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WO2020091058A1 - Accumulateur à électrolyte non aqueux - Google Patents

Accumulateur à électrolyte non aqueux Download PDF

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Publication number
WO2020091058A1
WO2020091058A1 PCT/JP2019/043093 JP2019043093W WO2020091058A1 WO 2020091058 A1 WO2020091058 A1 WO 2020091058A1 JP 2019043093 W JP2019043093 W JP 2019043093W WO 2020091058 A1 WO2020091058 A1 WO 2020091058A1
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Prior art keywords
electrode plate
porous layer
electrolyte secondary
secondary battery
aqueous electrolyte
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PCT/JP2019/043093
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English (en)
Japanese (ja)
Inventor
一郎 有瀬
村上　力
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to KR1020217015733A priority Critical patent/KR102538460B1/ko
Publication of WO2020091058A1 publication Critical patent/WO2020091058A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries especially lithium-ion secondary batteries, are widely used as batteries for personal computers, mobile phones, personal digital assistants, etc. because of their high energy density, and recently they have been developed as in-vehicle batteries. Has been.
  • non-aqueous electrolyte secondary battery for example, a porous layer containing a plate-like inorganic filler as described in Patent Document 1 and having a porosity of 60 to 90% is provided on at least one surface of a porous substrate.
  • a non-aqueous electrolyte secondary battery including a non-aqueous secondary battery separator that is laminated on.
  • the present invention has been made in view of the above problems, and an object thereof is to realize a non-aqueous electrolyte secondary battery having an excellent charge capacity after high rate discharge.
  • the non-aqueous electrolyte secondary battery according to Aspect 1 of the present invention is a porous layer containing an inorganic filler and a resin, a positive electrode plate having a capacitance per measurement area 900 mm 2 of 1 nF or more and 1000 nF or less, A negative electrode plate having a capacitance per measurement area of 900 mm 2 of 4 nF or more and 8500 nF or less, and the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer is 1.4 to 4.0.
  • the peak intensities I (hkl) and I (abc) of arbitrary diffraction planes (hkl) and (abc) orthogonal to each other measured by the wide-angle X-ray diffraction method of the porous layer are
  • the range of the maximum value of the peak intensity ratio calculated by the following formula (2) that satisfies the following formula (1) is in the range of 1.5 to 300.
  • the porous layer includes a polyolefin, a (meth) acrylate resin, a fluorine-containing resin, a polyamide resin, a polyester resin, and It includes a resin selected from the group consisting of water-soluble polymers.
  • the polyamide resin is an aramid resin.
  • the porous layer is laminated on one side or both sides of a polyolefin porous film.
  • the positive electrode plate contains a transition metal oxide and the negative electrode plate contains graphite.
  • the non-aqueous electrolyte secondary battery according to the embodiment of the present invention has excellent charge capacity after high rate discharge of the battery.
  • FIG. 3 is a schematic diagram showing a measurement target electrode which is a target of measurement of capacitance in an example of the present application.
  • FIG. 3 is a schematic diagram showing a probe electrode used for measuring capacitance in an example of the present application.
  • a non-aqueous electrolyte secondary battery according to an embodiment of the present invention includes a porous layer described below, a positive electrode plate and a negative electrode plate described below.
  • the non-aqueous electrolyte secondary battery according to the exemplary embodiment of the present invention may further include a polyolefin porous film described below.
  • the porous layer in one embodiment of the present invention is a porous layer containing an inorganic filler and a resin, and is an inorganic material on the surface of the porous layer (hereinafter, may be referred to as “porous layer surface”).
  • the aspect ratio of the projected image of the filler is in the range of 1.4 to 4.0, and arbitrary diffraction surfaces (hkl) and (abc) of the porous layer, which are measured by a wide-angle X-ray diffraction method and are orthogonal to each other.
  • the peak intensities of I (hkl) and I (abc) satisfy the following equation (1), and the maximum value of the peak intensity ratio calculated by the following equation (2) is in the range of 1.5 to 300. is there. I (hkl) > I (abc) ... (1), I (hkl) / I (abc) (2).
  • the porous layer may be arranged between the polyolefin porous film and at least one of the positive electrode plate and the negative electrode plate as a member constituting the non-aqueous electrolyte secondary battery.
  • the porous layer may be formed on one side or both sides of the polyolefin porous film.
  • the porous layer may be formed on the active material layer of at least one of the positive electrode plate and the negative electrode plate.
  • the porous layer may be disposed between the polyolefin porous film and at least one of the positive electrode plate and the negative electrode plate so as to be in contact with them.
  • the porous layer disposed between the polyolefin porous film and at least one of the positive electrode plate and the negative electrode plate may be one layer or two or more layers.
  • the porous layer is preferably an insulating porous layer containing a resin.
  • the porous layer is laminated on one side of the polyolefin porous film
  • the porous layer is preferably laminated on the surface of the polyolefin porous film facing the positive electrode plate. More preferably, the porous layer is laminated on the surface in contact with the positive electrode plate.
  • FIG. 1 shows a schematic diagram of the state of the inorganic filler in the porous layer when the orientation is high and when the orientation is low.
  • the left diagram of FIG. 1 is a schematic diagram showing the structure of the porous layer containing an inorganic filler when the orientation of the filler is large and the anisotropy is high, and the right diagram of FIG. 1 is the inorganic layer. It is a schematic diagram showing the structure of the said porous layer in case the orientation of a filler is small and anisotropy is low.
  • the porous layer in one embodiment of the present invention contains an inorganic filler and a resin.
  • the porous layer has a large number of pores inside and has a structure in which these pores are connected, and is a layer through which gas or liquid can pass from one surface to the other surface.
  • the porous layer in one embodiment of the present invention is used as a member constituting a laminated separator for a non-aqueous electrolyte secondary battery described later, the porous layer is for the non-aqueous electrolyte secondary battery.
  • the outermost layer of the laminated separator can be a layer in contact with the electrode plate.
  • the resin contained in the porous layer in one embodiment of the present invention is preferably insoluble in the electrolytic solution of the battery and is electrochemically stable in the usage range of the battery.
  • the resin include polyolefins; (meth) acrylate resins; fluorine-containing resins; polyamide resins; polyimide resins; polyester resins; rubbers; melting points or glass transition temperatures of 180 ° C. or higher.
  • Resins water-soluble polymers; polycarbonates, polyacetals, polyether ether ketones and the like.
  • polyolefin, (meth) acrylate resin, fluorine-containing resin, polyamide resin, polyester resin and water-soluble polymer are preferable.
  • polyethylene polyethylene, polypropylene, polybutene, ethylene-propylene copolymer and the like are preferable.
  • fluorine-containing resin examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Coalescence, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-trichloroethylene copolymer, vinylidene fluoride-vinyl fluoride copolymer, vinylidene fluoride-hexafluoro Examples thereof include propylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer and the like, and fluorine-containing rubber having a glass transition temperature of 23 ° C. or lower among the fluor
  • polyamide resin aramid resins such as aromatic polyamide and wholly aromatic polyamide are preferable.
  • the aramid resin examples include poly (paraphenylene terephthalamide), poly (metaphenylene isophthalamide), poly (parabenzamide), poly (metabenzamide), poly (4,4′-benzanilide terephthalate). Amide), poly (paraphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (metaphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (paraphenylene-2,6-naphthalenedicarboxylic acid amide), Poly (metaphenylene-2,6-naphthalenedicarboxylic acid amide), poly (2-chloroparaphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer, metaphenylene terephthalamide / 2 , 6-diclosure Paraphenylene terephthalamide copolymer and the like. Of these, poly (paraphenylene
  • polyester resin aromatic polyester such as polyarylate and liquid crystal polyester are preferable.
  • Examples of rubbers include styrene-butadiene copolymer and its hydride, methacrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl acetate and the like. Can be mentioned.
  • Examples of the resin having a melting point or glass transition temperature of 180 ° C. or higher include polyphenylene ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyamideimide, and polyetheramide.
  • water-soluble polymers examples include polyvinyl alcohol, polyethylene glycol, cellulose ether, sodium alginate, polyacrylic acid, polyacrylamide, polymethacrylic acid and the like.
