Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/52—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
  • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
  • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/423—Polyamide resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/426—Fluorocarbon polymers
• • 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
  • H01M50/431—Inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/431—Inorganic material
  • H01M50/434—Ceramics
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/409—Separators, membranes or diaphragms characterised by the material
  • H01M50/411—Organic material
  • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
  • H01M50/417—Polyolefins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
  • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• • 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 disclosure relates to a composition, a separator for an electrochemical device, an electrochemical device, and a secondary battery.
• Patent Document 1 describes a complex containing a fluorine-containing copolymer, an alkali metal salt, and an ionic liquid
• the fluorine-containing copolymer is Structural unit represented by general formula (1): - [CR 1 R 2 -CR 3 R 4 ] - (1)
• R 1 to R 4 are each independently H, F, Cl, CF 3 , OR 10 (R 10 is an organic group having 1 to 8 carbon atoms).
• R 1 to R 4 is one is F
• R 5 to R 8 are each independently H, F, an alkyl group having 1 to 3 carbon atoms, a functional group containing a heteroatom other than a fluorine atom, or a group containing the above functional group.
• at least one of R 5 to R 8 is a functional group containing a hetero atom other than a fluorine atom or a group containing the functional group.
• a composite is described in which the volatile component is 0.1% by mass or less based on the entire composite.
• Patent Document 2 describes a composition characterized by containing an inorganic filler, a copolymer of a fluoromonomer and a polymerizable vinyl compound having an amide bond, and a solvent.
• Patent Document 3 describes: (a) a polyolefin separator membrane base material; and (b) one or more types selected from the group consisting of the surface of the base material and a part of the pores present in the base material.
• An inorganic/inorganic composite porous separator membrane comprising an active layer coated with a mixture of inorganic particles and a binder polymer in a region, the active layer comprising a mixture of inorganic particles and a binder polymer in which the inorganic particles are bound to each other by the binder polymer.
• An organic/inorganic composite porous separator membrane is described, which is characterized in that a pore structure is formed by gaps between the membranes.
• An object of the present disclosure is to provide a composition for coating a separator for an electrochemical device, which can improve the heat shrinkage resistance of the separator.
• composition for coating a separator for an electrochemical device which contains a copolymer containing a fluoromonomer unit and an amide bond-containing monomer unit.
• the basic structure of a lithium ion secondary battery is that a non-aqueous electrolyte is placed between a positive electrode and a negative electrode, with a separator interposed if necessary.
• the separator is interposed between the positive electrode and the negative electrode to prevent contact between the active materials of both electrodes, and forms an ionic conduction path between the electrodes by flowing an electrolytic solution through the pores of the separator.
• the separator is required to have a function (shutdown function) to cut off the current and prevent excessive current if abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode, etc. The separator shuts down by blocking the microporous membrane when the temperature exceeds normal battery usage.
• porous membranes such as microporous polyolefin films made of polyethylene, polypropylene, etc. have been generally used as separators.
• these polyolefin porous membranes have high heat shrinkability, they have the problem of low dimensional stability at high temperatures.
• the separator may shrink and break due to heat, leading to an internal short circuit, which may lead to fire.
• the inventors of the present invention have conducted extensive studies and found that the heat shrinkage resistance of the separator can be improved by coating the separator with a composition containing a copolymer of a fluoromonomer and an amide bond-containing monomer. discovered.
• the composition of the present disclosure is a composition for coating a separator for an electrochemical device, and contains a copolymer of a fluoromonomer and an amide bond-containing monomer.
• the heat shrinkage resistance of the separator can be improved.
• composition of the present disclosure contains a copolymer of a fluoromonomer and an amide bond-containing monomer.
• alkyl group examples include alkyl groups having 1 to 3 carbon atoms, with a methyl group being preferred.
• the fluoroalkyl group is preferably a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.
• fluoromonomer fluorine atoms bonded to carbon atoms constituting the polymer main chain can be introduced into the above copolymer, which can further improve the heat shrinkage resistance of the separator when coated with it.
• (1) is preferred, and vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, monofluoroethylene, trifluorostyrene, and the general formula:
• CX 2 CXRf 1 (wherein, X is independently H or F, at least one of X is F, and at least one selected from the group consisting of fluoromonomers represented by Rf 1 is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms More preferably, it is a seed.
• fluoromonomers examples include tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and 2,3,3,3- because the heat shrinkage resistance of the separator can be further improved when the separator is coated. It is more preferably at least one selected from the group consisting of tetrafluoropropene, and tetrafluoroethylene is particularly preferred.
• the amide bond-containing monomer contains an amide bond and a polymerizable vinyl group.
• the above-mentioned amide bond refers to a bond between a carbonyl group and a nitrogen atom.
• the polymerizable vinyl group include a vinyl group, an allyl group, a vinyl ether group, a vinyl ester group, and an acrylic group.
• amide bond-containing monomers examples include N-vinyllactam compounds such as N-vinyl- ⁇ -propiolactam, N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, and N-vinyl-heptolactam, and N-vinylformamide.
