • the lengths a, b and c were 61 mm, 137 mm and 10 mm, respectively.
  • the negative electrode active material 96 parts by mass of soft carbon, acrylic resin: 2 parts by mass, CMC: 2 parts by mass, and water were mixed to prepare a negative electrode mixture-containing paste.
  • the negative electrode mixture-containing paste is applied to both sides of a copper foil having a thickness of 10 ⁇ m and dried to form a negative electrode mixture layer on both sides of the copper foil, and press treatment is performed to set the density of the negative electrode mixture layer to 1. After adjusting to 0 g / cm 3 , it was cut into a predetermined size to obtain a strip-shaped negative electrode.
  • the thickness of the negative electrode mixture layer of the obtained negative electrode was 61.5 ⁇ m.
  • FIG. 4 is a plan view schematically showing the battery negative electrode (however, in order to facilitate understanding of the structure of the negative electrode, the size of the negative electrode shown in FIG. 4 does not necessarily match the actual one).
  • the negative electrode 20 has a shape having a tab portion 23 punched out so that a part of the exposed portion of the negative electrode current collector 22 protrudes, and the shape of the forming portion of the negative electrode mixture layer 21 is a substantially rectangular shape with four corners curved.
  • the lengths d, e, and f were 64 mm, 142.5 mm, and 10 mm, respectively.
  • LiPF 6 is dissolved at a concentration of 1.2 mol / L in a solvent in which propylene carbonate (PC) and ⁇ -methyl- ⁇ -butyrolactone (MBL) are mixed at a volume ratio of 3: 7, and vinylene carbonate (VC) is further added to 2
  • PC propylene carbonate
  • MBL ⁇ -methyl- ⁇ -butyrolactone
  • VC vinylene carbonate
  • a laminated electrode body was formed using 18 positive electrodes for a battery in which a positive electrode mixture layer was formed on both sides of the positive electrode current collector and 19 negative electrodes for a battery in which a negative electrode mixture layer was formed on both sides of the negative electrode current collector.
  • the upper and lower ends are the negative electrodes for the battery, and the positive electrode for the battery and the negative electrode for the battery are interposed between them.
  • the tab portions between the positive electrodes and the tab portions between the negative electrodes were welded to each other with a ratio of 50%).
  • the laminated electrode body is inserted into the depression of an aluminum laminate film having a thickness of 5.7 mm, a width of 78 mm, and a height of 161 mm in which the depression is formed so that the laminated electrode body is accommodated, and the above-mentioned laminated electrode body is inserted thereon
  • the aluminum laminate film of the same size as the above was placed, and three sides of both aluminum laminate films were heat-welded.
  • the said non-aqueous electrolyte was inject
  • FIG. 5 is a plan view schematically showing a non-aqueous secondary battery
  • FIG. 5 is a cross-sectional view taken along the line II-II in FIG.
  • the nonaqueous secondary battery 100 includes a laminated electrode body 102 constituted by laminating a positive electrode and a negative electrode with a separator in an aluminum laminated film outer package 101 constituted by two aluminum laminated films, and a nonaqueous electrolytic solution. (Not shown) is housed, and the aluminum laminate film outer package 101 is sealed by heat-sealing the upper and lower aluminum laminate films at the outer peripheral portion thereof.
  • FIG. 6 in order to avoid complication of the drawing, each layer constituting the aluminum laminate film outer package 101 and the positive electrode, the negative electrode and the separator constituting the laminated electrode body 102 are shown separately. Absent.
  • Each positive electrode of the laminated electrode body 102 is integrated by welding the tab portions together, and the integrated product of the welded tab portions is connected to the positive electrode external terminal 103 in the battery 100, although not shown.
  • the negative electrodes of the laminated electrode body 102 are also integrated by welding the tab portions together, and the integrated product of the welded tab portions is connected to the negative electrode external terminal 104 in the battery 100.
  • the positive electrode external terminal 103 and the negative electrode external terminal 104 are drawn out to the outside of the aluminum laminate film exterior body 101 so that they can be connected to an external device or the like.
