WO2019087815A1 - Couche de mélange d'électrodes positives, électrode positive, batterie semi-secondaire et batterie secondaire - Google Patents

Couche de mélange d'électrodes positives, électrode positive, batterie semi-secondaire et batterie secondaire Download PDF

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WO2019087815A1
WO2019087815A1 PCT/JP2018/038968 JP2018038968W WO2019087815A1 WO 2019087815 A1 WO2019087815 A1 WO 2019087815A1 JP 2018038968 W JP2018038968 W JP 2018038968W WO 2019087815 A1 WO2019087815 A1 WO 2019087815A1
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positive electrode
mixture layer
semi
secondary battery
solid electrolyte
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PCT/JP2018/038968
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English (en)
Japanese (ja)
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阿部　誠
新平 尼崎
祐介 加賀
和明 直江
篤 宇根本
森島　慎
西村　勝憲
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株式会社日立製作所
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Priority to KR1020207007776A priority Critical patent/KR20200040844A/ko
Publication of WO2019087815A1 publication Critical patent/WO2019087815A1/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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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
    • H01M2300/0085—Immobilising or gelification of 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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 positive electrode mixture layer, a positive electrode, a semi secondary battery, and a secondary battery.
  • a negative electrode paste for use in the production of a negative electrode of a non-aqueous electrolyte secondary battery comprising: (A) a silicon-based negative electrode active material, (B) a binder containing a polyimide resin, or a polyamideimide resin, and (C) an ionic liquid And a negative electrode paste characterized by containing
  • the bonding between the aluminum fluoride formed on the surface of the positive electrode current collector and the positive electrode mixture layer is enhanced, and the adhesion between the positive electrode current collector and the positive electrode mixture layer Improves the quality.
  • a fluorine-based resin is used as the binder of the positive electrode mixture layer, depending on the amount of the binder in the positive electrode mixture layer and the amount of the solvent serving as the ion conduction path, the positive electrode mixture layer There is a possibility of peeling.
  • An object of the present invention is to provide a positive electrode mixture layer, a positive electrode, a semi-secondary battery, and a secondary battery which suppress peeling from a positive electrode current collector.
  • a positive electrode active material, a semi-solid electrolytic solution, and a positive electrode binder wherein the positive electrode binder contains a fluorine-based resin, the content of the positive electrode binder in the positive electrode mixture layer is A, the content of the semi solid electrolyte in the positive electrode mixture layer the case where the value obtained by dividing the amount of the positive electrode binder and B, a positive electrode mixture layer satisfying 3.6 ⁇ 1.2 ⁇ 10 2 a- B, a positive electrode containing it, half the secondary battery and the secondary battery .
  • a lithium ion secondary battery is an electrochemical device capable of storing or utilizing electrical energy by insertion and extraction of lithium ions to an electrode in an electrolyte. This is called by another name of a lithium ion battery, a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery, and any battery is an object of the present invention.
  • the technical concept of the present invention is also applicable to sodium ion secondary batteries, magnesium ion secondary batteries, calcium ion secondary batteries, zinc secondary batteries, aluminum ion secondary batteries and the like.
  • FIG. 1 is a cross-sectional view of an example of a secondary battery to which the present invention is applied.
  • FIG. 1 shows a laminated type secondary battery, and the secondary battery 1000 has a positive electrode 100, a negative electrode 200, a semi-solid electrolyte layer 300, and an outer package 500 for containing them.
  • the material of the exterior body 500 can be selected from materials having corrosion resistance to the non-aqueous electrolyte, such as aluminum, stainless steel, nickel plated steel, and the like.
  • the present invention is also applicable to a wound secondary battery.
  • an electrode assembly 400 including the positive electrode 100, the semi-solid electrolyte layer 300, and the negative electrode 200 is stacked.
  • the positive electrode 100 or the negative electrode 200 may be referred to as an electrode or an electrode for a secondary battery.
  • the positive electrode 100, the negative electrode 200, or the semisolid electrolyte layer 300 may be referred to as a secondary battery sheet. What the semi-solid electrolyte layer 300 and the positive electrode 100 or the negative electrode 200 have an integral structure may be called a semi-secondary battery.
  • the positive electrode 100 includes a positive electrode current collector 120 and a positive electrode mixture layer 110.
  • the positive electrode mixture layer 110 is formed on both sides of the positive electrode current collector 120.