  • the resin contained in the porous layer in the embodiment of the present invention may be one kind or a mixture of two or more kinds.
  • a fluorine-containing resin is preferable because it can be easily maintained.
  • the porous layer in one embodiment of the present invention contains an inorganic filler.
  • the lower limit of the content is preferably 50% by weight or more and 70% by weight or more based on the total weight of the filler and the resin constituting the porous layer in the embodiment of the present invention. More preferably, it is more preferably 90% by weight or more.
  • the upper limit of the content of the inorganic filler in the porous layer in the embodiment of the present invention is preferably 99% by weight or less, and more preferably 98% by weight or less.
  • the content of the filler is preferably 50% by weight or more from the viewpoint of heat resistance, and the content of the filler is preferably 99% by weight or less from the viewpoint of adhesion between the fillers.
  • the inorganic filler is not particularly limited as long as it is a filler that is stable in a non-aqueous electrolytic solution and is electrochemically stable. From the viewpoint of ensuring the safety of the battery, a filler having a heat resistant temperature of 150 ° C. or higher is preferable.
  • the inorganic filler is not particularly limited, but is usually an insulating filler.
  • the inorganic filler is preferably an inorganic material containing at least one element selected from the group consisting of aluminum element, zinc element, calcium element, zirconium element, silicon element, magnesium element, barium element, and boron element, and preferably Is an inorganic substance containing an aluminum element.
  • the inorganic filler preferably contains an oxide of the above element.
  • the inorganic filler titanium oxide, alumina (Al 2 O 3 ), zinc oxide (ZnO), calcium oxide (CaO), zirconia oxide (ZrO 2 ), silica, magnesia, barium oxide, boron oxide, Examples thereof include mica, wollastonite, attapulgite, and boehmite (alumina monohydrate).
  • the inorganic filler one kind of filler may be used alone, or two or more kinds of filler may be used in combination.
  • the inorganic filler in the porous layer in one embodiment of the present invention preferably contains alumina and a plate-like filler.
  • the plate-like filler include one or more fillers selected from the group consisting of zinc oxide (ZnO), mica, and boehmite, among oxides of the above-mentioned elements.
  • the volume average particle diameter of the inorganic filler is preferably in the range of 0.01 ⁇ m to 10 ⁇ m from the viewpoint of ensuring good adhesiveness and slipperiness, and moldability of the laminate.
  • the lower limit value is more preferably 0.05 ⁇ m or more, further preferably 0.1 ⁇ m or more.
  • the upper limit value is more preferably 5 ⁇ m or less, further preferably 1 ⁇ m or less.
  • the shape of the inorganic filler is arbitrary and is not particularly limited.
  • the shape of the inorganic filler may be a particle shape, for example, a spherical shape; an elliptical shape; a plate shape; a rod shape; an irregular shape; a fibrous shape; a spherical or columnar single particle such as a peanut shape and / or a tetrapot shape.
  • the shape may be any of the above.
  • the inorganic filler is preferably plate-like particles and / or non-aggregated primary particles.
  • the shape of the inorganic filler is such that the particles in the porous material are difficult to be most closely packed, voids are likely to be formed between the particles, bumps, dents, constrictions, ridges or bulges, and dendritic branches
  • a single particle is heat-fused such as an irregular shape such as a shape, a coral shape, or a tuft shape; a fibrous shape; a peanut shape and / or a tetrapot shape.
  • the shape of the inorganic filler is a shape in which spherical or columnar single particles such as peanut-shaped and / or tetrapot-shaped particles are heat-sealed.
  • the filler can improve the slipperiness by forming fine irregularities on the surface of the porous layer, but when the filler is plate-like particles and / or primary particles that are not aggregated, the filler is As a result, the irregularities formed on the surface of the porous layer become finer, and the adhesiveness between the porous layer and the electrode plate becomes better.
  • the oxygen atom mass percentage of the oxide of the element forming the inorganic filler contained in the porous layer is preferably 10% to 50%, and preferably 20% to 50%. Is more preferable.
  • the oxygen atomic mass percentage of the oxide of the element is in the above range, the affinity between the solvent or the dispersion medium in the coating liquid used in the method for producing a porous layer described later and the inorganic filler is suitable. It is possible to maintain a proper distance between the inorganic fillers. Thereby, the dispersibility of the coating liquid can be improved, and as a result, the "aspect ratio of the projected image of the inorganic filler on the surface of the porous layer" and the "orientation degree of the porous layer” can be defined appropriately.
  • the range can be controlled.
  • the aspect ratio of the inorganic filler itself contained in the porous layer in the embodiment of the present invention is such that, in a state where the inorganic filler is arranged on a plane, in an SEM image observed from vertically above the arrangement surface, overlapping in the thickness direction occurs. It is expressed as the average value of the ratio of the length of the short axis to the length of the long axis of 100 particles that are not present.
  • the length of the major axis is also referred to as the major axis diameter and the length of the minor axis is also referred to as the minor axis diameter.
  • the aspect ratio of the inorganic filler itself is preferably 1 to 10, more preferably 1.1 to 8, and even more preferably 1.2 to 5.
  • the aspect ratio of the inorganic filler itself is in the above range, when the porous layer in one embodiment of the present invention is formed by the method described below, in the resulting porous layer, the orientation of the filler, The uniformity of the distribution of the filler on the surface of the porous layer can be controlled within a preferable range.
  • the porous layer in one embodiment of the present invention may include other components than the above-mentioned inorganic filler and resin.
  • the other components include surfactants, waxes and binder resins.
  • the content of the other components is preferably 0% by weight to 50% by weight based on the weight of the entire porous layer.
  • the average film thickness of the porous layer in one embodiment of the present invention is preferably in the range of 0.5 ⁇ m to 10 ⁇ m per porous layer from the viewpoint of securing adhesiveness to the electrode plate and high energy density. More preferably, it is in the range of 1 ⁇ m to 5 ⁇ m.
  • the basis weight per unit area of the porous layer can be appropriately determined in consideration of the strength, film thickness, weight and handleability of the porous layer.
  • the basis weight per unit area of the porous layer is preferably 0.5 to 20 g / m 2 and more preferably 0.5 to 10 g / m 2 per porous layer.
  • the weight energy density and volume energy density of the non-aqueous electrolyte secondary battery can be increased.
  • the basis weight of the porous layer exceeds the above range, the non-aqueous electrolyte secondary battery tends to be heavy.
  • the porosity of the porous layer is preferably 20 to 90% by volume, and more preferably 30 to 80% by volume so that sufficient ion permeability can be obtained.
  • the pore size of the pores of the porous layer is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less. By setting the pore diameters to these sizes, the non-aqueous electrolyte secondary battery can obtain sufficient ion permeability.
  • the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer is in the range of 1.4 to 4.0 and is 1.5 to 2.3. It is preferably in the range.
  • a scanning electron microscope (SEM) is used to take an SEM image, which is an electron micrograph of the surface, immediately above the porous layer, that is, from above the vertical direction. It is a value obtained by creating a projected image of the filler and calculating the ratio of the major axis length / minor axis length of the projected image of the inorganic filler. That is, the aspect ratio refers to the shape of the inorganic filler observed when the inorganic filler on the surface of the porous layer is observed from directly above the porous layer.
  • FIG. 2 shows a schematic diagram of a projected image of the inorganic filler created from the SEM image of the surface of the porous layer described above.
  • the “surface” of the porous layer means the surface of the porous layer that can be observed by SEM from directly above the porous layer.
  • an SEM at an accelerating voltage of 5 kV is used from directly above the porous side of the laminated body by using a field emission scanning electron microscope JSM-7600F manufactured by JEOL Ltd.
  • the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer is an index showing the uniformity of the distribution of the inorganic filler on the porous layer, especially on the surface thereof.
  • the aspect ratio is close to 1
  • the shape and distribution of the constituent material on the surface of the porous layer are uniform, and it is easy to be densely packed.
  • the aspect ratio is large, the arrangement of the constituent components in the surface structure of the porous layer becomes non-uniform, and as a result, the uniformity of the shape and distribution of the openings of the surface of the porous layer deteriorates.