• acyclic N-vinylamide compounds such as N-methyl-N-vinylacetamide, N-allyl-N-methylformamide, acyclic N-allylamide compounds such as allyl urea, 1-(2-propenyl)-2-
• N-allyl lactam compounds such as pyrrolidone
• acrylamide compounds such as (meth)acrylamide, N,N-dimethylacrylamide, and N-isopropylacrylamide.
• a monomer having a lactam ring is preferred.
• the lactam ring is not particularly limited as long as it is a ring formed by an amide bond and a carbon atom, and may be monocyclic or polycyclic, but monocyclic is preferable. Furthermore, the lactam ring may have any substituent. Examples of the lactam ring include ⁇ -lactam ring, ⁇ -lactam ring, ⁇ -lactam ring, ⁇ -lactam ring, ⁇ -caprolactam ring, and ⁇ -heptalactam ring.
• An amide bond-containing monomer has a structure in which one or more hydrogen atoms bonded to a carbon atom or nitrogen atom forming a lactam ring is removed, and the remaining atomic group is bonded directly or indirectly to a polymerizable vinyl group. Can be done.
• the amide bond-containing monomer can have a structure in which one hydrogen atom bonded to a carbon atom or nitrogen atom forming a lactam ring is removed, and the remaining atomic group is bonded to a vinyl group or an allyl group.
• Amide bond-containing monomers include, among others, N-vinyl- ⁇ -propiolactam, N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl- ⁇ -caprolactam and N-vinyl-heptolactam. At least one selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone and N-vinyl- ⁇ -caprolactam is more preferable; -vinyl-2-pyrrolidone is more preferred.
• the copolymer may contain other monomer units.
• Other monomers are not particularly limited as long as they are copolymerizable with the fluoromonomer and the amide bond-containing monomer.
• Other monomer units include vinyl ester monomer units, vinyl ether monomer units, (meth)acrylic monomer units having polyethylene glycol in their side chains, vinyl monomer units having polyethylene glycol in their side chains, and long-chain hydrocarbon groups (meth) ) Acrylic monomer units, vinyl monomer units having a long-chain hydrocarbon group, and the like.
• the content of fluoromonomer units in the copolymer is 75 to 7 mol% based on the total monomer units, and the content of amide bond-containing monomer units in the copolymer is 75 to 7 mol% based on the total monomer units. On the other hand, it is preferably 25 to 93 mol%.
• the content of fluoromonomer units in the copolymer is more preferably 60 mol% or less, further preferably 55 mol% or less, particularly preferably 50 mol% or less, and most preferably 45 mol% or less.
• the content is preferably 15 mol% or more, further preferably 20 mol% or more, particularly preferably 35 mol% or more, and most preferably 40 mol% or more.
• the content of amide bond-containing monomer units in the copolymer is more preferably 40 mol% or more, still more preferably 45 mol% or more, particularly preferably 50 mol% or more, and most preferably 55 mol%. or more, more preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 65 mol% or less, and most preferably 60 mol% or less.
• the content of other monomer units in the copolymer is preferably 50 mol% or less, more preferably 35 mol% or less, even more preferably 25 mol% or less, even more preferably 15 mol% or less.
• the content is particularly preferably 5 mol% or less, and preferably 0 mol% or more.
• the copolymer may be a copolymer containing substantially only fluoromonomer units and amide bond-containing monomer units.
• composition of the copolymer can be measured, for example, by 1 H-NMR and 19 F-NMR.
• the weight average molecular weight (in terms of polystyrene) of the copolymer is preferably 10,000 to 500,000, more preferably 15,000 or more, even more preferably 20,000 or more, particularly preferably 30,000 or more, and more preferably 400,000 or less. It is.
• the weight average molecular weight can be measured by gel permeation chromatography (GPC) using dimethylformamide as a solvent.
• the copolymer can be suitably produced by a production method in which a fluoromonomer, an amide bond-containing monomer, and, if necessary, other monomers are polymerized in a reactor.
• polymerization method methods such as suspension polymerization, emulsion polymerization, and solution polymerization can be adopted.
• a polymerization method using a fluorine-containing solvent is preferable because a copolymer having a high molecular weight can be produced.
• the copolymer can be suitably produced, for example, by a production method in which at least a fluoromonomer and an amide bond-containing monomer are polymerized in a fluorine-containing solvent to obtain a copolymer.
• fluorine-containing solvents examples include hydrochlorofluoroalkanes such as CH 3 CClF 2 , CH 3 CCl 2 F, CF 3 CF 2 CCl 2 H, CF 2 ClCF 2 CFHCl; CF 2 ClCFClCF 2 CF 3 , CF 3 CFClCFClCF 3, etc.