  • Example 9 A non-aqueous secondary battery was prepared in the same manner as in Example 8 except that the solvent of the non-aqueous electrolyte was changed to a mixture of PC, MBL, and ethyl methyl carbonate (EMC) at a volume ratio of 3: 5: 2. Produced.
  • Example 10 A non-aqueous secondary battery was produced in the same manner as in Example 8 except that LiBF 4 was used in an amount of 1.0 mol / L instead of LiPF 6 as the lithium salt of the non-aqueous electrolyte.
  • Example 11 A non-aqueous secondary battery was produced in the same manner as in Example 9 except that LiBF 4 was used in an amount of 1.0 mol / L instead of LiPF 6 as the lithium salt of the non-aqueous electrolyte.
  • Example 12 A nonaqueous secondary battery was produced in the same manner as in Example 8 except that the solvent of the nonaqueous electrolyte was changed to a mixture of ethylene carbonate (EC) and MBL at a volume ratio of 3: 7.
  • EC ethylene carbonate
  • Example 13 A non-aqueous secondary battery was produced in the same manner as in Example 8, except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the non-aqueous electrolyte.
  • Example 14 A non-aqueous secondary battery was produced in the same manner as in Example 9 except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the non-aqueous electrolyte.
  • Example 15 A non-aqueous secondary battery was produced in the same manner as in Example 13 except that LiBF 4 was used in an amount of 1.0 mol / L instead of LiPF 6 as the lithium salt of the non-aqueous electrolyte.
  • Example 16 A non-aqueous secondary battery was produced in the same manner as in Example 14 except that LiBF 4 was used in an amount of 1.0 mol / L instead of LiPF 6 as the lithium salt of the non-aqueous electrolyte.
  • Example 17 A nonaqueous secondary battery was prepared in the same manner as in Example 9 except that a coating layer having a thickness of 1 ⁇ m per side was formed on both sides of an aluminum foil as a positive electrode current collector before forming the positive electrode mixture layer.
  • the said coating layer on a positive electrode electrical power collector is a coating liquid which mixed the water dispersion containing acetylene black: 59 mass parts, acrylic resin: 40 mass parts as a binder, and PVP: 1 mass part as a dispersing agent. Formed using.
  • Example 18 A nonaqueous secondary battery was produced in the same manner as in Example 17 except that the thickness of the coat layer on the surface of the positive electrode current collector was changed to 10 ⁇ m.
  • Example 19 The solvent of the non-aqueous electrolyte was changed to a mixture of EC and diethyl carbonate (DEC) at a volume ratio of 3: 7, and VC was added to the non-aqueous electrolyte in an amount of 2.5% by mass. Produced a non-aqueous secondary battery in the same manner as in Example 8.
  • DEC diethyl carbonate
  • Comparative Example 2 A nonaqueous secondary battery was produced in the same manner as in Example 8 except that the binder of the positive electrode mixture layer was changed to PVDF at the time of producing the positive electrode.
  • each battery is sequentially subjected to constant current-constant voltage charging under the above conditions and constant current discharge for 10 seconds at each current value of 10C, 20C, 30C, 40C, and 50C to obtain ⁇ V at each current value.
  • the maximum discharge pulse current exceeded 50 C, the current value was calculated by extending the straight line of the plot.
  • each battery subjected to constant current-constant voltage charging under the same conditions as the initial capacity measurement was stored in a constant temperature bath at 100 ° C. for 48 hours. Then, each battery was taken out from the thermostat, and after returning to room temperature, thickness was measured and the increase rate (%) of the thickness after high temperature storage was calculated
  • Table 2 shows the configurations of the nonaqueous electrolyte solutions according to the nonaqueous secondary batteries of Examples 8 to 19 and Comparative Example 2, and Table 3 shows the evaluation results.
  • the nonaqueous secondary batteries of Examples 8 to 19 using an olivine type compound as a positive electrode active material and using a positive electrode containing a specific binder were comparative examples using PVDF as the positive electrode binder.
  • the maximum discharge pulse current value was large and the output characteristics were excellent.
  • non-aqueous secondary batteries of Examples 8 to 18 using specific lactones as the non-aqueous electrolyte solvent have a general solvent configuration (combination of chain carbonate and cyclic carbonate) in the non-aqueous secondary battery.