  • the negative electrode 200 includes a negative electrode current collector 220 and a negative electrode mixture layer 210.
  • a negative electrode mixture layer 210 is formed on both sides of the negative electrode current collector 220.
  • the positive electrode mixture layer 110 or the negative electrode mixture layer 210 may be referred to as an electrode mixture layer, and the positive electrode current collector 120 or the negative electrode current collector 220 may be referred to as an electrode current collector.
  • the positive electrode current collector 120 has a positive electrode tab portion 130.
  • the negative electrode current collector 220 has a negative electrode tab portion 230.
  • the positive electrode tab portion 130 or the negative electrode tab portion 230 may be referred to as an electrode tab portion.
  • An electrode mixture layer is not formed on the electrode tab portion. However, the electrode mixture layer may be formed on the electrode tab portion as long as the performance of the secondary battery 1000 is not adversely affected.
  • the positive electrode tab portion 130 and the negative electrode tab portion 230 protrude to the outside of the exterior body 500, and a plurality of protruding positive electrode tab portions 130 and a plurality of negative electrode tab portions 230 are joined by ultrasonic bonding, for example. Then, parallel connection is formed in the secondary battery 1000.
  • the present invention can also be applied to a bipolar secondary battery in which electrical series connection is configured in the secondary battery 1000.
  • the positive electrode mixture layer 110 includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
  • the negative electrode mixture layer 210 includes a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
  • the semisolid electrolyte layer 300 has a semisolid electrolyte binder and a semisolid electrolyte.
  • a semi-solid electrolyte comprises carrier particles and a semi-solid electrolyte.
  • the positive electrode active material or the negative electrode active material may be referred to as an electrode active material
  • the positive electrode conductive agent or the negative electrode conductive agent may be referred to as an electrode conductive agent
  • the positive electrode binder or the negative electrode binder may be referred to as an electrode binder.
  • the pores of the electrode mixture layer may be filled with a semi-solid electrolyte.
  • a semi-solid electrolyte is injected into the secondary battery 1000 from one open side of the outer package 500 or a liquid injection hole, and the pores of the electrode mixture layer are filled with the semi-solid electrolyte.
  • the support particles contained in the semi-solid electrolyte are not required, and particles such as the electrode active material and the electrode conductive agent in the electrode mixture layer function as the support particles, and the particles retain the semi-solid electrolyte Do.
  • a slurry is prepared by mixing a semi-solid electrolyte, an electrode active material, an electrode conductive agent, and an electrode binder, and the prepared slurry is used as an electrode current collector. There is a method of applying together on top.
  • a separator such as a microporous film may be used.
  • polyolefin such as polyethylene and polypropylene and glass fiber can be used.
  • the semi-solid electrolyte solution is injected into the semi-solid electrolyte layer 300 by injecting the semi-solid electrolyte solution into the secondary battery 1000 from one open side of the outer package 500 or the injection hole. Be filled.
  • a semisolid electrolyte may be contained in any one or more of the positive electrode 100, the negative electrode 200, and the semisolid electrolyte layer 300.
  • Electrode conductive agent contained in the electrode mixture layer improves the conductivity of the electrode mixture layer.
  • the electrode conductive agent ketjen black, acetylene black, graphite and the like are suitably used, but not limited thereto.
  • Fe (MoO 4 ) 3 constituting a sulfur, a chalcogenide such as TiS 2 , MoS 2 , o 6 S 8 , TiSe 2 , a vanadium-based oxide such as V 2 O 5 , a halide such as FeF 3, or a polyanion such as Fe 2 (SO 4) 3, Li 3 Fe 2 (PO 4) 3, but such quinone organic crystals, but is not limited thereto.
  • the amounts of lithium and anion in the chemical composition may be deviated from the above-mentioned stoichiometric composition.
  • the positive electrode binder binds a positive electrode active material, a positive electrode conductive agent, and the like in the positive electrode 100.
  • a positive electrode binder it is desirable to contain a fluorine resin.
  • the fluorine-based resin include polyvinyl fluoride, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), and a copolymer of vinylidene fluoride and hexafluoropropylene (P (VdF-HFP)). You may use these positive electrode binders individually or in combination of multiple.