  • the aspect ratio is greater than 4.0, the uniformity of the shape and distribution of the porous layer, especially the surface openings thereof, is excessively reduced, so that a non-aqueous electrolyte secondary electrode incorporating the porous layer is used. It is considered that in the battery, a portion where the capacity of the porous layer to receive the electrolyte solution during the operation of the battery is reduced, and as a result, the rate characteristic of the non-aqueous electrolyte secondary battery is reduced.
  • the aspect ratio is less than 1.4, the porous layer, in particular, the distribution of the inorganic filler on the surface thereof has an excessively uniform structure, and as a result, the surface opening area of the porous layer is small.
  • the electrolyte receiving capacity of the porous layer during the operation of the battery decreases, and as a result, the battery rate of the non-aqueous electrolyte secondary battery decreases. It is considered that the characteristics are degraded.
  • the porous layer in one embodiment of the present invention has peak intensity I (hkl) of arbitrary diffraction planes (hkl) and (abc) orthogonal to each other in the porous layer measured by a wide-angle X-ray diffraction method, and It is preferable that I (abc) satisfies the following formula (1) and the maximum value of the peak intensity ratio calculated by the following formula (2) is in the range of 1.5 to 300. It is more preferably in the range of to 250. I (hkl) > I (abc) ... (1), I (hkl) / I (abc) (2).
  • the maximum value of the peak intensity ratio calculated by the above formula (2) is also referred to as “the orientation degree of the porous layer”.
  • the method for measuring the peak intensities I (hkl) and I (abc) and the peak intensity ratio I (hkl) / I (abc) is not particularly limited, but for example, the following (1) to (3) are used.
  • a method comprising the steps shown can be mentioned.
  • (1) A step of preparing a measurement sample by cutting a 2 cm square laminate (laminated porous film) obtained by laminating a porous layer on a substrate.
  • the measurement sample obtained in step (1) was attached to an Al holder with the porous layer side of the sample as the measurement surface, and an X-ray profile was obtained by a wide-angle X-ray diffraction method (2 ⁇ - ⁇ scan method). Measuring step.
  • the device for measuring the X-ray profile and the measurement conditions are not particularly limited.
  • RU-200R rotating anticathode type
  • CuK ⁇ rays are used as the X-ray source.
  • the output may be measured at 50 KV-200 mA and a scanning speed of 2 ° / min.
  • peak intensity I (hkl) of arbitrary diffractive surfaces (hkl) and (abc) orthogonal to each other in wide-angle X-ray diffraction measurement of the porous layer Based on the X-ray profile obtained in the step (2), peak intensity I (hkl) of arbitrary diffractive surfaces (hkl) and (abc) orthogonal to each other in wide-angle X-ray diffraction measurement of the porous layer.
  • the maximum value of the peak intensity ratio shown by the above formula (2) is an index showing the degree of orientation inside the porous layer.
  • a small peak intensity ratio represented by the formula (2) means that the degree of orientation in the internal structure of the porous layer is low, and a large peak intensity ratio represented by the formula (2) means that It shows that the internal structure of the texture layer has a high degree of orientation.
  • the maximum value of the peak intensity ratio represented by the formula (2) is larger than 300, the anisotropy of the internal structure of the porous layer becomes excessively high, and the ion permeation flow channel length inside the porous layer is increased. Therefore, as a result, in the non-aqueous electrolyte secondary battery incorporating the porous layer, the ion permeation resistance of the porous layer is increased, and the battery rate characteristic of the non-aqueous electrolyte secondary battery is considered to deteriorate. Be done.
  • the maximum value of the peak intensity ratio represented by the above formula (2) is less than 1.5, compared to the case where the porous layer having the peak intensity ratio of 1.5 or more is used,
  • the ions supplied from the electrodes are permeated at high speed. Therefore, the supply of ions from the electrode becomes rate-determining (that is, the ions are depleted on the electrode surface), and the limiting current, which is the battery operating current value condition, becomes small. As a result, it is considered that the battery rate characteristic of the non-aqueous electrolyte secondary battery is deteriorated.
  • the method for producing the porous layer according to the embodiment of the present invention is not particularly limited, but for example, one of the following steps (1) to (3) may be used on the substrate, A method of forming a porous layer containing the inorganic filler and the resin can be mentioned.
  • a porous layer can be manufactured by depositing the resin and then drying it to remove the solvent.
  • the coating liquid in steps (1) to (3) may be in a state in which the inorganic filler is dispersed and the resin is dissolved.
  • the solvent can be said to be a solvent for dissolving the resin and a dispersion medium for dispersing the resin or the inorganic filler.
  • a step of forming a porous layer by applying a coating liquid containing the inorganic filler and the resin onto a base material, and drying and removing the solvent in the coating liquid.
  • the liquid property of the coating liquid is made acidic by using a low-boiling organic acid.
  • the solvent does not adversely affect the base material, dissolves the resin uniformly and stably, and disperses the inorganic filler uniformly and stably.
  • the solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, acetone and water.
  • the deposition solvent for example, isopropyl alcohol or t-butyl alcohol is preferably used.
  • the low boiling point organic acid for example, paratoluenesulfonic acid, acetic acid, etc. can be used.
  • the orientation of the porous layer in one embodiment of the present invention that is, "the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer” and “the orientation degree of the porous layer”
  • the solid content concentration of the coating liquid containing the inorganic filler and the resin, and the coating shear rate when coating the coating liquid on the substrate The adjustment can be mentioned.
  • a suitable solid content concentration of the coating liquid may vary depending on the type of filler, etc., but generally it is preferably more than 20% by weight and 40% by weight or less. That the solid content concentration is within the above range, the viscosity of the coating liquid is appropriately maintained, and as a result, the "aspect ratio of the projected image of the inorganic filler on the surface of the porous layer" and the "orientation degree of the porous layer". Is preferable because it can be controlled within the above-mentioned preferable range.
  • the coating shear rate at the time of applying the coating liquid on the substrate may vary depending on the type of filler, etc., but generally it is preferably 2 (1 / s) or more and 4 (1 / s). More preferably, it is from s) to 50 (1 / s).
  • the inorganic filler for example, a shape in which spherical or columnar single particles such as peanut-shaped and / or tetrapot-shaped are heat-fused, spherical-shaped, elliptical-shaped, plate-shaped, rod-shaped, or irregular-shaped.
  • the coating shear rate is increased, a high shearing force is applied to the inorganic filler, so that the anisotropy tends to increase.
  • the coating shear rate is reduced, the shearing force is not applied to the inorganic filler, so that the inorganic filler tends to be oriented isotropically.
  • the inorganic filler is a long fiber diameter inorganic filler such as long wollastonite having a large fiber diameter
  • the coating shear rate is increased, the long fibers are entangled with each other, or the long blades of the doctor blade are long fibers. Tend to be in a disoriented orientation due to the trapping of the, and anisotropy tends to be low.
  • the coating shear rate is reduced, the long fibers do not become entangled with each other and do not get caught on the blade of the doctor blade, so that they tend to be oriented and the anisotropy tends to increase.
  • the capacitance of the measurement area 900 mm 2 per are, 1nF or more, or less 1000 nF, negative plates, the capacitance of the measurement area 900 mm 2 per are, 4nF above, 8500NF less Is.
  • the “measurement area” is in contact with the measurement target (positive electrode plate or negative electrode plate) in the measurement electrode (upper (main) electrode, probe electrode) of the LCR meter in the capacitance measuring method described later. It means the area of the part. Therefore, the value of the capacitance per measurement area Xmm 2 means that the measurement target and the measurement electrode are in contact with each other in the LCR meter so that the area of the measurement electrode at the overlapping position is Xmm 2. The measured value when the capacitance is measured.
  • the capacitance of the positive electrode plate is a value measured by bringing a measurement electrode (probe electrode) into contact with the positive electrode active material layer side surface of the positive electrode plate in the method for measuring the capacitance of the electrode plate described later. And mainly represents the polarization state of the positive electrode active material layer of the positive electrode plate.
  • the capacitance of the negative electrode plate is a value measured by bringing a measurement electrode into contact with the negative electrode active material layer side surface of the negative electrode plate in the method for measuring the capacitance of the electrode plate described later.
