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WO2019188590A1 - Batterie secondaire à électrolyte non aqueux et procédé de production de batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux et procédé de production de batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2019188590A1
WO2019188590A1 PCT/JP2019/011471 JP2019011471W WO2019188590A1 WO 2019188590 A1 WO2019188590 A1 WO 2019188590A1 JP 2019011471 W JP2019011471 W JP 2019011471W WO 2019188590 A1 WO2019188590 A1 WO 2019188590A1
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Prior art keywords
positive electrode
secondary battery
particles
particle layer
negative electrode
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English (en)
Japanese (ja)
Inventor
博道 加茂
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to JP2020510743A priority Critical patent/JP6846570B2/ja
Priority to CN201980031703.1A priority patent/CN112106245A/zh
Publication of WO2019188590A1 publication Critical patent/WO2019188590A1/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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
    • 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
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
    • 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 non-aqueous electrolyte secondary battery and a method for manufacturing a non-aqueous electrolyte secondary battery.
  • Lithium ion secondary batteries are characterized by higher energy density and electromotive force than lead acid batteries and nickel metal hydride batteries. For this reason, it is widely used as a power source for mobile phones, notebook computers and the like that are required to be small and light.
  • lithium ion secondary batteries those using a non-aqueous electrolyte solution in which a lithium salt is dissolved in an organic solvent are used as an electrolyte.
  • a lithium ion secondary battery is, for example, a positive electrode in which a positive electrode active material layer is provided on a positive electrode current collector, a negative electrode in which a negative electrode active material layer is provided on a negative electrode current collector, and a position between the positive electrode and the negative electrode.
  • a non-aqueous electrolyte solution are provided in the exterior body.
  • a lithium ion secondary battery having a porous insulating layer on the surface of an electrode.
  • a nonaqueous electrolyte secondary battery including a particle layer having a thickness of 2 ⁇ m on the surface of the positive electrode is described.
  • the particle layer includes inorganic particles, polycarboxylate, and styrene butadiene rubber.
  • the particle layer provided on the surface of the positive electrode functions as a filter for trapping non-aqueous electrolyte decomposition products generated by the reaction at the positive electrode and elements (elements other than lithium) eluted from the positive electrode active material. For this reason, by having the said particle layer, it can prevent that elements other than the said decomposition product or lithium precipitate on the negative electrode surface or a separator.
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery having a particle layer on the surface of an electrode, high mechanical strength, and excellent cycle characteristics, and a method for producing the non-aqueous electrolyte secondary battery.
  • a positive electrode including a positive electrode current collector and a positive electrode active material layer positioned on the surface of the positive electrode current collector, a negative electrode current collector, and a negative electrode active material layer positioned on the surface of the negative electrode current collector
  • a negative electrode a nonaqueous electrolyte containing lithium ions, a separator positioned between the positive electrode and the negative electrode, and a particle layer positioned on the surface of one or both of the positive electrode and the negative electrode.
  • the inorganic particles are at least one selected from the group consisting of magnesia particles, titania particles, alumina particles, silica particles, and lithium phosphate particles.
  • the inorganic particles have an average particle size of 1.3 ⁇ m or less.
  • the nonaqueous electrolyte secondary battery of the present invention has high mechanical strength and excellent cycle characteristics.
  • FIG. 1 is a schematic diagram of a cross section according to an embodiment of a nonaqueous electrolyte secondary battery (hereinafter, also simply referred to as a secondary battery) of the present invention.
  • a secondary battery 10 in FIG. 1 includes a positive electrode 1, a separator 2, a negative electrode 3, a particle layer 4, and an exterior body 5.
  • the positive electrode 1 and the negative electrode 3 have a flat plate shape that is rectangular in plan view.
  • the positive electrode 1 and the negative electrode 3 are opposed to each other.
  • a separator 2 is located between the positive electrode 1 and the negative electrode 3 facing each other.
  • the negative electrode 3, the separator 2, the positive electrode 1, the separator 2, and the negative electrode 3 are positioned in this order to form the laminate 20.
  • the laminate 20 and the non-aqueous electrolyte are located in the exterior body 5.
  • the particle layer 4 is located on the surface of the positive electrode 1.
  • the particle layer 4 is preferably located on the surface of the positive electrode 1 facing the negative electrode 3.
  • the positive electrode 1 has a plate-like positive electrode current collector 11 and positive electrode active material layers 12 located on both sides thereof.
  • the positive electrode active material layer 12 is located on a part of the surface of the positive electrode current collector 11.
  • a positive electrode current collector exposed portion 13 where the positive electrode active material layer 12 does not exist is located at the edge of the surface of the positive electrode current collector 11.
  • a lead wire (tab) (not shown) is connected to the positive electrode current collector 11 at an arbitrary portion of the exposed edge.
