WO2024024506A1 - 非水電解質二次電池 - Google Patents

非水電解質二次電池 Download PDF

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Publication number
WO2024024506A1
WO2024024506A1 PCT/JP2023/025694 JP2023025694W WO2024024506A1 WO 2024024506 A1 WO2024024506 A1 WO 2024024506A1 JP 2023025694 W JP2023025694 W JP 2023025694W WO 2024024506 A1 WO2024024506 A1 WO 2024024506A1
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Prior art keywords
heat
secondary battery
electrolyte secondary
layer
resistant layer
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PCT/JP2023/025694
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English (en)
French (fr)
Japanese (ja)
Inventor
真治 笠松
紀子 杉井
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Panasonic Energy Co Ltd
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Panasonic Energy Co Ltd
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Priority to EP23846237.8A priority Critical patent/EP4564577A4/en
Priority to JP2024536950A priority patent/JPWO2024024506A1/ja
Priority to CN202380054183.2A priority patent/CN119487692A/zh
Publication of WO2024024506A1 publication Critical patent/WO2024024506A1/ja
Anticipated expiration legal-status Critical
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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 disclosure relates to a non-aqueous electrolyte secondary battery.
  • non-aqueous electrolyte secondary batteries have been widely used as high-output, high-energy-density secondary batteries that include an electrode body in which a positive electrode and a negative electrode are placed facing each other with a separator in between.
  • Patent Document 1 discloses a technique in which the static friction coefficient of the surface of a separator is set to 0.45 or less in order to improve the ease of pulling out the winding core when manufacturing a wound electrode body.
  • Patent Document 2 discloses a separator including a base material and a layer containing a heat-resistant resin and inorganic particles formed on the base material.
  • Patent Document 3 discloses a base material and a functional layer formed on the base material that includes inorganic particles and resin particles, and the volume average particle diameter of the resin particles includes the inorganic particles.
  • a separator is disclosed that is greater than the thickness of the inorganic particle layer.
  • an object of the present disclosure is to provide a non-aqueous electrolyte secondary battery that can suppress plate deformation due to charge/discharge cycles.
  • a non-aqueous electrolyte secondary battery includes an electrode body in which a positive electrode and a negative electrode are wound together with a separator interposed therebetween, and an exterior body housing the electrode body, and the separator includes a base material layer and the a functional layer formed on a base layer, the functional layer comprising a heat-resistant layer containing a heat-resistant resin and inorganic particles, and a heat-resistant layer dispersed in the heat-resistant layer, the functional layer having an average thickness greater than the thickness of the heat-resistant layer. and resin particles having a particle diameter, and the resin particles are characterized in that they form convex portions protruding from the surface of the heat-resistant layer.
  • nonaqueous electrolyte secondary battery that can suppress plate deformation associated with charge/discharge cycles.
  • FIG. 1 is a schematic cross-sectional view of a nonaqueous electrolyte secondary battery that is an example of an embodiment.
  • FIG. 1 is a schematic cross-sectional view showing an example of a separator of this embodiment.
  • FIG. 3 is a diagram for explaining a method for evaluating electrode plate deformation.
  • FIG. 1 is a schematic cross-sectional view of a non-aqueous electrolyte secondary battery that is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 shown in FIG. It includes arranged insulating plates 18 and 19 and a battery case 15.
  • the battery case 15 includes an exterior body 16 that accommodates the electrode body 14, a nonaqueous electrolyte, and the like, and a sealing body 17 that closes an opening of the exterior body 16.
  • the battery case 15 is not limited to a cylindrical or rectangular metal case, and may be, for example, a resin case formed by laminating resin sheets (so-called laminate type).
  • the non-aqueous electrolyte includes, for example, a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents include esters, ethers, nitriles, amides, and mixed solvents of two or more of these.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a portion of hydrogen in these solvents is replaced with a halogen atom such as fluorine.
  • a lithium salt such as LiPF 6 is used as the electrolyte salt.
  • the nonaqueous electrolyte is not limited to a liquid electrolyte, and may be a solid electrolyte such as a gel polymer.
  • the exterior body 16 is, for example, a cylindrical metal container with a bottom.
  • a gasket 28 is provided between the exterior body 16 and the sealing body 17 to ensure airtightness inside the battery.
