WO2019156172A1 - Batterie secondaire au lithium-ion, structure d'électrode négative de batterie secondaire au lithium-ion, et procédé de production d'une batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion, structure d'électrode négative de batterie secondaire au lithium-ion, et procédé de production d'une batterie secondaire au lithium-ion Download PDF

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Publication number
WO2019156172A1
WO2019156172A1 PCT/JP2019/004432 JP2019004432W WO2019156172A1 WO 2019156172 A1 WO2019156172 A1 WO 2019156172A1 JP 2019004432 W JP2019004432 W JP 2019004432W WO 2019156172 A1 WO2019156172 A1 WO 2019156172A1
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Prior art keywords
negative electrode
lithium ion
ion secondary
secondary battery
adhesive layer
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PCT/JP2019/004432
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English (en)
Japanese (ja)
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利絵 寺西
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積水化学工業株式会社
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Priority to JP2019571148A priority Critical patent/JPWO2019156172A1/ja
Publication of WO2019156172A1 publication Critical patent/WO2019156172A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery, a negative electrode structure for a lithium ion secondary battery, and a method for producing a lithium ion secondary battery.
  • Lithium ion secondary batteries are used as large stationary power sources for power storage, power sources for electric vehicles, and the like, and in recent years, research on miniaturization and thinning of batteries has been progressing.
  • a lithium ion secondary battery includes both electrodes (a positive electrode and a negative electrode) in which an electrode active material layer is formed on the surface of a metal foil, and a separator disposed between both electrodes.
  • the separator plays a role of preventing a short circuit between both electrodes and holding an electrolytic solution.
  • a lithium ion secondary battery is manufactured by preparing a positive electrode and a negative electrode, which are constituent members thereof, and a separator or the like provided therebetween, and hot-pressing them.
  • Patent Document 1 discloses a technique for manufacturing a lithium ion secondary battery by providing an electrode adhesive layer on a separator made of a porous polymer substrate.
  • an object of the present invention is to provide a lithium ion secondary battery that has both good adhesion and rapid chargeability between the electrode and the separator and has high energy density.
  • the gist of the present invention is the following [1] to [10].
  • a negative electrode having a negative electrode active material layer, a positive electrode, a separator disposed between the negative electrode and the positive electrode, and disposed between at least one of the negative electrode and the positive electrode and the separator,
  • An adhesive layer for adhering the electrode wherein the adhesive layer contains 30 to 55% by volume of at least one resin selected from the group consisting of a polyvinylidene fluoride-hexafluoropropylene copolymer and an acrylic resin,
  • a lithium ion secondary battery in which the density of the negative electrode active material layer is 1.50 to 1.70 g / cm 3 .
  • the present invention it is possible to provide a lithium ion secondary battery that has both good adhesion and rapid chargeability between the electrode and the separator and high energy density.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the lithium ion secondary battery of the present invention.
  • the lithium ion secondary battery 10 includes a negative electrode 11, a positive electrode 12, a separator 13 disposed between the negative electrode 11 and the positive electrode 12, and an adhesive layer 14 disposed between the separator 13 and the negative electrode 11.
  • the negative electrode 11 includes a negative electrode current collector 11a and a negative electrode active material layer 11b laminated on the negative electrode current collector 11a.
  • the positive electrode 12 has a positive electrode current collector 12a and a positive electrode current collector 12a. And a positive electrode active material layer 12b laminated thereon.
  • An adhesive layer 14 is provided between the negative electrode active material layer 11b and the separator 13 so as to be in contact with both, and the two are adhered to each other.
  • the adhesive layer 14 is provided between the negative electrode active material layer 11 b and the separator 13, but may be provided between the positive electrode active material layer 12 b and the separator 13.
  • the adhesive layer 14 may be provided between both the negative electrode active material layer 11b and the separator 13 and between the positive electrode active material layer 12b and the separator 13, but is preferably provided on either one.
  • the adhesive layer improves the adhesion between the electrode and the separator, and it is possible to prevent problems such as floating of the separator when assembling a lithium ion secondary battery.
  • the adhesive layer used in the lithium ion secondary battery of the present invention is disposed between at least one of the negative electrode and the positive electrode and the separator, and adheres the separator and the electrode.
  • the adhesive layer is preferably disposed between the negative electrode and the separator from the viewpoint of improving the adhesion between the electrode and the separator. This is because the surface area of the negative electrode active material layer constituting the negative electrode is generally larger than the surface area of the positive electrode active material layer, and the area where the adhesive layer can be formed is larger in the negative electrode.
  • the adhesive layer is made of at least one resin selected from the group consisting of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and an acrylic resin (hereinafter also referred to as a specific resin) in an amount of 30 to 55 on the basis of the total amount of the adhesive layer. Contains by volume.
  • the specific resin it is preferable to use a polyvinylidene fluoride-hexafluoropropylene copolymer from the viewpoint of further improving the adhesion between the electrode and the separator.
