WO2013080867A1 - Film poreux, séparateur pour dispositif de stockage électrique et dispositif de stockage électrique - Google Patents

Film poreux, séparateur pour dispositif de stockage électrique et dispositif de stockage électrique Download PDF

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Publication number
WO2013080867A1
WO2013080867A1 PCT/JP2012/080234 JP2012080234W WO2013080867A1 WO 2013080867 A1 WO2013080867 A1 WO 2013080867A1 JP 2012080234 W JP2012080234 W JP 2012080234W WO 2013080867 A1 WO2013080867 A1 WO 2013080867A1
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porous film
porous
film
heat
porous layer
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PCT/JP2012/080234
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English (en)
Japanese (ja)
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葉子 若原
希 横山
東大路　卓司
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東レ株式会社
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Priority to JP2013547116A priority Critical patent/JP6082699B2/ja
Publication of WO2013080867A1 publication Critical patent/WO2013080867A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention provides a porous film suitable for use as a separator for an electricity storage device having excellent safety and having excellent film physical properties and high battery performance by providing a porous layer on the porous film, and the porous film
  • the present invention relates to a power storage device separator and a power storage device that use a battery.
  • a porous film made of polyolefin has excellent mechanical properties in addition to electrical insulation and ion permeability, and is therefore widely used especially for separator applications of lithium ion secondary batteries.
  • With increasing energy density studies have been made on increasing the diameter of a film, reducing the film thickness, increasing the porosity, and the like (see, for example, Patent Documents 1 and 2).
  • Patent Documents 1 and 2 studies have been made on increasing the diameter of a film, reducing the film thickness, increasing the porosity, and the like (see, for example, Patent Documents 1 and 2).
  • the porous film made by such a method has insufficient heat resistance and dimensional stability, and there is a safety problem that penetration of foreign matters mixed inside the battery cannot be prevented.
  • the base material is a porous layer composed of a heat-resistant resin and a heat-resistant particle or a binder that binds between other materials (between the heat-resistant particles, between the heat-resistant particles and the base material) and the heat-resistant particles.
  • Proposals for applying a thin film to a porous film have been made (for example, Patent Documents 3 and 4).
  • thin film coating cannot completely prevent the penetration of foreign matter inside the battery, and compensates for the lack of stiffness of the film that occurs when the thickness of the porous film as the base material is reduced.
  • Patent Document 5 a technique for improving the heat resistance by applying a thick film to the porous layer has been proposed (for example, Patent Document 5).
  • a layer having a low air permeability is applied thickly, a transparent film as a porous film is used.
  • the temper is lowered and the resistance value becomes large when used as a battery separator, resulting in poor electrical properties.
  • an object of the present invention is to solve the above-mentioned problems. That is, an object of the present invention is to provide a porous layer suitable for an electricity storage device separator having excellent safety and excellent film properties and high battery performance by providing a porous layer on a porous film made of a resin composition. To provide quality film.
  • the porous film of the present invention is a porous film composed of a porous layer containing heat-resistant particles and a binder and a porous film made of a resin composition.
  • the thickness of the porous layer is 8 to 30 ⁇ m, and the value of X represented by the following formula (1) is 3.0 or less ((s / 100 ml) / ⁇ m).
  • X (air permeability resistance of porous film ⁇ air resistance of porous film) / thickness of porous layer (1)
  • the porous film of the present invention has excellent safety when it is used as a separator for an electricity storage device, having excellent safety by providing a porous layer on the porous film, and having excellent film physical properties and high battery performance. Can be provided as a porous film.
  • FIG. 1 is a schematic view showing an apparatus for evaluating the stiffness of a film.
  • the porous film refers to a laminated film composed of a porous film and a porous layer.
  • the porous film is a microporous film made of a resin composition and having air permeability, and is used as a substrate for the porous film.
  • the resin composition which forms a porous film contains resin (A) and resin (A) is a main component in a porous film.
  • the main component means that it accounts for 80% by mass or more of the resin composition constituting the porous film.
  • the porous film according to the present invention includes a resin (A), preferably composed mainly of the resin (A), and has a large number of fine through-holes that penetrate both surfaces of the film and have air permeability. .
  • an olefin resin As the resin (A) contained in the resin composition, an olefin resin, a fluorine resin, an imide resin, a urethane resin, an acrylic resin, or the like can be used. Of these, olefin-based resins are preferable in that they are excellent in production, such as ease of processing and cost, and high ionic conductivity is obtained.
  • olefin resin a single polyolefin resin such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, or a random copolymer or a block copolymer of these monomers should be used. Can do. Moreover, the above-mentioned resin mixture can also be used as the resin (A).
  • the melting point of the porous film according to the present invention is preferably 110 ° C. or higher from the viewpoint of heat resistance.
  • the porous film may change dimensions when the porous layer is laminated on the porous film.
  • the melting point of the porous film refers to the melting point as a matter of course when showing a single melting point, for example, when the porous film has a plurality of melting points such as a mixture of polyolefins, Of these, the melting point appearing on the highest temperature side is defined as the melting point of the porous film.
  • the melting point of the porous film is more preferably 130 ° C. or higher from the viewpoint of heat resistance.
  • fusing point it is preferable that all of them exist in the said range.
  • a polypropylene resin of the type described later is used from the viewpoint of achieving both the heat resistance viewpoint described above and the workability for forming a through hole in the thickness direction of the film. It is preferable.
  • the porous film used for the substrate preferably has ⁇ -crystal forming ability.
  • the porous film can be produced by making the film porous by the ⁇ crystal method described later.
  • the porous film obtained by the ⁇ crystal method has excellent productivity and has a surface pore size (surface pore size) suitable for developing high adhesion due to the anchor effect when a porous layer is laminated. It can be suitably used as a film substrate.
  • the ⁇ crystal method refers to a method of forming a through hole in a film by stretching after forming a resin composition having ⁇ crystal forming ability into a sheet.
  • the resin composition used for the porous film may be imparted with ⁇ crystal-forming ability by a nucleating agent ( ⁇ crystal that can selectively form ⁇ crystal out of the crystal seeds of the resin (A) contained in the resin composition.
  • a nucleating agent ⁇ crystal that can selectively form ⁇ crystal out of the crystal seeds of the resin (A) contained in the resin composition.
  • a nucleating agent for example, as the ⁇ crystal nucleating agent for polypropylene resin, various pigment compounds and amide compounds can be mentioned, and in particular, amide compounds disclosed in JP-A-5-310665 can be preferably used.
  • the content of the ⁇ crystal nucleating agent is preferably 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the polypropylene resin.
  • the ⁇ crystal-forming ability indicates the abundance ratio of ⁇ -crystals in a polypropylene resin measured under the following conditions, and indicates how much ⁇ -crystals are formed. Value.
  • the ⁇ -crystal forming ability was measured by measuring 5 mg of a porous film, a resin composition forming the porous film, or polypropylene resin as the resin (A) from room temperature to 240 ° C. under a nitrogen atmosphere using a differential scanning calorimeter. The temperature is raised for 1 minute (first run), held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./minute.
  • the melting peak observed when the temperature is raised (second run) again at 10 ° C./minute after holding for 5 minutes is the melting peak of the ⁇ crystal at 145 ° C. to 157 ° C., 158 ° C. or higher
  • the melting at which the peak is observed is the melting peak of the ⁇ crystal, and the heat of fusion is determined.
  • the heat of fusion of the ⁇ crystal is ⁇ H ⁇ and the heat of fusion of the ⁇ crystal is ⁇ H ⁇ .
  • Crystal formation ability. ⁇ crystal forming ability (%) [ ⁇ H ⁇ / ( ⁇ H ⁇ + ⁇ H ⁇ )] ⁇ 100
  • the ⁇ -crystal forming ability of the polypropylene resin constituting (including) the porous film used for the substrate is 40 to 90% from the viewpoint of developing a high porosity and suitable air resistance. preferable. If the ⁇ -crystal forming ability is less than 40%, the amount of ⁇ -crystal is small at the time of film production, so the number of voids formed in the film is reduced by utilizing the transition to ⁇ -crystal, and as a result, only a film with low permeability is obtained. There may not be. In addition, when the ⁇ -crystal forming ability exceeds 90%, coarse pores are formed, and the function as a power storage device separator may not be provided.