  • the exterior body 16 has an overhanging portion 22 that supports the sealing body 17 and has, for example, a portion of a side surface thereof overhanging inward.
  • the projecting portion 22 is preferably formed in an annular shape along the circumferential direction of the exterior body 16, and supports the sealing body 17 on its upper surface.
  • the sealing body 17 has a structure in which a filter 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are stacked in order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected to each other at their central portions, and an insulating member 25 is interposed between their respective peripheral portions.
  • the lower valve body 24 deforms and ruptures to push the upper valve body 26 toward the cap 27, causing the lower valve body 24 and the upper valve The current path between bodies 26 is interrupted.
  • the upper valve body 26 breaks and gas is discharged from the opening of the cap 27.
  • the positive electrode lead 20 attached to the positive electrode 11 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 attached to the negative electrode 12 is insulated. It passes through the outside of the plate 19 and extends to the bottom side of the exterior body 16.
  • the positive electrode lead 20 is connected by welding or the like to the lower surface of the filter 23, which is the bottom plate of the sealing body 17, and the cap 27, which is the top plate of the sealing body 17 and electrically connected to the filter 23, serves as a positive terminal.
  • the negative electrode lead 21 is connected to the bottom inner surface of the exterior body 16 by welding or the like, and the exterior body 16 serves as a negative electrode terminal.
  • the positive electrode 11 includes a positive electrode current collector and a positive electrode mixture layer formed on the surface of the positive electrode current collector.
  • the positive electrode mixture layer is preferably formed on both sides of the positive electrode current collector.
  • a metal foil such as aluminum that is stable in the potential range of the positive electrode 11, a film with the metal disposed on the surface, or the like can be used.
  • the positive electrode mixture layer includes, for example, a positive electrode active material, a binder, a conductive agent, and the like.
  • the positive electrode 11 can be made, for example, by applying a positive electrode mixture slurry containing a positive electrode active material, a binder, a conductive agent, etc. onto a positive electrode current collector, drying the coating film, and then rolling the positive electrode mixture layer to form a positive electrode mixture layer. It can be produced by forming on both sides of a current collector.
  • Examples of the positive electrode active material contained in the positive electrode mixture layer include lithium transition metal oxides containing transition metal elements such as Co, Mn, and Ni.
  • Examples of lithium transition metal oxides include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1-y O 2 , Li x Co y M 1-y O z , Li x Ni 1 -y M y O z , Li x Mn 2 O 4 , Li x Mn 2-y M y O 4 , LiMPO 4 , Li 2 MPO 4 F (M; Na, Mg, Sc, Y, Mn, Fe, Co, At least one of Ni, Cu, Zn, Al, Cr, Pb, Sb, and B, 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.9, 2.0 ⁇ z ⁇ 2.3).
  • the positive electrode active materials are Li x NiO 2 , Li x Co y Ni 1-y O 2 , Li x Ni 1-y M y O z ( M; at least one of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0 .9, 2.0 ⁇ z ⁇ 2.3) and the like.
  • Inorganic particles such as tungsten oxide, aluminum oxide, and lanthanide-containing compounds may be fixed to the surface of the lithium transition metal oxide particles.
  • Examples of the conductive agent included in the positive electrode mixture layer include carbon materials such as carbon black (CB), acetylene black (AB), Ketjen black, carbon nanotubes (CNT), graphene, and graphite. These may be used alone or in combination of two or more.
  • Binders included in the positive electrode mixture layer include fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins.
  • fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • polyimide resins acrylic resins
  • acrylic resins and polyolefin resins.
  • CMC carboxymethyl cellulose
  • PEO polyethylene oxide
  • the negative electrode 12 includes a negative electrode current collector and a negative electrode mixture layer formed on the surface of the negative electrode current collector.
  • the negative electrode mixture layer is preferably formed on both sides of the negative electrode current collector.
  • a metal foil such as copper or copper alloy that is stable in the potential range of the negative electrode, a film having the metal disposed on the surface layer, or the like can be used.
  • the negative electrode mixture layer contains, for example, a negative electrode active material, a binder, and the like.
  • the negative electrode 12 can be made, for example, by applying a negative electrode mixture slurry containing a negative electrode active material, a binder, etc. onto a negative electrode current collector, drying the coating film, and then rolling the negative electrode mixture layer to the negative electrode current collector. It can be produced by forming it on both sides of.