  • ⁇ Positive Electrode Current Collector 120 As the positive electrode current collector 120, an aluminum foil having a thickness of 1 to 100 ⁇ m, or a perforated aluminum foil having a thickness of 10 to 100 ⁇ m and a hole having a hole diameter of 0.1 to 10 mm, an expanded metal, etc. The material that forms is used.
  • ⁇ Anode active material> lithium ions are desorbed in the discharge process, and lithium ions desorbed from the positive electrode active material in the positive electrode mixture layer 110 are inserted in the charge process.
  • a material of the negative electrode active material exhibiting a slight potential for example, carbon-based materials (eg, graphite, graphitizable carbon materials, amorphous carbon materials, organic crystals, activated carbon, etc.), conductive polymer materials (eg, polyacene) , Polyparaphenylene, polyaniline, polyacetylene, lithium complex oxide (eg, lithium titanate: Li 4 Ti 5 O 12 , Li 2 TiO 4, etc.), metallic lithium, metal alloyed with lithium (eg, aluminum, silicon) And tin and the like) or oxides thereof can be used, but the invention is not limited thereto.
  • carbon-based materials eg, graphite, graphitizable carbon materials, amorphous carbon materials, organic crystals, activated carbon, etc.
  • conductive polymer materials
  • the negative electrode binder binds the negative electrode active material, the negative electrode conductive agent, and the like in the negative electrode 200.
  • the negative electrode binder include, but are not limited to, styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride (PVDF) and mixtures thereof.
  • ⁇ Anode Current Collector 220 As the negative electrode current collector 220, a copper foil having a thickness of 1 to 100 ⁇ m, a perforated copper foil having a thickness of 1 to 100 ⁇ m and a hole diameter of 0.1 to 10 mm, an expanded metal, a foam metal plate or the like is used. Besides copper, stainless steel, titanium, nickel and the like can also be applied.
  • An electrode mixture layer is formed by adhering an electrode slurry obtained by mixing an electrode active material, an electrode conductive agent, an electrode binder and an organic solvent to an electrode current collector by a coating method such as a doctor blade method, dipping method, or spray method. Be done. Thereafter, the electrode mixture layer is dried in order to remove the organic solvent, and the electrode mixture layer is pressure-formed by a roll press to produce an electrode.
  • the electrode slurry may include a semi-solid electrolyte or a semi-solid electrolyte.
  • a plurality of electrode mixture layers may be stacked on the electrode current collector by performing application to drying a plurality of times.
  • the thickness of the electrode mixture layer is desirably equal to or more than the average particle diameter of the electrode active material.
  • the electrode active material powder contains coarse particles having an average particle diameter equal to or larger than the thickness of the electrode mixture layer, the coarse particles are removed in advance by sieve classification, air flow classification, etc., and particles smaller than the thickness of the electrode mixture layer It is desirable to
  • the content of the positive electrode binder in the positive electrode slurry is A
  • the content of the semisolid electrolyte in the positive electrode slurry is the content of the positive electrode binder
  • the positive electrode binder with which the positive electrode current collector 120 and the positive electrode mixture layer 110 sufficiently adhere to each other is disposed at the interface between the positive electrode current collector 120 and the positive electrode mixture layer 110, and peeling from the positive electrode current collector 120 Can be provided.
  • A is preferably 3 to 14, and more preferably 3 to 6.
  • the content of the positive electrode active material and the like contained in the positive electrode mixture layer 110 is determined depending on the content of the positive electrode binder and the semi-solid electrolyte. When A is larger than 14, the mass of the positive electrode active material that can be contained in the positive electrode 100 is reduced, and the energy density of the secondary battery 1000 may be reduced. If A is smaller than 3, adhesion between the positive electrode current collector 120 and the positive electrode mixture layer 110 may be reduced.
  • B is preferably 0.1 to 4 and more preferably 0.5 to 3.
  • B is larger than 4, the amount of positive electrode active materials that can be contained in the positive electrode 100 is reduced, and the energy density of the secondary battery 1000 may be reduced.
  • support particles can also be included in the electrode.
  • the support particles are preferably insulating particles and insoluble in a semisolid electrolytic solution containing an organic solvent or an ionic liquid.
  • oxide inorganic particles such as silica (SiO 2 ) particles, ⁇ -alumina (Al 2 O 3 ) particles, ceria (CeO 2 ) particles, zirconia (ZrO 2 ) particles and the like can be preferably used.