  • ⁇ crystal forming ability In order to make the ⁇ crystal forming ability within the range of 40 to 90%, it is preferable to use a polypropylene resin having a high isotactic index and to add the above ⁇ crystal nucleating agent.
  • the ⁇ crystal forming ability is more preferably 45 to 80%.
  • the polypropylene resin constituting the porous film is an isotactic polypropylene resin having a melt flow rate (hereinafter referred to as MFR, measurement conditions are 230 ° C., 2.16 kg) in the range of 2 to 30 g / 10 min. It is preferable. If the MFR is out of the above-described preferred range, it may be difficult to obtain a stretched film. More preferably, the MFR is 3 to 20 g / 10 minutes.
  • the isotactic index of the isotactic polypropylene resin is preferably 90 to 99.9%. If the isotactic index is less than 90%, the crystallinity of the resin is low, and it may be difficult to achieve high air permeability.
  • a commercially available resin can be used as the isotactic polypropylene resin.
  • a homopolypropylene resin can be used as the resin (A), and from the viewpoints of stability in the film-forming process, film-forming properties, and uniformity of physical properties, the polypropylene contains an ethylene component, butene, hexene, and octene.
  • a copolymer obtained by copolymerizing an ⁇ -olefin component such as 5% by mass or less may be used.
  • the form of the comonomer introduced into the polypropylene may be either random copolymerization or block copolymerization.
  • the above resin composition preferably contains a high melt tension polypropylene in the range of 0.5 to 5% by mass from the viewpoint of improving the film forming property.
  • High melt tension polypropylene is a polypropylene resin whose tension in the molten state is increased by mixing a high molecular weight component or a component having a branched structure into the polypropylene resin or by copolymerizing a long-chain branched component with polypropylene. .
  • This high melt tension polypropylene is commercially available, and for example, polypropylene resins PF814, PF633, and PF611 manufactured by Basel, polypropylene resin WB130HMS manufactured by Borealis, and polypropylene resins D114 and D206 manufactured by Dow can be used.
  • the resin composition preferably contains 1 to 10% by mass of an ethylene / ⁇ -olefin copolymer in order to improve void formation efficiency at the time of stretching and improve air permeability by increasing the pore diameter.
  • examples of the ethylene / ⁇ -olefin copolymer include linear low-density polyethylene and ultra-low-density polyethylene.
  • an ethylene / octene-1 copolymer obtained by copolymerizing octene-1 is preferably used. be able to.
  • As the ethylene-octene-1 copolymer a commercially available resin can be used.
  • the porous film used for the substrate is preferably stretched at least in a uniaxial direction.
  • the porosity and mechanical strength of the film may be insufficient.
  • a method of stretching the porous film in at least a uniaxial direction it is preferable to stretch the film at a predetermined ratio after heating by a tenter method, a roll method, an inflation method, or a combination thereof.
  • the stretching may be uniaxial stretching or biaxial stretching.
  • any of simultaneous biaxial stretching, sequential stretching, and multistage stretching for example, a combination of simultaneous biaxial stretching and sequential stretching may be used, but sequential biaxial stretching is preferable from the viewpoint of productivity.
  • the resin composition contains an antioxidant, a heat stabilizer, an antistatic agent, a lubricant composed of inorganic or organic particles, and various additives such as an antiblocking agent, a filler, and an incompatible polymer. May be.
  • an antioxidant for the purpose of suppressing oxidative deterioration due to the thermal history of the polyolefin resin, it is preferable to blend 0.01 to 0.5 parts by mass of an antioxidant with respect to 100 parts by mass of the polyolefin resin.
  • the porous film used for the substrate preferably has an average pore diameter of 40 to 400 nm as measured according to the bubble point method (half dry method) of JIS K 3832 (1990). If the average hole diameter of the through-hole is less than 40 nm, the characteristics when used as a separator are insufficient, and if it exceeds 400 nm, the heat-resistant particles are likely to fall off or slightly short-circuit, causing problems such as adversely affecting the battery life. There is a fear.
  • the air resistance of the porous film used as the substrate of the porous film is preferably 50 to 500 seconds / 100 ml. If the air permeability resistance is less than 50 seconds / 100 ml, it may be difficult to maintain insulation when the separator is used. On the other hand, if it exceeds 500 seconds / 100 ml, the air resistance of the porous film is large when used as a substrate of the porous film, and the battery characteristics when used as a separator tend to deteriorate.
  • the air resistance of the porous film is more preferably 80 to 400 seconds / 100 ml, still more preferably 100 to 300 seconds / 100 ml.
  • the porous film used in the present invention preferably has a porosity of 50% or more and less than 80%, and more preferably 65% or more and less than 75%. If it is less than 50%, the number of pores on the surface will be small, so that the adhesion to the porous film may be insufficient when the porous layer is laminated. If it is 80% or more, it may be insufficient from the viewpoint of separator characteristics and strength.
  • the resin (A) As a method for controlling the through-hole, air resistance and porosity of the porous film used in the present invention within such preferable ranges, when a polypropylene resin is used as the resin (A), the ethylene / ⁇ -olefin copolymer is used as described above. This can be achieved by using a resin composition mixed at a specific ratio. Furthermore, it can achieve effectively by employ
  • the porous film used in the present invention has a number of holes (Y) having a pore diameter of 0.01 ⁇ m or more and less than 0.5 ⁇ m and a diameter of 0.5 ⁇ m or more and less than 10 ⁇ m when the surface pore diameter of the porous film is measured by the method described later.
  • the value of (Y) / (Z), which is the ratio to the number of holes (Z), is preferably from 0.1 to 4, more preferably from 0.4 to 3. If the value of (Y) / (Z) is less than 0.1, there are too many large-diameter apertures on the surface of the porous film, and the air permeability decreases because the coating liquid enters the apertures too much during coating. There is a case.
  • the surface pore diameter of the porous film As a method for controlling the surface pore diameter of the porous film within such a preferable range, it can be achieved by stretching and making a resin composition containing the above-described polypropylene resin to which the ⁇ crystal nucleating agent is added.
  • the surface pore diameter of the porous film can be confirmed by taking a surface image using a scanning electron microscope and performing image analysis.
  • the porous film of the present invention forms a porous layer on at least one side of the porous film obtained as described above, but for the purpose of improving the adhesion between the porous film and the porous layer before the formation of the porous layer, It is preferable to perform surface treatment for easy adhesion, such as corona discharge treatment, on the surface of the porous film.
  • surface treatment include corona discharge treatment in air, an oxygen atmosphere, a nitrogen atmosphere, plasma treatment, and the like, but simple corona discharge treatment is preferable.
  • the porous film of the present invention is provided with a porous layer containing heat-resistant particles and a binder on at least one side of the above-described porous film.
  • the porous film of this invention can express the heat resistance in high temperature which cannot be achieved only by a porous film by laminating
  • the porous layer will be described in detail below.
  • the heat-resistant particles used for the porous layer refer to particles whose shape is maintained at least up to 200 ° C. “Holding the shape” means that the aspect ratio and average particle diameter of the particles at room temperature do not change even at 200 ° C. More preferably, the shape is maintained up to 300 ° C, and still more preferably the shape is maintained up to 330 ° C. That is, it is preferable that the phase transition accompanied by the melting point, softening point, thermal decomposition temperature, or volume change of the particles does not occur up to the above temperature. Specifically, particles that do not exhibit a melting point and are maintained in shape up to at least 330 ° C.
  • thermoplastic resins having a melting point of 250 ° C. or higher, or resins having substantially no melting point, such as polyphenylene sulfide, polyether ether ketone, polysulfone, polyimide, polyamideimide, polyetherimide And the like, and the like.
  • thermoplastic resins having a melting point of 250 ° C. or higher, or resins having substantially no melting point, such as polyphenylene sulfide, polyether ether ketone, polysulfone, polyimide, polyamideimide, polyetherimide And the like, and the like.