  • the particle layer 4 covers the positive electrode active material layer 12, and a part of the particle layer 4 is located on the surface of the positive electrode current collector exposed portion 13.
  • the negative electrode 3 has a plate-shaped negative electrode current collector 31 and negative electrode active material layers 32 located on both sides thereof.
  • the negative electrode active material layer 32 is located on a part of the surface of the negative electrode current collector 31.
  • a negative electrode current collector exposed portion 33 where the negative electrode active material layer 32 does not exist is located at the edge of the surface of the negative electrode current collector 31.
  • a lead-out wiring (tab) (not shown) is connected to the negative electrode current collector 31 at an arbitrary portion of the exposed edge.
  • the laminated body 20 and a non-aqueous electrolyte are accommodated in the exterior body 5 and sealed.
  • the particle layer includes particles and a binder.
  • the particles are referred to as particles A, and when the particle layer includes other components described later, a mixture of the particles and other components is referred to as particles A.
  • the particle layer 4 in the secondary battery 10 is infiltrated with the electrolytic solution. As the electrolytic solution infiltrates into the particle layer 4, a slight gap is formed between the binder and the particles. Since lithium ions and the like permeate through the particle layer 4 through the gap, the particle layer 4 has ion conductivity.
  • the particles contained in the particle layer are preferably particles that do not occlude and release lithium ions. “Occlusion and release of lithium ions” means that a lithium ion secondary battery including the positive electrode 1 and the negative electrode 3 occludes or releases lithium ions to the extent that it interferes with the charge / discharge operation. .
  • the particles may be inorganic particles or organic particles.
  • a / B which is the ratio of the specific surface area A of the particles A to the specific surface area B of particles (hereinafter also referred to as “particles B”) contained in a positive electrode active material layer described later, is preferably more than 0.2 and less than 1.5. More than 0.3 and less than 1.1 is more preferable, and more than 0.3 and less than 0.8 is more preferable. If the A / B exceeds the lower limit of the range, the mechanical strength and cycle characteristics of the secondary battery are improved, and the increase in internal resistance is suppressed. When the A / B is less than the upper limit of the range, the mechanical strength and cycle characteristics of the secondary battery are improved.
  • the “specific surface area” is a BET specific surface area measured by a BET gas adsorption method using nitrogen as an adsorption gas.
  • the specific surface area of the particles A so long as it has the effect of the present invention is not particularly limited, but is preferably 1 ⁇ 30m 2 / g, more preferably 2 ⁇ 25m 2 / g, more preferably 3 ⁇ 20m 2 / g, 3 ⁇ 8 m 2 / g is particularly preferred.
  • the particles A include inorganic particles in that the peel strength of the particle layer and the mechanical strength of the secondary battery become higher.
  • the inorganic particles may be particles made of an inorganic material that does not occlude and release lithium ions.
  • One kind of inorganic particles in the particle layer may be used, or two or more kinds may be used in combination.
  • the inorganic particles are preferably inorganic oxide particles, for example.
  • the inorganic oxide particles include at least one selected from the group consisting of magnesia (magnesium oxide) particles, titania (titanium oxide) particles, alumina (aluminum oxide) particles, silica (silicon dioxide) particles, and lithium phosphate particles.
  • At least one selected from the group consisting of magnesia particles, titania particles, alumina particles, and lithium phosphate particles is more preferable, and at least one selected from the group consisting of magnesia particles, titania particles, and alumina particles is more preferable.
  • the average particle diameter of the inorganic particles is preferably 1.3 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less from the viewpoint of improving the mechanical strength of the secondary battery and suppressing the increase in internal resistance.
  • 0.7 ⁇ m or less is particularly preferable, and 0.6 ⁇ m or less is most preferable.
  • the lower limit of the average particle diameter of the inorganic particles is not particularly limited as long as it has the effect of the present invention, but is preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more.
  • the upper limit value and lower limit value mentioned above can be combined arbitrarily.
  • the combination of the upper limit value and the lower limit value is preferably 0.1 ⁇ m or more and 1.3 ⁇ m or less, more preferably 0.1 ⁇ m or more and 1.0 ⁇ m or less, further preferably 0.3 ⁇ m or more and 0.8 ⁇ m or less, and 0.3 ⁇ m or more and 0 or less.
  • 0.7 ⁇ m or less is particularly preferable, and 0.3 ⁇ m or more and 0.6 ⁇ m or less is most preferable.
  • the particles A may contain particles other than inorganic particles, for example, organic particles.
  • the particle layer contains organic particles, the internal resistance of the secondary battery can be further reduced.
  • the organic particles may be particles made of an organic material that does not occlude and release lithium ions.
  • the organic particles in the particle layer may be one kind or a combination of two or more kinds.