• Perfluoroalkanes such as perfluorocyclobutane , CF3CF2CF2CF3 , CF3CF2CF2CF3 , CF3CF2CF2CF2CF3 ; CF _ _ _ 2 HCF2CF2CF2H , CF3CFHCF2CF2CF3 , CF3CF2CF2CF2H , CF3CF2CFHCF2CF3 , CF3CFHCF2CF3 , CF2 HCF2 _ _ _ _ _ _ _ _ _ _ _ _ _ CF2CF2H , CF2HCFHCF2CF2CF3 , CF3CF2CF2CF2CF2CF2H , CF3CH ( CF3 ) CF3CF2CF3 , CF3CF ( CF _ _ _ _ 3 ) CFHCF 2 CF 3 , CF 3 CF (CF 3 ) CFHC
• fluorine-containing solvent at least one selected from the group consisting of hydrofluorocarbons, (perfluoroalkyl)alkyl ethers, and hydrofluoroalkyl ethers is preferable, since a copolymer having a higher molecular weight can be produced. Hydrofluoroalkyl ethers are more preferred.
• fluorine-containing solvent examples include CF 3 CH 2 CF 2 CH 3 , CF 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CH 2 OCF 2 CHF 2 and CF 3 CF 2 CH 2 OCF 2 CHF 2 At least one selected from the group is preferred, and CF 3 CH 2 OCF 2 CHF 2 is more preferred.
• a polymerization initiator a surfactant, and a chain transfer agent can be used, and conventionally known ones can be used for each.
• a radical polymerization initiator can be used as the polymerization initiator.
• polymerization initiators include: Dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, disec-butyl peroxydicarbonate; t-Butylperoxyisobutyrate, t-butylperoxypivalate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, 1,1,3,3- Peroxy esters such as tetramethylbutylperoxy-2-ethylhexanoate and t-amylperoxypivalate; Dialkyl peroxides such as di-t-butyl peroxide; Di[fluoro(or fluorochloro)acyl]peroxides; etc. are listed as representative examples.
• di[fluoro(or fluorochloro)acyl]peroxides include diacyl represented by [(RfCOO)-] 2 (Rf is a perfluoroalkyl group, an ⁇ -hydroperfluoroalkyl group, or a fluorochloroalkyl group); Examples include peroxide.
• di[fluoro(or fluorochloro)acyl]peroxides include di( ⁇ -hydro-dodecafluoroheptanoyl) peroxide, di( ⁇ -hydro-tetradecafluorooctanoyl) peroxide, di( ⁇ - - Hydro-hexadecafluorononanoyl) peroxide, di(perfluorobutyryl) peroxide, di(perfluoroparelyl) peroxide, di(perfluorohexanoyl) peroxide, di(perfluoroheptanoyl) peroxide oxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di( ⁇ -chloro-hexafluorobutyryl) peroxide, di( ⁇ -chloro-decafluorohexanoyl) peroxide, Di( ⁇ -chloro-tetradeca
• chain transfer agents include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetic acid esters such as ethyl acetate and butyl acetate; methanol , alcohols such as ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
• hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane
• aromatics such as toluene and xylene
• ketones such as acetone
• acetic acid esters such as ethyl acetate and butyl acetate
• methanol alcohols such as ethanol
• mercaptans such as methyl mercap
• the polymerization temperature is not particularly limited, but from the viewpoint of polymerization rate and cost required for temperature control, it is preferably 0 to 95°C, more preferably 15 to 95°C.
• the polymerization pressure is not particularly limited, but from the viewpoint of polymerization rate and pressure resistance of the reactor, it is preferably 0.3 to 1.5 MPaG, more preferably 0.4 MPaG or more, and more preferably 1.0 MPaG or less. be.
• the copolymer can be recovered by taking out the slurry from the reactor, washing it, and drying it.
• the composition of the present disclosure further contains an inorganic filler.
• the heat shrinkage resistance of the separator can be further improved.
• the inorganic filler is preferably an inorganic filler containing at least one element selected from the group consisting of Mg, Al, Si, Ti, Zr, and Ba.
• the inorganic filler is preferably at least one selected from the group consisting of metal oxide particles and metal hydroxide particles. Further, as the inorganic filler, metal oxide particles containing at least one element selected from the group consisting of Mg, Al, Si, Ti, Zr, and Ba are more preferable.
• the metal oxide particles are preferably at least one selected from the group consisting of magnesium oxide, silicon oxide, aluminum oxide, barium oxide, zirconium oxide, and titanium oxide.
• the metal hydroxide particles are preferably at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, and zirconium hydroxide.
• the inorganic filler at least one kind selected from the group consisting of magnesium oxide, silicon oxide, aluminum oxide and zirconium oxide is particularly preferable, and at least one kind selected from the group consisting of magnesium oxide and aluminum oxide is more preferable.
• the average particle diameter of the inorganic filler is preferably 25 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, particularly preferably 1 ⁇ m or less, and preferably 0.02 ⁇ m or more.
• the average particle diameter of the inorganic filler is a value obtained by measurement using a transmission electron microscope, a laser particle size distribution analyzer, or the like.
• the content ratio of the copolymer and the inorganic filler is preferably 0.1/99.9 to 49.9/50 in terms of mass ratio. .1, more preferably 1/99 or more, still more preferably 5/95 or more, particularly preferably 10/90 or more, more preferably 45/55 or less, still more preferably 40/ 60 or less.