  • calcium carbonate, alumina, and silica are preferable from the viewpoint that electrochemical stability and air permeability resistance can be within a preferable range, and calcium carbonate is more preferable from the viewpoint of dispersibility and adhesiveness to the binder.
  • the average particle size of the heat-resistant particles used in the porous layer of the present invention is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 8 ⁇ m, from the viewpoint of achieving both air permeability and mechanical properties of the porous layer. .
  • the average particle diameter is less than 0.05 ⁇ m, the heat-resistant particles enter the film from the open surface of the porous film, the air resistance of the porous film increases, the heat-resistant particle filling efficiency increases, and the porosity of the porous layer May decrease or air permeability may deteriorate.
  • the average particle diameter exceeds 10 ⁇ m, the thickness of the porous layer may not be controlled.
  • the average particle diameter of the heat resistant particles refers to a value obtained by measuring the heat resistant particles in the porous film. Specifically, it can be confirmed by observing the surface of the porous film using a scanning electron microscope and evaluating it by a method described later.
  • the ratio of the heat-resistant particles contained in the porous layer is preferably 60% by mass or more and less than 95% by mass, and more preferably 80% by mass or more and less than 95% by mass.
  • the heat resistance of the porous layer is not sufficiently exhibited, and when the porous layer is laminated on the porous film, the shrinkage of the porous film becomes significant, or the air resistance due to the formation of the porous layer Deterioration is remarkable and the output characteristics of the battery may be inferior.
  • the proportion of heat-resistant particles contained in the porous layer of the porous film of the present invention is determined by peeling and collecting the porous layer from the porous film, analyzing the powder X-rays and identifying the heat-resistant particle species, and then analyzing the organic component by combustion analysis. It can obtain
  • the heat-resistant particles used in the porous layer include a heat-resistant particle having an aspect ratio (heat-resistant particle long diameter / heat-resistant particle short diameter) of 2 or more and an aspect ratio (heat-resistant particle long diameter / heat-resistant particle short).
  • the mixture is preferably a mixture with heat-resistant particles having a diameter of less than 2.
  • the ratio of heat-resistant particles having an aspect ratio of 2 or more is preferably 5 to 95% by mass, more preferably 10 to 95% by mass, still more preferably 40 to 95% by mass, and further 45 to 90% by mass. Particularly preferred.
  • the proportion of heat-resistant particles having an aspect ratio of less than 2 is preferably 95 to 5% by mass, more preferably 90 to 5% by mass, further preferably 60 to 5% by mass, and further 55 to 10% by mass. It is particularly preferred.
  • the heat-resistant particles in the porous layer can be prevented from being filled, the formation of pores in the porous layer can be promoted, and the heat-resistant particles can be arranged in various directions. It is possible to impart balanced heat resistance and foreign matter resistance in the longitudinal direction and width direction of the film.
  • the mixing ratio of the heat-resistant particles having each aspect ratio is out of the above range, the porosity of the porous layer is out of the preferable range, and heat resistance and foreign matter resistance may be deteriorated or air permeability may be deteriorated.
  • the aspect ratio of the heat-resistant particles in the porous layer and the ratio of the heat-resistant particles according to the aspect ratio can be confirmed using a method described later.
  • the thickness of the porous layer (coating thickness when formed by coating (thickness after coating and drying)) is 8 to 30 ⁇ m from the viewpoint of imparting stiffness to the porous film. More preferably, it is 9 to 25 ⁇ m, and further preferably 10 to 20 ⁇ m.
  • the thickness of the porous layer is less than 8 ⁇ m, the stiffness of the porous film is weak, and as a separator, wrinkles and necking occur when transported with tension in the battery assembly process, or the porous film is used as a separator In some cases, the resistance to foreign matters may deteriorate.
  • thickness exceeds 30 micrometers when a porous film is bent, it will become easy to produce a crack and peeling.
  • the stiffness of the porous film can be evaluated based on the presence or absence of wrinkles and creases and the presence or absence of dimensional change (necking) in the width direction when the porous film is conveyed under tension as described later.
  • the presence / absence of cracks / peeling when the porous film is bent and the foreign matter resistance of the porous film or the porous film can be evaluated by the method described later.
  • the thickness of the porous layer As a method for controlling the thickness of the porous layer to such a preferable range, it is achieved by controlling the coating amount of the coating liquid on the porous film, the transport speed of the porous film, etc. when using the coating method described later. can do.
  • the thickness of the porous layer can be confirmed by a method described later.
  • the porosity of the porous layer is preferably from 50% to 85%, more preferably from 60% to 85%, and from 65% to 80%. Further preferred. When the porosity of the porous layer is less than 50%, the porosity of the porous layer is lower than the porosity of the porous film, and the air permeability may be lowered when the porous film is formed. On the other hand, if the porosity exceeds 85%, the heat resistance of the porous film may be reduced, or when the porous film is used as a battery separator, the resistance at the time of contamination may deteriorate.
  • a method for controlling the porosity of the porous layer to such a preferable range can be achieved by using the heat-resistant particles having the aspect ratio described above at the mixing ratio described above.
  • the porosity of the porous layer can be confirmed by a method described later.
  • the ratio of the porosity of the porous film and the porosity of the porous layer is It calculated
  • Porosity ratio between porous film and porous layer (Pa) / (Pb)
  • the binder used for the porous layer refers to a material capable of binding between other materials (between heat-resistant particles, between heat-resistant particles and a substrate, etc.).
  • the binder used for the porous layer includes polyvinylidene fluoride (PVDF), acrylic, ethylene vinyl alcohol (EVA: a structural unit derived from vinyl acetate of 20 to 35 mol%), ethylene -Ethylene-acrylic acid copolymers such as ethyl acrylate copolymer (EEA), fluorinated rubber, styrene butadiene rubber (SBR), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), crosslinked acrylic Examples thereof include resins, polyurethanes, epoxy resins, modified polyolefins, silicon alkoxides, zirconium compounds, colloidal silica, and oxirane ring-containing compounds. In particular, a compound that can be dispersed or melted in water is preferably used as the binder. As the binder, those exemplified above may be used alone or in combination of
  • the blending ratio of the binder in the coating liquid for forming the porous layer is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the heat resistant particles from the viewpoint of adhesiveness, and 1 to 20 parts by mass. Part is more preferable, and 5 to 15 parts by weight is still more preferable.
  • the blending ratio of the binder is less than 1 part by mass, the adhesion between the heat-resistant particles and between the porous layer and the substrate is insufficient, and the particles may fall off or the porous layer may be peeled off.
  • it exceeds 30 mass parts since the hole inside a porous layer is obstruct
  • the coating liquid used for forming the porous layer has a thickening effect that makes the viscosity of the coating liquid in a coatable range, and adsorbs on the surface of the heat-resistant particles in the coating liquid.
  • cellulose and / or cellulose salt include hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, and sodium and ammonium salts thereof.
  • the blending ratio of the thickener in the coating liquid forming the porous layer is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the heat-resistant particles. Part is more preferable.
  • the addition effect of a thickener can be exhibited, without impairing physical properties, such as air permeability resistance.
  • the viscosity of the coating solution cannot be adjusted to an appropriate range for coating, and defects such as repellency and streaks are induced during coating to form a porous layer. There is a case.
  • the thickener may block the voids in the porous layer and cause a decrease in air resistance.
  • the materials are bound by melting the binder.
  • the binder is melted, the anchor effect is exhibited by the melted binder entering the pores of the heat-resistant particles and part of the surface openings of the porous film, and exhibits a strong binding force. Therefore, it is possible to prevent the heat-resistant particles from falling off the porous layer and the porous layer from being peeled off from the porous film.
  • the binding property between the heat-resistant particles of the porous film of the present invention can be evaluated by the rate of change ⁇ k of the coefficient of friction ⁇ k when the film running test is performed with the surface of the porous layer in contact with the roll.
  • the rate of change ⁇ k of the friction coefficient ⁇ k when the film running test is carried out so that the surface of the porous layer is in contact with the roll is preferably less than 500%, more preferably less than 300%.