  • the negative electrode active material contained in the negative electrode mixture layer is not particularly limited as long as it can reversibly insert and release lithium ions, and carbon-based active materials such as graphite are generally used.
  • the graphite may be natural graphite such as flaky graphite, lumpy graphite, or earthy graphite, or artificial graphite such as lumpy artificial graphite or graphitized mesophase carbon microbeads.
  • metals that alloy with Li such as Si and Sn, metal compounds containing Si, Sn, etc., lithium titanium composite oxide, etc. may be used.
  • As the negative electrode active material other than the carbon-based active material a silicon-based active material is preferable.
  • silicon-based active materials include Si-containing compounds represented by SiO x (0.5 ⁇ x ⁇ 1.6), or lithium silicate represented by Li 2y SiO (2+y) (0 ⁇ y ⁇ 2). Examples include Si-containing compounds in which fine particles of Si are dispersed in the phase.
  • the content of the silicon-based active material in the negative electrode mixture layer is, for example, preferably 1% by mass to 15% by mass, and preferably 5% by mass to 10% by mass, based on the total mass of the negative electrode active material. More preferred.
  • a conductive film is formed on the particle surface of the silicon-based active material.
  • the constituent material of the conductive film include at least one selected from carbon materials, metals, and metal compounds. Among these, carbon materials such as amorphous carbon are preferred.
  • the carbon film can be formed, for example, by a CVD method using acetylene, methane, etc., or by a method of mixing coal pitch, petroleum pitch, phenol resin, etc. with silicon-based active material particles and heat-treating the mixture.
  • a conductive film may be formed by fixing a conductive filler such as carbon black to the particle surface of the silicon-based active material using a binder.
  • the binder contained in the negative electrode mixture layer may be a fluororesin such as PTFE or PVDF, PAN, polyimide, acrylic resin, polyolefin, etc., but preferably styrene-butadiene. Rubber (SBR) is used.
  • the negative electrode mixture layer may contain CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA), or the like.
  • FIG. 2 is a schematic cross-sectional view showing an example of the separator of this embodiment.
  • the separator 13 includes a base material 30 and a functional layer 32 formed on the base material 30.
  • the functional layer 32 may be provided on one side of the base material 30, or may be provided on both sides of the base material 30.
  • the base material 30 is, for example, a porous sheet having ion permeability and insulation properties, and specifically includes a microporous thin film, a woven fabric, a nonwoven fabric, and the like.
  • the material of the base material 30 is not particularly limited, but includes, for example, polyolefin such as polyethylene, polypropylene, a copolymer of polyethylene and ⁇ -olefin, acrylic resin, polystyrene, polyester, cellulose, polyimide, polyphenylene sulfide, polyether ether ketone, Examples include fluororesin.
  • the functional layer 32 includes a heat-resistant layer 34 containing a heat-resistant resin and inorganic particles, and resin particles 36 that are dispersed in the heat-resistant layer 34 and have an average particle diameter (D50) larger than the thickness of the heat-resistant layer 34.
  • the resin particles 36 having an average particle diameter (D50) larger than the thickness of the heat-resistant layer 34 form convex portions 36a protruding from the surface of the heat-resistant layer 34.
  • the convex portion 36a made of the resin particles 36 adheres to the electrode (positive electrode 11 or negative electrode 12) facing the separator 13, and the adhesion between the separator 13 and the electrode is improved, so that the charging/discharging cycle It is thought that it will be possible to suppress the deformation of the electrode plate caused by this.
  • the separator 13 may be provided between the positive electrode 11 and the negative electrode 12 so that the functional layer 32 faces the positive electrode 11, or the functional layer 32 may be provided on one side of the base material 30.
  • a separator 13 may be provided between the positive electrode 11 and the negative electrode 12 so as to face the negative electrode 12 .
  • Examples of the inorganic particles included in the heat-resistant layer 34 include metal oxide particles, metal nitride particles, metal fluoride particles, metal carbide particles, and the like.
  • metal oxide particles include aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, nickel oxide, silicon oxide, manganese oxide, and the like.
  • metal nitride particles include titanium nitride, boron nitride, aluminum nitride, magnesium nitride, and silicon nitride.