  • the content of the specific resin in the adhesive layer is preferably 32 to 48% by volume, and preferably 35 to 45% by volume. Is more preferable.
  • an acrylic resin for example, a homopolymer of (meth) acrylate monomer, a copolymer of two or more (meth) acrylate monomers, a (meth) acrylate monomer, and these can be copolymerized Examples thereof include copolymers with other vinyl monomers.
  • (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid.
  • examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • Examples of other vinyl monomers copolymerizable with the (meth) acrylic acid ester monomer include acrylic acid, methacrylic acid, styrene, methylstyrene, vinyl acetate, acrylonitrile, itaconic acid, maleic acid and the like.
  • acrylic resins polymethyl acrylate, polymethyl methacrylate, and the like can be suitably used.
  • the adhesive layer preferably contains a urea resin from the viewpoint of improving the adhesion between the electrode and the separator.
  • the urea resin is a synthetic resin obtained by reacting urea with formaldehyde.
  • the content of urea resin in the adhesive layer is preferably 5 to 70% by volume, more preferably 10 to 65% by volume, and further preferably 25 to 35% by volume based on the total amount of the adhesive layer. .
  • urea resin has a low degree of decrease in rapid chargeability even when the content is increased. Therefore, the content is relatively increased to improve adhesiveness while maintaining rapid chargeability. it can.
  • the total amount of the urea resin in the adhesive layer and insulating fine particles described later is preferably 70% by volume or less, and preferably 65% by volume or less based on the total amount of the adhesive layer.
  • the adhesive layer may contain other resins other than the specific resin and urea resin as long as the effects of the present invention are not hindered.
  • Other resins include fluorine-containing resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polyvinyl acetate, polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), and polyether nitrile. (PEN), polyethylene (PE), polypropylene (PP), polyacrylonitrile (PAN), acrylonitrile-butadiene rubber, styrene butadiene rubber, poly (meth) acrylic acid, carboxymethylcellulose, hydroxyethylcellulose, and polyvinyl alcohol.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PI polyimide
  • PA polyamide
  • PVC polyvinyl chloride
  • PEN polyether nitrile
  • PE polyethylene
  • carboxymethyl cellulose and the like may be used in the form of a salt such as a sodium salt.
  • the content of the other resin in the adhesive layer is preferably 10% by volume or less, more preferably 5% by volume or less, and still more preferably 0% by volume.
  • the adhesive layer preferably further contains insulating fine particles to form an insulating layer.
  • the adhesive layer also functions as an insulating layer, and it is possible to effectively prevent a short circuit between the positive electrode and the negative electrode.
  • the insulating fine particles are not particularly limited as long as they are insulating, and may be either organic particles or inorganic particles.
  • organic particles include, for example, polymethyl methacrylate, styrene-acrylic acid copolymer, acrylonitrile resin, polyamide resin, polyimide resin, poly (2-acrylamido-2-methylpropanesulfonic acid lithium), polyacetal resin, Examples thereof include particles composed of an organic compound such as an epoxy resin, a polyester resin, a phenol resin, and a melamine resin.
  • Inorganic particles include silicon dioxide, silicon nitride, alumina, boehmite, titania, zirconia, boron nitride, zinc oxide, tin dioxide, niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 5 ), potassium fluoride, fluorine And particles composed of inorganic compounds such as lithium fluoride, clay, zeolite, and calcium carbonate.
  • the inorganic particles may be particles composed of a known composite oxide such as niobium-tantalum composite oxide or magnesium-tantalum composite oxide.
  • the insulating fine particles may be particles in which each of the above materials is used alone or in combination of two or more.
  • the insulating fine particles may be fine particles containing both an inorganic compound and an organic compound.
  • inorganic-organic composite particles in which the surface of particles made of an organic compound is coated with an inorganic oxide may be used.
  • inorganic particles are preferable, and alumina particles and boehmite particles are particularly preferable.
  • the average particle diameter of the insulating fine particles is not particularly limited as long as it is smaller than the thickness of the adhesive layer, and is, for example, 0.001 to 1 ⁇ m, preferably 0.05 to 0.8 ⁇ m, more preferably 0.1 to 0.6 ⁇ m. is there.
  • the average particle diameter means the particle diameter (D50) at a volume integration of 50% in the particle size distribution of the insulating fine particles obtained by the laser diffraction / scattering method.
  • the insulating fine particles may be used alone as an average particle diameter within the above range, or may be used by mixing two kinds of insulating fine particles having different average particle diameters.
