WO2016017366A1 - 多孔質膜 - Google Patents
多孔質膜 Download PDFInfo
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- WO2016017366A1 WO2016017366A1 PCT/JP2015/069109 JP2015069109W WO2016017366A1 WO 2016017366 A1 WO2016017366 A1 WO 2016017366A1 JP 2015069109 W JP2015069109 W JP 2015069109W WO 2016017366 A1 WO2016017366 A1 WO 2016017366A1
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- porous membrane
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- ether
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—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
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a porous membrane.
- Nonaqueous electrolyte secondary batteries such as lithium ion secondary batteries are widely used as batteries used in personal computers, cellular phones, portable information terminals, and the like.
- a separator is usually used as a member for separating a positive electrode and a negative electrode.
- a porous film made of polyolefin has been used as a separator, but it has a problem that heat resistance is not sufficient.
- Patent Document 1 proposes a separator in which a porous film made of polyolefin and a porous film made of polyvinyl alcohol are laminated.
- a separator in which a porous film made of polyolefin and a porous film containing an inorganic powder are laminated is easy to curl, and there is a problem that workability at the time of battery assembly is lowered.
- the present invention includes the following inventions.
- a porous membrane comprising a compound having a hydrophobic group and a nonionic hydrophilic group, an inorganic powder, and a binder resin.
- the inorganic powder is a metal oxide, a metal hydroxide, or a metal carbonate.
- a porous film according to any one of [1] to [5] and another porous film different from the porous film according to any one of [1] to [5] are laminated. Laminated porous film.
- a coating liquid comprising a compound having a hydrophobic group and a nonionic hydrophilic group, an inorganic powder, a binder resin, and a solvent.
- a separator for a non-aqueous electrolyte secondary battery comprising the porous film according to any one of [1] to [5].
- the present invention it is possible to obtain a laminated porous film that is difficult to curl, in which a porous film made of polyolefin and a porous film containing an inorganic powder are laminated.
- the porous membrane of the present invention (hereinafter sometimes referred to as the present porous membrane) has a structure having pores connected to the inside thereof. Since this porous membrane is porous, gas, liquid, ions, etc. can be transmitted from one surface to the other, and since it contains inorganic powder, it has high heat resistance and includes this porous membrane. Shape stability at high temperatures can be imparted to the laminated porous film. Therefore, this porous membrane is suitably included in the separator for nonaqueous electrolyte batteries.
- the present porous membrane includes a compound having a hydrophobic group and a nonionic hydrophilic group (hereinafter sometimes referred to as the present compound), thereby causing curl generated in the laminated porous film including the porous membrane. Can be suppressed.
- a porous membrane made of polyolefin and a porous membrane containing an inorganic powder have different polarities, and therefore have a different affinity for water and may have different water absorption when placed in the same environment. Therefore, a laminated porous film in which a porous film made of polyolefin and a porous film containing inorganic powder are laminated, respectively, when the porous film made of polyolefin and the porous film containing inorganic powder absorb water.
- Inorganic powders generally have a high polarity and thus have a strong interaction with water.
- Such an inorganic powder interacts with the nonionic hydrophilic group of the present compound, whereby the present compound adheres to the surface of the inorganic powder, and the hydrophobic group of the present compound causes the inorganic powder to It is considered that the interaction between the inorganic powder and water can be reduced by covering the surface. Therefore, the moisture content of the present porous membrane can be lowered, and curling is suppressed because it becomes close to the moisture content of the porous membrane made of polyolefin.
- the water content of the porous membrane is preferably less than 0.15% by mass.
- the amount of curling is reduced, and the charge / discharge cycle characteristics of the non-aqueous electrolyte secondary battery using the porous membrane tend to be high. There is.
- Nonionic hydrophilic group examples include a group having a polyoxyethylene structure and a hydroxy group. Moreover, this compound preferably does not have an ionic group such as an anionic group and a cationic group.
- An anionic group in this specification is an acid group having a pKa of less than 10 such as a salt such as a sulfonate and a carboxylate, and a sulfonic acid and a carboxylic acid. That is, a general hydroxy group having a pKa of 10 or more corresponds to a nonionic group, not an anionic group.
- hydrophobic group examples include a hydrocarbon group, a group containing a fluorocarbon group, a group containing silicon, and the like, and preferably a hydrocarbon group.
- the hydrocarbon group is preferably a hydrocarbon group having 3 to 30 carbon atoms.
- the hydrocarbon group having 3 to 30 carbon atoms is propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group.
- the group containing a fluorocarbon group is preferably a fluorocarbon group having 3 to 30 carbon atoms.
- Examples of the group containing a fluorocarbon group having 3 to 30 carbon atoms include groups in which part or all of the hydrogen atoms of the hydrocarbon group are replaced with fluorine atoms.