  • the capacity recovery rate after high-temperature storage was higher than that of the non-aqueous secondary battery of Example 19 and the rate of increase in thickness was small, and the battery was excellent in high-temperature storage characteristics.
  • Example 20 As in Example 8, except that a nonwoven fabric (average pore diameter: 0.8 ⁇ m, thickness: 25 ⁇ m, porosity: 55%) composed of polyethylene nanofibers (average fiber diameter 500 nm) was used as the separator. Three types of non-aqueous secondary batteries were prepared.
  • Example 21 A nonaqueous secondary battery was produced in the same manner as in Example 20, except that the positive electrode current collector was changed to the aluminum foil having a plurality of through holes used in Example 3.
  • Example 22 Non-aqueous secondary as in Example 20, except that a coating layer having a thickness of 0.3 ⁇ m per side was formed on both sides of the aluminum foil as the positive electrode current collector before forming the positive electrode mixture layer. A battery was produced.
  • the said coating layer on a positive electrode electrical power collector is a coating liquid which mixed the water dispersion containing acetylene black: 59 mass parts, acrylic resin binder: 40 mass parts, and polyvinylpyrrolidone: 1 mass part as a dispersing agent. Formed using.
  • Example 23 The non-aqueous electrolyte was changed to one prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a solvent in which ethylene carbonate, diethyl carbonate and ⁇ -methyl- ⁇ -butyrolactone were mixed at a volume ratio of 30:20:50.
  • a nonaqueous secondary battery was fabricated in the same manner as in Example 20 except that.
  • Example 24 In the same manner as in Example 20, three types of non-aqueous secondary batteries having different average pore diameters of the nonwoven fabric were produced.
  • the average pore diameter of the used nonwoven fabric is three types of 0.008 ⁇ m, 0.8 ⁇ m and 2 ⁇ m.
  • the voltage drop at each current value: ⁇ V and the current value at that time: I were plotted on the vertical and horizontal axes, respectively, to determine the resistance value (DCR) of each battery during discharge.
  • the voltage rise at each current value: ⁇ V and the current value at that time: I were plotted on the vertical and horizontal axes, respectively, to determine the resistance value (DCR) for charging each battery.
  • the ratio between the maintenance capacity (mAh) and the rated capacity was defined as a capacity maintenance ratio, and the ratio between the recovery capacity (mAh) and the rated capacity was determined as a capacity recovery ratio, and the high-temperature storage characteristics of each battery were evaluated.
  • the non-aqueous secondary batteries of Examples 20 to 23 using nonwoven fabrics having appropriate average pore diameters as separators are the batteries of Example 8 using general-purpose polyethylene microporous films.
  • the battery resistance can be lowered, and a battery having excellent output characteristics that can cope with both discharging with a large current and charging with a large current can be constructed.
  • a short circuit due to lithium dendrite precipitation during charging did not occur, and excellent results in high temperature storage characteristics and charge / discharge cycle characteristics were obtained.
  • the nonwoven fabric when a nonwoven fabric is used as the separator of the nonaqueous secondary battery of the present invention, if the average pore diameter is too large, lithium dendrite precipitation is caused. Since the output characteristics are liable to deteriorate if the average pore diameter is too small, the nonwoven fabric preferably has an average pore diameter of 0.1 to 1 ⁇ m.
  • Example 25 ⁇ Binder composition> Butadiene: 6 parts by mass, styrene, 11.5 parts by mass, methyl methacrylate: 3.5 parts by mass, acrylic acid: 0.5 parts by mass and itaconic acid: 2.5 parts by mass, sodium dodecylbenzenesulfonate: 0 Together with 1 part by weight, potassium persulfate: 1 part by weight, sodium bisulfite: 0.5 part by weight, ⁇ -methylstyrene dimer: 0.2 part by weight, dodecyl mercaptan: 0.1 part by weight and water: 200 parts by weight The mixture was put into an autoclave and reacted at 70 ° C. for 2 hours.