  • the content of the insulating fine particles contained in the adhesive layer is preferably 45 to 70% by volume, and 52 to 68% by volume based on the total amount of the adhesive layer. More preferably, the content is 55 to 65% by volume. Further, when the urea resin is contained in the adhesive layer, the content of the insulating fine particles contained in the adhesive layer is preferably 20 to 65% by volume, and preferably 20 to 60% by volume based on the total amount of the adhesive layer. More preferably, it is more preferably 25 to 35% by volume.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 1 to 10 ⁇ m. By setting the thickness of the insulating layer to 10 ⁇ m or less, quick chargeability is improved. Moreover, the adhesiveness of an electrode and a separator improves by setting it as 1 micrometer or more. From the viewpoint of quick chargeability and adhesiveness, the thickness of the adhesive layer is more preferably 1.5 to 8.5 ⁇ m, and further preferably 3 to 7 ⁇ m.
  • the negative electrode in the lithium ion secondary battery of the present invention has a negative electrode active material layer, preferably a negative electrode current collector and a negative electrode active material layer laminated on the negative electrode current collector.
  • the negative electrode active material layer typically includes a negative electrode active material and a negative electrode binder.
  • the density of the negative electrode active material layer is 1.50 to 1.70 g / cc. When the density of the negative electrode active material layer is less than 1.50 g / cc, the energy density of the lithium ion secondary battery is lowered. When the density of the negative electrode active material layer exceeds 1.70 g / cc, the quick chargeability deteriorates.
  • the density of the negative electrode active material layer is preferably 1.53 to 1.60 g / cc from the viewpoint of improving both energy density and rapid chargeability.
  • the method for adjusting the density of the negative electrode active material layer is not particularly limited, and can be adjusted, for example, by adjusting the type, blending amount, average particle size, and the like of the negative electrode active material. Further, the negative electrode having the negative electrode current collector on which the negative electrode active material layer is formed is sandwiched between two flat jigs, and the entire surface of the negative electrode active material layer is uniformly pressed in the thickness direction. it can. For example, the density of the negative electrode active material layer can be adjusted by a method of pressing the negative electrode with a roll press or the like.
  • Examples of the negative electrode active material used in the negative electrode active material layer include carbon materials such as graphite and hard carbon, composites of tin compounds and silicon and carbon, lithium, and the like. Among these, carbon materials are preferable, and graphite is preferable. More preferred.
  • the negative electrode active material is not particularly limited, but the average particle diameter is preferably 0.5 to 50 ⁇ m, and more preferably 1 to 30 ⁇ m.
  • the average particle diameter of the negative electrode active material means a particle diameter (D50) at a volume integration of 50% in the particle size distribution of the negative electrode active material obtained by a laser diffraction / scattering method.
  • the content of the negative electrode active material in the negative electrode active material layer is preferably 50 to 98.5% by mass, more preferably 60 to 98% by mass, based on the total amount of the negative electrode active material layer.
  • the negative electrode active material layer may contain a conductive additive.
  • a conductive additive a material having higher conductivity than the negative electrode active material is used, and specific examples include carbon materials such as ketjen black, acetylene black, carbon nanotube, and rod-like carbon.
  • the conductive auxiliary agent content is preferably 1 to 30% by mass, preferably 2 to 25% by mass, based on the total amount of the negative electrode active material layer. Is more preferable.
  • the negative electrode active material layer is preferably configured by binding a negative electrode active material, or a negative electrode active material and a conductive auxiliary agent with a negative electrode binder.
  • the negative electrode binder include fluorine-containing resins such as polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene (PTFE), and polymethyl acrylate (PMA).
  • Acrylic resin such as polymethyl methacrylate (PMMA), polyvinyl acetate, polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), polyether nitrile (PEN), polyethylene (PE), polypropylene (PP) , Polyacrylonitrile (PAN), acrylonitrile butadiene rubber, styrene butadiene rubber, poly (meth) acrylic acid, carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol.
  • binders may be used individually by 1 type, and 2 or more types may be used together.
  • carboxymethyl cellulose and the like may be used in the form of a salt such as a sodium salt.
  • the content of the negative electrode binder in the negative electrode active material layer is preferably 1.5 to 40% by mass, more preferably 2.0 to 25% by mass, based on the total amount of the negative electrode active material layer.
  • the thickness of the negative electrode active material layer is not particularly limited, but is preferably 10 to 200 ⁇ m, and more preferably 50 to 150 ⁇ m.
  • the negative electrode current collector examples include conductive metals such as copper, aluminum, titanium, nickel, and stainless steel. Among these, aluminum or copper is preferable, and copper is more preferable.
  • the negative electrode current collector is generally made of a metal foil, and the thickness thereof is not particularly limited, but is preferably 1 to 50 ⁇ m.
  • the positive electrode in the lithium ion secondary battery of the present invention has a positive electrode active material layer, and preferably has a positive electrode current collector and a positive electrode active material layer laminated on the positive electrode current collector.
  • the positive electrode active material layer typically includes a positive electrode active material and a positive electrode binder.
  • the positive electrode active material include a metal acid lithium compound.
  • the metal acid lithium compound include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ).
  • olivine type lithium iron phosphate (LiFePO 4 ) may be used.