  • organic materials constituting the organic particles include, for example, poly ⁇ -olefin, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid, polymethacrylic acid ester, polysilicone (polymethylsilsesquioxane, etc.), polystyrene, Polydivinylbenzene, styrene-divinylbenzene copolymer, polyamide, polyimide, polycarbonate, urea resin, urethane resin, melamine resin, phenol resin, benzoguanamine-formaldehyde condensate, polysulfone, polyacrylonitrile, polyacetal, thermoplastic polyimide, etc. .
  • the upper limit of the average particle diameter of the organic particles is preferably 2 ⁇ m or less, and more preferably 1 ⁇ m or less in consideration of a suitable thickness of the particle layer.
  • the lower limit of the average particle diameter of the organic particles is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more from the viewpoint of dispersibility with respect to the dispersion medium.
  • the upper limit value and lower limit value mentioned above can be combined arbitrarily.
  • the combination of the upper limit value and the lower limit value is preferably 0.01 ⁇ m or more and 2 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 1 ⁇ m or less.
  • the average particle size of the inorganic particles and organic particles is the volume from the small diameter side of the particle size distribution obtained by measurement with a laser diffraction particle size distribution analyzer (for example, Partica LA-960 manufactured by Horiba, Ltd., SALD-3000J manufactured by Shimadzu). It is the particle size (that is, the volume average particle size) at which the cumulative total is 50%. Details of the measurement conditions will be described later in Examples.
  • a laser diffraction particle size distribution analyzer for example, Partica LA-960 manufactured by Horiba, Ltd., SALD-3000J manufactured by Shimadzu.
  • the content of inorganic particles with respect to all particles (100 parts by mass) contained in the particle layer is preferably 50 to 100 parts by mass, more preferably 60 to 100 parts by mass, still more preferably 70 to 100 parts by mass, and more preferably 80 to 100 parts by mass. Part by mass is particularly preferred.
  • the content of the inorganic particles is at least the lower limit of the above range, the mechanical strength of the secondary battery and the adhesive strength to the separator are further increased.
  • the content of the inorganic particles is not more than the upper limit of the above range, the liquid retention of the insulating layer is increased, and the increase in internal resistance of the secondary battery can be further reduced.
  • the content of organic particles relative to all particles (100 parts by mass) contained in the particle layer is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, 30 parts by mass or less is more preferable, and 20 parts by mass or less is particularly preferable.
  • the content of the organic particles is not more than the above upper limit value, the internal resistance of the secondary battery can be further reduced while maintaining the peel strength of the particle layer and the mechanical strength of the secondary battery.
  • the lower limit of the content of the organic particles is not particularly limited as long as it has the effect of the present invention, but is, for example, more than 0 parts by mass.
  • the content of the organic particles is preferably more than 0 parts by mass and 50 parts by mass or less, more preferably more than 0 parts by mass and 40 parts by mass or less, further preferably more than 0 parts by mass and 30 parts by mass or less, and more than 0 parts by mass and more than 20 parts by mass. Part or less is particularly preferable.
  • the total content of the particles in the particle layer is preferably 70 to 98% by mass, more preferably 85 to 95% by mass with respect to the total mass (100% by mass) of the particle layer.
  • the total content of the particles is not less than the lower limit of the above range, the mechanical strength and ionic conductivity of the secondary battery are increased, and the increase in cell resistance is reduced.
  • the peel strength of the particle layer is further increased.
  • the binder is a polymer that binds the particles to each other in the particle layer.
  • those used as binders for electrodes of non-aqueous secondary batteries can be applied.
  • PAA polyacrylic acid
  • PAALi polyacrylic acid lithium
  • PVDF polyvinylidene fluoride
  • PVDF-HFP Polyvinylidene fluoride-hexafluoropropylene copolymer
  • SBR styrene butadiene rubber
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PEG polyethylene glycol
  • CMC carboxymethyl cellulose
  • poly Examples include acrylonitrile (PAN) and polyimide (PI).
  • the molecular weight of the binder is appropriately set in consideration of the dispersibility and binding properties of the particles.
  • a binder may be used individually by 1 type and may use 2 or more types together. When using 2 or more types together, the combination and ratio may be appropriately selected according to the purpose.
  • an aqueous binder dispersible in water is preferable.
  • Specific examples of the aqueous binder include CMC, PAA, PAALi, PVA, PEO, and PEG.
  • the binder content is preferably 1.5 to 20 parts by mass and more preferably 4 to 20 parts by mass with respect to 100 parts by mass of the particles in the particle layer.
  • the binder content of the binder is not less than the lower limit of the above range, the binding force and peel strength between the particles are further increased.
  • the content of the binder is not more than the upper limit of the above range, the mechanical strength of the secondary battery is increased while reducing the cell resistance.
  • the thickness of the particle layer is preferably 1.5 to 20 ⁇ m, more preferably 2 to 15 ⁇ m, and particularly preferably 2 to 10 ⁇ m.
  • the “thickness of the particle layer” is a value obtained by observing the thickness of any 10 positions in the cross section of the particle layer with a scanning electron microscope (SEM) and calculating the average.