  • Mainly represents the polarization state of the negative electrode active material layer of the negative electrode plate.
  • ions as charge carriers are released from the negative electrode plate during discharge.
  • the ions pass through the separator for non-aqueous electrolyte secondary battery, and are then taken into the positive electrode plate.
  • the ions are solvated by the electrolyte solvent in the negative electrode plate and the surface of the negative electrode plate, and desolvated in the positive electrode plate and the surface of the positive electrode plate.
  • the ions are Li + when the non-aqueous electrolyte secondary battery is a lithium ion secondary battery, for example.
  • the degree of solvation of the above-mentioned ions is influenced by the polarization state of the negative electrode active material layer of the negative electrode plate.
  • the degree of desolvation of the above-mentioned ions is influenced by the polarization state of the positive electrode active material layer of the positive electrode plate.
  • the electrostatic capacities of the negative electrode plate and the positive electrode plate within a suitable range, that is, by adjusting the polarization state of the negative electrode active material layer and the positive electrode active material layer to a suitable state, the above-mentioned solvation and desolvation can be performed.
  • Solvation can be moderately promoted.
  • the permeability of ions as charge carriers can be improved, and the discharge output characteristics of the non-aqueous electrolyte secondary battery can be improved especially when a large discharge current with a time rate of 10 C or more is applied.
  • the capacitance per measurement area 900 mm 2 is 4 nF or more and 8500 nF or less, and 4 nF or more and 3000 nF or less. Is preferable and 4nF or more and 2600nF or less is more preferable.
  • the lower limit value of the capacitance may be 100 nF or more, 200 nF or more, and 1000 nF or more.
  • the capacitance of the negative electrode plate per measured area of 900 mm 2 is less than 4 nF, the polarizability of the negative electrode plate is low, so that it hardly contributes to the promotion of solvation. Therefore, no improvement in output characteristics occurs in the non-aqueous electrolyte secondary battery incorporating the negative electrode plate.
  • the capacitance per measured area 900 mm 2 in the negative electrode plate is larger than 8500 nF, the polarizability of the negative electrode plate becomes too high, and the affinity between the inner wall of the void of the negative electrode plate and the ions becomes high. Pass. Therefore, the movement (release) of ions from the negative electrode plate is hindered. Therefore, the output characteristics of the non-aqueous electrolyte secondary battery incorporating the negative electrode plate are rather deteriorated.
  • the positive electrode plate in one embodiment of the present invention has a capacitance per measurement area 900 mm 2 of 1 nF or more and 1000 nF or less, preferably 2 nF or more and 600 nF or less, and 2 nF or more. , 400 nF or less is more preferable. Further, the lower limit value of the capacitance may be 3 nF or more.
  • the positive electrode plate when the capacitance per 900 mm 2 of the measurement area is less than 1 nF, the positive electrode plate has a low polarizability and thus hardly contributes to the desolvation. Therefore, the improvement of the output characteristics does not occur in the non-aqueous electrolyte secondary battery incorporating the positive electrode plate.
  • the capacitance per 900 mm 2 of measured area when the capacitance per 900 mm 2 of measured area is larger than 1000 nF, the polarizability of the positive electrode plate becomes too high, so that the desolvation proceeds excessively. Therefore, the solvent for moving inside the positive electrode plate is desolvated, and the affinity between the inner wall of the void inside the positive electrode plate and the desolvated ions becomes too high. Therefore, the movement of ions inside the positive electrode plate is hindered. Therefore, the output characteristics of the non-aqueous electrolyte secondary battery incorporating the positive electrode plate are rather deteriorated.
  • the capacitances of the positive electrode plate and the negative electrode plate can be controlled by adjusting the surface areas of the positive electrode active material layer and the negative electrode active material layer, respectively. Specifically, for example, the surfaces of the positive electrode active material layer and the negative electrode active material layer are ground with sandpaper or the like to increase the surface area, thereby increasing the capacitance.
  • the electrostatic capacities of the positive electrode plate and the negative electrode plate can be controlled by adjusting the relative permittivity of the material forming each of the positive electrode plate and the negative electrode plate.
  • the relative permittivity can be adjusted by changing the shape of voids, the void ratio, and the distribution of voids in each of the positive electrode plate and the negative electrode plate.
  • the relative permittivity can also be adjusted by adjusting the materials forming each of the positive electrode plate and the negative electrode plate.
  • the capacitance of the electrode plate (positive electrode plate or negative electrode plate) per measurement area 900 mm 2 in one embodiment of the present invention is CV: 0.010V, SPEED: SLOW2, AVG: 8, CABLE using an LCR meter. 1 m, OPEN: All, SHORT: All DCBIAS 0.00V, and the frequency is 300 KHz.
  • the capacitance of the electrode plate before being incorporated into the non-aqueous electrolyte secondary battery is measured.
  • the capacitance is a unique value determined by the shape (surface area) of the solid insulating material (electrode plate), the constituent material, the shape of voids, the void ratio, the distribution of voids, and the like. Therefore, the capacitance of the electrode plate after being incorporated in the non-aqueous electrolyte secondary battery is also the same as the capacitance value measured before being incorporated in the non-aqueous electrolyte secondary battery.
  • the positive electrode plate and the negative electrode plate from the battery that has undergone a charge / discharge history after being incorporated into the non-aqueous electrolyte secondary battery, and measure the electrostatic capacities of the positive electrode plate and the negative electrode plate.
  • the electrode laminate member for non-aqueous electrolyte secondary battery
  • it is expanded to form one electrode plate ( Take out the positive electrode plate or the negative electrode plate).
  • a sample piece is obtained by cutting out this electrode plate into the same size as the electrode plate to be measured in the above-described capacitance measuring method.
  • the test piece is washed several times (for example, three times) in diethyl carbonate (hereinafter sometimes referred to as DEC).
  • DEC diethyl carbonate
  • the above-mentioned cleaning is performed by adding a test piece to DEC and then cleaning the test piece by replacing the DEC with a new DEC and cleaning the test piece several times (for example, three times) to adhere to the surface of the electrode plate.
  • This is a step of removing the electrolytic solution, the electrolytic solution decomposition product, the lithium salt, and the like.
  • the obtained washed electrode plate is sufficiently dried and then used as an electrode to be measured.
  • the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer is in the range of 1.4 to 4.0, and the porous layer is measured by the wide-angle X-ray diffraction method.
  • I (hkl) and I (abc) of the above satisfy the above equation, and the range of the maximum value of the peak intensity ratio calculated by the above equation (2) is in the range of 1.5 to 300 (condition 1)
  • the porous layer has a structure that easily retains the electrolytic solution, and the migration path of ions as charge carriers is optimized, so that the permeability of ions is promoted.
  • the capacitance per 900 mm 2 of the measurement area of the positive electrode plate is 1 nF or more and 1000 nF or less and the capacitance per 900 mm 2 of the measurement area of the negative electrode plate is 4 nF or more and 8500 nF or less (condition 2).
  • the polarization of the electrode active material layer becomes appropriate, desolvation / solvation of ions as charge carriers is promoted, and the permeability of the ions is improved.
  • the pores of the porous layer have an appropriate dense structure, and the ions as charge carriers are
  • the permeability and the acceptability of the electrolytic solution are compatible with each other, and the polarization of the electrode active material layer is appropriate. Therefore, solvation and desolvation of ions as charge carriers also proceed smoothly. As a result, the non-uniformity of the capacity in the electrode surface direction due to the high rate discharge is suppressed, that is, the uneven concentration of ions as charge carriers is eliminated.
  • the charge capacity of the non-aqueous electrolyte secondary battery according to one embodiment of the present invention at 1 C charge after high rate discharge (10 C discharge) is preferably 14.5 mAh or more, and more preferably 15 mAh or more. preferable.
  • charge capacity at 1C charge after high-rate discharge (10C discharge) is a value measured by the measuring method described in the examples.
  • the positive electrode plate in one embodiment of the present invention is not particularly limited as long as the capacitance per measurement area 900 mm 2 is within the above range.