  • a metal using a plurality of metals other than lithium may be used, and an NCM (nickel cobalt manganese) -based oxide, an NCA (nickel cobalt aluminum-based) oxide or the like called a ternary system may be used.
  • NCM nickel cobalt manganese
  • NCA nickel cobalt aluminum-based oxide
  • the average particle size of the positive electrode active material is not particularly limited, but is preferably 0.5 to 50 ⁇ m, and more preferably 1 to 30 ⁇ m.
  • the average particle diameter of a positive electrode active material means the particle size (D50) by 50% of volume integration in the particle size distribution of the positive electrode active material calculated
  • the content of the positive electrode active material in the positive electrode active material layer is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, based on the total amount of the positive electrode active material layer.
  • the positive electrode active material layer may contain a conductive additive.
  • the conductive auxiliary agent a material having higher conductivity than the positive electrode active material is used, and specific examples thereof include carbon materials such as ketjen black, acetylene black, carbon nanotube, and rod-like carbon.
  • the conductive auxiliary agent content is preferably 0.5 to 30% by mass, based on the total amount of the positive electrode active material layer, and is 1 to 25% by mass. More preferred is 1.5 to 10% by mass.
  • the material for the positive electrode current collector is the same as the compound used for the negative electrode current collector, but preferably aluminum or copper, more preferably aluminum.
  • the positive electrode current collector is generally made of a metal foil, and the thickness thereof is not particularly limited, but is preferably 1 to 50 ⁇ m.
  • the lithium ion secondary battery of this invention is equipped with the separator arrange
  • the short circuit between the positive electrode and the negative electrode is effectively prevented by the separator.
  • the separator may hold an electrolyte described later.
  • the separator include a porous polymer film, a nonwoven fabric, and glass fiber. Among these, a porous polymer film is preferable.
  • the porous polymer film include olefin-based porous films such as ethylene-based porous films.
  • the lithium ion secondary battery of the present invention includes an electrolyte.
  • the electrolyte is not particularly limited, and a known electrolyte used in a lithium ion secondary battery may be used.
  • an electrolytic solution is used as the electrolyte.
  • the electrolytic solution include an electrolytic solution containing an organic solvent and an electrolyte salt.
  • the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, ⁇ -butyrolactone, sulfolane, dimethyl sulfoxide, acetonitrile, dimethylformamide, dimethylacetamide, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrohydra.
  • Examples thereof include polar solvents such as furan, 2-methyltetrahydrofuran, dioxolane, and methyl acetate, or a mixture of two or more of these solvents.
  • Examples of the electrolyte salt include LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiCF 3 CO 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 CF 2 CF 3 ) 2 , LiN (COCF 3 ). 2 and lithium-containing salts such as LiN (COCF 2 CF 3 ) 2 , lithium bisoxalate borate (LiB (C 2 O 4 ) 2.
  • the electrolyte may be a gel electrolyte that further includes a polymer compound in the electrolyte solution.
  • the polymer compound include a fluorine-based polymer such as polyvinylidene fluoride and a polyacrylic polymer such as poly (meth) methyl acrylate.
  • the gel electrolyte may be used as a separator.
  • the electrolyte may be disposed between the negative electrode and the positive electrode.
  • the electrolyte solution is filled in a battery cell in which the negative electrode, the positive electrode, and the separator described above are housed.
  • the electrolyte may be applied on the negative electrode or the positive electrode and disposed between the negative electrode and the positive electrode.
  • the lithium ion secondary battery may have a multilayer structure in which a plurality of negative electrodes and positive electrodes are stacked.
  • the negative electrode and the positive electrode may be provided alternately along the stacking direction.
  • the separator may be disposed between each negative electrode and each positive electrode, and the adhesive layer may be provided at least at one place between the negative electrode and the separator and between the positive electrode and the separator. It is preferable to provide an adhesive layer.
  • the manufacturing method of the lithium ion secondary battery of this invention is not specifically limited, It is preferable to prepare a negative electrode, a positive electrode, and a separator, and to include the process (1) and process (2) mentioned later.
  • the negative electrode can be obtained by applying the composition for negative electrode active material layer to one or both surfaces of the negative electrode current collector and drying it.
  • the applied negative electrode active material layer composition is dried to form a negative electrode active material layer.
  • the composition for negative electrode active material layers is a slurry containing at least one solvent selected from a negative electrode active material, a negative electrode binder, an organic solvent, and water.
  • the negative electrode active material layer may be formed by applying the composition for negative electrode active material layer onto a substrate other than the negative electrode current collector and drying it.
  • a known release sheet may be mentioned.
  • the negative electrode active material layer formed on the substrate may be peeled off from the substrate and transferred onto the negative electrode current collector.
  • the negative electrode active material layer formed on the negative electrode current collector or the substrate is preferably pressure-pressed. It is possible to adjust the density of the negative electrode active material by pressing with pressure. (Manufacture of positive electrode)
  • the positive electrode can be produced by the same method as the production of the negative electrode described above. That is, in manufacturing the negative electrode, the negative electrode can be read as the positive electrode.