  • butadiene 31.5 parts by mass, styrene, 31.5 parts by mass, methyl methacrylate: 8 parts by mass, acrylonitrile: 4 parts by mass, acrylic acid: 0.5 parts by mass and itaconic acid: 0.5 parts by mass
  • styrene 31.5 parts by mass
  • methyl methacrylate 8 parts by mass
  • acrylonitrile 4 parts by mass
  • acrylic acid 0.5 parts by mass
  • itaconic acid 0.5 parts by mass
  • the pH of the composition after completion of the reaction is adjusted to 7.5, and the remaining monomer component is treated by steam distillation, whereby a polymer having a unit represented by the general formula (1) in the molecule (A ) Containing the binder B2 for the positive electrode mixture layer was synthesized.
  • a belt-like positive electrode was produced in the same manner as in Example 8 except that the binder B2 was used for the preparation of the positive electrode mixture-containing composition and the binder of the positive electrode mixture layer was changed to B2.
  • a nonaqueous secondary battery was produced in the same manner as in Example 8 except that the positive electrode was used.
  • Example 26 A nonaqueous secondary battery was produced in the same manner as in Example 25 except that the positive electrode current collector was changed to the aluminum foil having a plurality of through holes used in Example 3.
  • Example 27 Nonaqueous secondary as in Example 25, except that a coating layer having a thickness of 0.3 ⁇ m per side was formed on both sides of the aluminum foil as the positive electrode current collector before forming the positive electrode mixture layer. A battery was produced.
  • the said coating layer on a positive electrode electrical power collector is a coating liquid which mixed the water dispersion containing acetylene black: 59 mass parts, acrylic resin binder: 40 mass parts, and polyvinylpyrrolidone: 1 mass part as a dispersing agent. Formed using.
  • Example 28 Implementation was conducted except that the conductive assistant for the positive electrode was changed to acetylene black: 2.5 parts by mass, graphite: 1.5 parts by mass, and carbon nanotubes (average length 2 ⁇ m, average diameter 10 nm): 1 part by mass.
  • a nonaqueous secondary battery was produced in the same manner as in Example 25.
  • Example 29 The non-aqueous electrolyte was changed to one prepared by dissolving LiPF 6 at a concentration of 1 mol / L in a solvent in which ethylene carbonate, diethyl carbonate and ⁇ -methyl- ⁇ -butyrolactone were mixed at a volume ratio of 30:20:50.
  • a nonaqueous secondary battery was fabricated in the same manner as in Example 25 except that.
  • the positive electrode mixture-containing composition according to Example 1 using the binder synthesized in the coexistence of PVDF and the positive electrode mixture-containing composition according to Comparative Example 1 using PVDF as the binder were 12 hours after preparation. Later, it thickened and lost its fluidity.
  • the formation of the positive electrode mixture layer of the positive electrode according to the nonaqueous secondary battery of the present invention does not contain a fluorine-containing ethylenic unit such as vinylidene fluoride or the proportion thereof from the viewpoint of productivity. It is desirable to use a binder with a small amount.
  • the voltage drop at each current value: ⁇ V and the current value at that time: I were plotted on the vertical and horizontal axes, respectively, to determine the resistance value (DCR) of each battery during discharge.
  • the voltage rise at each current value: ⁇ V and the current value at that time: I were plotted on the vertical and horizontal axes, respectively, to determine the resistance value (DCR) for charging each battery.
  • the lithium iron phosphate which is an olivine type compound is used as a positive electrode active material, and the positive electrode mixture layer contains a polymer (A) having a unit represented by the general formula (1) in the molecule.
  • the non-aqueous secondary batteries of Examples 25 to 29 using the binder B2 that does not contain the fluorine-containing ethylenic unit when charged with a large current compared to the battery of Example 8 using the binder B1, In any of the discharges, the DCR value could be further reduced, and even more excellent output characteristics were exhibited.
  • Example 30 Preparation of non-aqueous electrolyte> LiPF 6 is dissolved at a concentration of 1.2 mol / L in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of 3: 7, and further vinylene carbonate (2.5% by mass) VC) and 1.0% by mass of phosphoric acid (tris) trimethylsilyl were added to prepare a non-aqueous electrolyte.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • VC vinylene carbonate
  • tris phosphoric acid
  • a nonaqueous secondary battery was produced in the same manner as in Example 8 except that the nonaqueous electrolyte was used.