  • the rate of change K of the friction coefficient ⁇ k of the porous layer is 500% or more, the heat-resistant particles may fall off during film running, and white powder may be generated.
  • the porous film is used as a separator, the removal of the heat-resistant particles may cause defects such as the yield of the battery assembly process and contamination with foreign matter.
  • change rate K it can achieve by using the above-mentioned binder.
  • the binding property between the porous layer and the porous film can be evaluated by the peel strength when the porous film is peeled off at the porous layer / porous film interface.
  • the peel strength is an index of the binding force between the porous film and the porous layer, and the higher the peel strength, the higher the binding force between the heat-resistant particles and the substrate and between the heat-resistant particles in the porous layer.
  • the peel strength can be evaluated by the method described later.
  • the peel strength when peeled at the porous layer / porous film interface is preferably 10 to 500 g / 25 mm width, and more preferably 20 to 300 g / 25 mm width.
  • the peel strength is less than 10 g / 25 mm, the porous layer is more easily peeled off than the porous film, and when the porous film is used as a separator, partial peeling may occur in the cutting / slit process.
  • the peel strength exceeds 500 g / 25 mm width, when the battery using the porous film as a separator generates heat, the binding property between the porous film and the porous layer is too strong. It may be difficult to maintain the shape.
  • the peel strength within a preferable range it can be achieved by making the surface pore diameter of the porous film into a preferable range and / or using the above binder.
  • a resin (B) having a melting point or softening point lower than that of the porous film should be used as the binder. Is preferred.
  • the melting point or softening point of the resin (B) used as the binder is preferably 70 to 120 ° C, more preferably 80 to 110 ° C.
  • the heat resistance of the porous film may be lowered.
  • the melting point or softening point is higher than 120 ° C., it is necessary to process at a high temperature when the resin (B) melts and bonds between the heat-resistant particles and between the heat-resistant particles and the base material. May cause deterioration of characteristics such as air resistance and flatness.
  • the melting point or softening point of the resin (B) used as the binder can be confirmed by a method described later.
  • the binder used for the porous layer is a resin containing a carboxyl group and / or a hydroxyl group (B) from the viewpoint of improving the binding property between the heat resistant particles and between the heat resistant particles and the substrate. ) Is preferable.
  • B a hydroxyl group
  • the wettability of the interface for binding can be improved, and stronger binding properties can be expressed.
  • Examples of the resin (B) containing a carboxyl group and / or a hydroxyl group in the molecular structure include an acrylate copolymer and a modified polyolefin into which an unsaturated carboxylic acid skeleton is introduced.
  • an acrylate copolymer and a modified polyolefin into which an unsaturated carboxylic acid skeleton is introduced.
  • a modified polyolefin from the viewpoint of laminating the porous layer within a range in which the heat-resistant particles and the heat-resistant particles and the base material are melt-bonded by fusing the resin (B) and the characteristics of the porous film can be maintained. It is preferable to use a modified polyolefin.
  • the modified polyolefin when the porous layer contains a modified polyolefin as a binder, the modified polyolefin preferably comprises an olefin skeleton and an unsaturated carboxylic acid skeleton.
  • the olefin skeleton include olefins having 2 to 6 carbon atoms such as propylene, ethylene, isobutylene, 1-butene, 1-pentene, 1-hexene, and the unsaturated carboxylic acid skeleton includes at least one carboxylic acid skeleton in the molecule.
  • thermoplastic resin particles having a melting point of 120 to 150 ° C. can be added from the viewpoint of imparting shutdown property to the porous film.
  • the shutdown property refers to a characteristic that, when a porous film is used as a separator, the through-holes of the porous film are blocked by components contained in the film when the battery is abnormally heated and the flow of ions is blocked. If the melting point of the thermoplastic resin particles is less than 120 ° C, the operating environment will shut down the through-holes of the film at a low temperature of about 120 ° C, which is not a problem for other materials of the electricity storage device, and will malfunction Will occur.
  • the melting point exceeds 150 ° C.
  • a self-heating reaction may start in the electricity storage device before shutting down.
  • the shutdown preferably functions at 125 to 150 ° C. from the viewpoint of the thermal stability of the positive electrode.
  • the highest temperature melting point may be within the above range.
  • thermoplastic resin particles when thermoplastic resin particles are added to the porous layer, it is not particularly limited as long as it is composed of a thermoplastic resin whose melting point falls within the above range, but it is not limited to a heat composed of a polyolefin resin.
  • Plastic resin particles are preferable, and thermoplastic resin particles made of polyolefin resins such as polyethylene, polyethylene copolymer, polypropylene, and polypropylene copolymer are particularly preferable.
  • the average particle size of the thermoplastic resin particles is preferably 0.5 to 5 ⁇ m, more preferably 0.8 to 3 ⁇ m.
  • the blending ratio of the thermoplastic particles in the porous layer is preferably 10 to 40% by mass, more preferably 15 to 35% by mass. preferable.
  • the amount is less than 10% by mass, when the porous film is used as a separator, the pores in the porous layer may not be sufficiently blocked during heat generation, and shutdown performance may not be exhibited.
  • it exceeds 40 mass% the heat resistance at the time of using a porous film as a separator may fall.
  • a method for forming a porous layer a method of applying a coating solution containing heat-resistant particles, a binder and other compositions is preferably employed.
  • the coating liquid is obtained by dispersing heat-resistant particles, a binder, and other compositions in water, for example, ion exchange water or pure water.
  • any generally performed method may be used, for example, a reverse coating method, a bar coating method, a coating liquid prepared by dispersing heat-resistant particles or the like in ion-exchanged water or the like.
  • An organic solvent can be added to the coating liquid for forming the porous layer of the present invention for the purpose of reducing the surface tension of the coating liquid and improving the familiarity of the porous film as the substrate and the heat-resistant particles.
  • the organic solvent include alcohol (methanol, ethanol, isopropanol, etc.) and acetone.
  • the boiling point of the organic solvent to be used is preferably 50 ° C. or more and less than 120 ° C., more preferably 60 ° C. Above 100 ° C. If the boiling point of the organic solvent is 120 ° C.
  • volatilization in the drying process is difficult, and the organic solvent may remain in the porous film.
  • the temperature is lower than 50 ° C.
  • the volatilization during use of the coating liquid is remarkable, the solid content concentration (the amount of solid content in the coating liquid) as the coating liquid fluctuates, and the production and management of the coating liquid become complicated. In some cases, it may be inferior in properties, or there may be poor drying due to uneven thickness or partial leather tension during coating.
  • the ratio of the organic solvent added to the coating liquid for forming the porous layer is preferably 5 to 15% by mass, and preferably 7 to 13% by mass in the total amount of the coating liquid.
  • the ratio of the organic solvent in the coating liquid is below the above range, the effect of reducing the surface tension of the coating liquid is low, and repelling may occur during coating.
  • the coating liquid may permeate into the apertures on the surface of the porous film as the base material and cause clogging.
  • the drying temperature in the step of applying the coating liquid to the porous film is preferably 80 to 120 ° C., more preferably 90 to 120 ° C. from the viewpoint of melting and binding the binder.
  • the temperature is lower than 80 ° C., the binder may not be melted so that the binding property is poor, or the residual moisture content in the porous layer may be increased, which may cause problems when used as a battery separator.
  • the temperature exceeds 120 ° C., the porous film may shrink and deteriorate characteristics such as air resistance and flatness.
  • the air resistance of the porous film according to the present invention is preferably 50 to 500 seconds / 100 ml. If the air permeability resistance is less than 50 seconds / 100 ml, the insulation between the electrodes cannot be sufficiently maintained, and the safety may be inferior. Moreover, when it exceeds 500 seconds / 100 ml, it exists in the tendency for the output characteristic of the battery at the time of using a porous film as a separator to deteriorate.
  • the air resistance of the porous film is preferably 80 to 490 seconds / 100 ml, more preferably 150 to 390 seconds / 100 ml, although it depends on the application.