- perfluoropropyl group isoperfluoropropyl group, perfluorobutyl group, isoperfluorobutyl group, sec-perfluorobutyl group, t-perfluorobutyl group, perfluoropentyl group, isoperfluoropentyl group, Fluorohexyl group, isoperfluorohexyl group, perfluoroheptyl group, isoperfluoroheptyl group, perfluorooctyl group, isoperfluorooctyl group, perfluorononyl group, isoperfluorononyl group, perfluorodecyl group, perfluoro Undecyl group, perfluorododecyl group, perfluorotridecyl group, perfluorotetradecyl group, perfluoropentadecyl group, perfluorohexadecyl group, perfluoro
- Nyl group perfluorononacosenyl group, perfluorotriacontenyl group, perfluoropropynyl group 2-perfluoropropynyl group, isoperfluoropropynyl group, perfluorobutynyl group, isoperfluorobutynyl group, perfluoropentynyl group, perfluorohexynyl group, perfluoroheptynyl group, perfluorooctynyl Group, perfluorononynyl group, perfluorodecynyl group, perfluoroundecynyl group, perfluorododecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group, hexadecynyl group, heptadecynyl group, perfluorooctadecynyl group,
- Examples of the group containing silicon include an alkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, an alkylsiloxane, a dialkylsiloxane, and a trialkylsiloxane.
- the present compound is preferably a nonionic surfactant.
- this compound examples include polyethylene glycol-polypropylene glycol diblock copolymers, polyethylene glycol-polypropylene glycol block copolymers such as polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymers; polyoxyethylene alkyl ether, polyoxyethylene Compounds having a polyoxyethylene structure such as alkyl phenyl ether, polyethylene glycol fatty acid ester, polyethylene oxide polypropylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide copolymer; and polyoxyethylene sorbitan fatty acid ester, etc. Sorbitan derivatives of Polyoxyethylene alkyl ether is preferred.
- polyoxyethylene alkyl ether polyoxyethylene methyl ether, polyoxyethylene ethyl ether, polyoxyethylene propyl ether, polyoxyethylene isopropyl ether, polyoxyethylene butyl ether, polyoxyethylene isobutyl ether, polyoxyethylene sec-butyl ether, Polyoxyethylene-t-butyl ether, polyoxyethylene pentyl ether, polyoxyethylene isopentyl ether, polyoxyethylene hexyl ether, polyoxyethylene isohexyl ether, polyoxyethylene heptyl ether, polyoxyethylene isoheptyl ether, polyoxyethylene Octyl ether, polyoxyethylene isooctyl ether, polyoxyethylene Nyl ether, polyoxyethylene isononyl ether, polyoxyethylene decyl ether, polyoxyethylene undecyl ether, polyoxyethylene dodecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene tetradecyl ether,
- the content of the present compound with respect to 100 parts by mass of the inorganic powder is preferably 0.05 to 10 parts by mass. Preferably it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, More preferably, it is 0.3 mass part or more. Moreover, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1.5 parts by mass or less. If the content of the present compound exceeds 10 parts by mass with respect to 100 parts by mass of the inorganic powder, the heat resistance of the porous membrane tends to be impaired.
- Inorganic powder examples include metal oxides, metal hydroxides, metal carbonates, metal nitrides, metal carbides, metal hydroxides, and metal sulfates, preferably metal oxides, metal hydroxides. And metal carbonates, more preferably metal oxides.
- the metal oxide may contain other metal components such as metal hydroxide and metal carbonate.
- the ratio of the other metal components contained in the metal oxide is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the metal oxide. Preferably it is 5 mass% or less, Most preferably, it is 1 mass% or less.
- alumina is preferable from the viewpoint of further improving chemical stability and shape stability at high temperature, and ⁇ -alumina is more preferable.
- Specific inorganic powders include calcium oxide, magnesium oxide, titanium oxide, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, talc, clay, kaolin. , Silica, hydrotalcite, diatomaceous earth, mica, zeolite, glass and the like. These can be used alone or in combination of two or more.
- the proportion of the inorganic powder in the present porous membrane usually exceeds 50% by mass of the present porous membrane, preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. is there. Moreover, Preferably it is 99.5 mass% or less, More preferably, it is 99 mass% or less, More preferably, it is 98 mass% or less.
- the binder resin binds inorganic powders, and the present porous film and other porous film different from the present porous film (hereinafter sometimes referred to as other porous film). It also has a function of binding.
- the binder resin is preferably a resin that is insoluble in the electrolyte solution of the non-aqueous electrolyte secondary battery and is electrochemically stable within the usage range of the non-aqueous electrolyte secondary battery.
- binder resin examples include polyolefins such as polyethylene and polypropylene; fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene; vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and ethylene-tetrafluoro.
- Fluorine-containing rubbers such as ethylene copolymers; styrene-butadiene copolymers and their hydrides; (meth) acrylate copolymers, acrylonitrile-acrylate copolymers, and styrene-acrylate copolymers ) Acrylate ester copolymer; Rubber such as ethylene propylene rubber; Polyvinyl acetate; Polyphenylene ether, Polysulfone, Polyethersulfone, Polyphenylene sulfide, Polyetherimide, Polyamide, Polyethylene Resins having a melting point or glass transition temperature of 180 ° C.
- a fluorine-containing resin such as imide, polyamideimide, polyetheramide, polyester, aromatic polyester, and polyetheretherketone; polycarbonate; polyacetal; and carboxyalkyl cellulose, alkyl cellulose, hydroxyalkyl cellulose And polymers such as water-soluble resins such as starch, polyvinyl alcohol, sodium alginate, polyethylene glycol, cellulose ether, polyacrylic acid, polyacrylamide, and polymethacrylic acid.
- a fluorine-containing resin, a fluorine-containing rubber, a resin having a melting point or glass transition temperature of 180 ° C. or higher, and a water-soluble resin are preferable.