  • Example 31 The non-aqueous electrolyte solution was changed to a mixture of propylene carbonate (PC) and ⁇ -methyl- ⁇ -butyrolactone (MBL) at a volume ratio of 3: 7 in the same manner as in Example 30. A secondary battery was produced.
  • PC propylene carbonate
  • MBL ⁇ -methyl- ⁇ -butyrolactone
  • Example 32 A non-aqueous secondary battery was prepared in the same manner as in Example 30 except that the solvent of the non-aqueous electrolyte was changed to a mixture of PC, MBL, and ethyl methyl carbonate (EMC) at a volume ratio of 3: 5: 2. Produced.
  • Example 33 A nonaqueous secondary battery was fabricated in the same manner as in Example 30, except that LiBF 4 was used in an amount that would give a concentration of 1.0 mol / L instead of LiPF 6 as the lithium salt of the nonaqueous electrolyte.
  • Example 34 A non-aqueous secondary battery was produced in the same manner as in Example 31 except that LiBF 4 was used in an amount of 1.0 mol / L instead of LiPF 6 as the lithium salt of the non-aqueous electrolyte.
  • Example 35 A non-aqueous secondary battery was produced in the same manner as in Example 32 except that LiBF 4 was used in an amount of 1.0 mol / L instead of LiPF 6 as the lithium salt of the non-aqueous electrolyte.
  • Example 36 A non-aqueous secondary battery was produced in the same manner as in Example 30 except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the non-aqueous electrolyte.
  • Example 37 A non-aqueous secondary battery was produced in the same manner as in Example 31 except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the non-aqueous electrolyte.
  • Example 38 A nonaqueous secondary battery was fabricated in the same manner as in Example 32, except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the nonaqueous electrolyte.
  • Example 39 A nonaqueous secondary battery was produced in the same manner as in Example 33 except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the nonaqueous electrolyte.
  • Example 40 A nonaqueous secondary battery was produced in the same manner as in Example 34, except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the nonaqueous electrolytic solution.
  • Example 41 A nonaqueous secondary battery was produced in the same manner as in Example 35, except that LiBOB was further added in an amount of 0.03 mol / L as the lithium salt of the nonaqueous electrolyte.
  • Example 42 A nonaqueous secondary battery was produced in the same manner as in Example 30, except that the amount of phosphoric acid (tris) trimethylsilyl added in the nonaqueous electrolytic solution was changed to 0.1% by mass.
  • Comparative Example 3 LiNi 0.5 Co 0.2 Mn 0.3 O 2 as positive electrode active material: 93.7 parts by mass, acetylene black as conductive aid: 4.0 parts by mass, and PVDF as a binder at 2.0
  • a positive electrode was prepared in the same manner as in Example 8 except that a positive electrode mixture-containing composition was prepared by mixing 0.3 part by mass of polyvinyl pyrrolidone (PVP) as a dispersant with 0.3 part by mass and NMP. .
  • PVP polyvinyl pyrrolidone
  • a nonaqueous secondary battery was produced in the same manner as in Example 30 except that this positive electrode was used.
  • Example 19 For the nonaqueous secondary batteries of Example 19, Examples 30 to 42, and Comparative Example 3, the following evaluations were performed after measuring the rated capacity under the above conditions.
  • required by the said method is each Example: 1480 ppm and comparative example 3: 370 ppm.
  • the water content of each non-aqueous secondary battery as a whole was 1960 ppm for each example and 850 ppm for Comparative Example 3.
  • each battery subjected to constant current-constant voltage charging under the same conditions as the initial capacity measurement was stored in a constant temperature bath at 100 ° C. for 48 hours. Then, each battery was taken out from the thermostat and returned to room temperature, and then a constant current discharge was performed at 1 C until the battery voltage reached 2.0V. Further, constant current-constant voltage charging and constant current discharging were performed under the same conditions as those for initial capacity measurement, and the discharge capacity (recovery capacity) was measured. A value obtained by dividing the obtained recovery capacity by the initial capacity was expressed as a percentage to obtain a capacity recovery rate.