  • the method for producing a lithium ion secondary battery of the present invention preferably includes the following steps (1) and (2).
  • Step (1) is a step of forming an adhesive layer on one surface selected from the separator and the electrode.
  • Step (2) is a step in which the other selected from the separator and the electrode is bonded to the adhesive layer formed in step (1) by hot pressing to obtain a laminate.
  • an electrode means either a positive electrode or a negative electrode.
  • the step (1) is preferably a step of forming an adhesive layer on the surface of the negative electrode
  • the step (2) is a step of bonding the separator and the adhesive layer formed in the step (1) by hot pressing. It is preferable that it is the process of making it.
  • Step (1) is a step of forming an adhesive layer on one surface selected from the separator and the electrode.
  • An adhesive layer may be formed on one or both surfaces of the separator to form a separator structure for a lithium ion secondary battery including the separator and the adhesive layer.
  • a positive electrode structure for a lithium ion secondary battery having a positive electrode and an adhesive layer formed by forming an adhesive layer on the surface of the electrode, specifically on the surface of the negative electrode active material layer or the positive electrode active material layer, or the negative electrode It is good also as a negative electrode structure for lithium ion secondary batteries provided with a contact bonding layer.
  • an electrode structure for a lithium ion secondary battery including an electrode and an adhesive layer from the viewpoint of preventing problems such as floating of the separator and improving workability.
  • a negative electrode structure for a lithium ion secondary battery comprising a negative electrode having a negative electrode active material layer and an adhesive layer.
  • the adhesive layer is formed using the adhesive layer composition.
  • the adhesive layer composition includes at least one resin selected from the group consisting of a polyvinylidene fluoride-hexafluoropropylene copolymer and an acrylic resin, and, if necessary, a urea resin, other resins, insulating fine particles, a solvent, etc.
  • the adhesive layer can be formed by applying the composition for the adhesive layer on the surface of the separator, the negative electrode active material layer, or the positive electrode active material layer and drying it.
  • the method for applying the adhesive layer composition is not particularly limited, and examples thereof include a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a bar coating method, a gravure coating method, and a screen printing method.
  • the bar coating method or the gravure coating method is preferable from the viewpoint of uniformly applying the adhesive composition and improving the adhesion between the electrode and the separator.
  • the drying temperature is not particularly limited, but is, for example, 40 to 120 ° C., preferably 50 to 90 ° C. Further, the drying time is not particularly limited, but is, for example, 1 to 10 minutes.
  • Step (2) is a step in which the other selected from the separator and the electrode is bonded to the adhesive layer formed in step (1) by hot pressing to obtain a laminate.
  • the step (2) when an adhesive layer is formed on the separator in the step (1), the adhesive layer on the separator and the electrode are bonded by hot pressing, and the step (1) is applied on the electrode.
  • the adhesive layer on the electrode and the separator are bonded by hot pressing.
  • a plurality of structures obtained in the step (1) are prepared and overlapped with a plurality of other members. What is necessary is just to heat press.
  • a negative electrode structure for a lithium ion secondary battery is obtained by the step (1), a plurality of negative electrode structures for a lithium ion secondary battery, a plurality of separators, and a plurality of positive electrodes are prepared. And superposition so as to be disposed between the positive electrode and the positive electrode, followed by hot pressing.
  • the temperature of the hot press is preferably 60 to 120 ° C, more preferably 70 to 100 ° C.
  • the pressure at the time of hot pressing is preferably 0.2 to 2 MPa, more preferably 0.2 to 1 MPa, and further preferably 0.3 to 0.7 MPa. By hot pressing under such conditions, the adhesion between the electrode and the separator can be improved.
  • the positive electrode, the negative electrode, or the separator is laminated on the laminate obtained in the step (2) and hot-pressed again.
  • a lithium ion secondary battery may be obtained.
  • the lithium ion secondary battery produced through the steps (1) and (2) is usually used in a battery cell.
  • the battery cell may be any of a square shape, a cylindrical shape, a lamination method and the like.
  • the obtained lithium ion secondary battery was evaluated by the following evaluation methods.
  • Adhesive strength A separator (polyethylene porous film) was placed on the adhesive layer side of the electrode having the adhesive layer produced in the examples and comparative examples, and 1 using a flat plate hot press machine at 80 ° C. and 0.6 MPa. The laminate was obtained by pressing for a minute. A double-sided tape was affixed to a SUS plate, and a laminate cut out to 2 cm ⁇ 5 cm was stuck on the SUS plate so that the electrode and the double-sided tape overlapped.