  • a solid electrolyte may be used as the support particles.
  • the solid electrolyte include particles of inorganic solid electrolytes such as oxide-based solid electrolytes such as Li-La-Zr-O and sulfide-based solid electrolytes such as Li 10 Ge 2 PS 12 .
  • the average particle diameter of the primary particles of the support particles is 1 nm to 10 ⁇ m, since it is considered that the holding amount of the semi-solid electrolytic solution is proportional to the specific surface area of the support particles.
  • the average particle size of the primary particles of the support particles is larger than 10 ⁇ m, the support particles may not be able to properly hold a sufficient amount of the semisolid electrolyte solution, and it may be difficult to form a semisolid electrolyte.
  • the average particle size of the primary particles of the support particles is smaller than 1 nm, the surface-to-surface force between the support particles becomes large, and the support particles are easily aggregated, which may make it difficult to form a semisolid electrolyte. is there.
  • the average particle diameter of the primary particles of the support particles is more preferably 1 nm to 50 nm, and still more preferably 1 nm to 10 nm.
  • the average particle size of the primary particles of the supported particles can be measured using a known particle size distribution measuring device using a laser scattering method.
  • the semi-solid electrolyte has a semi-solid electrolyte solvent, an optional low viscosity organic solvent.
  • the semi-solid electrolyte solvent has a mixture (complex) of an ether-based solvent and a solvated electrolyte salt that exhibits similar properties to the ionic liquid or ionic liquid.
  • the ionic liquid or ether solvent may be referred to as a main solvent.
  • An ionic liquid is a compound which dissociates into a cation and an anion at normal temperature, and maintains the liquid state.
  • the ionic liquid may be referred to as an ionic liquid, a low melting point molten salt or a room temperature molten salt.
  • the semi-solid electrolyte solvent preferably has low volatility, specifically, one having a vapor pressure of 150 Pa or less at room temperature, from the viewpoint of the stability in the air and the heat resistance in the secondary battery.
  • the content of the semi-solid electrolyte in the electrode mixture layer is preferably 20% by volume to 40% by volume. If the content of the semi-solid electrolyte is less than 20% by volume, the ion conduction path inside the electrode mixture layer may not be sufficiently formed, and the rate characteristics may be degraded. In addition to the possibility that the semisolid electrolyte may leak from the electrode mixture layer when the content of the semisolid electrolyte is more than 40% by volume, the active material may be insufficient to cause a decrease in energy density. There is sex.
  • the ionic liquid is composed of cations and anions.
  • the ionic liquid is classified into imidazolium type, ammonium type, pyrrolidinium type, piperidinium type, pyridinium type, morpholinium type, phosphonium type, sulfonium type and the like according to the cationic species.
  • Examples of cations constituting the imidazolium-based ionic liquid include alkyl imidazolium cations such as 1-etyl-3-methylimidazolium and 1-butyl-3-methylimidazolium (BMI).
  • Examples of the cation constituting the ammonium-based ionic liquid include N, N, N-trimethyl-N in addition to N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME) and tetraamyllammonium. There is an alkyl ammonium cation such as -propylammonium.
  • Examples of the cation constituting the pyrrolidinium-based ionic liquid include alkyl pyrrolidinium cations such as N-methyl-N-propylpyrolidinium (Py13) and 1-butyl-1-methylpyrolidinium.
  • Examples of the cation constituting the piperidinium-based ionic liquid include alkyl piperidinium cations such as N-methyl-N-propylpiperidinium (PP13) and 1-butyl-1-methylpiperidinium.
  • Examples of the cation constituting the pyridinium-based ionic liquid include alkyl pyridinium cations such as 1-butylpyridinium and 1-butyl-4-methylpyridine.
  • Examples of the cation constituting the morpholinium-based ionic liquid include alkyl morpholinium such as 4-ethyl-4-methylmorpholinium.
  • Examples of the cation constituting the phosphonium-based ionic liquid include alkyl phosphonium cations such as tetrabutylphosphonium and tributylmlyphosphonium.
  • Examples of the cation constituting the sulfonium-based ionic liquid include alkylsulfonium cations such as trimethylsulfonylium and tributhylsulfonium.