  • metal fluoride particles include aluminum fluoride, lithium fluoride, sodium fluoride, magnesium fluoride, calcium fluoride, barium fluoride, and the like.
  • metal carbide particles include silicon carbide, boron carbide, titanium carbide, and tungsten carbide.
  • the inorganic particles are porous aluminosilicate such as zeolite (M 2/n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O, M is a metal element, n is the valence of M, x ⁇ 2, y ⁇ 0). It may be a salt, a layered silicate such as talc (Mg 3 Si 4 O 10 (OH) 2 ), or a mineral such as barium titanate (BaTiO 3 ) or strontium titanate (SrTiO 3 ). In addition, these may be used alone or in combination of two or more.
  • zeolite M 2/n O ⁇ Al 2 O 3 ⁇ xSiO 2 ⁇ yH 2 O
  • M is a metal element
  • n is the valence of M, x ⁇ 2, y ⁇ 0
  • It may be a salt, a layered silicate such as talc (Mg 3 Si 4 O 10 (OH) 2 ), or a mineral such as bar
  • the average particle diameter (D50) of the inorganic particles is preferably in the range of 0.1 ⁇ m to 1.0 ⁇ m, for example.
  • D50 refers to a particle size at which the cumulative frequency in the volume-based particle size distribution is 50% from the smallest particle size, and is also referred to as the median diameter.
  • the particle size distribution of the inorganic particles can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrac Bell Co., Ltd.) using water as a dispersion medium.
  • the content of inorganic particles contained in the heat-resistant layer 34 is preferably in the range of 15% by mass to 85% by mass, and more preferably in the range of 30% by mass to 60% by mass, based on the total mass of the heat-resistant layer 34.
  • the heat-resistant resin included in the heat-resistant layer 34 is preferably a resin that does not melt or decompose in a temperature range of less than 200° C., for example.
  • nitrogen-containing aromatic polymers and the like can be mentioned because of their high heat resistance.
  • a nitrogen-containing aromatic polymer is a polymer containing a nitrogen atom and an aromatic ring in its main chain, such as aromatic polyamide (hereinafter sometimes referred to as "aramid”), aromatic polyimide (hereinafter referred to as "polyimide”), ), aromatic polyamideimide (hereinafter sometimes referred to as "polyamideimide”), and the like.
  • aramid examples include meta-oriented aromatic polyamide (hereinafter sometimes referred to as “meta-aramid”) and para-oriented aromatic polyamide (hereinafter sometimes referred to as “para-aramid”). These may be used alone or in combination of two or more.
  • the content of the heat-resistant resin is preferably 15% by mass to 85% by mass, more preferably 40% by mass to 70% by mass, based on the total mass of the heat-resistant layer 34, for example, in terms of improving the heat resistance of the separator 13. .
  • the thickness of the heat-resistant layer 34 is preferably smaller than the thickness of the base material 30, and is, for example, 0.5 ⁇ m to 5 ⁇ m.
  • the heat-resistant layer 34 further contains a binder.
  • the binder has a function of bonding individual inorganic particles to each other and bonding the inorganic particles to the base material 30.
  • binders include fluororesins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polyimide resins, acrylic resins, polyolefin resins, styrene-butadiene rubber (SBR), and nitrile-based resins.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • polyimide resins acrylic resins
  • polyolefin resins polyolefin resins
  • SBR styrene-butadiene rubber
  • nitrile-based resins examples include butadiene rubber (NBR), carboxymethyl cellulose (CMC) or a salt thereof, polyvinyl alcohol (PVA), and the like. These may be used alone or
  • the resin particles 36 dispersed in the heat-resistant layer 34 need to have an average particle diameter (D50) larger than the thickness of the heat-resistant layer 34.
  • the average particle diameter (D50) of the resin particles 36 is preferably 1 ⁇ m to 10 ⁇ m larger than the thickness of the heat-resistant layer 34. If the average particle diameter (D50) of the resin particles 36 is 1 ⁇ m or more than the thickness of the heat-resistant layer 34, for example, convex portions 36a protruding from the surface of the heat-resistant layer 34 are likely to be formed, and good adhesion with the electrodes is ensured. Can be secured. Moreover, if the average particle diameter (D50) of the resin particles 36 is 10 ⁇ m or less than the thickness of the heat-resistant layer 34, falling off of the resin particles 36 from the heat-resistant layer 34 is suppressed.