  • Adhesive strength is 2 N / m or more
  • B Adhesive force is 1 N / m or more and less than 2 N / m
  • C Adhesive strength is 0.5 N / m or more and less than 1 N / m
  • D Adhesive force is less than 0.5 N / m
  • the lithium ion secondary batteries produced in the examples and comparative examples were charged and discharged under the following conditions, the discharge capacity was calculated, and the energy density was determined by the following formula (1) using the discharge capacity.
  • a constant current charge of 10 mA was performed, and then the current was decreased as soon as 4.2 V was reached, and the constant voltage charge was completed when the charge reached 0.5 mA. Thereafter, a constant current discharge of 10 mA was performed, and when discharging was performed to 2.5 V, a discharge was completed, and a discharge capacity was calculated.
  • the area and thickness of each positive electrode, negative electrode, and separator are as follows.
  • Positive electrode 20 cm 2 , 100 ⁇ m
  • Negative electrode 20 cm 2 , thickness is as described in Table 1
  • Separator 20 cm 2 , 15 ⁇ m
  • (Energy density) (discharge capacity) / (total volume of positive electrode, negative electrode, separator) (1)
  • the obtained energy density was evaluated according to the following evaluation criteria.
  • C 173 mAh / cm 3 or more
  • D less than 173 mAh / cm 3
  • Example 1 Preparation of positive electrode 100 parts by mass of Li (Ni—Co—Al) O 2 (NCA oxide) having an average particle diameter of 10 ⁇ m as a positive electrode active material, 4 parts by mass of acetylene black as a conductive additive, and polyvinylidene fluoride as an electrode binder 4 parts by mass of (PVDF) and N-methylpyrrolidone (NMP) as a solvent were mixed.
  • PVDF Li (Ni—Co—Al) O 2
  • NMP N-methylpyrrolidone
  • the positive electrode current collector coated with the composition for the positive electrode active material layer on both sides is pressure-pressed at 400 kN / m, punched out to 100 mm ⁇ 200 mm square of electrode dimensions, and the positive electrode having the positive electrode active material layer on both sides It was.
  • the area where the positive electrode active material was applied was 100 mm ⁇ 180 mm.
  • coated the composition for negative electrode active material layers on both surfaces was press-pressed by the linear pressure of 500 kN / m, and it was set as the negative electrode.
  • the density of the negative electrode active material layer was 1.55 g / cc.
  • the dimension of the negative electrode was 110 mm ⁇ 210 mm, and the area on which the negative electrode active material layer was applied was 110 mm ⁇ 190 mm.
  • LiPF 6 as an electrolyte salt is dissolved in a solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of 3: 7 (EC: DEC) so as to be 1 mol / liter. Prepared.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PVDF-HFP Polyvinylidene fluoride hexafluoropropylene
  • AHP200 average particle size 0.4 ⁇ m
  • the above mixture was mixed with NMP so that the solid content concentration was 30% by mass, gently stirred with a stirrer for 30 minutes, and filtered with a filter having an aperture of 80 ⁇ m to obtain an adhesive layer composition.
  • the viscosity of the composition was 1800 mPa ⁇ s under the conditions of a B-type viscometer, 60 rpm, and 25 ° C.
  • the obtained composition for an adhesive layer was applied to the entire surface of the negative electrode active material layer with a bar coater.
  • a coating film formed by applying the composition is dried at 60 ° C., thereby forming an adhesive layer on the surface of the negative electrode active material layer, and having the adhesive layer (that is, a negative electrode structure for a lithium ion secondary battery) Got.
  • the thickness of the adhesive layer was measured and found to be 4 ⁇ m.
  • a laminate-type cell was manufactured by injecting the electrolytic solution obtained above from one side left without being sealed and vacuum-sealing.
  • Example 2 A lithium ion secondary battery was obtained in the same manner as in Example 1 except that 68 parts by volume of alumina particles and 32 parts by volume of PVDF-HFP powder were used to produce an electrode having an adhesive layer.
  • Example 3 A lithium ion secondary battery was obtained in the same manner as in Example 1, except that 52 parts by volume of alumina particles and 48 parts by volume of PVdF-HFP powder were used for producing an electrode having an adhesive layer.
  • Example 4 The production of the positive electrode, the production of the negative electrode, and the adjustment of the electrolyte solution were performed in the same manner as in Example 1.
  • the production of the electrode having the adhesive layer and the production of the lithium ion secondary battery were performed as follows. Obtained. (Production of electrode having adhesive layer) Polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) powder while applying moderate shearing force to 60 parts by volume of alumina particles (product name: AHP200, average particle size 0.4 ⁇ m) as insulating fine particles was mixed to obtain a mixture.
  • PVDF-HFP Polyvinylidene fluoride hexafluoropropylene
  • the above mixture was mixed with NMP so that the solid content concentration was 30% by mass, gently stirred with a stirrer for 30 minutes, and filtered with a filter having an aperture of 80 ⁇ m to obtain an adhesive layer composition.
  • the viscosity of the composition was 1800 mPa ⁇ s under the conditions of a B-type viscometer, 60 rpm, and 25 ° C.