- a fluorine-containing resin, a fluorine-containing rubber, and a resin having a melting point and a glass transition temperature of 180 ° C. or higher are preferable because of higher stability in the use range of the nonaqueous electrolyte battery.
- a water-soluble resin is preferable in terms of process and environmental load.
- water-soluble resins carboxyalkyl cellulose, alkyl cellulose, hydroxyalkyl cellulose, starch, polyvinyl alcohol, and sodium alginate are preferable, and cellulose ether is more preferable.
- These binder resins may be used alone or in combination of two or more.
- Examples of the cellulose ether include carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), carboxyethyl cellulose, methyl cellulose, ethyl cellulose, cyanethyl cellulose, and oxyethyl cellulose.
- CMC carboxymethyl cellulose
- HEC hydroxyethyl cellulose
- carboxyethyl cellulose methyl cellulose
- ethyl cellulose cyanethyl cellulose
- oxyethyl cellulose oxyethyl cellulose.
- CMC and HEC excellent in chemical and thermal stability are preferable, and CMC is more preferable.
- the polyamide is preferably an aromatic polyamide, particularly preferably a para-oriented aromatic polyamide (hereinafter sometimes referred to as “para-aramid”).
- Para-aramid is usually obtained by condensation polymerization of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4,4′-biphenylene, It consists essentially of repeating units that are bonded together in the opposite orientation, such as 1,5-naphthalene, 2,6-naphthalene, etc., in an orientation extending coaxially or in parallel.
- para-aramid examples include poly (paraphenylene terephthalamide), poly (parabenzamide), poly (4,4′-benzanilide terephthalamide), poly (paraphenylene-4,4′-biphenylenedicarboxylic amide), poly (Paraphenylene-2,6-naphthalenedicarboxylic acid amide), poly (2-chloro-paraphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer, etc.
- Para-aramid having a structure conforming to the orientation type may be mentioned.
- the polyimide is preferably an aromatic polyimide, more preferably a wholly aromatic polyimide.
- the aromatic polyimide is usually produced by condensation polymerization of an aromatic dianhydride and a diamine.
- the dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and the like.
- Examples include anhydrides, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
- diamine examples include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, and 1,5 ′.
- diamine examples include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, and 1,5 ′.
- the polyamideimide is preferably an aromatic polyamideimide.
- Aromatic polyamideimides are usually obtained from these condensation polymerizations using aromatic dicarboxylic acids and aromatic diisocyanates, and can also be obtained from these condensation polymerizations using aromatic dianhydrides and aromatic diisocyanates. Can do.
- Examples of the aromatic dicarboxylic acid include isophthalic acid and terephthalic acid.
- Examples of the aromatic dianhydride include trimellitic anhydride.
- Examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, orthotolylane diisocyanate, and m-xylene diisocyanate.
- the ratio of the inorganic powder to the total amount of the binder resin and the inorganic powder in the present porous membrane is usually more than 50% by mass, preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably. Is 95% by mass or more. Moreover, Preferably it is 99.5 mass% or less, More preferably, it is 99 mass% or less, More preferably, it is 98 mass% or less.
- the proportion of the inorganic powder is within the specific range, the present porous membrane having an excellent balance between ion permeability and difficulty in powder removal can be obtained. Powder falling is a phenomenon in which inorganic powder is peeled off from the porous membrane.
- the present porous membrane may contain other components as long as the function of the present porous membrane is not impaired.
- other components include a dispersant, a plasticizer, and a pH adjuster.
- the thickness of the porous membrane is usually 0.1 to 20 ⁇ m, preferably 1 to 10 ⁇ m.
- the thickness is less than 0.1 ⁇ m, the heat resistance of the separator for a non-aqueous electrolyte secondary battery including the porous membrane tends to be insufficient.
- the thickness of the present porous membrane is 0.
- the separator If it is less than 1 ⁇ m, there is a risk that the separator will contract without being able to resist the thermal contraction of the porous membrane made of polyolefin when heat is generated due to an accident or the like in the non-aqueous electrolyte secondary battery, and if it exceeds 20 ⁇ m The thickness of the separator increases, and the battery capacity may be reduced.
- the porosity of the present porous membrane is usually 20 to 80% by volume, preferably 30 to 70% by volume. If the porosity is less than 20% by volume, the amount of electrolyte retained may be reduced, and if it exceeds 80% by volume, the heat resistance of the porous membrane may be impaired. There is a risk that it will not be possible.
- the pore diameter of the porous membrane of the present porous membrane is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less, from the viewpoint of having excellent ion permeability and preventing particles from entering the positive electrode and the negative electrode.
- the permeability of this porous membrane is usually expressed by air permeability.
- the air permeability of the present porous membrane is usually 30 to 1000 sec / 100 cc, preferably 50 to 800 sec / 100 cc.
- the basis weight of the present porous membrane is usually 4 to 20 g / m 2 , preferably 5 to 12 g / m 2 . If the basis weight is less than 4 g / m 2 , the strength may be insufficient. If the basis weight is more than 20 g / m 2 , the thickness of the porous membrane may increase and the battery capacity may decrease.
- This porous membrane is used as a separator for a non-aqueous electrolyte secondary battery as a laminated porous film laminated with other porous membranes (hereinafter sometimes referred to as this laminated porous film).