• composition of the present disclosure further contains a solvent.
• solvents examples include water; nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethylformamide; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; ethyl acetate.
• nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethylformamide
• ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone
• ethyl acetate examples include water; nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and dimethylformamide; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and
• ester solvents such as butyl acetate
• ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve, methyl cellosolve, diglyme, triglyme
• aromatic hydrocarbon solvents such as xylene, toluene, solvent naphtha; n-pentane, n-hexane , n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, mineral spirit, and other aliphatic hydrocarbon solvents; mixed solvents thereof, and the like.
• ester (1) represented by general formula (1) at least one selected from the group consisting of ester (1) represented by general formula (1) and ketone (2) represented by general formula (2) can also be used.
• R 1 and R 2 are independently H, a C 1 to C 10 linear or branched aliphatic group, or a C 6 to C 10 aromatic group.
• R 1 and R 2 in general formula (1) are independently H, a C 1 to C 10 linear or branched aliphatic group, or a C 6 to C 10 aromatic group.
• the number of carbon atoms in the aliphatic group of R 1 is 1 to 10, preferably 2 or more, more preferably 3 or more, preferably 7 or less, and more preferably 5 or less.
• the aliphatic group for R 1 is preferably an alkyl group.
• the alkyl group may be linear or branched.
• the aromatic group of R 1 has 6 to 10 carbon atoms.
• the hydrogen atom bonded to the carbon atom of the aromatic ring of the aromatic group may be substituted or unsubstituted.
• the substituent include an alkyl group such as a methyl group, and a halo group such as a chlorine atom.
• the aromatic group for R 1 is preferably a phenyl group or a benzyl group.
• R 1 is preferably a C 1 to C 10 linear or branched aliphatic group, a C 1 to C 10 linear or branched alkyl group, or a C 2 to C 10 linear alkyl group.
• a linear or branched alkenyl group is more preferable, a methyl group, an ethyl group, a propyl group, a vinyl group, an isopropenyl group, a butyl group or a pentyl group is preferable, and a propyl group, a butyl group or a pentyl group is more preferable.
• These groups may be linear or branched, but are preferably linear.
• the number of carbon atoms in the aliphatic group of R 2 is 1 to 10, preferably 3 or more, more preferably 4 or more, preferably 8 or less, and more preferably 6 or less.
• the aliphatic group for R 2 is preferably an alkyl group.
• the alkyl group may be linear or branched.
• the aromatic group of R 2 has 6 to 10 carbon atoms.
• the hydrogen atom bonded to the carbon atom of the aromatic ring of the aromatic group may be substituted or unsubstituted.
• the substituent include an alkyl group such as a methyl group, and a halo group such as a chlorine atom.
• the aromatic group for R 2 is preferably a phenyl group or a benzyl group.
• R 2 is preferably a C 1 to C 10 linear or branched aliphatic group, more preferably a C 1 to C 10 linear or branched alkyl group, such as a methyl group or an ethyl group.
• R 2 is preferably a C 1 to C 10 linear or branched aliphatic group, more preferably a C 1 to C 10 linear or branched alkyl group, such as a methyl group or an ethyl group.
• propyl group, butyl group, pentyl group or hexyl group are preferable, and butyl group, pentyl group or hexyl group is more preferable.
• These groups may be linear or branched, but are preferably linear.
• ester (1) represented by the general formula (1) examples include ethyl acetate, ethyl butyrate, butyl methacrylate, propyl propionate, ethyl butyrate, butyl butyrate, butyl pentanoate, butyl hexanoate, pentyl butyrate, and pentyl pentanoate. , pentyl hexanoate, hexyl butyrate, hexyl pentanoate and hexyl hexanoate, and butyl butyrate is more preferred.
• R 3 and R 4 in the general formula (2) are independently H, a C 1 to C 10 linear or branched aliphatic group, or a C 6 to C 10 aromatic group.
• the number of carbon atoms in the aliphatic groups of R 3 and R 4 is 1 to 10, preferably 3 or less, and more preferably 2 or less.
• the aliphatic group for R 3 is preferably an alkyl group.
• the alkyl group may be linear or branched.
• the aromatic group of R 3 and R 4 has 6 to 10 carbon atoms.
• the hydrogen atom bonded to the carbon atom of the aromatic ring of the aromatic group may be substituted or unsubstituted.
• the substituent include an alkyl group such as a methyl group, and a halo group such as a chlorine atom.
• the aromatic group for R 3 and R 4 is preferably a phenyl group or a benzyl group.
• R 3 and R 4 are preferably C 1 to C 10 linear or branched aliphatic groups, more preferably C 1 to C 10 linear or branched alkyl groups, and methyl groups. , ethyl group, propyl group, butyl group, pentyl group or hexyl group are preferable, and methyl group or ethyl group is more preferable. These groups may be linear or branched, but are preferably linear.