  • the porous layer As a method for setting the air permeability resistance of the porous film in the above range, it can be efficiently achieved by making the porous layer have heat-resistant particles having an aspect ratio of 2 or more.
  • the air resistance of the porous film can be confirmed by a method described later.
  • the value of X represented by the following formula (1) is 3.0 ((s / 100 ml) / ⁇ m) or less. This value indicates the ratio of the difference between the permeation resistance of the porous film and the permeation resistance of the porous film per unit thickness of the porous layer, and is generally the increment of the permeation resistance due to the provision of the porous layer on the porous film. The relationship of thickness is shown.
  • X (air permeability resistance of porous film ⁇ air resistance of porous film) / thickness of porous layer (1)
  • X is 0 to 3.0 because the air resistance of the porous film in which the porous layer is laminated on the porous film is equal to or higher than the air resistance of the porous film. More preferably, it is 0.03 to 2.5, and further preferably 0.1 to 2.0.
  • the method of setting the value of X in the above range can be achieved by setting the porosity of the porous layer to be equal to or higher than the porosity of the porous film, and using the heat-resistant particles having different aspect ratios in combination.
  • the heat shrinkage rate in the longitudinal direction and the width direction of the porous film at 150 ° C. is preferably 0 to 3%, and more preferably 0 to 2%. If the thermal shrinkage rate in the longitudinal direction and width direction of the porous film at 150 ° C. is greater than 3%, it may easily shrink due to the generated heat and cause a short circuit when used as a battery separator. It may not be possible to maintain sex. On the other hand, if it is less than 0%, it may affect the dimensional stability of the battery itself when used as a battery separator, which may cause problems. In order to make the heat shrinkage rate in the longitudinal direction and the width direction of the porous film at 150 ° C. within the above range, it can be effectively achieved by making the porous layer have heat-resistant particles having an aspect ratio of 2 or more. The heat shrinkage rate of the porous film or the porous film can be confirmed by a method described later.
  • the manufacturing method of the porous film used as the base material of a porous film is demonstrated.
  • the manufacturing method of a porous film is not limited to this, the polypropylene porous film by (beta) crystal method is demonstrated as an example.
  • a resin composition for forming a porous film 94 parts by mass of a commercially available homopolypropylene resin having an MFR of 8 g / 10 minutes, 1 part by mass of a commercially available MFR of 2.5 g / 10 minutes and a high melt tension polypropylene resin, and a melt index of 18 g / 10 minutes
  • the melting temperature is preferably 270 to 300 ° C.
  • the mixed raw material is supplied to a single-screw melt extruder, and melt extrusion is performed at 200 to 230 ° C. And after removing a foreign material, a modified polymer, etc. with the filter installed in the middle of the polymer pipe
  • the surface temperature of the cast drum is preferably 105 to 130 ° C. from the viewpoint of controlling the ⁇ crystal form performance of the cast film to be high.
  • the end portion is sprayed with spot air to adhere to the drum.
  • the polymer may be brought into close contact with the cast drum using a method in which air is blown over the entire surface from the contact state of the entire sheet on the drum using an air knife or an electrostatic application method as necessary.
  • the obtained unstretched sheet is biaxially oriented to form pores in the porous film.
  • a biaxial orientation method the film is stretched in the longitudinal direction of the film and then stretched in the width direction, or the sequential biaxial stretching method in which the film is stretched in the width direction and then stretched in the longitudinal direction. Any simultaneous biaxial stretching method can be used. It is preferable to employ a sequential biaxial stretching method from the viewpoint that it is easy to obtain a highly permeable film, and it is particularly preferable to stretch in the width direction after stretching in the longitudinal direction.
  • the temperature at which the unstretched sheet is stretched in the longitudinal direction is controlled.
  • a temperature control method a method using a temperature-controlled rotating roll, a method using a hot air oven, or the like can be adopted.
  • the stretching temperature in the longitudinal direction is preferably 90 to 135 ° C., more preferably 100 to 120 ° C.
  • the draw ratio is 3 to 6 times, more preferably 4 to 5.5 times.
  • the end of the film is gripped and introduced into a stenter type stretching machine. Then, it is preferably heated to 140 to 155 ° C. and stretched 5 to 12 times, more preferably 6 to 10 times in the width direction.
  • the transverse stretching speed at this time is preferably 300 to 5,000% / min, more preferably 500 to 3,000% / min.
  • heat setting is performed in the stenter as it is, and the temperature is preferably from the transverse stretching temperature to 160 ° C. Further, the heat setting may be performed while relaxing in the longitudinal direction and / or the width direction of the film, and in particular, the relaxation rate in the width direction is preferably 5 to 35% from the viewpoint of thermal dimensional stability.
  • the coating liquid for forming the porous layer contains calcium carbonate A (aspect ratio 3, average particle diameter 3 ⁇ m) 0.75 to 14.25 mass% as heat-resistant particles, and calcium carbonate B (aspect ratio 1, average particle diameter 1.0 ⁇ m) 14.25 to 0.75% by mass, modified polyethylene emulsion (solid content concentration 20% by mass) 0.75 to 22.5% by mass as a binder, and carboxymethyl cellulose 0.075 to 1.5% by mass as a thickener. It is prepared by mixing with 5 to 15% by mass of isopropyl alcohol and 79.175 to 46% by mass of ion-exchanged water.
  • the coating solution is stirred for 4 hours, it is coated on the porous film by a coating method using a die coater and dried at 100 ° C. for 1 minute to form a porous layer having a laminated thickness of 8 to 30 ⁇ m to form a porous film.
  • a coating method using a die coater and dried at 100 ° C. for 1 minute to form a porous layer having a laminated thickness of 8 to 30 ⁇ m to form a porous film.
  • the porous film of the present invention Since the porous film of the present invention has excellent heat resistance, flatness, and gas permeability, it can be suitably used as a separator for an electricity storage device.
  • the separator made of the porous film of the present invention is provided between the positive electrode and the negative electrode of the electricity storage device and can efficiently permeate ions in the electrolytic solution while preventing contact between the electrodes.
  • examples of the electricity storage device include various batteries, particularly non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries, and electric double layer capacitors such as lithium ion capacitors. Since such an electricity storage device can be repeatedly used by charging and discharging, it can be used as a power supply device for industrial devices, household equipment, electric vehicles, hybrid electric vehicles, and the like.
  • the electricity storage device using the porous film of the present invention as a separator can be suitably used for industrial equipment and automobile power supply devices because of the excellent characteristics of the separator.
  • ⁇ crystal forming ability [ ⁇ H ⁇ / ( ⁇ H ⁇ + ⁇ H ⁇ )] ⁇ 100
  • the sample used for the measurement of the thickness is selected from a total of 10 arbitrary positions at intervals of at least 5 cm in the longitudinal direction, and the average of the measured values of the 10 samples is the thickness of the porous film of the sample (la), the thickness of the porous film ( lb) and the porous layer thickness (lc).
  • Porosity of porous film and porous layer, porosity ratio of porous film and porous layer Porosity of porous film The porous film was cut into a size of 50 mm ⁇ 40 mm and used as a sample. Using an electronic hydrometer (SD-120L manufactured by Mirage Trading Co., Ltd.), the specific gravity was measured in an atmosphere having a room temperature of 23 ° C. and a relative humidity of 65%. The measurement was performed three times, and the average value was defined as the specific gravity ⁇ of the film. Next, the measured film was hot-pressed at 280 ° C. and 5 MPa, and then rapidly cooled with water at 25 ° C. to prepare a sheet from which pores were completely erased.
  • SD-120L manufactured by Mirage Trading Co., Ltd. the specific gravity was measured in an atmosphere having a room temperature of 23 ° C. and a relative humidity of 65%. The measurement was performed three times, and the average value was defined as the specific gravity ⁇ of the film.
  • the measured film was hot-pressed at
  • Porosity of porous layer (Pb) A porous film fixed on a sample stage of a scanning electron microscope was measured using a sputtering apparatus so that a cross section in the longitudinal direction of the film could be seen under the conditions of a degree of vacuum of 10 ⁇ 3 Torr, a voltage of 0.25 KV, and a current of 12.5 mA. After performing the ion etching process for a minute to cut the cross section, the surface was subjected to gold sputtering with the same apparatus, and observed with a scanning electron microscope at a magnification of 10,000 times.