  • the content of the resin particles 36 dispersed in the heat-resistant layer 34 is, for example, 1% by mass based on the mass of the heat-resistant resin contained in the heat-resistant layer 34, in order to ensure good adhesion with the electrode.
  • the range is preferably 15% by weight, more preferably 3% by weight to 7% by weight.
  • 10 to 35 convex portions 36a formed by the resin particles 36 are arranged in a range of 100 ⁇ m x 100 ⁇ m when the surface of the functional layer 32 is viewed from above in order to ensure good adhesion with the electrode.
  • the resin particles 36 for example, a known polymer that can be used as a binder when forming the functional layer 32 can be used.
  • the monomer units constituting the resin particles 36 (polymer) include aromatic vinyl monomer units, (meth)acrylic acid ester monomer units, fluorine-containing monomer units, and the like.
  • (meth)acrylic means acrylic and/or methacryl.
  • the expression that the resin particles 36 (polymer) "contains a monomer unit” means that a repeating unit derived from the monomer is contained in the polymer obtained using the monomer. .
  • aromatic vinyl monomers that can form aromatic vinyl monomer units include, but are not limited to, styrene, ⁇ -methylstyrene, styrene sulfonic acid, butoxystyrene, vinylnaphthalene, and the like. It will be done.
  • (meth)acrylic acid ester monomers that can form the (meth)acrylic acid ester monomer unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and t-butyl acrylate.
  • Butyl acrylate such as acrylate, octyl acrylate such as pentyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, alkyl acrylate such as nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate, etc.
  • esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate, octyl methacrylates such as pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, and 2-ethylhexyl methacrylate.
  • fluorine-containing monomers that can form fluorine-containing monomer units include, but are not limited to, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinyl trifluoride chloride, and fluorine-containing monomer units.
  • fluorine-containing monomer units include vinyl oxide, perfluoroalkyl vinyl ether, and the like.
  • the resin particles 36 may contain crosslinkable monomer units.
  • the crosslinkable monomer unit is a monomer that can form a crosslinked structure during or after polymerization by heating or irradiation with energy rays.
  • monomers that can form crosslinkable monomer units include polyfunctional monomers having two or more polymerization-reactive groups in the monomer.
  • polyfunctional monomers examples include divinyl compounds such as allyl methacrylate and divinylbenzene; Acrylic acid ester compounds; tri(meth)acrylic acid ester compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate; ethylenically unsaturated monomers containing epoxy groups such as allyl glycidyl ether and glycidyl methacrylate; etc. Can be mentioned.
  • the resin particles 36 can be prepared by, for example, polymerizing a monomer composition containing the above-mentioned monomers in an aqueous solvent such as water.
  • the polymerization method is not particularly limited, and may be, for example, a suspension polymerization method, an emulsion polymerization aggregation method, a pulverization method, or the like. Further, as the polymerization reaction, any reaction such as radical polymerization or living radical polymerization can be used.
  • the monomer composition used when preparing the resin particles 36 includes a chain transfer agent, a polymerization regulator, a polymerization reaction retarder, a reactive fluidizing agent, a filler, a flame retardant, an anti-aging agent, a coloring agent, etc.
  • Other compounding agents can be blended in arbitrary blending amounts.
  • a slurry composition for a functional layer is prepared by mixing inorganic particles, a heat-resistant resin, resin particles 36, water as a dispersion medium, and other components used as necessary (e.g., a binder).
  • a slurry composition for a functional layer is prepared by mixing inorganic particles, a heat-resistant resin, resin particles 36, water as a dispersion medium, and other components used as necessary (e.g., a binder).
  • the separator 13 of this embodiment can be produced by applying the functional layer slurry onto the base material and drying it.
  • Example 1 [Preparation of positive electrode] 100 parts by mass of LiNi 0.88 Co 0.09 Al 0.03 O 2 , 1 part by mass of acetylene black (AB), and 0.9 parts by mass of polyvinylidene fluoride (PVDF) were mixed, and N- An appropriate amount of methyl-2-pyrrolidone (NMP) was added to prepare a positive electrode mixture slurry. Next, the positive electrode mixture slurry was applied to both sides of a 15 ⁇ m thick aluminum foil, and the coating film was dried.