- porous membranes include, for example, papermaking such as viscose rayon and natural cellulose; mixed paper obtained by making fibers such as cellulose and polyester; electrolytic paper; kraft paper; manila paper; polyethylene nonwoven fabric, polypropylene nonwoven fabric, Polyester non-woven fabric, glass fiber, porous polyolefin (for example, porous polyethylene, porous polypropylene), porous polyester, aramid fiber, polybutylene terephthalate non-woven fabric, para-type wholly aromatic polyamide, polyvinylidene fluoride, tetrafluoroethylene, fluoride
- Non-woven fabrics or porous membranes such as copolymers of vinylidene and propylene hexafluoride, fluorine-containing resins such as fluororubber; membranes such as proton conducting polymers;
- a porous film made of polyolefin hereinafter sometimes referred to as a polyolefin film) is preferred.
- the present laminated porous film may have a plurality of other porous films and the present porous film.
- the present porous film may be laminated on both surfaces of the other porous film.
- this porous film may contain the different this compound, inorganic powder, and binder resin, respectively.
- the polyolefin membrane melts and becomes non-porous when the battery generates heat intensely, thereby giving a shutdown function to the laminated porous film.
- the present porous membrane has heat resistance at a high temperature at which shutdown occurs, the present laminated porous film has shape stability even at a high temperature.
- the water content of the laminated porous membrane is preferably less than 0.15% by mass. If the water content of the porous membrane is 0.15% by mass or more, the charge / discharge cycle characteristics of the battery may be impaired.
- the 50% breakdown voltage of the non-aqueous electrolyte secondary battery including the laminated porous film as a separator for a non-aqueous electrolyte secondary battery is preferably 4.40 V or more.
- the non-aqueous electrolyte secondary battery has a large battery voltage of 4.40 V or more, and even when the battery capacity is large, abnormal heat generation when an internal short circuit occurs is suppressed, that is, excellent safety against an internal short circuit. It becomes a thing.
- the membrane resistance of the present laminated porous film is preferably 0.25 to 5.00 ⁇ ⁇ cm 2 from the viewpoint of battery characteristics (ion permeability and load characteristics). If the membrane resistance is less than 0.25 ⁇ ⁇ cm 2 , the ion permeability is excellent, but the risk of occurrence of a short-circuit may increase, and if it exceeds 5.00 ⁇ ⁇ cm 2 , good ion permeability May not be obtained, and battery characteristics may be deteriorated.
- the thickness of the other porous membrane and / or the present porous membrane may be increased or the porosity may be decreased. The thickness of the porous membrane and / or the porous membrane may be reduced or the porosity may be increased.
- the thickness of the laminated porous film is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m. If the thickness of the laminated porous film is less than 5 ⁇ m, the laminated porous film may be easily broken, and if it exceeds 75 ⁇ m, the thickness of the laminated porous film is increased and the battery capacity is increased. There is a risk of becoming smaller.
- the volume basis weight of the porous membrane contained in the laminated porous film is usually 0.5 to 20 cc / m 2 , preferably 1 to 10 cc / m 2 from the viewpoint of stability during heating and battery characteristics. is there. If the volume basis weight is less than 0.5 cc / m 2 , the laminated porous film may be easily broken when heated. If it exceeds 20 cc / m 2 , the thickness of the laminated porous film May become thicker and the battery capacity may be reduced. When this porous membrane is laminated on both surfaces of other porous membranes, the volume per unit area is the sum of both surfaces.
- the air permeability of the laminated porous film is usually 50 to 2000 sec / 100 cc, preferably 70 to 1000 sec / 100 cc. If the air permeability exceeds 2000 sec / 100 cc, battery characteristics (ion permeability, load characteristics) may be impaired.
- the present laminated porous film may include other porous films and porous layers other than the present porous film, such as an adhesive layer and a protective layer, as long as the object of the present invention is not impaired.
- polyolefin film examples include a high molecular weight homopolymer or copolymer obtained by polymerizing ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, or the like. Can be mentioned. High molecular weight polyethylene is preferable. These polyolefins may be used alone or in combination of two or more.
- the average molecular weight is preferably 1 ⁇ 10 5 to 15 ⁇ 10 6 .
- the proportion of the polyolefin contained in the polyolefin film is usually more than 50% by volume of the total solid content contained in the polyolefin film, preferably 70% by volume or more, more preferably 90% by volume or more, and still more preferably 95%. Volume% or more.
- the polyolefin film may contain components other than polyolefin as long as the function of the polyolefin film is not impaired.
- the thickness of the polyolefin film is usually 4 to 50 ⁇ m, preferably 5 to 30 ⁇ m. If the thickness is less than 4 ⁇ m, the strength of the laminated porous film may be insufficient, and if it exceeds 50 ⁇ m, the thickness of the laminated porous film may be increased, and the battery capacity may be reduced. is there.
- the porosity of the polyolefin film is usually 20 to 80% by volume, preferably 30 to 70% by volume. If the porosity is less than 20% by volume, the amount of electrolyte retained may be reduced, and if it exceeds 80% by volume, there may be insufficient pore formation at a high temperature at which shutdown occurs. Otherwise, the current may not be cut off.
- the pore size of the polyolefin membrane has excellent ion permeability when this laminated porous film is used as a separator for non-aqueous electrolyte secondary batteries, and prevents particles from entering the positive and negative electrodes Therefore, the thickness is preferably 3 ⁇ m or less, and more preferably 1 ⁇ m or less.