  • the area of the void portion (S 1 ) and the total area of the porous layer (S 2 ) in the observed image are calculated for the porous layer portion using an image analyzer, and are applied to the following formula:
  • the porosity (Pb) of the porous layer was determined. Taking 10 observation images and calculating the porosity by the above operation, the average of 10 points was defined as the porosity (Pb) of the porous layer of the sample.
  • Porous layer porosity (Pb) Area of voids in porous layer (S 1 ) / total area of porous layer (S 2 ) ⁇ 100 C.
  • Air permeability resistance of porous film and porous film Air permeability resistance of porous film A square of 150 mm in length on one side of the porous film was taken as a cut sample, using a B-shaped Gurley tester of JIS P 8117 (2009) at 23 ° C. and relative humidity of 65%. The permeation time of 100 ml of air was measured at three arbitrary locations. The average value of the permeation times at three locations was defined as the air resistance (Ga) of the porous film.
  • Air permeability resistance of porous film A 65 mm wide PP tape (Sumitomo 3M Co., Ltd., 313D) was applied to the porous layer side of the porous film used in A, and then peeled off to remove the porous layer from the porous film. did. Using a JIS P 8117 (2009) B-shaped Gurley tester for the part from which the porous layer of the above sample was removed, the transmission time of 100 ml of air at any of three locations at 23 ° C. and a relative humidity of 65% It was measured. The average value of the permeation times at the three locations was defined as the air resistance (Gb) of the porous film.
  • Gb air resistance
  • the number of holes having a diameter of 0.01 ⁇ m or more and less than 0.5 ⁇ m is (Y)
  • the number of holes having a diameter of 0.5 ⁇ m or more and less than 10 ⁇ m is (Z)
  • the cross section After cutting the cross section by performing ion etching treatment for 10 minutes under the conditions of Torr, voltage of 0.25 KV, and current of 12.5 mA, the cross section was subjected to gold sputtering with the same apparatus, and using a scanning electron microscope SEM, While observing the porous layer at an observation magnification of 1,000 times, analysis and mapping of elements specific to the heat-resistant particles in the porous layer using micro-part X-ray analysis (EDX) is performed. The shape was imaged. About the obtained image, using image analysis software, the area ratio of the heat-resistant particles having an aspect ratio of 2 or more and the heat-resistant particles of less than 2 is obtained, and the value is determined as the content ratio of the heat-resistant particles according to the aspect ratio in the porous layer. did. In addition, said ratio corresponds substantially with the mass ratio of the heat-resistant particle according to aspect ratio at the time of coating liquid preparation.
  • EDX micro-part X-ray analysis
  • Friction coefficient change rate K (%) Friction coefficient at the 50th repetition (K50) / Friction coefficient at the first repetition (K1) ⁇ 100 ⁇ : Change rate of less than 300% ⁇ : Change rate of 300% or more and less than 500% ⁇ : Change rate of 500% or more
  • the stiffness of the porous film and the porous film was evaluated using the film conveying machine shown in FIG. As shown in FIG. 1, the film transport machine 10 transports the porous film or the porous film 1 unwound from the unwinding roll 2 with a transport tension of 5 N using a roll 4 having a holding angle of 90 °. Take up with take-up roll 3. The presence or absence of wrinkling at point A and the difference in film width between point B and point C were evaluated for the presence or absence of necking according to the following criteria. The roll diameter used is ⁇ 90 mm, and the roll material is hard chrome. ⁇ : No wrinkles and necking ⁇ : Wrinkles and / or necking
  • a negative electrode, a porous film or a porous film, and a positive electrode are stacked in this order so that the positive electrode active material and the negative electrode active material face each other, and a small stainless steel container with a lid (manufactured by Hosen Co., Ltd., HS cell, spring pressure) 1 kgf).
  • the container and the lid are insulated, the container is in contact with the negative electrode copper foil, and the lid is in contact with the positive electrode aluminum foil.
  • the measured secondary battery was measured under an atmosphere of 25 ° C. Constant current charging was performed until the current value reached 1.5 V at a current value of 1.5 mA, and constant voltage charging was performed until the current value reached 50 ⁇ A at a voltage of 4.2 V. Subsequently, constant current discharge was performed to a voltage of 2.7 V at a current value of 3 mA. The charging / discharging operation was performed 4 times. Next, constant current charging was performed until the current value became 1.5 V at a current value of 1.5 mA, and constant voltage charging was performed until the current value reached 50 ⁇ A at a voltage of 4.2 V. Subsequently, constant current discharge was performed up to a voltage of 2.7 V at a current value of 15 mA, and the discharge capacity was measured.
  • Example 1 Reference Example 1 Example 2, Comparative Example 5: Reference Example 2 Examples 3 to 5, 7 to 16, Comparative Example 2: Reference Example 3 Example 6, Comparative Example 4: Reference Example 4 Comparative Example 3: Reference Example 5
  • Tests ⁇ 1> and ⁇ 2> were performed using unpressed samples, respectively. ⁇ : No short circuit between the press samples of the tests ⁇ 1> and ⁇ 2> ⁇ : Only the press sample of the test ⁇ 2> is short-circuited X: Both the press samples of the tests ⁇ 1> and ⁇ 2> are short-circuited
  • density polyethylene density 0.95, viscosity average molecular weight 250,000
  • the resulting porous film had an air resistance of 200 s / 100 ml and a porosity of 40%.
  • the composition was weighed and mixed according to the formulation shown in Table 2-1, to prepare a coating solution for forming a porous layer. This was coated on one side of the porous film (the surface in contact with the drum at the time of melt extrusion, hereinafter referred to as D side) using a die coater so that the laminated thickness after drying was 10 ⁇ m, at 100 ° C. A porous layer was formed by drying for 1 minute to produce a porous film. The evaluation results of the obtained porous film are shown in Table 3-1.
  • Example 2 As a resin composition for forming a porous film, polypropylene (Sumitomo Chemical Co., Ltd., FLX80E4) 51.85% by mass, propylene copolymer (Mitsui Chemicals Co., Ltd., Tafmer XM) 47.8% by mass, antioxidant A Ciba Specialty Chemicals IRGANOX1010 and IRGAFOS168 are blended in 0.15% and 0.1% by weight and calcium stearate 0.1% by weight, mixed with a Henschel mixer (trade name), and then mixed into a twin screw extruder from a weighing hopper.
  • polypropylene Suditomo Chemical Co., Ltd., FLX80E4
  • propylene copolymer Mitsubishi Chemicals Co., Ltd., Tafmer XM 47.8% by mass
  • antioxidant A Ciba Specialty Chemicals IRGANOX1010 and IRGAFOS168 are blended in 0.15% and 0.1% by weight and calcium stearate 0.1% by weight,
  • the raw material was supplied to the substrate, melted and kneaded at 300 ° C., discharged from the die in a strand shape, cooled and solidified in a water bath at 25 ° C., and cut into a chip shape to obtain a chip material.
  • This chip raw material was supplied to a 20 mm extruder equipped with a T die having a lip width of 120 mm, melted at an extrusion temperature of 280 ° C. and a discharge rate of 4 kg / h, and extruded from the lip of the T die into a film shape. While controlling the thickness of the unstretched sheet with the clearance of the lip of the T-die, it is solidified while being air-cooled with an air knife on the non-contact surface with the cast drum at 80 ° C., and is unstretched with a width of 100 mm and a thickness of 200 ⁇ m It was created.
  • This unstretched sheet is stretched in the transverse direction (TD direction) under the conditions of a stretching temperature of 23 ° C., a deformation rate of 200% / second, and a stretching ratio of 6 times while restraining the machine direction (MD direction) using a film stretcher. Thereafter, the film was further stretched in the machine direction (MD direction) under the conditions of a stretching temperature of 100 ° C., a deformation rate of 1,000% / second, and a stretching ratio of 5 times to obtain a porous film having a thickness of 15 ⁇ m.