  • the relationship between the particle layer thickness T ( ⁇ m) and the average particle size D ( ⁇ m) of the inorganic particles is expressed by (average particle size D) / (particle layer thickness T).
  • the ratio (D / T) is, for example, preferably 0.02 to 0.50, more preferably 0.04 to 0.40, and even more preferably 0.05 to 0.30. When the ratio (D / T) is within the above range, the mechanical strength of the secondary battery is further improved.
  • the particle layer may contain other components in addition to the particles and the binder as long as the effects of the present invention are not impaired.
  • other components include polyvinyl pyrrolidone.
  • the total content of the other components is preferably more than 0% by mass and less than 5% by mass, more than 0% by mass and more than 3% by mass with respect to the total mass (100% by mass) of the particle layer. % Or less is more preferable.
  • a sample containing the particles A can be obtained by cutting out the part of the particle layer that does not overlap the positive electrode active material in the positive electrode of the secondary battery. Moreover, about the part which overlaps with a positive electrode active material, the sample containing particle
  • grains A can be obtained by shaving off only the part of a particle layer visually.
  • the binder can be removed from the sample by ultrasonic cleaning in an organic solvent capable of dissolving the binder, solid-liquid separation, and subsequent drying.
  • organic solvent include N-methylpyrrolidone. If the steps from ultrasonic cleaning in an organic solvent and solid-liquid separation are one cleaning, the cleaning is usually performed 1 to 10 times, and preferably 2 to 5 times.
  • the temperature of the organic solvent at the time of washing is usually 20 to 80 ° C., more preferably 40 to 70 ° C.
  • the drying after the solid-liquid separation may be performed at normal pressure or at reduced pressure.
  • the drying temperature is not particularly limited, but is usually 20 to 200 ° C.
  • the particles A are fractionated by appropriately selecting conditions that can remove the binder substantially completely from the above-described conditions.
  • the particle layer in the secondary battery immediately after the production of the secondary battery may be used, or the charge / discharge described in the examples described later is performed.
  • the particle layer in the secondary battery after this may be sufficient.
  • the particle layer can be formed by applying a coating liquid (slurry) to at least one surface of the positive electrode and the negative electrode and then drying to remove the diluting solvent and the like.
  • the coating solution contains particles, a binder, and, if necessary, a dilution solvent and optional other components.
  • the coating method is not particularly limited, and for example, a doctor blade method, various coater methods, a printing method, and the like are applied.
  • the particles contained in the coating solution the above-described inorganic particles and organic particles are used.
  • a binder what is used as a binder of the electrode of the above-mentioned non-aqueous secondary battery is used.
  • the dilution solvent may be any solvent that can disperse the particles and the binder.
  • the use amount of the dilution solvent can be appropriately adjusted according to the coating workability and the like.
  • An example of a diluent solvent is N-methylpyrrolidone.
  • a ′ / B which is the ratio of the specific surface area A ′ of the particles (hereinafter also referred to as “particle A ′”) contained in the coating solution to the specific surface area B of particles (particle B) contained in the positive electrode active material layer described later. Is preferably more than 0.2 and less than 1.5, more preferably more than 0.3 and less than 1.1, and still more preferably more than 0.3 and less than 0.8. If A ′ / B exceeds the lower limit of the range, the mechanical strength and cycle characteristics of the secondary battery are improved, and an increase in internal resistance is suppressed. When A ′ / B is less than the upper limit of the range, the mechanical strength and cycle characteristics of the secondary battery are improved.
  • the content of the particles with respect to 100 parts by mass of the coating solution is preferably 3 to 60 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 50 parts by mass.
  • the content of the binder with respect to 100 parts by mass of the coating solution is preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass.
  • the viscosity of the coating solution is preferably 30 to 3000 cps, more preferably 30 to 2000 cps, and further preferably 100 to 1800 cps.
  • Drying temperature and drying time are not particularly limited.
  • the drying temperature is usually 60 to 200 ° C, preferably 60 to 150 ° C.
  • the positive electrode current collector and the positive electrode active material layer are not particularly limited as long as they have the effects of the present invention, and known materials can be used.
  • a conductive metal foil is used as the positive electrode current collector.
  • the positive electrode active material layer includes particles (particle B) and a binder.
  • the particle B include a positive electrode active material and a conductive additive.
  • the mixture is referred to as a particle B.
  • the specific surface area of the particles B is preferably 5 ⁇ 20m 2 / g, more preferably 10 ⁇ 15m 2 / g. If the specific surface area is not less than the lower limit of the above range, the load characteristics as a cell are further enhanced. If the specific surface area is not more than the upper limit of the above range, the binding property is further enhanced.