  • a sheet-shaped positive electrode plate in which a positive electrode mixture containing a positive electrode active material, a conductive agent and a binder is carried on a positive electrode current collector is used as the positive electrode active material layer.
  • the positive electrode plate may carry the positive electrode mixture on both surfaces of the positive electrode current collector, or may carry the positive electrode mixture on one surface of the positive electrode current collector.
  • the positive electrode active material includes, for example, a material that can be doped with lithium ions and dedoped.
  • a transition metal oxide is preferable as the material.
  • Specific examples of the transition metal oxide include transition metals such as V, Mn, Fe, Co, and Ni, and / or lithium composite oxides containing at least one oxide of the transition metal. Be done.
  • Examples of the conductive agent include natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, carbonaceous materials such as organic polymer compound fired bodies, and the like.
  • the conductive agent may be used alone or in combination of two or more kinds.
  • binder examples include polyvinylidene fluoride, vinylidene fluoride copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. , Ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, thermoplastic polyimide, thermoplastic resin such as polyethylene and polypropylene , Acrylic resin, and styrene-butadiene rubber.
  • the binder also has a function as a thickener.
  • Examples of the positive electrode current collector include conductors such as Al, Ni, and stainless steel. Among them, Al is more preferable because it is easily processed into a thin film and is inexpensive.
  • Examples of the method for producing a sheet-shaped positive electrode plate include a method in which a positive electrode active material, a conductive agent, and a binder are pressure-molded on a positive electrode current collector; a positive electrode active material, a conductive agent, and A method of fixing the binder to the positive electrode current collector by applying the paste to the positive electrode current collector, applying the paste to the positive electrode current collector, and then drying and pressing the paste, and the like.
  • the negative electrode plate in one embodiment of the present invention is not particularly limited as long as the capacitance per measurement area 900 mm 2 is within the above range.
  • a sheet-shaped negative electrode plate in which a negative electrode mixture containing a negative electrode active material, a conductive agent and a binder is carried on a negative electrode current collector is used as the negative electrode active material layer.
  • the negative electrode plate may carry the negative electrode mixture on both surfaces of the negative electrode current collector, or may carry the negative electrode mixture on one surface of the negative electrode current collector.
  • conductive agent and the binder those described as the conductive agent and the binder contained in the positive electrode active material layer can be used.
  • the negative electrode active material examples include materials that can be doped / dedoped with lithium ions, lithium metal, lithium alloys, and the like.
  • Specific examples of the material include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and organic polymer compound calcined materials; at a potential lower than that of the positive electrode.
  • Examples thereof include chalcogen compounds such as oxides and sulfides, which are doped and dedoped with lithium ions.
  • the potential flatness is high, and since a large energy density can be obtained when combined with the positive electrode because the average discharge potential is low, those containing graphite are preferable, such as natural graphite and artificial graphite.
  • a carbonaceous material containing a graphite material as a main component is more preferable.
  • the negative electrode active material may contain graphite as a main component and additionally contain silicon.
  • Examples of the negative electrode current collector include Cu, Ni, and stainless steel. Particularly, in a lithium ion secondary battery, Cu is more preferable because it is difficult to form an alloy with lithium and is easily processed into a thin film.
  • Examples of the method for producing the sheet-shaped negative electrode plate include, for example, a method in which the negative electrode active material is pressure-molded on a negative electrode current collector; the negative electrode active material is made into a paste using an appropriate organic solvent, and then the paste is used as a negative electrode. A method of coating the current collector, then drying and then applying pressure to fix the current collector to the negative electrode current collector, and the like.
  • the paste preferably contains the conductive agent and the binder.
  • the non-aqueous electrolyte secondary battery in one embodiment of the present invention may include a polyolefin porous film.
  • a polyolefin porous film may only be called a "porous film.”
  • the porous film contains a polyolefin-based resin as a main component and has a large number of pores connected to the inside thereof, so that a gas and a liquid can pass from one surface to the other surface.
  • the porous film alone can serve as a separator for a non-aqueous electrolyte secondary battery. It can also be a base material of the laminated separator for a non-aqueous electrolyte secondary battery in which the above-mentioned porous layer is laminated.
  • a laminate in which the porous layer is laminated in the present specification, also referred to as "non-aqueous electrolyte secondary battery laminated separator” or “laminated separator” .
  • the separator for a non-aqueous electrolyte secondary battery in one embodiment of the present invention may further include other layers such as an adhesive layer, a heat resistant layer, and a protective layer, in addition to the polyolefin porous film.
  • the proportion of polyolefin in the porous film is 50% by volume or more of the entire porous film, more preferably 90% by volume or more, and further preferably 95% by volume or more. Further, it is more preferable that the polyolefin contains a high molecular weight component having a weight average molecular weight of 5 ⁇ 10 5 to 15 ⁇ 10 6 . In particular, when the polyolefin contains a high molecular weight component having a weight average molecular weight of 1,000,000 or more, the strength of the separator for a non-aqueous electrolyte secondary battery is improved, which is more preferable.
  • the polyolefin which is a thermoplastic resin
  • a copolymer may be used.
  • the homopolymer include polyethylene, polypropylene and polybutene.
  • the copolymer include ethylene-propylene copolymer.
  • polyethylene is more preferable because it can block excessive current from flowing at lower temperatures. Note that blocking the flow of this excessive current is also referred to as shutdown.
  • the polyethylene include low density polyethylene, high density polyethylene, linear polyethylene (ethylene- ⁇ -olefin copolymer), and ultrahigh molecular weight polyethylene having a weight average molecular weight of 1,000,000 or more. Among these, ultrahigh molecular weight polyethylene having a weight average molecular weight of 1,000,000 or more is more preferable.
  • the thickness of the porous film is preferably 4 to 40 ⁇ m, more preferably 5 to 30 ⁇ m, and further preferably 6 to 15 ⁇ m.
  • the basis weight per unit area of the porous film can be appropriately determined in consideration of strength, film thickness, weight and handleability.
  • the basis weight is preferably 4 to 20 g / m 2 , and preferably 4 to 12 g / m 2 so that the weight energy density and the volume energy density of the non-aqueous electrolyte secondary battery can be increased. More preferably, it is more preferably 5 to 10 g / m 2 .
  • the air permeability of the porous film is preferably 30 to 500 sec / 100 mL in Gurley value, and more preferably 50 to 300 sec / 100 mL.
  • the air permeability of the laminated separator for a non-aqueous electrolyte secondary battery in which the above-mentioned porous layer is laminated on the porous film is preferably 30 to 1000 sec / 100 mL in terms of Gurley value, and is 50 to 800 sec / 100 mL. Is more preferable. Since the laminated separator for a non-aqueous electrolyte secondary battery has the above-mentioned air permeability, it is possible to obtain sufficient ion permeability in the non-aqueous electrolyte secondary battery.
  • the porosity of the porous film is preferably 20 to 80% by volume so as to increase the holding amount of the electrolytic solution and to surely prevent the flow of an excessive current at a lower temperature. It is more preferably 30 to 75% by volume.
  • the pore size of the pores of the porous film is 0.3 ⁇ m or less so that sufficient ion permeability can be obtained and particles can be prevented from entering the positive electrode and the negative electrode. Is preferable, and 0.14 ⁇ m or less is more preferable.
  • the method for producing the polyolefin porous film is not particularly limited.
  • a sheet-shaped polyolefin resin composition is prepared by kneading a polyolefin resin, a pore-forming agent such as an inorganic filler and a plasticizer, and optionally an antioxidant and the like and then extruding the kneaded product. After removing the pore-forming agent from the sheet-shaped polyolefin resin composition with an appropriate solvent, the polyolefin resin composition from which the pore-forming agent has been removed may be stretched to produce a polyolefin porous film. it can.
  • the above-mentioned inorganic filler is not particularly limited, and examples thereof include inorganic fillers, specifically calcium carbonate and the like.
  • the plasticizer is not particularly limited, and examples thereof include low molecular weight hydrocarbons such as liquid paraffin.
  • a method including the following steps can be mentioned.