  • the battery after the measurement was subjected to constant current discharge at a current value of 0.1 C until the battery voltage reached 2.0 V, and then the battery voltage was adjusted to 3.85 V at a current value of 0.1 C.
  • Current charging was performed, and the charging capacity (0.1 C charging capacity) was measured.
  • constant current discharge was performed at a current value of 0.1 C until the voltage reached 2.0 V, and then constant current charging was performed until the battery voltage reached 3.85 V at a current value of 10 C.
  • the charge capacity (10 C charge capacity) was measured.
  • the value obtained by dividing the 10C discharge capacity by the 0.1C discharge capacity (capacity ratio) and the value obtained by dividing the 10C charge capacity by the 0.1C charge capacity (capacity ratio) are expressed as percentages, respectively. evaluated.
  • Tables 9 and 10 show the configurations of the nonaqueous secondary batteries of Examples 30 to 42, Example 19 and Comparative Example 3, and Tables 11 and 12 show the evaluation results.
  • non-aqueous secondary batteries of Example 30, Examples 33 to 36, and Examples 40 to 41 using the non-aqueous electrolyte containing the phosphoric acid compound are non-aqueous electrolytes that do not contain the compound. It has an excellent charge / discharge characteristic equivalent to that of the battery of Example 19 using the above, and it can be seen that the addition of the compound can improve the high-temperature storage characteristic without causing deterioration of the charge / discharge performance. It was.
  • non-aqueous secondary battery of the present invention is excellent in charge / discharge characteristics at a large current, it can be suitably used for in-vehicle or industrial storage batteries by taking advantage of the above characteristics, and is conventionally known. It can also be used for the same applications as non-aqueous secondary batteries such as lithium ion secondary batteries.

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Abstract

L'invention concerne : une batterie secondaire non aqueuse ayant d'excellentes caractéristiques de charge et de décharge avec un courant de forte intensité ; et un procédé de fabrication de cette batterie secondaire non aqueuse. Une batterie secondaire non aqueuse selon la présente invention est caractérisée en ce qu'elle comporte : une électrode positive qui a une couche de mélange d'électrode positive, qui contient un matériau actif d'électrode positive, un liant et un assistant conducteur, sur une surface ou les deux surfaces d'un collecteur ; une électrode négative qui a une couche de mélange d'électrode négative, qui contient un matériau actif d'électrode négative et un liant, sur une surface ou les deux surfaces d'un collecteur ; un séparateur ; et une solution électrolytique non aqueuse qui contient un sel de lithium et un solvant organique. Cette batterie secondaire non aqueuse est également caractérisée en ce que la couche de mélange d'électrode positive contient un composé de type olivine formant le matériau actif d'électrode positive, tout en contenant, en tant que liant, un polymère (A) qui a un motif représenté par la formule générale (1) dans chaque molécule. (Dans la formule générale (1), R1 représente H ou un groupe méthyle ; et R2 représente un groupe alkyle ayant 1 à 18 atomes de carbone.)
PCT/JP2016/074829 2015-08-28 2016-08-25 Batterie secondaire non aqueuse et procédé de fabrication de celle-ci WO2017038628A1 (fr)

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JP7323713B2 (ja) 2021-03-19 2023-08-08 積水化学工業株式会社 非水電解質二次電池用正極、並びにこれを用いた非水電解質二次電池、電池モジュール、及び電池システム
WO2022202576A1 (fr) * 2021-03-25 2022-09-29 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux
WO2022210910A1 (fr) * 2021-03-31 2022-10-06 パナソニックＩｐマネジメント株式会社 Électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux l'utilisant
WO2022210902A1 (fr) * 2021-03-31 2022-10-06 パナソニックＩｐマネジメント株式会社 Dispersion liquide de matériau conducteur, pâte d'électrode positive pour batterie secondaire à électrolyte non aqueux, électrode positive pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
JP7288479B2 (ja) 2021-04-19 2023-06-07 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
JP2022165058A (ja) * 2021-04-19 2022-10-31 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池

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