  • Positive electrode active materials include layered rock salt type lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum compound, spinel type lithium manganate, lithium nickel manganese oxide, olivine type lithium iron phosphate, etc. And one or more selected from the group consisting of these transition metal compounds are preferred.
  • Examples of the conductive auxiliary agent include acetylene black, ketjen black, and carbon nanofiber.
  • the binder include a fluororesin such as polyvinylidene fluoride.
  • the positive electrode active material layer is formed, for example, by applying a positive electrode slurry in which a positive electrode active material, a conductive additive, and a binder are dispersed in a solvent to the surface of the positive electrode current collector. Examples of the solvent include N-methylpyrrolidone.
  • the fractionation of the particles B for the specific surface area measurement can be performed in the same manner as the above-mentioned [Method for fractionating the particles A for the measurement of the specific surface area]. That is, a sample containing the particles B can be obtained by cutting off a portion of the positive electrode active material layer that does not overlap with the particle layer in the positive electrode in the secondary battery. Moreover, about the part which overlaps with a particle layer, the sample containing particle
  • the removal of the binder from the sample can be performed by the same method as the removal of the binder described in the above-mentioned “Method for separating particles A for measurement of specific surface area”.
  • the positive electrode active material layer for separating the particles B and measuring the specific surface area the positive electrode active material layer in the secondary battery immediately after the production of the secondary battery may be used, or the charge / discharge described in the examples described later. It may be a positive electrode active material layer in the secondary battery after performing the above. Especially, it is preferable to use the positive electrode active material layer in the secondary battery after charging / discharging. In addition, before and after charging / discharging, it confirmed separately that the value of the specific surface area of the particle
  • the negative electrode current collector and the negative electrode active material layer are not particularly limited, and known materials can be used.
  • a conductive metal foil is used, and for example, copper, stainless steel, nickel, titanium, or an alloy thereof is used.
  • the negative electrode active material layer is formed, for example, by applying a negative electrode slurry obtained by dispersing a negative electrode active material, a binder, and, if necessary, a conductive additive added in a solvent to the surface of the negative electrode current collector.
  • Examples of the negative electrode active material include metal lithium, lithium alloy, carbon-based materials that can occlude and release lithium ions (carbon powder, graphite powder, etc.), and metal oxide materials, and are selected from the group consisting of these materials.
  • the conductive auxiliary agent for example, acetylene black, carbon nanotube, or the like can be used.
  • the binder include fluororesins such as polyvinylidene fluoride, styrene butadiene rubber, carboxymethyl cellulose, and the like.
  • the material of the separator is not particularly limited, and examples thereof include a microporous polymer film or nonwoven fabric made of an olefin resin (polyolefin) or a cellulose material, and a woven fabric or nonwoven fabric made of glass fiber. Especially, from a viewpoint of improving adhesiveness with a particle layer, an olefin resin or a cellulose material is preferable, and an olefin resin is more preferable.
  • the olefin-based resin may be a single polyolefin or a mixture of two or more different polyolefins (for example, a mixture of polyethylene and polypropylene), or a copolymer of different olefins. Particularly preferred are polyethylene and polypropylene.
  • the mass average molecular weight (Mw) of the olefin resin is not particularly limited, and is preferably 1 ⁇ 10 4 to 1 ⁇ 10 7 , for example, from the viewpoint of obtaining sufficient mechanical strength, and is preferably 1 ⁇ 10 4 to 15 ⁇ 10 6. More preferably, 1 ⁇ 10 5 to 5 ⁇ 10 6 is even more preferable.
  • the “mass average molecular weight” means a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.
  • the air permeability of the separator to which the particle layer adheres is preferably 50 to 200 seconds / 100 cc, and more preferably 120 to 180 seconds / 100 cc.
  • the air permeability of the separator is equal to or higher than the lower limit of the above range, the permeability and permeability of the electrolytic solution can be sufficiently obtained.
  • the air permeability of the separator is not more than the upper limit of the above range, the adhesion strength of the particle layer to the separator is further increased.
  • the air permeability is determined by measuring with a Gurley type densometer (manufactured by Toyo Seiki etc.).
  • the thickness of the separator is not particularly limited, and can be set to, for example, 5 ⁇ m to 30 ⁇ m from the viewpoint of obtaining sufficient mechanical strength.
  • the size of the separator in the vertical and horizontal directions is preferably equal to or larger than the size of the electrode current collector, and more preferably larger than the size of the electrode current collector, for example, about 0.1 cm to 5 cm.
  • Nonaqueous electrolyte can be used in the nonaqueous electrolyte secondary battery. It may be a non-aqueous electrolyte that is a mixture of an electrolyte and a non-aqueous solvent, or a polymer solid electrolyte that is a mixture of an electrolyte and a polymer.
  • the polymer solid electrolyte includes those containing a non-aqueous solvent as a plasticizer.
  • the electrolyte those used in known lithium ion secondary batteries can be used.