• the ketone (2) represented by general formula (2) is preferably at least one selected from the group consisting of acetone and methyl ethyl ketone.
• Water can also be used as a solvent.
• a copolymer is produced by a production method in which monomers are emulsion polymerized in water
• a polymer composition containing a copolymer and water is usually obtained. It can be used as a solvent in the disclosed compositions.
• composition of the present disclosure is particularly suitable for N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, acetone, and methyl ethyl ketone because of its excellent stability and coating properties. It is preferable to contain at least one member selected from the group consisting of N-methyl-2-pyrrolidone, and more preferably N-methyl-2-pyrrolidone.
• the content of the copolymer is preferably 0.1 to 20% by weight, more preferably 1% by weight, based on the weight of the composition.
• the content is more preferably 3% by mass or more, particularly preferably 10% by mass or more, most preferably 13% by mass or more, and more preferably 16% by mass or less.
• compositions of the present disclosure may also contain organic fillers.
• organic filler a non-conductive crosslinked polymer is preferred, and crosslinked polystyrene, crosslinked polymethacrylate, and crosslinked acrylate are more preferred.
• compositions of the present disclosure may also contain other polymers such as polyacrylates, polymethacrylates, polyacrylonitrile, polyamideimides, acrylic rubbers, carboxyalkylcelluloses, alkylcelluloses, hydroxyalkylcelluloses.
• the separator for electrochemical devices of the present disclosure includes a base material and a coating layer formed from the above composition.
• the coating layer is formed directly on the base material.
• the coating layer may be provided only on one side of the base material, or may be provided on both sides. Further, the coating layer may be provided so as to cover the entire base material on which the coating layer is provided, or may be provided so as to cover only a part of the base material.
• the weight of the coating layer is in the range of 0.5 to 50.0 g/m 2 from the viewpoint of heat shrinkage resistance, adhesion with electrodes, and ionic conductivity. is preferred.
• the weight of the coating layer when forming the coating layer on both sides of the base material is preferably 1.0 g/m 2 or more, more preferably 3.0 g/m 2 or more, and preferably 25.0 g/m 2 or more. 2 or less, more preferably 20.0 g/m 2 or less.
• the thickness of the coating layer per side is preferably 1 to 5 ⁇ m. When the thickness of the coating layer is within the above range, membrane rupture strength and insulation properties can be ensured, and curling of the base material is less likely to occur.
• the base material a porous base material having pores or voids inside is preferable.
• the porous substrate may be a microporous membrane, a porous sheet made of a fibrous material such as a nonwoven fabric, or a paper-like sheet, or a microporous membrane or porous sheet laminated with one or more other porous layers. Examples include composite coating layers.
• a microporous membrane is a membrane that has many micropores inside and has a structure in which these micropores are connected, allowing gas or liquid to pass through from one surface to the other. means.
• the material constituting the base material can be either an organic material or an inorganic material that has electrical insulation properties.
• an organic material as the constituent material of the base material, and it is more preferable to use a thermoplastic resin, such as polyethylene, polypropylene, polyimide, polyamide, polyamideimide, It is more preferable to use at least one selected from the group consisting of polyethylene terephthalate, polyester, and polyacetal.
• the shutdown function is a function that prevents thermal runaway of the battery by dissolving the thermoplastic resin and blocking the pores of the base material when the battery temperature rises, thereby blocking the movement of ions.
• thermoplastic resin a thermoplastic resin having a melting point of less than 200° C. is suitable, and polyolefin is particularly preferred.
• a microporous polyolefin membrane is suitable as the base material using polyolefin.
• a polyolefin microporous membrane that has sufficient mechanical properties and ion permeability and is used in conventional separators for non-aqueous secondary batteries can be used.
• the polyolefin microporous membrane contains polyethylene from the viewpoint of having the above-mentioned shutdown function.
• the weight average molecular weight of the polyolefin is preferably 100,000 to 5,000,000. If the weight average molecular weight is less than 100,000, it may be difficult to ensure sufficient mechanical properties. Moreover, if it exceeds 5 million, the shutdown characteristics may deteriorate or molding may become difficult.
• Such a microporous polyolefin membrane can be produced, for example, by the following method. That is, (i) a step of extruding the molten polyolefin resin through a T-die to form a sheet, (ii) a step of subjecting the sheet to crystallization treatment, (iii) a step of stretching the sheet, and (iv) a step of heat-treating the sheet.
• a method of forming a microporous membrane by sequentially performing the following steps is mentioned.
• a step of melting a polyolefin resin together with a plasticizer such as liquid paraffin extruding it through a T-die, cooling it and forming it into a sheet
• a step of stretching the sheet examples include a method in which a microporous membrane is formed by sequentially performing a step of extracting a plasticizer from a sheet and (iv) a step of heat-treating the sheet.
• Porous sheets made of fibrous materials include polyesters such as polyethylene terephthalate, polyolefins such as polyethylene and polypropylene, heat-resistant polymers such as aromatic polyamides, polyimides, polyethersulfones, polysulfones, polyetherketones, and polyetherimides.