- the polyolefin membrane has a structure having pores connected to the inside thereof, and allows gas, liquid, ions, etc. to pass from one surface to the other surface.
- the transmittance is usually expressed by air permeability.
- the air permeability of the polyolefin membrane is usually 30 to 1000 sec / 100 cc, preferably 50 to 800 sec / 100 cc.
- the basis weight of the polyolefin film is usually 4 to 15 g / m 2 , preferably 5 to 12 g / m 2 . If the basis weight is less than 4 g / m 2 , the strength of the laminated porous film may be insufficient, and if it exceeds 15 g / m 2 , the thickness of the laminated porous film increases, resulting in a battery capacity. May become smaller.
- a coating liquid containing the present compound, an inorganic powder, and a binder resin (hereinafter sometimes referred to as the present coating liquid) is applied to a substrate, and then the porous film is prepared. After forming the film and then removing the base material, and after applying the coating liquid to the base material, it is immersed in a solvent that can be mixed with the coating liquid and does not dissolve the binder resin. And a method of forming a porous film by drying and then removing the substrate.
- This coating solution usually contains a solvent that dissolves the binder resin.
- the coating liquid may contain a pH adjuster, a dispersant, a plasticizer, alcohol, and the like as long as the object of the present invention is not impaired, and preferably contains alcohol.
- Examples of the alcohol include methanol, ethanol, 1-propanol, isopropyl alcohol, 2-butanol, tert-butyl alcohol, 1-butanol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, pentyl alcohol, isopentyl alcohol, hexyl.
- Examples include alcohol, isohexyl alcohol, heptyl alcohol, isoheptyl alcohol, octyl alcohol, isooctyl alcohol, octyl alcohol, isooctyl alcohol, nonyl alcohol, isononyl alcohol, decyl alcohol, ethylene glycol, propylene glycol, and butanediol. .
- the content of alcohol in the present coating solution is not particularly limited, and may be set to such an amount that a property that allows easy application to other porous membranes can be obtained.
- the alcohol content in the present coating liquid is preferably 1 to 1000 parts by weight, more preferably 2 to 500 parts by weight, and further preferably 3 to 300 parts by weight with respect to 1 part by weight of the binder resin. It is even more preferably 5 to 200 parts by mass.
- polyolefin film there can be used a film or sheet formed using polyolefin, which is uniaxially or biaxially stretched to form fine pores.
- a method for producing a polyolefin film for example, as described in JP-A-7-29563, there is a method in which a plasticizer is added to a thermoplastic resin to form a film, and then the plasticizer is removed with an appropriate solvent. Can be mentioned.
- the polyolefin film is formed from a polyolefin resin containing a high molecular weight polyethylene having a weight average molecular weight exceeding 1,000,000 and a low molecular weight polyolefin having a weight average molecular weight of 10,000 or less, from the viewpoint of production cost, It is preferable to manufacture by the method including each process.
- A 100 parts by mass of high molecular weight polyethylene, 5 to 200 parts by mass of low molecular weight polyolefin, and 100 to 400 parts by mass of an inorganic filler such as calcium carbonate are kneaded to obtain a polyolefin resin composition.
- a sheet is formed using the polyolefin resin composition.
- the inorganic filler is removed from the sheet obtained in the step (b).
- the sheet obtained in step (c) is stretched to obtain a polyolefin film. It is a method including.
- Method for producing the present laminated porous film As a method of laminating the present porous membrane and other porous membranes, the method of separately producing the other porous membrane and the present porous membrane and laminating each, and the other porous membrane, Examples of the method include forming the porous film by applying the coating solution, and the latter method is preferable because it is simpler.
- Examples of a method for forming the porous film by applying the coating liquid to another porous film include a method including the following steps.
- a coating liquid in which an inorganic powder is dispersed in a solution in which the present compound and binder resin are dissolved in a solvent is prepared.
- B) The coating liquid is applied to another porous film to form a coating film.
- C) The binder resin is precipitated from the coating film by means such as solvent removal or immersion in a solvent that does not dissolve the binder resin, and dried as necessary.
- examples of the solvent that dissolves the binder resin include polar amide solvents and polar urea solvents. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), and tetramethylurea.
- an alkali metal or alkaline earth metal chloride for the purpose of improving the solubility of para-aramid in a solvent.
- Specific examples include lithium chloride and calcium chloride.
- the amount of the chloride added is preferably in the range of 0.5 to 6.0 moles, more preferably in the range of 1.0 to 4.0 moles per 1.0 mole of amide groups in the paraamide. If the chloride is less than 0.5 mol, the solubility of para-aramid may be insufficient, and if it exceeds 6.0 mol, the solubility of the chloride in the solvent may be substantially exceeded, which may be undesirable.
- the ratio of the chloride to the total amount of the coating solution is preferably in the range of 2 to 10% by mass.
- the solubility of para-aramid may be insufficient, and when it exceeds 10% by mass, the solubility of the chloride will be insufficient. There is.
- the binder resin is an aromatic polyimide
- dimethyl sulfoxide, cresol, o-chlorophenol, etc. are preferably used in addition to those exemplified as a solvent for dissolving the aromatic polyamide. it can.