  • anion to be paired with these cations examples include bis (trifluoromethanesulfonyl) imide (TFSI), bis (fluorosulfonyl) imide, tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), bis (pentafluoroethanesulfonyl) imide (BETI), trifluoromethanesulfonate ( Triflate), acetate, dimethyl phosphate, dicyanamide, trifluoro (trifluoromethyl) borate and the like. You may use these ionic liquids individually or in combination of multiple.
  • the ionic liquid may contain an electrolyte salt.
  • the electrolyte salt those which can be uniformly dispersed in a solvent can be used.
  • Lithium having a cation and the above anion can be used as a lithium salt, for example, lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (pentafluoroethane) Examples include, but are not limited to, sulfonyl) imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium triflate and the like. These electrolyte salts may be used alone or in combination of two or more.
  • the ether solvent constitutes a solvated electrolyte salt and a solvated ionic liquid.
  • ether-based solvents known to exhibit similar properties to the ionic liquid glyme (R-O (CH 2 CH 2 O) n-R '(R, R' is a saturated hydrocarbon, n represents symmetry represented by an integer)
  • glyme R-O (CH 2 CH 2 O) n-R '(R, R' is a saturated hydrocarbon, n represents symmetry represented by an integer
  • Generic name of glycol diether can be used.
  • tetraglyme tetraethylene dimethyl glycol, G4
  • triglyme triethylene glycol dimethyl ether, G3
  • pentag lime pentag lime
  • pentag lime pentag lime
  • pentag lime pentag lime
  • a lithium salt such as LiFSI, LiTFSI, LiBETI
  • LiFSI lithium salt
  • LiTFSI LiTFSI
  • LiBETI lithium salt
  • a mixture of an ether solvent and a solvated electrolyte salt may be used alone or in combination as a semisolid electrolyte solvent.
  • the weight ratio of the main solvent in the semi-solid electrolyte is not particularly limited, the weight ratio of the main solvent to the total of the solvents in the semi-solid electrolyte is 30% to 70% from the viewpoint of battery stability and high-speed charge and discharge.
  • the content is preferably 40% to 60%, and more preferably 45% to 55%.
  • a fluorine-based resin is preferably used as the semi-solid electrolyte binder.
  • a fluorine-based resin PVdF or P (VdF-HFP) is suitably used.
  • These semisolid electrolyte binders may be used alone or in combination.
  • the semisolid electrolyte is constituted by supporting or holding the semisolid electrolyte on the carrier particles.
  • a semi-solid electrolyte and supporting particles are mixed at a specific volume ratio, an organic solvent such as methanol is added and mixed, a slurry of the semi-solid electrolyte is prepared, and then the slurry is The mixture is spread in a petri dish, and the organic solvent is distilled off to obtain a semisolid electrolyte powder, and the like.
  • the semi-solid electrolyte layer 300 serves as a medium for transferring lithium ions between the positive electrode 100 and the negative electrode 200.
  • the semi-solid electrolyte layer 300 also acts as an insulator of electrons and prevents a short circuit between the positive electrode 100 and the negative electrode 200.
  • the semisolid electrolyte layer 300 As a method of producing the semisolid electrolyte layer 300, a method of compression molding semisolid electrolyte powder into a pellet shape by a molding die or the like, a method of adding a semisolid electrolyte binder to a semisolid electrolyte powder and mixing to make a sheet There is. By adding and mixing the powder of the semisolid electrolyte binder to the semisolid electrolyte, the highly flexible sheet-like semisolid electrolyte layer 300 can be manufactured.
  • a semisolid electrolyte layer 300 can be manufactured by adding and mixing a solution of a binder in which a semisolid electrolyte binder is dissolved in a dispersion solvent to the semisolid electrolyte and distilling off the dispersion solvent.
  • the semisolid electrolyte layer 300 may be produced by applying and drying on an electrode.
  • the content of the semisolid electrolyte in the semisolid electrolyte layer 300 is preferably 70% by volume to 90% by volume. If the content of the semi-solid electrolyte is less than 70% by volume, the interfacial resistance between the electrode and the semi-solid electrolyte layer 300 may increase. When the content of the semi-solid electrolyte is greater than 90% by volume, the semi-solid electrolyte may leak out of the semi-solid electrolyte layer 300.