  • A a step of kneading an ultrahigh molecular weight polyethylene, a low molecular weight polyethylene having a weight average molecular weight of 10,000 or less, a pore forming agent such as calcium carbonate or a plasticizer, and an antioxidant to obtain a polyolefin resin composition
  • B a step of rolling the obtained polyolefin resin composition with a pair of rolling rollers and gradually cooling it while pulling it with a take-up roller having a different speed ratio to form a sheet
  • C a step of removing the pore forming agent from the obtained sheet with a suitable solvent
  • D A step of stretching the sheet from which the pore forming agent has been removed at an appropriate stretching ratio.
  • Method for producing laminated separator for non-aqueous electrolyte secondary battery examples include, for example, in the above-mentioned “method for producing a porous layer”, as the base material to which the coating liquid is applied, The method of using a polyolefin porous film can be mentioned.
  • Non-aqueous electrolyte The non-aqueous electrolyte that can be included in the non-aqueous electrolyte secondary battery according to the embodiment of the present invention is not particularly limited as long as it is a non-aqueous electrolyte that is generally used in non-aqueous electrolyte secondary batteries.
  • a non-aqueous electrolyte obtained by dissolving a lithium salt in an organic solvent can be used.
  • lithium salt examples include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , Li 2 B 10 Cl. 10 , lower aliphatic carboxylic acid lithium salt, LiAlCl 4 and the like.
  • the lithium salt may be used alone or in combination of two or more kinds.
  • organic solvent that constitutes the non-aqueous electrolytic solution
  • examples of the organic solvent that constitutes the non-aqueous electrolytic solution include carbonates, ethers, esters, nitriles, amides, carbamates and sulfur-containing compounds, and fluorine-containing compounds introduced into these organic solvents. Fluorine organic solvents and the like can be mentioned.
  • the organic solvent may be used alone or in combination of two or more.
  • a conventionally known manufacturing method can be adopted.
  • a positive electrode plate, a polyolefin porous film, and a negative electrode plate are arranged in this order to form a member for a non-aqueous electrolyte secondary battery.
  • the porous layer may be present between the polyolefin porous film and at least one of the positive electrode plate and the negative electrode plate.
  • the member for a non-aqueous electrolyte secondary battery is put in a container which is a casing of the non-aqueous electrolyte secondary battery. After filling the inside of the container with the non-aqueous electrolyte, the container is sealed while reducing the pressure. Thereby, the non-aqueous electrolyte secondary battery according to the embodiment of the present invention can be manufactured.
  • Film thickness (unit: ⁇ m)
  • the thickness of the polyolefin porous film and the porous layer, and the thickness of the positive electrode plate and the negative electrode plate were measured using a high precision digital length measuring machine (VL-50) manufactured by Mitutoyo Corporation.
  • the thickness of the electrode active material layer was a value obtained by subtracting the thickness of the uncoated portion from the thickness of the coated portion of each electrode plate.
  • An OHP film was placed on the obtained SEM image to create a projected image laid out along the contours of the particles of the inorganic filler, and the projected image was taken by a digital still camera.
  • the obtained photograph data is imported into a computer, and the aspect ratio of each of 100 particles is calculated using the free image analysis software IMAGEJ issued by the National Institutes of Health (NIH).
  • the average was defined as the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer in the porous layer (hereinafter also referred to as the surface filler aspect ratio).
  • each filler particle was approximated to an ellipse, the major axis diameter and the minor axis diameter were calculated, and the value obtained by dividing the major axis diameter by the minor axis diameter was taken as the aspect ratio per filler.
  • the peak intensities I (hkl) and I (abc) of arbitrary diffraction planes (hkl) and (abc) orthogonal to each other in the wide-angle X-ray diffraction measurement of the porous layer are expressed by the following formula (1 ).
  • the peak intensity ratio calculated by I (hkl) / I (abc) in the case of satisfying (1) is calculated, and the maximum value of the peak intensity ratio is calculated. I (hkl) > I (abc) ... (1).
  • a part of the electrode plate on which the 3 cm ⁇ 3 cm square electrode active material layer was formed and a part on which the 1 cm ⁇ 1 cm square electrode active material layer was not formed were cut out as one piece from the electrode plate to be measured.
  • a tab lead having a length of 6 cm and a width of 0.5 cm was ultrasonically welded to a portion of the cut electrode plate where the electrode active material layer was not formed to obtain an electrode plate for measuring capacitance (Fig. 3).
  • the tab lead of the positive electrode plate was made of aluminum, and the tab lead of the negative electrode plate was made of nickel.
  • a 5 cm x 4 cm square and a 1 cm x 1 cm square for tab lead welding were cut out as one piece.
  • a tab lead having a length of 6 cm and a width of 0.5 cm was ultrasonically welded to a tab lead welding portion of the cut current collector to obtain a probe electrode (measurement electrode) (FIG. 4).
  • a 20 ⁇ m thick aluminum probe electrode is used as the probe electrode for measuring the capacitance of the positive electrode plate, and a 20 ⁇ m thick copper probe electrode is used as the probe electrode for measuring the capacitance of the negative electrode plate.
  • a laminate was prepared by stacking the probe electrode and a portion (3 cm ⁇ 3 cm square portion) of the electrode plate for measurement on which the electrode active material layer was formed.
  • the obtained laminated body was sandwiched between two silicone rubbers, and further sandwiched between each of the silicone rubbers with two SUS plates at a pressure of 0.7 MPa to obtain a laminated body for measurement.
  • the tab lead was taken out from the laminate used for the measurement, and the voltage terminal and the current terminal of the LCR meter were connected from the side closer to the electrode plate of the tab lead.
  • the plate was cut into a size of 14.5 cm 2 (4.5 cm ⁇ 3 cm + 1 cm ⁇ 1 cm).
  • the cut-out positive electrode plate had a mass of 0.215 g and a thickness of 58 ⁇ m.
  • the positive electrode current collector was cut into the same size, the mass was 0.078 g and the thickness was 20 ⁇ m.
  • the porosity of the negative electrode active material layer included in the negative electrode plate 1 in Example 1 below was measured by the following method.
  • the porosities of the negative electrode active material layers included in the other negative electrode plates in the following Examples and Comparative Examples were also measured by the same method.
  • Negative electrode plate (graphite / styrene-1,3-butadiene copolymer / sodium carboxymethylcellulose (weight ratio 98/1/1)) carried on one side of negative electrode current collector (copper foil) It was cut into a size of 0.5 cm 2 (5 cm ⁇ 3.5 cm + 1 cm ⁇ 1 cm). The cut negative electrode plate had a mass of 0.266 g and a thickness of 48 ⁇ m. When the negative electrode current collector was cut into the same size, the mass was 0.162 g and the thickness was 10 ⁇ m.
  • the true densities of the materials forming the negative electrode mixture were 2.2 g / cm 3 for graphite, 1 g / cm 3 for styrene-1,3-butadiene copolymer, and 1.6 g / cm 3 for sodium carboxymethyl cellulose. It was cm 3 .
  • the porosity ⁇ of the negative electrode active material layer calculated based on the following formula using these values was 31%.
  • ⁇ [1- ⁇ 1.49 ⁇ (98/100) /2.2+1.49 ⁇ (1/100) /1+1.49 ⁇ (1/100) /1.6 ⁇ ]
  • ⁇ 100 31% (7)
  • Charge capacity after high-rate discharge of non-aqueous electrolyte secondary battery Non-aqueous electrolyte secondary battery manufactured in Examples and Comparative Examples by the method shown in the following steps (A) to (B) The charge capacity during 1C charging after high rate discharge (10C discharge) was measured.
  • CC-CV charging is a charging method in which charging is performed with a set constant current, and after reaching a predetermined voltage, the current is reduced while maintaining the voltage.
  • CC discharge is a method of discharging to a predetermined voltage with a set constant current. The same applies to the following.
  • the charge capacity at the time of 1C charge in the third cycle when measuring the 10C discharge rate characteristics was measured and used as the charge capacity (mAh) after high rate discharge.
  • the designed capacity of the non-aqueous electrolyte secondary batteries manufactured in Examples and Comparative Examples was 20.5 mAh.