• a porous sheet made of a fibrous material or a mixture of these fibrous materials can be used.
• the base material may be a composite base material further laminated with a functional layer.
• a composite base material is preferable in that further functions can be added by a functional layer.
• the functional layer for example, from the viewpoint of imparting heat resistance, a porous layer made of a heat-resistant resin or a porous layer made of a heat-resistant resin and an inorganic filler can be used.
• the heat-resistant resin include one or more heat-resistant polymers selected from aromatic polyamide, polyimide, polyethersulfone, polysulfone, polyetherketone, and polyetherimide.
• the inorganic filler metal oxides such as alumina, metal hydroxides such as magnesium hydroxide, etc. can be suitably used.
• the composite method include a method of coating a porous sheet with a functional layer, a method of bonding with an adhesive, a method of thermocompression bonding, and the like.
• a porous base material made of at least one selected from the group consisting of polyethylene, polypropylene, polyimide, polyamide, polyethylene terephthalate, polyester, and polyacetal is preferable.
• the thickness of the base material is preferably in the range of 5 to 50 ⁇ m from the viewpoint of obtaining good mechanical properties and internal resistance.
• the upper limit of the film thickness is more preferably 40 ⁇ m, and still more preferably 30 ⁇ m. Further, the lower limit of the film thickness is more preferably 10 ⁇ m.
• the Gurley value of the base material is preferably 500 sec/100 cc Air or less, more preferably 300 sec/100 cc Air or less.
• the above Gurley value is also preferably 50 sec/100 cc Air or more.
• the Gurley value is a value obtained by measuring with a Gurley densometer according to JIS P 8117.
• the porosity of the base material is preferably 30 to 70%, more preferably 35 to 60%.
• the sample volume (cm 3 ) here is calculated as 10 cm x 10 cm x thickness (cm).
• the average pore diameter of the base material is preferably 0.01 to 0.5 ⁇ m, more preferably 0.1 to 0.3 ⁇ m.
• a separator for electrochemical devices can be manufactured by coating the above composition on a base material.
• the coating method is not particularly limited as long as the surface of the substrate can be covered with a coating layer formed from the composition, but for example, the above composition is applied onto the substrate and a coating film is formed.
• One example is a method of drying. More specifically, the coating method includes a method of roll coating the above composition on a substrate, a method of dipping the substrate in the above composition, a method of coating the above composition on the substrate and a more suitable method. An example of this method is to immerse it in a coagulating solution.
• a separator for an electrochemical device may be produced by producing a film using the above composition and laminating the obtained film and a base material by a method such as lamination.
• An example of a method for producing a film using the above composition is a method in which the above composition is cast onto a film having a smooth surface such as a polyester film or an aluminum film, and then peeled off.
• the air permeability of the separator for electrochemical devices is preferably 1000 s/100 mL or less, more preferably 800 s/100 mL or less, even more preferably 500 s/100 mL or less, and preferably 50 s/100 mL or more. Air permeability can be measured using an air permeability tester.
• the Gurley value of the separator for electrochemical devices is preferably 1000 sec/100 cc Air or less, more preferably 800 sec/100 cc Air or less, and even more preferably 500 sec/100 cc Air or less.
• the above Gurley value is also preferably 50 sec/100 cc Air or more.
• the Gurley value is a value obtained by measuring with a Gurley densometer according to JIS P 8117.
• the rate of increase in Gurley value of the separator for electrochemical devices is preferably 500% or less, more preferably 400% or less, and even more preferably 250% or less. It is also preferable that the rate of increase in Gurley value is 103% or more.
• Gurley value increase rate (%) (Gurley value of electrochemical device separator/Gurley value of base material only) x 100
• the separator for electrochemical devices of the present disclosure can be applied to electrochemical devices.
• the electrochemical device of the present disclosure includes the above separator for electrochemical devices.
• Examples of electrochemical devices include batteries such as secondary batteries and capacitors.
• the battery may be a primary battery, a storage battery (secondary battery), or a power storage element.
• the battery may be a non-aqueous electrolyte battery.
• Nonaqueous electrolyte batteries include all batteries that include an electrolyte and a power generation element. Examples of non-aqueous electrolyte batteries include lithium ion primary batteries, lithium ion secondary batteries, nickel hydride batteries, lithium ion capacitors, and electric double layer capacitors.
• the separator for electrochemical devices of the present disclosure can constitute a secondary battery together with a positive electrode, a negative electrode, and a nonaqueous electrolyte.
• the secondary batteries lithium ion secondary batteries are particularly preferred.
• Typical configurations when the separator for an electrochemical device of the present disclosure is applied to a lithium ion secondary battery will be described below, but the electrochemical device of the present disclosure is not limited to these configurations.
• the positive electrode is composed of a positive electrode mixture containing a positive electrode active material, which is a positive electrode material, and a current collector.
• the positive electrode active material there is no particular restriction on the positive electrode active material as long as it is capable of electrochemically intercalating and deintercalating lithium ions.