  • lithium hexafluorophosphate LiPF 6
  • lithium boron tetrafluoride LiBF 4
  • lithium bis (fluorosulfonyl) lithium salts such as imide (LiN (SO 2 F) 2 , LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiN (SO 2 CF 3 ) 2 , LiTFSI).
  • the electrolyte may be used alone or in combination of two or more.
  • non-aqueous solvent for example, carbonates, esters, ethers, lactones, nitriles, amides, sulfones and the like can be used.
  • a nonaqueous solvent may be used individually by 1 type, and 2 or more types of mixed solvents may be sufficient as it.
  • Examples thereof include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetonitrile, propionitrile, nitromethane, N, N-dimethylformamide, Examples thereof include dimethyl sulfoxide, sulfolane, and ⁇ -butyrolactone.
  • the non-aqueous electrolyte secondary battery according to the present invention includes a step of forming a particle layer described in [Particle Layer Formation Method] described above.
  • a known assembly process can be applied except that at least one of the positive electrode on which the particle layer is formed and the negative electrode on which the particle layer is formed is used.
  • the assembly process includes, for example, an operation of laminating a negative electrode, a separator, and a positive electrode, an operation of accommodating the laminated body in the exterior body, an operation of filling the exterior body with a nonaqueous electrolyte, and an operation of sealing the exterior body.
  • a / B which is the ratio of the specific surface area A of the particles contained in the particle layer to the specific surface area B of the particles contained in the positive electrode active material layer, is more than 0.2 and less than 1.5.
  • the internal resistance of the nonaqueous electrolyte secondary battery of the present embodiment is preferably 90 to 250 m ⁇ , more preferably 90 to 180 m ⁇ , and further preferably 90 to 130 m ⁇ .
  • the capacity maintenance ratio measured by the method described in the examples described later is preferably 80 to 95%, more preferably 85 to 95%, and still more preferably 90 to 95%.
  • the puncture strength measured by the method described in the examples described later is preferably 20 to 100N, more preferably 40 to 100N, and further preferably 60 to 100N.
  • the capacity maintenance rate of the secondary battery is preferably 90 to 95%
  • the puncture strength is preferably 35 to 80 N
  • the capacity maintenance rate is 90 to 95%. More preferably, the piercing strength is 40 to 60N.
  • the internal resistance of the secondary battery is preferably 90 to 130 m ⁇
  • the capacity retention is preferably 85 to 95%
  • the internal resistance is 90 to 130 m ⁇
  • the capacity retention rate is more preferably 90 to 95%.
  • the particle layer is present not only on the positive electrode active material layer but also on the surface of the positive electrode current collector on the surface of the positive electrode current collector on which the positive electrode active material layer is provided. . That is, as shown in FIG. 1, a part of the particle layer 4 is present on the surface of the positive electrode current collector exposed portion 13. There is a possibility that a state in which no separator is present between the opposing negative electrode active material layer 32 and the positive electrode current collector exposed portion 13 may occur due to thermal contraction or displacement of the separator. In such a case, the negative electrode active material layer 32 and the positive electrode current collector exposed portion 13 can be prevented from coming into contact with each other by the particle layer 4 existing between them.
  • the distance from the edge of the positive electrode active material layer 12 to the edge of the particle layer 4 is preferably 1 mm or more, and more preferably 2 mm or more.
  • the upper limit of x is not particularly limited as long as it has the above effect, but may be, for example, 20 mm or less, or 8 mm or less.
  • the combination of the upper limit value and the lower limit value is preferably 1 mm or more and 20 mm or less, and more preferably 2 mm or more and 8 mm or less.
  • the particle layer 4 is provided on the surface of the positive electrode 1.
  • the same particle layer may be provided on the surface of the negative electrode 3, or may be provided on both the surface of the positive electrode 1 and the surface of the negative electrode 3.
  • 3 shows a secondary battery 10 having a particle layer 4 on the surface of the negative electrode 3 and no particle layer on the surface of the positive electrode 1
  • FIG. 4 shows a particle layer 4 on both the surface of the positive electrode 1 and the surface of the negative electrode 3.
  • the secondary battery 10 which has is shown. 3 and 4 are the same as those described in FIG.
  • a part of the particle layer may be present on the surface of the negative electrode current collector exposed portion as in the case of the positive electrode.
  • the distance from the edge of the negative electrode active material layer to the edge of the particle layer is preferably 1 mm or more, and more preferably 2 mm or more.
  • the upper limit of the distance from the edge of the negative electrode active material layer to the edge of the particle layer is not particularly limited as long as the above effect is obtained, but may be, for example, 20 mm or less, or 8 mm or less.
  • the combination of the upper limit value and the lower limit value is preferably 1 mm or more and 20 mm or less, and more preferably 2 mm or more and 8 mm or less.
  • one positive electrode 1, two negative electrodes 3, and two separators 2 are stacked as shown in FIG. 1, but a unit in which a negative electrode, a separator, and a positive electrode are stacked in this order.