  • Example 1 ⁇ Production of polyolefin porous film> A polyolefin porous film was produced using polyethylene. Specifically, 70 parts by weight of ultra high molecular weight polyethylene powder (340M, manufactured by Mitsui Chemicals, Inc.) and 30 parts by weight of polyethylene wax having a weight average molecular weight of 1000 (FNP-0115, manufactured by Nippon Seiro Co., Ltd.) are mixed. To obtain mixed polyethylene. With respect to 100 parts by weight of the obtained mixed polyethylene, 0.4 parts by weight of an antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals Co., Ltd.), and an antioxidant (P168, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.
  • an antioxidant Irg1010, manufactured by Ciba Specialty Chemicals Co., Ltd.
  • P168 manufactured by Ciba Specialty Chemicals Co., Ltd.
  • This sheet was immersed in an aqueous hydrochloric acid solution prepared by mixing 0.5 mol% of a nonionic surfactant in 4 mol / L hydrochloric acid to dissolve and remove calcium carbonate. Then, the said sheet
  • the porosity of the polyolefin porous film was 53%, the basis weight was 7 g / m 2 , and the film thickness was 16 ⁇ m.
  • This polyolefin porous film was used as a polyolefin porous film 1.
  • a vinylidene fluoride-hexafluoropropylene copolymer (manufactured by Arkema Ltd .; trade name “KYNAR2801”) was used.
  • the inorganic filler 1, the vinylidene fluoride-hexafluoropropylene copolymer and the solvent (N-methyl-2-pyrrolidinone manufactured by Kanto Chemical Co., Inc.) were mixed in the following proportions. That is, 10 parts by weight of vinylidene fluoride-hexafluoropropylene copolymer was mixed with 90 parts by weight of inorganic filler 1, and the solid content (inorganic filler 1 and vinylidene fluoride-hexafluoropropylene copolymer) in the resulting mixed liquid was mixed.
  • the solvent was mixed so that the concentration of) was 37% by weight.
  • the resulting mixed liquid was stirred and mixed with a thin film swivel type high speed mixer (Filmiku (registered trademark) manufactured by PRIMIX Corporation) to obtain a uniform coating liquid.
  • the obtained coating liquid was applied to one side of the polyolefin porous film 1 by a doctor blade method at a coating shear rate of 3.9 (1 / s), and was applied to one side of the polyolefin porous film 1.
  • a coating film was formed.
  • the coating film was dried at 65 ° C. for 20 minutes to form the porous layer 1 on one surface of the polyolefin porous film 1. Thereby, a laminate 1 of the polyolefin porous film 1 and the porous layer 1 was obtained.
  • the basis weight of the porous layer 1 was 7 g / m 2 and the thickness was 4 ⁇ m.
  • the maximum values of the aspect ratio and the peak intensity ratio of the projected image of the inorganic filler on the surface of the porous layer were measured. The results are shown in Table 1.
  • Preparation of non-aqueous electrolyte secondary battery A positive electrode plate manufactured by applying LiNi 0.5 Mn 0.3 Co 0.2 O 2 / conductive agent / PVDF (weight ratio 92/5/3) to an aluminum foil was used. The positive electrode plate is cut out of an aluminum foil so that the size of the part where the positive electrode active material layer is formed is 45 mm ⁇ 30 mm, and the part where the width of 13 mm is not formed and the positive electrode active material layer is not formed remains on the outer periphery. To obtain a positive electrode plate 1.
  • the positive electrode active material layer had a thickness of 58 ⁇ m and a density of 2.50 g / cm 3 .
  • a negative electrode plate manufactured by applying graphite / styrene-1,3-butadiene copolymer / sodium carboxymethyl cellulose (weight ratio 98/1/1) to a copper foil was used.
  • a copper foil was applied to the negative electrode plate so that the size of the portion on which the negative electrode active material layer was formed was 50 mm ⁇ 35 mm, and the portion on the outer periphery of which the width was 13 mm and the negative electrode active material layer was not formed remained. It was cut out to obtain a negative electrode plate 1.
  • the negative electrode active material layer had a thickness of 49 ⁇ m and a density of 1.40 g / cm 3 .
  • a non-aqueous electrolyte secondary battery was manufactured by the following method using the positive electrode plate, the negative electrode plate, and the laminated body 1.
  • the positive electrode plate 1 and the negative electrode plate 1 are so arranged that the entire main surface of the positive electrode active material layer of the positive electrode plate 1 is included in the range of the main surface of the negative electrode active material layer of the negative electrode plate 1 (overlaps with the main surface).
  • the positive electrode plate 1 and the negative electrode plate 1 are so arranged that the entire main surface of the positive electrode active material layer of the positive electrode plate 1 is included in the range of the main surface of the negative electrode active material layer of the negative electrode plate 1 (overlaps with the main surface).
  • the non-aqueous electrolyte secondary battery member 1 was placed in a pre-made bag formed by laminating an aluminum layer and a heat-sealing layer, and 0.25 mL of the non-aqueous electrolyte solution was placed in this bag. It was The non-aqueous electrolyte solution was prepared by dissolving LiPF 6 in a mixed solvent prepared by mixing ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 3: 5: 2 so that the concentration of LiPF 6 was 1 mol / L. Prepared. Then, the inside of the bag was depressurized and the bag was heat-sealed to manufacture the non-aqueous electrolyte secondary battery 1.
  • Example 2 ⁇ Production of laminate of polyolefin porous film and porous layer>
  • Got The pulverized product was used as an inorganic filler 2.
  • the above-mentioned inorganic filler 2 was used to prepare the coating liquid 2, and the coating liquid 2 was applied to one side of the polyolefin porous film 1 by shearing.
  • a laminate 2 of a polyolefin porous film 1 and a porous layer 2 was prepared in the same manner as in Example 1 except that the porous layer 2 was formed by coating at a speed of 7.9 (1 / s). Obtained.
  • the maximum value of the aspect ratio and the peak intensity ratio of the projected image of the inorganic filler 2 on the surface of the porous layer was measured using the obtained laminate 2. The results are shown in Table 1.
  • a non-aqueous electrolyte secondary battery 2 was produced in the same manner as in Example 1 except that the laminate 2 was used instead of the laminate 1.
  • Example 3 ⁇ Production of laminate of polyolefin porous film and porous layer>
  • ⁇ -alumina Suditomo Chemical Co., Ltd., trade name: AKP3000
  • hexagonal plate-shaped zinc oxide Sakai Chemical Industry Co., Ltd., trade name: XZ-1000F
  • a mixture oxygen atom mass percentage 47%) in which 99 parts by weight of ⁇ -alumina and 1 part by weight of hexagonal zinc oxide were mixed in a mortar was used as the inorganic filler 3.
  • the coating liquid 3 was prepared by mixing a solvent so that the concentration of the coating liquid was 40% by weight, and the coating liquid 3 was applied to one surface of the polyolefin porous film 1 at a shear rate of 39.4 (1 / s).
  • a laminated body 3 of the polyolefin porous film 1 and the porous layer 3 was obtained in the same manner as in Example 1 except that the porous layer 3 was formed by coating with (1).
  • the maximum value of the aspect ratio and the peak intensity ratio of the projected image of the inorganic filler 3 on the surface of the porous layer was measured using the obtained laminate 3. The results are shown in Table 1.
  • a non-aqueous electrolyte secondary battery 3 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1.
  • Example 4 ⁇ Production of laminate of polyolefin porous film and porous layer>
  • spherical alumina Suditomo Chemical Co., Ltd., trade name AA03
  • mica Wired Chemical Industries, Ltd., trade name: non-swelling synthetic mica
  • the inorganic filler 4 was a mixture (oxygen atom mass percentage 45%) in which 50 parts by weight of spherical alumina and 50 parts by weight of mica were mixed in a mortar.
  • a non-aqueous electrolyte secondary battery 4 was produced in the same manner as in Example 1 except that the laminate 4 was used instead of the laminate 1.
  • Example 5 ⁇ Production of laminate of polyolefin porous film and porous layer>
  • wollastonite (Hayashi Kasei Co., Ltd., trade name: Wollastonite VM-8N) having an oxygen atomic mass percentage of 41% was used.