- the solvent for dissolving the binder resin includes water, alcohols such as methanol, ethanol, isopropanol, acetone, toluene, xylene, hexane, N-methylpyrrolidone, N, N- Examples thereof include dimethylacetamide, N, N-dimethylformamide, etc., alone or in combination within a compatible range.
- alcohols such as methanol, ethanol, isopropanol, acetone, toluene, xylene, hexane, N-methylpyrrolidone, N, N-
- dimethylacetamide, N, N-dimethylformamide, etc. alone or in combination within a compatible range.
- 80% by mass or more of the medium is preferably water, and only water is more preferable.
- the solvent contains water
- a hydrophilic treatment By subjecting other porous membranes to a hydrophilic treatment, applicability is further improved, and a more homogeneous main porous membrane can be obtained.
- This hydrophilization treatment is particularly effective when the concentration of water in the solvent is high.
- Other methods for hydrophilizing the porous membrane may be any method, and specific examples include chemical treatment with acid or alkali, corona treatment, plasma treatment and the like.
- the corona treatment is limited to modification by corona discharge only in the vicinity of the surface of other porous membranes. There is an advantage that high coatability can be secured without changing the properties of the coating.
- the removal of the solvent from the coating liquid applied on the other porous film is generally performed by heating and drying.
- the coating film before heat-drying can be immersed in a solvent that does not dissolve the binder resin to precipitate the binder resin, and then the solvent can be removed by heat-drying.
- the temperature which does not change the air permeability of the other porous membrane after drying is preferable.
- the method of applying the present coating solution to other porous membranes is not particularly limited as long as it is a method that enables uniform wet coating, and conventionally known methods can be employed.
- a capillary coating method, a spin coating method, a slit die coating method, a spray coating method, a roll coating method, a screen printing method, a flexographic printing method, a bar coater method, a gravure coater method, a die coater method, and the like can be employed.
- the thickness of the porous film to be formed can be controlled by adjusting the coating amount of the coating solution, the concentration of the coating solution, and the content ratio of the inorganic powder and the binder resin.
- a resin film, a metal belt, a drum, or the like can be used as a support during coating.
- Examples of the method for preparing the coating liquid include a method of stirring by a method such as a mechanical stirring method, an ultrasonic dispersion method, a high-pressure dispersion method, or a media dispersion method. Since the inorganic powder can be dispersed more uniformly, the high pressure dispersion method is more preferable.
- the nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, a separator for a nonaqueous electrolyte secondary battery sandwiched between opposing surfaces of the positive electrode and the negative electrode, and a nonaqueous electrolyte.
- Non-aqueous electrolyte for example, a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent can be used.
- Lithium salts include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , One or a mixture of two or more of lower aliphatic carboxylic acid lithium salts, LiAlCl 4 and the like can be mentioned.
- the lithium salt is selected from the group consisting of LiPF 6 containing fluorine, LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiC (CF 3 SO 2 ) 3 among these. It is preferable to use those containing at least one selected from the above.
- non-aqueous electrolyte examples include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di (methoxycarbonyloxy ) Carbonates such as ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.
- Ethers such as methyl formate, methyl acetate and Y-butyrolactone; nitriles such as acetonitrile and butyronitrile; amino acids such as N, N-dimethylformamide and N, N-dimethylacetamide Carbamates such as 3-methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 1,3-propane sultone, or those obtained by introducing a fluorine group into the aforementioned substances can be used. Use a mixture of two or more of these.
- cyclic carbonates and acyclic carbonates or mixtures of cyclic carbonates and ethers are more preferred.
- ethylene carbonate and dimethyl have a wide operating temperature range and are hardly decomposable even when a graphite material such as natural graphite or artificial graphite is used as the negative electrode active material.
- a mixture comprising carbonate and ethyl methyl carbonate is preferred.
- the positive electrode a material in which a mixture containing a positive electrode active material, a conductive agent and a binder is supported on a current collector is usually used.
- the positive electrode active material a material containing a material capable of doping and dedoping lithium ions, a carbonaceous material as a conductive agent, and a thermoplastic resin as a binder can be used.
- the material that can be doped / undoped with lithium ions include lithium composite oxides containing at least one transition metal such as V, Mn, Fe, Co, and Ni.
- lithium composite oxides having an ⁇ -NaFeO 2 type structure such as lithium nickelate and lithium cobaltate
- lithium composite oxides having a spinel type structure such as lithium manganese spinel are preferable in that the average discharge potential is high. Can be mentioned.
- the lithium composite oxide may contain various metal elements, particularly at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, Ag, Mg, Al, Ga, In, and Sn.
- Use of lithium nickelate is preferable because cycle characteristics in use at a high capacity are improved.
- binder examples include polyvinylidene fluoride, vinylidene fluoride copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene -Tetrafluoroethylene copolymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymers, thermoplastic resins such as thermoplastic polyimide, polyethylene, and polypropylene.
- Examples of the conductive agent include carbonaceous materials such as natural graphite, artificial graphite, cokes, and carbon black.
- carbonaceous materials such as natural graphite, artificial graphite, cokes, and carbon black.
- the conductive material each may be used alone, for example, artificial graphite and carbon black may be mixed and used.
- a material capable of doping and dedoping lithium ions, lithium metal, or a lithium alloy can be used as the negative electrode.
- Materials that can be doped / undoped with lithium ions include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and fired organic polymer compounds, and lower potential than the positive electrode.
- chalcogen compounds such as oxides and sulfides for doping and dedoping lithium ions.