  • Example 1 LiNiMnCoO 2 as a positive electrode active material, acetylene black as an electrode conductive agent, LiTFSI and G 4 as a semi-solid electrolyte, silica, and PVdF as a positive electrode binder were mixed at a ratio (mass%) of 84: 7: 0: 9. Next, the viscosity of the mixed material was appropriately adjusted using n-methyl pyrrolidone as a solvent. Next, a mixed material containing n-methyl pyrrolidone is coated on a 15 ⁇ m thick aluminum foil (positive electrode current collector 120) with a comma coater so that the single-sided coating amount is 18.7 mg / cm 2 , The agent layer 110 was produced.
  • the positive electrode mixture layer 110 applied to the aluminum foil was dried at 120 ° C. to remove n-methylpyrrolidone from the positive electrode mixture layer 110. Next, hand pressing was performed on the positive electrode mixture layer 110 so that the density of the positive electrode mixture layer 110 was 2.47 g / cc, and a positive electrode 100 was produced.
  • Example 2 to 17 The peel test was evaluated in the same manner as in Example 1 with the configurations of the positive electrode mixture layer and the positive electrode as shown in Table 1.
  • Table 1 shows the structures of the positive electrode mixture layers and the positive electrodes of Examples 2 to 17 and the results of peeling tests.
  • Comparative Examples 1 and 2 The peel test was evaluated in the same manner as in Example 1 with the configurations of the positive electrode mixture layer and the positive electrode as shown in Table 1.
  • Table 1 shows the configurations of the positive electrode mixture layers and the positive electrodes of Comparative Examples 1 and 2 and the results of peeling tests.
  • the present invention it was demonstrated that according to the present invention, it is possible to provide a positive electrode mixture layer, a positive electrode, a semi-secondary battery, and a secondary battery, which suppress peeling from the positive electrode current collector.
  • the present invention is not limited to the embodiments described above, but includes various modifications.
  • the embodiments described above are described in detail in order to explain the present invention in an easy-to-understand manner, and are not necessarily limited to those having all the configurations described.
  • part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment.

Abstract

L'invention concerne une couche de mélange d'électrodes positives qui supprime la séparation d'un collecteur de courant d'électrode positive. La couche de mélange d'électrodes positives comprend un matériau actif d'électrode positive, un électrolyte semi-solide et un liant d'électrode positive, le liant d'électrode positive comprenant une résine à base de fluor ; et lorsque A est la teneur du liant d'électrode positive dans la couche de mélange d'électrodes positives et B est une valeur obtenue par division de la teneur en électrolyte semi-solide dans la couche de mélange d'électrodes positives par le contenu du liant d'électrode positive, 3,6 < 1,2×102A-B est satisfait.
PCT/JP2018/038968 2017-10-30 2018-10-19 Couche de mélange d'électrodes positives, électrode positive, batterie semi-secondaire et batterie secondaire WO2019087815A1 (fr)

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JP2017208757A JP2019083095A (ja) 2017-10-30 2017-10-30 正極合剤層、正極、半二次電池、二次電池

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0495363A (ja) * 1990-07-31 1992-03-27 Sanyo Electric Co Ltd 非水系二次電池
JPH0997611A (ja) * 1995-09-29 1997-04-08 Toray Ind Inc 電池用電極および二次電池
JP2000082470A (ja) * 1998-09-03 2000-03-21 Toyota Motor Corp リチウムイオン２次電池
JP2017059432A (ja) * 2015-09-17 2017-03-23 株式会社日立製作所 擬似固体電解質およびそれを用いた全固体リチウム二次電池
WO2018030150A1 (fr) * 2016-08-08 2018-02-15 株式会社日立製作所 Électrolyte solide et cellule tout solide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013069517A (ja) 2011-09-22 2013-04-18 Shin Etsu Chem Co Ltd 負極ペースト、負極電極及びその製造方法、並びに非水電解質二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0495363A (ja) * 1990-07-31 1992-03-27 Sanyo Electric Co Ltd 非水系二次電池
JPH0997611A (ja) * 1995-09-29 1997-04-08 Toray Ind Inc 電池用電極および二次電池
JP2000082470A (ja) * 1998-09-03 2000-03-21 Toyota Motor Corp リチウムイオン２次電池
JP2017059432A (ja) * 2015-09-17 2017-03-23 株式会社日立製作所 擬似固体電解質およびそれを用いた全固体リチウム二次電池
WO2018030150A1 (fr) * 2016-08-08 2018-02-15 株式会社日立製作所 Électrolyte solide et cellule tout solide

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