  • a non-aqueous electrolyte secondary battery 5 was produced in the same manner as in Example 1 except that the laminate 5 was used instead of the laminate 1.
  • Example 6 ⁇ Production of laminate of polyolefin porous film and porous layer> The same layered product 3 as in Example 3 was used.
  • ⁇ Preparation of non-aqueous electrolyte secondary battery> (Preparation of positive electrode plate)
  • the surface of the same positive electrode plate as the positive electrode plate 1 on the positive electrode active material layer side was polished three times using a polishing cloth sheet (model number TYPE PE A GRIT No100) manufactured by Nagatsuka Industry Co., Ltd. to obtain a positive electrode plate 2.
  • the positive electrode active material layer of the positive electrode plate 2 had a thickness of 38 ⁇ m and a porosity of 40%.
  • the negative electrode plate 1 was used as the negative electrode plate.
  • a non-aqueous electrolyte secondary battery 6 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1 and the positive electrode plate 2 was used instead of the positive electrode plate 1.
  • Example 7 ⁇ Production of laminate of polyolefin porous film and porous layer> The same layered product 3 as in Example 3 was used.
  • ⁇ Preparation of non-aqueous electrolyte secondary battery> (Preparation of positive electrode plate)
  • the surface of the same positive electrode plate as the positive electrode plate 1 on the positive electrode active material layer side was polished 5 times using a polishing cloth sheet (model number TYPE AA GRIT No100) manufactured by Nagatsuka Industry Co., Ltd. to obtain a positive electrode plate 3.
  • the positive electrode active material layer of the positive electrode plate 3 had a thickness of 38 ⁇ m and a porosity of 40%.
  • the negative electrode plate 1 was used as the negative electrode plate.
  • a non-aqueous electrolyte secondary battery 7 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1 and the positive electrode plate 3 was used instead of the positive electrode plate 1.
  • Example 8 ⁇ Production of laminate of polyolefin porous film and porous layer> The same layered product 3 as in Example 3 was used.
  • the surface of the same negative electrode plate as the negative electrode plate 1 on the negative electrode active material layer side was polished three times using a polishing cloth sheet (model number TYPE AA GRIT No100) manufactured by Nagatsuka Industry Co., Ltd. to obtain a negative electrode plate 2.
  • the negative electrode active material layer of the negative electrode plate 2 had a thickness of 38 ⁇ m and a porosity of 31%.
  • a non-aqueous electrolyte secondary battery 8 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1 and the negative electrode plate 2 was used instead of the negative electrode plate 1.
  • Example 9 ⁇ Production of laminate of polyolefin porous film and porous layer> The same layered product 3 as in Example 3 was used.
  • a non-aqueous electrolyte secondary battery 9 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1 and the negative electrode plate 3 was used instead of the negative electrode plate 1.
  • a non-aqueous electrolyte secondary battery 10 was produced in the same manner as in Example 1 except that the laminate 6 was used instead of the laminate 1.
  • a non-aqueous electrolyte secondary battery 11 was produced in the same manner as in Example 1 except that the laminate 7 was used instead of the laminate 1.
  • the coating liquid 8 was applied to one side of the polyolefin porous film 1 by a doctor blade method to obtain a coating shear rate of 1.3
  • a laminated body 8 of the polyolefin porous film 1 and the porous layer 8 was obtained in the same manner as in Example 1 except that the porous layer 8 was formed by applying 1 / s).
  • the maximum value of the aspect ratio and the peak intensity ratio of the projected image of the inorganic filler 8 on the surface of the porous layer was measured using the obtained layered product 8. The results are shown in Table 1.
  • a non-aqueous electrolyte secondary battery 12 was produced in the same manner as in Example 1 except that the laminate 8 was used instead of the laminate 1.
  • the coating solution 9 was applied to one side of the polyolefin porous film 1 by a doctor blade method to obtain a coating shear rate of 0.4 (1 / S) was applied to form the porous layer 9 to obtain a laminate 9 of the polyolefin porous film 1 and the porous layer 9 in the same manner as in Example 1.
  • the maximum value of the aspect ratio and the peak intensity ratio of the projected image of the inorganic filler 9 on the surface of the porous layer was measured using the obtained laminate 9. The results are shown in Table 1.
  • a non-aqueous electrolyte secondary battery 13 was produced in the same manner as in Example 1 except that the laminate 9 was used instead of the laminate 1.
  • ⁇ Preparation of non-aqueous electrolyte secondary battery> (Preparation of positive electrode plate)
  • the surface of the same positive electrode plate as the positive electrode plate 1 on the positive electrode active material layer side was polished 10 times using a polishing cloth sheet (model number TYPE AA GRIT No100) manufactured by Nagatsuka Kogyo Co., Ltd. to obtain a positive electrode plate 4.
  • the positive electrode active material layer of the positive electrode plate 4 had a thickness of 38 ⁇ m and a porosity of 40%.
  • the negative electrode plate 1 was used as the negative electrode plate.
  • a non-aqueous electrolyte secondary battery 14 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1 and the positive electrode plate 4 was used instead of the positive electrode plate 1.
  • the surface of the same negative electrode plate as the negative electrode plate 1 on the negative electrode active material layer side was polished 10 times using a polishing cloth sheet (model number TYPE PE A GRIT No100) manufactured by Nagatsuka Industry Co., Ltd. to obtain a negative electrode plate 4.
  • the negative electrode active material layer of the negative electrode plate 4 had a thickness of 38 ⁇ m and a porosity of 31%.
  • a non-aqueous electrolyte secondary battery 15 was produced in the same manner as in Example 1 except that the laminate 3 was used instead of the laminate 1 and the negative electrode plate 4 was used instead of the negative electrode plate 1.
  • Table 1 shows the results of measuring the charge capacities of the non-aqueous electrolyte secondary batteries 1 to 15 obtained in Examples and Comparative Examples after high rate discharge.
  • the aspect ratio of the projected image of the inorganic filler on the surface of the porous layer is in the range of 1.4 to 4.0, and the maximum value of the peak intensity ratio (I (hkl) / I (abc) ) is a range of 1.5 to 300, the capacitance of the measurement area 900 mm 2 per positive electrode plate, or 1nF, or less 1000 nF, the capacitance of the measurement area 900 mm 2 per negative electrode plate, 4nF above,
  • the non-aqueous electrolyte secondary batteries obtained in Examples 1 to 9 having 8500 nF or less are compared with the non-aqueous electrolyte secondary batteries obtained in Comparative Examples 1 to 6 which do not satisfy any of the conditions. It was also shown to exhibit excellent charge capacity after high rate discharge.
  • the non-aqueous electrolyte secondary battery according to the present invention has excellent charge capacity after high rate discharge. Therefore, the non-aqueous electrolyte secondary battery according to the present invention can be widely used in the field of manufacturing non-aqueous electrolyte secondary batteries.

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Abstract

L'objet de la présente invention concerne un accumulateur à électrolyte non aqueux qui a une excellente capacité de charge après une décharge à haut débit. Cet accumulateur à électrolyte non aqueux comporte une couche poreuse qui contient une charge inorganique et une résine, et une plaque d'électrode positive et une plaque d'électrode négative dont la capacité électrostatique par 900 mm² d'aire de surface mesurée est comprise dans une plage prédéfinie, le facteur de forme de l'image projetée de la charge inorganique sur la surface de la couche poreuse, et le ratio d'intensité de crête (I(hkl)/I(abc)) de tous plans de diffraction orthogonale (hkl) et (abc) mesuré avec une diffraction aux rayons X à grand angle, sont compris dans une plage prédéfinie. <sb />
PCT/JP2019/043093 2018-11-01 2019-11-01 Accumulateur à électrolyte non aqueux Ceased WO2020091058A1 (fr)

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JP2018106879A (ja) * 2016-12-26 2018-07-05 トヨタ自動車株式会社 絶縁層付き負極
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JP2005222773A (ja) * 2004-02-04 2005-08-18 Toshiba Corp 非水電解質二次電池及び非水電解質二次電池用負極
WO2014208454A1 (fr) * 2013-06-27 2014-12-31 旭化成イーマテリアルズ株式会社 Séparateur pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux
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