  • NMP methyl-2-pyrrolidone
  • a positive electrode mixture layer is formed on both sides of the positive electrode current collector.
  • a positive electrode was prepared. An exposed portion where the positive electrode mixture layer was not formed and the positive electrode current collector was exposed was provided at the center in the longitudinal direction of the positive electrode, and an aluminum positive electrode lead was welded to the exposed portion.
  • [Preparation of negative electrode] 95 parts by mass of graphite powder, 5 parts by mass of Si oxide, 1 part by mass of sodium carboxymethyl cellulose (CMC-Na), and 1 part by mass of a dispersion of styrene-butadiene rubber (SBR) were mixed, and then mixed with water. An appropriate amount of was added to prepare a negative electrode mixture slurry. Next, the negative electrode mixture slurry was applied to both sides of a copper foil having a thickness of 8 ⁇ m, and the coating film was dried. After rolling the coating film using a roller, it was cut into a predetermined electrode size to produce a negative electrode in which negative electrode mixture layers were formed on both sides of the negative electrode current collector. An exposed part where the negative electrode mixture layer is not formed and the negative electrode current collector is exposed is provided at one longitudinal end of the negative electrode (the end located on the inside of the electrode body), and a nickel negative electrode is placed in the exposed part. Welded the leads.
  • a porous base material made of polyethylene and having a thickness of 12 ⁇ m was prepared.
  • acrylic resin particles made of polymer
  • an acrylic binder binder
  • a slurry for the functional layer was prepared by adding an appropriate amount of water.
  • This functional layer slurry was applied to the entire area of one side of the base material using a microgravure coater, and the coating film was heated and dried in an oven at 50°C for 4 hours to form an average thickness of 3 ⁇ m on one side of the base material.
  • a separator was obtained in which a functional layer including a heat-resistant layer was formed.
  • a positive electrode and a negative electrode were spirally wound with a separator in between to produce a wound electrode body.
  • the separator was arranged so that the functional layer of the separator faced the positive electrode.
  • the number of turns of the electrode body was 18 times with the positive electrode as a reference.
  • Non-aqueous electrolyte 5 parts by mass of vinylene carbonate (VC) is added to 100 parts by mass of a mixed solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) are mixed at a volume ratio of 3:7, and lithium hexafluorophosphate is added.
  • VC vinylene carbonate
  • DMC dimethyl carbonate
  • LiPF 6 dissolving
  • a cross section of this charged non-aqueous electrolyte secondary battery near the winding center of the electrode body was observed using an X-ray CT device (SMX-225CT FPD HR manufactured by Shimadzu Corporation).
  • SMX-225CT FPD HR manufactured by Shimadzu Corporation.
  • FIG. 3 when deformation (bending) of the electrode plate (at least one of the positive electrode 11 and the negative electrode 12) is confirmed so that the angle ⁇ is 150° or less, it is determined that the electrode plate is deformed. The presence or absence was evaluated. The number of batteries evaluated was three.
  • Example 2 In producing the separator, para-aramid, ⁇ -Al 2 O 3 powder (inorganic particles) with an average particle diameter (D50) of 0.8 ⁇ m, acrylic resin particles with an average particle diameter (D50) of 4 ⁇ m, and an acrylic binder (binder ) was mixed at a solid content mass ratio of 100:150:9:5, but a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and the deformation of the electrode plate was evaluated.
  • Example 3 In producing the separator, para-aramid, ⁇ -Al 2 O 3 powder (inorganic particles) with an average particle diameter (D50) of 0.8 ⁇ m, acrylic resin particles with an average particle diameter (D50) of 4 ⁇ m, and an acrylic binder (binder) were used. ) were mixed at a solid content mass ratio of 100:150:18:5, but a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and the deformation of the electrode plate was evaluated.
  • Example 4 In producing the separator, para-aramid, ⁇ -Al 2 O 3 powder (inorganic particles) with an average particle diameter (D50) of 0.8 ⁇ m, acrylic resin particles with an average particle diameter (D50) of 6 ⁇ m, and an acrylic binder (binder ) was mixed at a solid content mass ratio of 100:150:15:5, but a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and the deformation of the electrode plate was evaluated.