  • Table 1-1 shows the characteristics of the obtained porous film.
  • the resulting porous film had an air resistance of 200 s / 100 ml and a porosity of 50%.
  • compositions were weighed and mixed according to the formulation shown in Table 2-1, to prepare a coating solution for forming a porous layer. This was coated on one side of the porous film (the surface in contact with the drum at the time of melt extrusion, hereinafter referred to as D side) using a die coater so that the laminated thickness after drying was 10 ⁇ m, at 100 ° C. A porous layer was formed by drying for 1 minute to produce a porous film. The evaluation results of the obtained porous film are shown in Table 3-1.
  • Example 3 As a resin composition for forming a porous film, polypropylene (Sumitomo Chemical Co., Ltd., FLX80E4) 94.45% by mass, ethylene-octene-1 copolymer Dow Chemical Engage 8411 (melt index: 18 g / 10) N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide (manufactured by Shin Nippon Rika Co., Ltd., Nu) -100, hereinafter simply expressed as ⁇ crystal nucleating agent), 0.3% by weight of IRGANOX 1010 and IRGAFOS 168 made by Ciba Specialty Chemicals, which are antioxidants, and 0.15% and 0.1% by weight, respectively, in this ratio
  • the raw materials are fed from the weighing hopper to the twin screw extruder so that they are mixed, melt kneaded at 300 ° C, and discharged from the die into strands. To, it cooled and solidified at 25 ° C.
  • This chip raw material is supplied to a single screw extruder and melt extruded at 220 ° C. After removing foreign matter with a 25 ⁇ m cut sintered filter, it is discharged from a T die to a cast drum whose surface temperature is controlled at 120 ° C., An unstretched sheet having a thickness of 200 ⁇ m and a width of 250 mm was obtained by casting on a drum so as to be indirectly for 15 seconds. Next, preheating was performed using a ceramic roll heated to 120 ° C., and the film was stretched 4.5 times in the longitudinal direction of the film. After cooling, the end portion was introduced into a tenter type stretching machine by holding it with a clip, and stretched 6 times at 145 ° C.
  • Example 4 The chip raw material of Example 3 is supplied to a single screw extruder, melt extruded at 220 ° C., foreign matter is removed by a 25 ⁇ m cut sintered filter, and then discharged from a T-die to a cast drum whose surface temperature is controlled at 120 ° C. Then, it was cast so as to be indirectly on the drum for 15 seconds to obtain an unstretched sheet having a thickness of 200 ⁇ m and a width of 250 mm. Next, preheating was performed using a ceramic roll heated to 120 ° C., and the film was stretched 4.5 times in the longitudinal direction of the film.
  • the end portion was introduced into a tenter type stretching machine by holding it with a clip, and stretched 6 times at 145 ° C. As it was, heat treatment was performed at 155 ° C. for 6 seconds while relaxing 10% in the width direction to obtain a porous film having a thickness of 15 ⁇ m.
  • Table 1-1 shows the characteristics of the obtained porous film.
  • the resulting porous film had an air resistance of 200 s / 100 ml and a porosity of 70%.
  • the composition was weighed and mixed according to the formulation shown in Table 2-1, to prepare a coating solution for forming a porous layer.
  • Example 5 Compositions were weighed and mixed according to the formulation shown in Table 2-1, to prepare a coating solution for forming a porous layer.
  • a coating solution was applied to one side of the porous film of Example 4 (the side that contacted the drum during melt extrusion, hereinafter referred to as D side) using a die coater so that the laminated thickness after drying was 10 ⁇ m, and 100 ° C. Was dried for 1 minute to form a porous layer, and a porous film was produced.
  • Table 1-1 shows the characteristics of the porous film of Example 5, and Table 3-1 shows the evaluation results of the obtained porous film.
  • Example 6 Compositions were weighed and mixed according to the formulation shown in Table 2-1, to prepare a coating solution for forming a porous layer.
  • a coating solution was applied using a die coater so that the laminated thickness after drying was 25 ⁇ m, and 100 ° C. Was dried for 1 minute to form a porous layer, and a porous film was produced.
  • Table 1-1 shows the characteristics of the porous film of Example 6, and Table 3-1 shows the evaluation results of the obtained porous film.
  • Examples 7 to 16 Compositions were weighed and mixed according to the formulation shown in Table 2-1, to prepare a coating solution for forming a porous layer.
  • a coating solution was applied to one side of the porous film of Example 4 (the side that contacted the drum during melt extrusion, hereinafter referred to as D side) using a die coater so that the laminated thickness after drying was 10 ⁇ m, and 100 ° C. Was dried for 1 minute to form a porous layer, and a porous film was produced.
  • Table 1-1 shows the characteristics of the porous films of Examples 7 to 16, and Table 3-1 shows the evaluation results of the porous films of Examples 7 to 16.
  • Example 1 The porous film before forming the porous layer in Example 4 was evaluated as it was.
  • Table 1-2 shows the characteristics of the porous film of Comparative Example 1
  • Table 3-2 shows the evaluation results of the porous film of Comparative Example 1.
  • Comparative Example 2 The composition was weighed and mixed according to the formulation shown in Table 2-2 to prepare a coating solution for forming a porous layer. A coating solution was applied to one side of the porous film of Example 4 (the side that contacted the drum during melt extrusion, hereinafter referred to as D side) using a die coater so that the laminated thickness after drying was 10 ⁇ m, and 100 ° C. Was dried for 1 minute to form a porous layer, and a porous film was produced.
  • Table 1-2 shows the characteristics of the porous film of Comparative Example 2
  • Table 3-2 shows the evaluation results of the porous film of Comparative Example 2.
  • Example 3 The composition was weighed and mixed according to the formulation shown in Table 2-2 to prepare a coating solution for forming a porous layer.
  • a coating solution was applied using a die coater so that the laminated thickness after drying was 3 ⁇ m, and 100 ° C. Was dried for 1 minute to form a porous layer, and a porous film was produced.
  • Table 1-2 shows the characteristics of the porous film of Comparative Example 3
  • Table 3-2 shows the evaluation results of the porous film of Comparative Example 3.
  • Example 4 The composition was weighed and mixed according to the formulation shown in Table 2-2 to prepare a coating solution for forming a porous layer.
  • a coating solution was applied using a die coater so that the laminated thickness after drying was 45 ⁇ m, and 100 ° C. Was dried for 1 minute to form a porous layer, and a porous film was produced.
  • Table 1-2 shows the characteristics of the porous film of Comparative Example 4, and Table 3-2 shows the evaluation results of the porous film of Comparative Example 4.
  • the obtained porous film had an air resistance of 260 s / 100 ml and a porosity of 35%.
  • the composition was weighed and mixed according to the formulation shown in Table 2-2 to prepare a coating solution for forming a porous layer. This was coated on one side of the porous film (the surface in contact with the drum at the time of melt extrusion, hereinafter referred to as D side) using a die coater so that the laminated thickness after drying was 10 ⁇ m, at 100 ° C. A porous layer was formed by drying for 1 minute to produce a porous film.
  • Table 3-2 shows the evaluation results of the porous film of Comparative Example 5.
  • the air permeability resistance of the obtained porous film was 202 s / 100 ml, and the porosity was 40%. A porous layer was not formed on this porous film and was evaluated as it was.
  • Table 3-2 shows the evaluation results of the porous film of Reference Example 1 in which no porous layer was formed.
  • Example 2 The resin composition of Example 2 was supplied to the extruder used in Example 2, melted at an extrusion temperature of 280 ° C., extruded from the lip of a T die, and formed into a film shape at a cast drum at 80 ° C., in contact with the drum. The surface was solidified while being air-cooled with an air knife to produce an unstretched sheet having a width of 100 mm and a thickness of 250 ⁇ m. The thickness of the unstretched sheet was adjusted by the clearance of the lip of the T die. This unstretched sheet was stretched in the same manner as in Example 2 to obtain a porous film having a thickness of 25 ⁇ m. The evaluation results of the obtained porous film are shown in Table 1-2.