  • the number of units can be arbitrarily changed.
  • the positive electrode active material layer 12 and the particle layer 4 are provided on both surfaces of the positive electrode current collector 11, but may be provided only on one surface of the positive electrode current collector 11.
  • the negative electrode active material layer and the particle layer may be provided on both surfaces of the negative electrode current collector, or may be provided only on one surface of the negative electrode current collector.
  • the conductivity is rate-limiting at the positive electrode and the ion conductivity is often rate-limiting at the negative electrode.
  • the shape of the secondary battery is not limited to the shape of the present embodiment, and can be adjusted to various shapes such as a cylindrical shape, a square shape, a coin shape, and a sheet shape.
  • Electrolytic solution Ethylene carbonate (EC): Diethyl carbonate (DEC) was mixed in a volume ratio of 3: 7, and LiPF 6 was dissolved as an electrolyte to a concentration of 1 mol / liter to prepare a non-aqueous electrolytic solution. did.
  • Al 2 O 3 -1 (specific surface area: 4 m 2 / g, average particle size: 0.3 ⁇ m) Al 2 O 3 -2 (specific surface area: 10 m 2 / g, average particle size: 0.3 ⁇ m) Al 2 O 3 -3 (specific surface area: 11 m 2 / g, average particle size: 0.3 ⁇ m) Al 2 O 3 -4 (specific surface area: 17 m 2 / g, average particle size: 0.3 ⁇ m) Al 2 O 3 -5 (specific surface area: 3 m 2 / g, average particle size: 0.3 ⁇ m) Al 2 O 3 -6 (specific surface area: 4 m 2 / g, average particle size: 1.2 ⁇ m) Al 2 O 3 -7 (specific surface area: 4 m 2 / g, average particle size: 2.0 ⁇ m) Al 2 O 3 -8 (specific surface area: 2 m 2 / g, average particle size: 0.3 ⁇ m) Al 2 O 3 -8 (specific surface area: 2 m 2
  • Example 1 (Formation of particle layer) A coating solution was prepared by uniformly mixing 100 parts by mass of inorganic particles, 10 parts by mass of polyvinylidene fluoride (Kureha # 7200) and 500 parts by mass of N-methylpyrrolidone. Al 2 O 3 -1 was used as the inorganic particles. The obtained coating solution was applied to both sides of the positive electrode obtained in Production Example 1 and dried to form particle layers on both sides of the positive electrode. The thickness of each particle layer after drying was 5 ⁇ m. As shown in FIG. 1, the particle layer 4 was continuously formed on the positive electrode active material layer 12 of the positive electrode and on the positive electrode current collector exposed portion 13 adjacent thereto. The distance (x) from the edge of the positive electrode active material layer 12 to the edge of the particle layer 4 was 5 mm. The solid content of the binder in the particle layer was 10 parts by mass with respect to 100 parts by mass of all particles.
  • a polyethylene porous film (melting point: 128 ° C.) was used.
  • two negative electrodes obtained in Production Example 1 one positive electrode on which a particle layer was formed, and two separators were laminated in this order: negative electrode, separator, positive electrode, separator, and negative electrode.
  • a terminal tab is electrically connected to each of the positive electrode current collector exposed portion and the negative electrode current collector exposed portion, and the laminate is sandwiched between aluminum laminate films so that the terminal tab protrudes to the outside. Sealed by laminating.
  • a secondary battery (laminated cell) was manufactured by injecting the electrolytic solution obtained in Production Example 1 from one side left without sealing and vacuum sealing.
  • Puncture strength The puncture strength was measured using the apparatus comprised like FIG.
  • the puncture strength is a measure of the mechanical strength of the lithium ion secondary battery.
  • reference numeral 41 denotes a negative electrode obtained in Production Example 1
  • 42 denotes a separator used in Example 1
  • 43 denotes a nickel piece
  • 44 denotes a particle layer
  • 45 denotes an aluminum foil used in Production Example 1.
  • the particle layer 44 is formed on the aluminum foil 45 under the same conditions as in the first embodiment.
  • Reference numeral 51 denotes a pressing jig that applies pressure in a direction in which the negative electrode 41 and the aluminum foil 45 (positive electrode) approach each other, and this pressure is measured by an autograph.
  • Reference numeral 52 is a receiving plate made of SUS304.
  • the nickel small piece 43 used what was described in the JIS C8714 forced internal short circuit test.
  • the pressing jig 51 is lowered to increase the pressure for pressing the negative electrode 41 against the aluminum foil 45 (positive electrode)
  • the nickel small piece 43 penetrates the separator 42 and the particle layer 44 to cause conduction (short circuit).