- a carbonaceous material a carbonaceous material mainly composed of graphite materials such as natural graphite and artificial graphite, because it has a high potential flatness and a low average discharge potential, so that a large energy density can be obtained when combined with a positive electrode. Is preferred.
- the negative electrode current collector Cu, Ni, stainless steel, or the like can be used, but Cu is particularly preferable in a lithium secondary battery in that it is difficult to form an alloy with lithium and it can be easily processed into a thin film.
- a method of supporting the mixture containing the negative electrode active material on the negative electrode current collector a method of pressure molding, or a method of pasting into a paste using a solvent or the like and applying pressure to the current collector by pressing after drying Is mentioned.
- the shape of the battery of the present invention is not particularly limited, and may be any of a paper type, a coin type, a cylindrical type, a square type, a laminate type, and the like.
- each physical property of the laminated porous film was measured by the following method.
- Curl measurement The laminated porous film was cut into a square of 8 cm ⁇ 8 cm square, held at room temperature at a dew point of ⁇ 30 ° C. for 1 day, and then the height of the raised end was measured. The appearance was judged according to the following criteria. C shows a completely curled state, A and B are preferable, and A is more preferable. A: No lifting at the end. B: Only the end portion is lifted, but most of the portions other than the end portion are not lifted and are in a flat state. C: Both ends approach and are wound into a cylindrical shape.
- Example 1 100 parts by mass of alumina fine particles (manufactured by Sumitomo Chemical Co., Ltd .; trade name “AKP3000”), 3 parts by mass of carboxymethyl cellulose (manufactured by Daicel Finechem Co., Ltd., product number 1110), polyoxyethylene alkyl ether (manufactured by Sanyo Chemical Industries, Ltd .; Sanmorin) (Registered trademark) 11) Water is added to 0.5 parts by weight of the mixture so that the solid content is 29% by weight, and the resulting mixture is rotated and revolved by a mixer “Awatori Netaro” (Sinky Co., Ltd.) A registered trademark) and stirred and mixed twice at room temperature and 2000 rpm for 30 seconds.
- alumina fine particles manufactured by Sumitomo Chemical Co., Ltd .; trade name “AKP3000”
- carboxymethyl cellulose manufactured by Daicel Finechem Co., Ltd., product number 1110
- polyoxyethylene alkyl ether manufactured
- Example 2 A laminated porous film (2) was obtained in the same manner as in Example 1 except that 0.5 part by mass of the polyoxyethylene alkyl ether in Example 1 was changed to 1 part by mass.
- the basis weight of the porous film in the laminated porous film (2) was 6.6 g / m 2 .
- Table 1 shows the physical properties of the laminated porous film (2).
- Example 1 A laminated porous film (3) was obtained in the same manner as in Example 1 except that 0.5 part by mass of the polyoxyethylene alkyl ether in Example 1 was not added. The basis weight of this porous membrane in the laminated porous film (3) was 6.9 g / m 2 . Table 1 shows the physical properties of the laminated porous film (3).