  • the air permeability resistance of the obtained porous film was 210 s / 100 ml, and the porosity was 52%. A porous layer was not formed on this porous film and was evaluated as it was.
  • Table 3-2 shows the evaluation results of the porous film of Reference Example 2 in which no porous layer was formed.
  • Example 3 The resin composition of Example 4 was supplied to the extruder used in Example 4 and melt extrusion was performed at 220 ° C. After removing foreign matters with a 25 ⁇ m cut sintered filter, the surface temperature was controlled from the T die to 120 ° C. It was discharged onto the cast drum and cast so as to be indirectly on the drum for 15 seconds to obtain an unstretched sheet having a thickness of 250 ⁇ m and a width of 250 mm. The thickness of the unstretched sheet was adjusted by increasing the discharge amount. This unstretched sheet was stretched in the same manner as in Example 3 to obtain a porous film having a thickness of 25 ⁇ m. The evaluation results of the obtained porous film are shown in Table 1-2.
  • the resulting porous film had an air resistance of 205 s / 100 ml and a porosity of 70%. A porous layer was not formed on this porous film and was evaluated as it was.
  • Table 3-2 shows the evaluation results of the porous film of Reference Example 3 in which no porous layer was formed.
  • Example 4 The resin composition of Example 4 was supplied to the extruder used in Example 4 and melt extrusion was performed at 220 ° C. After removing foreign matters with a 25 ⁇ m cut sintered filter, the surface temperature was controlled from the T die to 120 ° C. It was discharged onto the cast drum and cast so as to be indirectly on the drum for 15 seconds to obtain an unstretched sheet having a thickness of 320 ⁇ m and a width of 250 mm. The thickness of the unstretched sheet was adjusted by increasing the discharge amount. This unstretched sheet was stretched in the same manner as in Example 3 to obtain a porous film having a thickness of 40 ⁇ m. The evaluation results of the obtained porous film are shown in Table 1-2.
  • the air permeability resistance of the obtained porous film was 215 s / 100 ml, and the porosity was 70%. A porous layer was not formed on this porous film and was evaluated as it was.
  • Table 3-2 shows the evaluation results of the porous film of Reference Example 4 in which no porous layer was formed.
  • Example 5 The resin composition of Example 4 was supplied to the extruder used in Example 4 and melt extrusion was performed at 220 ° C. After removing foreign matters with a 25 ⁇ m cut sintered filter, the surface temperature was controlled from the T die to 120 ° C. It was discharged onto the cast drum and cast so as to be indirectly on the drum for 15 seconds to obtain an unstretched sheet having a thickness of 144 ⁇ m and a width of 250 mm. The thickness of the unstretched sheet was adjusted by lowering the discharge amount. This unstretched sheet was stretched in the same manner as in Example 3 to obtain a porous film having a thickness of 18 ⁇ m. The evaluation results of the obtained porous film are shown in Table 1-2.
  • the resulting porous film had an air resistance of 207 s / 100 ml and a porosity of 70%. A porous layer was not formed on this porous film and was evaluated as it was.
  • Table 3-2 shows the evaluation results of the porous film of Reference Example 5 in which no porous layer was formed.
  • the porous film of the present invention has safety by providing a porous layer on the porous film, and has excellent film physical properties and high battery performance. It can be suitably used as a separator of a lithium ion battery that is a battery.

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  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention vise à procurer un film poreux qui a une excellente sécurité et qui est approprié comme séparateur pour un dispositif de stockage électrique ayant d'excellentes propriétés de film et des performances de batterie élevées. La présente invention porte sur un film poreux constitué par une couche à pores multiples comprenant des particules résistant à la chaleur et un liant et un film à pores multiples comprenant une composition de résine, ledit film poreux étant caractérisé en ce que l'épaisseur de la couche à pores multiples est de 8 à 30 µm et en ce que la valeur (X) exprimée par la formule (1) montrée ci-dessous et de 3,0 ((s/100 ml)/ģm) ou moins. X = ((résistance à l'air du film poreux) - (résistance à l'air du film à pores multiples)/(épaisseur du film à pores multiples)) (1)
PCT/JP2012/080234 2011-11-28 2012-11-21 Film poreux, séparateur pour dispositif de stockage électrique et dispositif de stockage électrique WO2013080867A1 (fr)

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WO2014002701A1 (fr) * 2012-06-29 2014-01-03 三菱樹脂株式会社 Film poreux laminé, séparateur pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
WO2015161920A1 (fr) * 2014-04-25 2015-10-29 Treofan Germany Gmbh & Co. Kg Film orienté biaxialement, à couches poreuses renfermant des particules
JP2015201323A (ja) * 2014-04-08 2015-11-12 住友化学株式会社 セパレータの製造方法
KR20160101895A (ko) 2013-12-26 2016-08-26 데이진 가부시키가이샤 비수계 이차전지용 세퍼레이터 및 비수계 이차전지
JP2017538248A (ja) * 2014-10-24 2017-12-21 エルジー・ケム・リミテッド 有機無機複合多孔層を含む二次電池用セパレータ及びこの製造方法
JP2019079827A (ja) * 2013-08-22 2019-05-23 ユニチカ株式会社 多孔質フィルム
WO2019158266A1 (fr) * 2018-02-16 2019-08-22 Treofan Germany Gmbh & Co. Kg Feuille de séparateur à propriétés mécaniques améliorées
JP2019145457A (ja) * 2018-02-23 2019-08-29 トヨタ自動車株式会社 非水電解液二次電池

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WO2022158950A2 (fr) * 2021-01-25 2022-07-28 주식회사 엘지화학 Séparateur pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant
EP4184699A2 (fr) * 2021-01-25 2023-05-24 Lg Chem, Ltd. Séparateur pour batterie secondaire au lithium et batterie secondaire au lithium comprenant celui-ci

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JP2008123996A (ja) * 2006-10-16 2008-05-29 Hitachi Maxell Ltd 非水電解質電池用セパレータおよび非水電解質電池
JP2008210794A (ja) * 2007-01-30 2008-09-11 Asahi Kasei Chemicals Corp 多層多孔膜及びその製造方法
JP2009143060A (ja) * 2007-12-12 2009-07-02 Asahi Kasei Chemicals Corp 多層多孔膜
WO2010134585A1 (fr) * 2009-05-21 2010-11-25 旭化成イーマテリアルズ株式会社 Film poreux multicouche
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WO2014002701A1 (fr) * 2012-06-29 2014-01-03 三菱樹脂株式会社 Film poreux laminé, séparateur pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
US9818999B2 (en) 2012-06-29 2017-11-14 Mitsubishi Chemical Corporation Multilayer porous film, separator for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
JP2019079827A (ja) * 2013-08-22 2019-05-23 ユニチカ株式会社 多孔質フィルム
KR20160101895A (ko) 2013-12-26 2016-08-26 데이진 가부시키가이샤 비수계 이차전지용 세퍼레이터 및 비수계 이차전지
JP2015201323A (ja) * 2014-04-08 2015-11-12 住友化学株式会社 セパレータの製造方法
WO2015161920A1 (fr) * 2014-04-25 2015-10-29 Treofan Germany Gmbh & Co. Kg Film orienté biaxialement, à couches poreuses renfermant des particules
JP2017538248A (ja) * 2014-10-24 2017-12-21 エルジー・ケム・リミテッド 有機無機複合多孔層を含む二次電池用セパレータ及びこの製造方法
US10541399B2 (en) 2014-10-24 2020-01-21 Lg Chem, Ltd. Secondary battery separator comprising organic/inorganic composite porous layer, and manufacturing method therefor
WO2019158266A1 (fr) * 2018-02-16 2019-08-22 Treofan Germany Gmbh & Co. Kg Feuille de séparateur à propriétés mécaniques améliorées
JP2019145457A (ja) * 2018-02-23 2019-08-29 トヨタ自動車株式会社 非水電解液二次電池
JP7108960B2 (ja) 2018-02-23 2022-07-29 トヨタ自動車株式会社 非水電解液二次電池

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