  • the obtained composition for an adhesive layer was applied to the entire surface of the positive electrode active material layer with a bar coater. A coating film formed by applying the composition is dried at 60 ° C., thereby forming an adhesive layer on the surface of the positive electrode active material layer, and having the adhesive layer (that is, a positive electrode structure for a lithium ion secondary battery) Got.
  • the thickness of the adhesive layer was measured and found to be 4 ⁇ m.
  • Ten sheets of the negative electrode obtained above, nine positive electrodes having an adhesive layer, and 18 separators were laminated to obtain a temporary laminate.
  • the negative electrode and the positive electrode were alternately disposed, and a separator was disposed between each negative electrode and the positive electrode.
  • As the separator a polyethylene porous film was used.
  • the temporary laminate was pressed for 1 minute at 80 ° C. and 0.6 MPa to obtain a laminate.
  • the ends of the exposed portions of the positive electrode current collectors of the positive electrodes were joined together by ultrasonic fusion, and terminal tabs that protruded to the outside were joined.
  • a laminate-type cell was manufactured by injecting the electrolytic solution obtained above from one side left without being sealed and vacuum-sealing.
  • Example 5 A lithium ion secondary battery was obtained in the same manner as in Example 1 except that the production of the electrode having the adhesive layer was changed as follows. (Production of electrode having adhesive layer) Polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) powder while applying moderate shear force to 30 parts by volume of alumina particles (product name: AHP200, average particle size 0.4 ⁇ m) as insulating fine particles 40 parts by volume and 30 parts by volume of polymethylurea ("Pergopack M6" manufactured by AlmaVale) were mixed to obtain a mixture.
  • PVDF-HFP Polyvinylidene fluoride hexafluoropropylene
  • the above mixture was mixed with NMP so that the solid content concentration was 30% by mass, gently stirred with a stirrer for 30 minutes, and filtered with a filter having an aperture of 80 ⁇ m to obtain an adhesive layer composition.
  • the viscosity of the composition was 1800 mPa ⁇ s under the conditions of a B-type viscometer, 60 rpm, and 25 ° C.
  • the obtained composition for an adhesive layer was applied to the entire surface of the negative electrode active material layer with a bar coater. A coating film formed by applying the composition is dried at 60 ° C., thereby forming an adhesive layer on the surface of the negative electrode active material layer, and having the adhesive layer (that is, a negative electrode structure for a lithium ion secondary battery) Got.
  • the thickness of the adhesive layer was measured and found to be 4 ⁇ m.
  • Example 6 In the production of the negative electrode, a lithium ion secondary battery was obtained in the same manner as in Example 1 except that the pressure of the pressure press was 600 kN / m and the density of the negative electrode active material layer was 1.62 g / cc. .
  • Example 3 A lithium ion secondary battery was obtained in the same manner as in Example 1 except that 80 parts by volume of alumina particles and 20 parts by volume of PVDF-HFP were used for producing an electrode having an adhesive layer.
  • Example 4 A lithium ion secondary battery was obtained in the same manner as in Example 1 except that 40 parts by volume of alumina particles and 60 parts by volume of PVDF-HFP were used for producing an electrode having an adhesive layer.
  • the lithium ion secondary battery containing 30 to 55% by volume of a specific resin and having a negative electrode active material layer density of 1.55 to 1.70 g / cm 3 is: Adhesive strength, quick chargeability, and energy density were all good.
  • the content of the specific resin is out of the range of 30 to 55% by volume or the density of the negative electrode active material is out of the range of 1.55 to 1.70 g / cm 3 , the adhesive strength, rapid chargeability, and The result was inferior in the physical property balance of energy density.

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  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne une batterie secondaire au lithium-ion qui comprend : une électrode négative comprenant une couche de matériau actif d'électrode négative ; une électrode positive ; un séparateur qui est disposé entre l'électrode négative et l'électrode positive ; et une couche adhésive qui est disposée entre le séparateur et l'électrode négative et/ou l'électrode positive et qui fait adhérer le séparateur et la ou les électrodes. La couche adhésive contient de 30 à 55 % en volume d'au moins un type de résine choisi dans le groupe constitué de copolymères de fluorure de polyvinylidène/hexafluoropropylène et de résines acryliques. La densité de la couche de matériau actif d'électrode négative est de 1,50 à 1,70 g/cm3. La présente invention permet de fournir une batterie secondaire au lithium-ion qui a de bonnes propriétés de charge rapide, une bonne adhérence entre un séparateur et une électrode, et une densité d'énergie élevée.