  • 2V was applied between the negative electrode 41 and the aluminum foil 45 (positive electrode)
  • the resistance value between the positive electrode and the negative electrode was measured while lowering the pressing jig 51, and the resistance value was 10 ⁇ or less. Judgment was conducted, and the pressure at that time was defined as the piercing strength of the particle layer.
  • a sample including the positive electrode active material layer was taken out from the positive electrode, and the particle layer formed between the positive electrode active material and the separator was scraped off with a spatula to obtain particles in the positive electrode active material layer.
  • Pretreatment of sample The particles in the particle layer taken out above or the particles in the positive electrode active material layer were immersed in NMP at 60 ° C. Next, ultrasonic cleaning was performed for 10 minutes, and after filtering the solid content, 90% of NMP was removed by vacuum drying at 130 ° C. for 4 hours. After performing the washing
  • Examples 2 to 16, Comparative Examples 1 and 2 Manufacture of a secondary battery in the same manner as in Example 1 except that the inorganic particles shown in Table 1 and the positive electrode were used and the particle layer on the positive electrode surface was made to have the film thickness shown in Table 1 on both sides. And evaluated. The evaluation results are shown in Table 1.
  • the ratio of the specific surface area A of the particles contained in the particle layer to the specific surface area B of the particles contained in the positive electrode active material layer is A / Both the capacity retention ratio and the piercing strength were higher than those of Comparative Example 1 in which B was 1.5 or more.
  • the secondary batteries of Examples 1 to 16 had higher capacity retention and piercing strength and lower internal resistance than Comparative Example 2 in which A / B was 0.2 or less.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

La présente invention concerne une batterie secondaire à électrolyte non aqueux (10) qui comporte : une électrode positive (1) qui comprend un collecteur d'électrode positive (11) et une couche de matériau actif d'électrode positive (12) qui est disposée sur la surface du collecteur d'électrode positive (11) ; une électrode négative (3) qui comprend un collecteur d'électrode négative (31) et une couche de matériau actif d'électrode négative (32) qui est disposée sur la surface du collecteur d'électrode négative (31) ; un électrolyte non aqueux qui contient des ions lithium ; un séparateur (2) qui est disposé entre l'électrode positive (1) et l'électrode négative (3) ; et une couche de particules (4) qui est disposée sur l'une ou les deux de la surface de l'électrode positive (1) et de la surface de l'électrode négative (3). Cette batterie secondaire à électrolyte non aqueux (10) est conçue de telle sorte que le rapport des zones de surface spécifiques A des particules contenues dans la couche de particules (4) aux zones de surface spécifiques B des particules contenues dans la couche de matériau actif d'électrode positive (12), à savoir A/B est supérieur à 0,2 mais inférieure à 1,5.
PCT/JP2019/011471 2018-03-26 2019-03-19 Batterie secondaire à électrolyte non aqueux et procédé de production de batterie secondaire à électrolyte non aqueux Ceased WO2019188590A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024090824A (ja) * 2022-12-23 2024-07-04 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 正極板、非水電解質二次電池、及び正極板の製造方法

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JP7323713B2 (ja) * 2021-03-19 2023-08-08 積水化学工業株式会社 非水電解質二次電池用正極、並びにこれを用いた非水電解質二次電池、電池モジュール、及び電池システム

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1125956A (ja) * 1997-07-07 1999-01-29 Fuji Photo Film Co Ltd 正極シートとこれを用いた非水電解質二次電池
JP2006210003A (ja) * 2005-01-25 2006-08-10 Nissan Motor Co Ltd 電池用電極
JP2008027634A (ja) * 2006-07-19 2008-02-07 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2012074359A (ja) * 2010-09-03 2012-04-12 Gs Yuasa Corp 電池

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5219387B2 (ja) * 2007-03-12 2013-06-26 三洋電機株式会社 非水電解質二次電池
JPWO2015004841A1 (ja) * 2013-07-08 2017-03-02 パナソニック株式会社 非水電解質二次電池
CN105580165B (zh) * 2013-07-24 2018-08-14 日产自动车株式会社 非水电解质二次电池用正极以及使用了该正极的非水电解质二次电池
JP6597267B2 (ja) * 2015-12-15 2019-10-30 株式会社豊田自動織機 リチウムイオン二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1125956A (ja) * 1997-07-07 1999-01-29 Fuji Photo Film Co Ltd 正極シートとこれを用いた非水電解質二次電池
JP2006210003A (ja) * 2005-01-25 2006-08-10 Nissan Motor Co Ltd 電池用電極
JP2008027634A (ja) * 2006-07-19 2008-02-07 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2012074359A (ja) * 2010-09-03 2012-04-12 Gs Yuasa Corp 電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024090824A (ja) * 2022-12-23 2024-07-04 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 正極板、非水電解質二次電池、及び正極板の製造方法
JP7692398B2 (ja) 2022-12-23 2025-06-13 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 正極板、非水電解質二次電池、及び正極板の製造方法

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