  • Example 5 In producing the separator, para-aramid, ⁇ -Al 2 O 3 powder (inorganic particles) with an average particle diameter (D50) of 0.8 ⁇ m, acrylic resin particles with an average particle diameter (D50) of 10 ⁇ m, and an acrylic binder (binder ) were mixed at a solid content mass ratio of 100:150:24:5, but a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and the deformation of the electrode plate was evaluated.
  • Example 6 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that meta-aramid was used as the heat-resistant resin in producing the separator, and plate deformation was evaluated.
  • Example 7 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that polyamideimide was used as the heat-resistant resin in producing the separator, and plate deformation was evaluated.
  • a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, except that acrylic resin particles with an average particle diameter (D50) of 4 ⁇ m were not used in the preparation of the separator, and the plate deformation was evaluated. went.
  • Table 1 summarizes the evaluation results of electrode plate deformation in Examples 1 to 7 and Comparative Examples. Out of the three batteries evaluated, if no plate deformation has occurred in any of the batteries, it will be evaluated as ⁇ , and if it is confirmed that plate deformation has occurred in even one battery, it will be evaluated as ⁇ . doing.
  • the functional layer includes a heat-resistant layer containing a heat-resistant resin and inorganic particles, and a heat-resistant layer that is dispersed in the heat-resistant layer.
  • the separator includes resin particles that are present in the heat-resistant layer and have an average particle diameter larger than the thickness of the heat-resistant layer, and the resin particles form convex portions that protrude from the surface of the heat-resistant layer. It becomes possible to suppress deformation of the electrode plate due to cycles.
  • a non-aqueous electrolyte secondary battery comprising an electrode body in which a positive electrode and a negative electrode are wound with a separator interposed therebetween, and an exterior body housing the electrode body,
  • the separator has a base layer and a functional layer formed on the base layer,
  • the functional layer includes a heat-resistant layer containing a heat-resistant resin and inorganic particles, and resin particles that are dispersed in the heat-resistant layer and have an average particle diameter larger than the thickness of the heat-resistant layer,
  • the resin particles form convex portions protruding from the surface of the heat-resistant layer.
  • Nonaqueous electrolyte secondary battery 11 Positive electrode, 12 Negative electrode, 13 Separator, 14 Electrode body, 15 Battery case, 16 Exterior body, 17 Sealing body, 18, 19 Insulating plate, 20 Positive electrode lead, 21 Negative electrode lead, 22 Overhang part , 23 filter, 24 lower valve body, 25 insulating member, 26 upper valve body, 27 cap, 28 gasket, 30 base material, 32 functional layer, 34 heat-resistant layer, 36 resin particles, 36a convex portion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)
PCT/JP2023/025694 2022-07-27 2023-07-12 非水電解質二次電池 Ceased WO2024024506A1 (ja)

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WO2026048340A1 (ja) * 2024-08-28 2026-03-05 パナソニックＩｐマネジメント株式会社 非水電解質二次電池

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JP2011126275A (ja) 2009-11-20 2011-06-30 Mitsubishi Plastics Inc 積層多孔フィルム、電池用セパレータおよび電池
JP2015099777A (ja) * 2013-11-19 2015-05-28 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． リチウム電池用セパレータ、それを含むリチウム電池及び該リチウム電池の製造方法
WO2020175079A1 (ja) 2019-02-28 2020-09-03 日本ゼオン株式会社 電気化学素子用機能層、電気化学素子用機能層付きセパレータ、及び電気化学素子
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JPWO2019176421A1 (ja) * 2018-03-16 2021-03-11 三洋電機株式会社 非水電解質二次電池用セパレータ、非水電解質二次電池、及び非水電解質二次電池用セパレータの製造方法
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JP2011126275A (ja) 2009-11-20 2011-06-30 Mitsubishi Plastics Inc 積層多孔フィルム、電池用セパレータおよび電池
JP2015099777A (ja) * 2013-11-19 2015-05-28 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． リチウム電池用セパレータ、それを含むリチウム電池及び該リチウム電池の製造方法
WO2020175079A1 (ja) 2019-02-28 2020-09-03 日本ゼオン株式会社 電気化学素子用機能層、電気化学素子用機能層付きセパレータ、及び電気化学素子
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WO2026048340A1 (ja) * 2024-08-28 2026-03-05 パナソニックＩｐマネジメント株式会社 非水電解質二次電池

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