• a substance containing lithium and at least one transition metal is preferable, such as a lithium-transition metal composite oxide such as a lithium-cobalt composite oxide, a lithium-nickel composite oxide, a lithium-manganese composite oxide, or a lithium-containing transition metal. Examples include phosphoric acid compounds.
• the positive electrode mixture further contains a binder, a thickener, and a conductive material.
• any material can be used as long as it is safe for the solvent and electrolyte used during electrode manufacturing, such as polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride, etc. Tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, styrene-butadiene rubber, isoprene rubber, butadiene rubber, ethylene- Examples include acrylic acid copolymers and ethylene-methacrylic acid copolymers.
• thickeners examples include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.
• Examples of the conductive material for the positive electrode include carbon materials such as graphite, carbon black, carbon nanotubes, and carbon fiber.
• Examples of the material for the positive electrode current collector include metals such as aluminum, titanium, and tantalum, or alloys thereof. Among these, aluminum or its alloy is preferred.
• the positive electrode may be manufactured by a conventional method.
• the above-mentioned binder, thickener, conductive material, solvent, etc. are added to the above-mentioned positive electrode active material to form a slurry-like positive electrode mixture, which is applied to a current collector, dried, and then pressed to form a high
• a method of densification is a method of densification.
• the negative electrode is composed of a negative electrode mixture containing negative electrode material and a current collector.
• negative electrode materials carbonaceous materials that can occlude and release lithium ions such as thermal decomposition products of organic substances, artificial graphite, and natural graphite under various thermal decomposition conditions; carbonaceous materials that can occlude and release lithium ions such as tin oxide and silicon oxide. Possible metal oxide materials; lithium metal; various lithium alloys, etc. may be mentioned. These negative electrode materials may be used in combination of two or more types.
• Examples of carbonaceous materials that can absorb and release lithium ions include artificial graphite or purified natural graphite produced by high-temperature treatment of graphitizable pitch obtained from various raw materials, or refined natural graphite prepared by adding pitch or other organic matter to the surface of these graphites. Those obtained by carbonization after treatment are preferred.
• the negative electrode mixture further contains a binder, a thickener, and a conductive material.
• the binder include the same binders as those described above that can be used for the positive electrode.
• the thickener include those similar to the above-mentioned thickeners that can be used for the positive electrode.
• the conductive material for the negative electrode include metal materials such as copper and nickel; carbon materials such as graphite and carbon black.
• Examples of the material for the negative electrode current collector include copper, nickel, and stainless steel. Among these, copper is preferred because it is easy to process into a thin film and from the cost standpoint.
• the negative electrode may be manufactured by a conventional method. For example, a method of adding the above-mentioned binder, thickener, conductive material, solvent, etc. to the above-mentioned negative electrode material to form a slurry, applying it to a current collector, drying it, and then pressing it to make it denser. .
• non-aqueous electrolyte a solution obtained by dissolving a known electrolyte salt in a known organic solvent for dissolving the electrolyte salt may be used.
• Organic solvents for dissolving electrolyte salts include, but are not limited to, propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, dimethyl carbonate, and diethyl.
• hydrocarbon solvents such as carbonate, ethyl methyl carbonate, and vinylene carbonate
• fluorine solvents such as fluoroethylene carbonate, fluoroether, and fluorinated carbonate can be used.
• electrolyte salts examples include LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiCl, LiBr, CH 3 SO 3 Li, CF 3 SO 3 Li, LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , cesium carbonate, etc.
• the concentration of the electrolyte salt is preferably 0.8 mol/liter or more, more preferably 1.0 mol/liter or more.
• the upper limit depends on the organic solvent for dissolving the electrolyte salt, but is usually 1.5 mol/liter.
• the shape of the lithium ion secondary battery is arbitrary, and includes, for example, a cylindrical shape, a square shape, a laminate shape, a coin shape, and a large size. Note that the shapes and configurations of the positive electrode, negative electrode, and separator can be changed depending on the shape of each battery.
• a composition for coating a separator for an electrochemical device which contains a copolymer containing a fluoromonomer unit and an amide bond-containing monomer unit.
• the fluoromonomer is selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and 2,3,3,3-tetrafluoropropene.
• composition according to the first aspect wherein the composition is at least one of: ⁇ 3>
• a composition according to the first or second aspect in which the amide bond-containing monomer has a lactam ring.
• amide bond-containing monomer is N-vinyl-2-pyrrolidone.
• the content of fluoromonomer units in the copolymer is 75 to 7 mol% based on the total monomer units
• the amide bond content of the copolymer is there is provided a composition according to any one of the first to fourth aspects, wherein the content of monomer units is 25 to 93 mol% based on the total monomer units.
• a composition according to any one of the first to fifth aspects containing an inorganic filler.
• the first to third particles further contain an inorganic filler containing at least one element selected from the group consisting of Mg, Al, Si, Ti, Zr, and Ba.
• a composition according to any of the sixth aspects is provided.