PCT/JP2019/004432 2018-02-08 2019-02-07 Batterie secondaire au lithium-ion, structure d'électrode négative de batterie secondaire au lithium-ion, et procédé de production d'une batterie secondaire au lithium-ion WO2019156172A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021131877A1 (fr) * 2019-12-26 2021-07-01 三洋電機株式会社 Batterie secondaire et son procédé de production
CN113708010A (zh) * 2021-09-01 2021-11-26 东莞新能安科技有限公司 电化学装置和电子装置
JP2022127915A (ja) * 2021-02-22 2022-09-01 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 二次電池
JP2023549990A (ja) * 2021-10-12 2023-11-30 寧徳時代新能源科技股▲分▼有限公司 セパレーター、二次電池及び電力消費装置

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998038688A1 (fr) * 1997-02-28 1998-09-03 Asahi Kasei Kogyo Kabushiki Kaisha Batterie d'accumulateurs non aqueuse et son procede de production
WO2005029614A1 (fr) * 2003-09-18 2005-03-31 Matsushita Electric Industrial Co., Ltd. Accumulateur lithium-ion
JP2009529762A (ja) * 2006-03-10 2009-08-20 エルジー・ケム・リミテッド 多孔性活性層がコートされた電極、その製造方法及びこれを備えた電気化学素子
JP2014165097A (ja) * 2013-02-27 2014-09-08 Nippon Zeon Co Ltd リチウムイオン二次電池耐熱層用スラリーの製造方法及びリチウムイオン二次電池用電極の製造方法
WO2016002567A1 (fr) * 2014-06-30 2016-01-07 帝人株式会社 Séparateur pour piles rechargeables à électrolyte non aqueux et pile rechargeable à électrolyte non aqueux
JP2017115102A (ja) * 2015-12-25 2017-06-29 三星エスディアイ株式会社Samsung SDI Co., Ltd. グラフト共重合体、二次電池用バインダ組成物、二次電池用セパレータ、二次電池およびグラフト共重合体の製造方法
JP2017162699A (ja) * 2016-03-10 2017-09-14 三星エスディアイ株式会社Samsung SDI Co., Ltd. 巻回型二次電池用セパレータ（ｓｅｐａｒａｔｏｒ）、巻回型二次電池用セパレータの製造方法、扁平状巻回素子、巻回型二次電池、及び巻回型二次電池の製造方法
WO2017187707A1 (fr) * 2016-04-28 2017-11-02 日立化成株式会社 Procédé de charge d'accumulateur lithium-ion, système d'accumulateur lithium-ion, et dispositif de stockage d'électricité

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998038688A1 (fr) * 1997-02-28 1998-09-03 Asahi Kasei Kogyo Kabushiki Kaisha Batterie d'accumulateurs non aqueuse et son procede de production
WO2005029614A1 (fr) * 2003-09-18 2005-03-31 Matsushita Electric Industrial Co., Ltd. Accumulateur lithium-ion
JP2009529762A (ja) * 2006-03-10 2009-08-20 エルジー・ケム・リミテッド 多孔性活性層がコートされた電極、その製造方法及びこれを備えた電気化学素子
JP2014165097A (ja) * 2013-02-27 2014-09-08 Nippon Zeon Co Ltd リチウムイオン二次電池耐熱層用スラリーの製造方法及びリチウムイオン二次電池用電極の製造方法
WO2016002567A1 (fr) * 2014-06-30 2016-01-07 帝人株式会社 Séparateur pour piles rechargeables à électrolyte non aqueux et pile rechargeable à électrolyte non aqueux
JP2017115102A (ja) * 2015-12-25 2017-06-29 三星エスディアイ株式会社Samsung SDI Co., Ltd. グラフト共重合体、二次電池用バインダ組成物、二次電池用セパレータ、二次電池およびグラフト共重合体の製造方法
JP2017162699A (ja) * 2016-03-10 2017-09-14 三星エスディアイ株式会社Samsung SDI Co., Ltd. 巻回型二次電池用セパレータ（ｓｅｐａｒａｔｏｒ）、巻回型二次電池用セパレータの製造方法、扁平状巻回素子、巻回型二次電池、及び巻回型二次電池の製造方法
WO2017187707A1 (fr) * 2016-04-28 2017-11-02 日立化成株式会社 Procédé de charge d'accumulateur lithium-ion, système d'accumulateur lithium-ion, et dispositif de stockage d'électricité

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021131877A1 (fr) * 2019-12-26 2021-07-01 三洋電機株式会社 Batterie secondaire et son procédé de production
JP2022127915A (ja) * 2021-02-22 2022-09-01 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 二次電池
JP7202407B2 (ja) 2021-02-22 2023-01-11 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 二次電池
CN113708010A (zh) * 2021-09-01 2021-11-26 东莞新能安科技有限公司 电化学装置和电子装置
JP2023549990A (ja) * 2021-10-12 2023-11-30 寧徳時代新能源科技股▲分▼有限公司 セパレーター、二次電池及び電力消費装置
JP7483911B2 (ja) 2021-10-12 2024-05-15 寧徳時代新能源科技股▲分▼有限公司 セパレーター、二次電池及び電力消費装置

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