• it further contains an inorganic filler, and the content ratio of the copolymer and the inorganic filler (copolymer): (inorganic filler) is a mass ratio,
• a composition according to any of the first to seventh aspects is provided, wherein the composition is 0.1:99.9 to 49.9:50.1.
• a separator for an electrochemical device comprising a base material and a coating layer formed from the composition according to any one of the first to ninth aspects.
• the separator for an electrochemical device according to the tenth aspect in which the base material is formed of an organic material.
• an electrochemical device including the separator for an electrochemical device according to the tenth or eleventh aspect.
• a secondary battery including the separator for an electrochemical device according to the tenth or eleventh aspect.
• Air permeability> It was measured using an air permeability tester (manufactured by Kumagai Riki Kogyo Co., Ltd.). The air permeability (s/100 mL) was calculated by multiplying the time (s) required for the gas to pass from 0 mL to 25 mL on the scale by 4.
• ⁇ Coating film thickness> The thickness was measured using a high-precision thickness measuring machine (HKT-1240). The film thickness of only the base material before coating and the film thickness of the coated separator were measured, and the difference between the values was calculated as the coating film thickness.
• ⁇ Synthesis example 1> In an autoclave with a volume of 500 mL, 245 g of HFE-347pc-f (CF 3 CH 2 OCF 2 CHF 2 ), 9.7 g of N-vinyl-2-pyrrolidone, 35 g of tetrafluoroethylene, and 70% by weight of t-butyl peroxide as an initiator were added. 0.5 g of a hydrocarbon solution of oxypivalate (hereinafter abbreviated as "perbutyl PV”) was charged, and a polymerization reaction was carried out at 50°C.
• perbutyl PV hydrocarbon solution of oxypivalate
• Polymer a has a ratio of polymerized units based on tetrafluoroethylene/polymerized units based on N-vinyl-2-pyrrolidone measured by NMR measurement of 38/62 (molar ratio), and a weight average molecular weight measured by GPC measurement. It was 320,000.
• Polymer b has a ratio of polymerized units based on tetrafluoroethylene/polymerized units based on N-vinyl-2-pyrrolidone measured by NMR measurement of 38/62 (molar ratio), and a weight average molecular weight measured by GPC measurement. It was 240,000.
• Polymer c has a ratio of polymerized units based on tetrafluoroethylene/polymerized units based on N-vinyl-2-pyrrolidone measured by NMR measurement of 41/59 (molar ratio), and a weight average molecular weight measured by GPC measurement. It was 320,000.
• Polymer d has a ratio of polymerized units based on tetrafluoroethylene/polymerized units based on N-vinyl-2-pyrrolidone measured by NMR measurement of 41/59 (molar ratio), and a weight average molecular weight measured by GPC measurement. It was 250,000.
• Example 1 Polymer a, aluminum oxide (alumina) powder (average particle size 0.67 ⁇ m), and N-methylpyrrolidone (NMP) were mixed in a container at a ratio of 12.2 parts by mass, 18.7 parts by mass, and 69.1 parts by mass, respectively.
• a coating composition was prepared by adding zirconia beads, mixing using a bead mill, and then filtering the zirconia beads.
• NMP/water was mixed in a ratio of 55/45 to obtain a phase-separated liquid.
• a coating composition was applied to both sides of a polyethylene separator, and the applied separator was immersed in a phase separation liquid for 3 minutes. Next, the separator was immersed in water for 3 minutes and dried in an oven at 80° C. for 30 minutes to produce a coated separator. The air permeability and area retention rate of the manufactured separator were measured. The results are shown in Table 1.
• Example 2 Polymer b, aluminum oxide (alumina) powder (average particle size 0.67 ⁇ m), and N-methylpyrrolidone (NMP) were mixed in a container at a ratio of 15.4 parts by mass, 23.1 parts by mass, and 61.5 parts by mass, respectively.
• a separator was manufactured in the same manner as in Example 1 except for the following, and the obtained separator was evaluated. The results are shown in Table 1.
• Example 5 Polymer e, aluminum oxide (alumina) powder (average particle size 0.67 ⁇ m), and N-methylpyrrolidone (NMP) are mixed in a container at a ratio of 10.0 parts by mass, 15.0 parts by mass, and 75.0 parts by mass, respectively. After that, a separator was manufactured in the same manner as in Example 1, and the obtained separator was evaluated. The results are shown in Table 1.
• Example 6 After blending polymer c, magnesium oxide powder (average particle size 0.54 ⁇ m), and N-methylpyrrolidone (NMP) in a container at a ratio of 10.0 parts by mass, 15.0 parts by mass, and 75.0 parts by mass, respectively. A separator was manufactured in the same manner as in Example 1, and the obtained separator was evaluated. The results are shown in Table 1.
• Comparative example 1 A separator was produced in the same manner as in Example 5 using polymer f, and the obtained separator was evaluated. The results are shown in Table 1.
• Comparative example 2 A separator was produced in the same manner as in Example 6 using polymer f, and the obtained separator was evaluated. The results are shown in Table 1.
• Comparative example 3 A polyethylene separator (uncoated raw fabric) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

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