- the laminated porous films (1) and (2) obtained in Examples 1 and 2 were able to reduce the curl amount while maintaining high dimensional retention and air permeability.
- the present invention it is possible to obtain a laminated porous film that is difficult to curl, in which a porous film made of polyolefin and a porous film containing an inorganic powder are laminated.
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Abstract
Description
非水電解液二次電池には、通常、正極と負極とを分離する部材としてセパレータが用いられている。従来、セパレータにはポリオレフィンからなる多孔質膜が用いられてきたが、耐熱性が十分でないという問題を有していた。
耐熱性に優れたセパレータとして、例えば、特許文献1には、ポリオレフィンからなる多孔質膜に、無機粉末とポリビニルアルコールからなる多孔質膜を積層したセパレータが提案されている。
[1] 疎水性基及びノニオン性の親水性基を有する化合物と、無機粉末と、バインダー樹脂と、を含む多孔質膜。
[2] 疎水性基及びノニオン性の親水性基を有する化合物がノニオン性界面活性剤である[1]に記載の多孔質膜。
[3] 無機粉末が、金属酸化物、金属水酸化物、又は金属炭酸化物である[1]又は[2]に記載の多孔質膜。
[4] ノニオン性の親水性基が、ポリオキシエチレン構造を有する[1]~[3]のいずれかに記載の多孔質膜。
[5] バインダー樹脂が、水溶性の樹脂である[1]~[4]のいずれかに記載の多孔質膜。
[6] [1]~[5]のいずれかに記載の多孔質膜と、[1]~[5]のいずれかに記載の多孔質膜とは異なるその他の多孔質膜と、が積層された積層多孔質フィルム。
[7] 疎水性基及びノニオン性の親水性基を有する化合物と、無機粉末と、バインダー樹脂と、溶媒と、を含む塗工液。
[8] [1]~[5]のいずれかに記載の多孔質膜を含む非水電解液二次電池用セパレータ。
[9] [8]に記載の非水電解液二次電池用セパレータを用いた非水電解液二次電池。
[10] [6]に記載の積層多孔質フィルムを含む非水電解液二次電池用セパレータ。
[11] [10]に記載の非水電解液二次電池用セパレータを用いた非水電解液二次電池。
本発明の多孔質膜(以下、本多孔質膜ということがある)は、その内部に連結した細孔を有する構造である。本多孔質膜は、多孔質であるため、一方の面から他方の面に気体、液体及びイオン等が透過可能であり、さらに、無機粉末を含むため耐熱性が高く、本多孔質膜を含む積層多孔質フィルムに高温時における形状安定性を付与することができる。よって、本多孔質膜は、非水電解液電池用セパレータに好適に含まれる。
ポリオレフィンからなる多孔質膜と、無機粉末を含む多孔質膜とは、極性が異なるため、水との親和性が異なり、同じ環境に置かれたときの吸水量が異なることがある。そのため、ポリオレフィンからなる多孔質膜と無機粉末を含む多孔質膜とが積層された積層多孔質フィルムは、当該ポリオレフィンからなる多孔質膜と当該無機粉末を含む多孔質膜とが吸水したときにそれぞれの膜の寸法変化量に違いが生じ、カールが発生する。
無機粉末は一般的に極性が高いため、水との相互作用が強い。このような無機粉末と、本化合物が有するノニオン性の親水性基とが、相互作用することによって、無機粉末の表面に本化合物が付着し、そして、本化合物が有する疎水性基によって無機粉末の表面を覆うことによって、無機粉末と水との相互作用を低減することができると考えられる。よって、本多孔質膜の水分含有量を低くすることができ、ポリオレフィンからなる多孔質膜の水分含有量と近くなるためカールは抑制される。
ノニオン性の親水性基をしては、ポリオキシエチレン構造を有する基、及びヒドロキシ基等が挙げられる。また、本化合物は、好ましくはアニオン性基及びカチオン性基等のイオン性基を有さない。本明細書におけるアニオン性基とは、スルホン酸塩及びカルボン酸塩等の塩、及び、スルホン酸及びカルボン酸等のpKaが10未満の酸基のことである。すなわち、pKaが10以上である一般的なヒドロキシ基はアニオン性基ではなく、ノニオン性基に該当する。
また、前記炭化水素基及びフッ化炭素基は、エーテル結合、チオエーテル結合、エステル結合、及びアミド結合等で連結されていてもよい。
無機粉末100質量部に対する、本化合物の含有量が10質量部を超えると本多孔質膜の耐熱性を損なう傾向がある。
無機粉末としては、金属酸化物、金属水酸化物、金属炭酸化物、金属窒化物、金属炭化物、金属水酸化物、及び金属の硫酸塩等が挙げられ、好ましくは、金属酸化物、金属水酸化物、及び金属炭酸化物であり、さらに好ましくは金属酸化物である。
バインダー樹脂は、無機粉末同士を結着させるものであり、また、本多孔質膜と、本多孔質膜とは異なるその他の多孔質膜(以下、その他の多孔質膜ということがある)とを結着させる機能も有する。バインダー樹脂は、非水電解液二次電池の電解液に対して不溶であり、非水電解液二次電池の使用範囲で電気化学的に安定である樹脂が好ましい。バインダー樹脂としては、例えば、ポリエチレン、及びポリプロピレン等のポリオレフィン;ポリフッ化ビニリデン、及びポリテトラフルオロエチレン等の含フッ素樹脂;フッ化ビニリデン-ヘキサフルオロプロピレン-テトラフルオロエチレン共重合体、及びエチレン-テトラフルオロエチレン共重合体等の含フッ素ゴム;スチレン-ブタジエン共重合体及びその水素化物;メタクリル酸エステル共重合体、アクリロニトリル-アクリル酸エステル共重合体、及びスチレン-アクリル酸エステル共重合体等の(メタ)アクリル酸エステル共重合体;エチレンプロピレンラバー等のゴム類;ポリ酢酸ビニル;ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルアミド、ポリエステル、芳香族ポリエステル、及びポリエーテルエーテルケトン等の融点やガラス転移温度が180℃以上の樹脂;ポリカーボネート;ポリアセタール;並びに、カルボキシアルキルセルロース、アルキルセルロース、ヒドロキシアルキルセルロース、澱粉、ポリビニルアルコール、アルギン酸ナトリウム、ポリエチレングリコール、セルロースエーテル、ポリアクリル酸、ポリアクリルアミド、及びポリメタクリル酸等の水溶性の樹脂等の重合体が挙げられる。中でも、含フッ素樹脂、含フッ素ゴム、融点やガラス転移温度が180℃以上の樹脂、及び水溶性の樹脂が好ましい。含フッ素樹脂、含フッ素ゴム、及び融点やガラス転移温度が180℃以上の樹脂は、非水電解液電池の使用範囲での安定性がより高いため好ましい。水溶性の樹脂は、プロセスや環境負荷の点で好ましい。水溶性の樹脂の中でも、カルボキシアルキルセルロース、アルキルセルロース、ヒドロキシアルキルセルロース、澱粉、ポリビニルアルコール、アルギン酸ナトリウムが好ましく、セルロースエーテルがより好ましい。これらのバインダー樹脂は、単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
空隙率が20体積%未満では電解液の保持量が少なくなる恐れがあり、80体積%を超えると本多孔質膜の耐熱性を損なう恐れがある、すなわち電池が激しく発熱したときに電流が遮断できなくなる恐れがある。
本多孔質膜は、その他の多孔質膜と積層した積層多孔質フィルム(以下、本積層多孔質フィルムということがある)として非水電解液二次電池用セパレータに用いられる。その他の多孔質膜としては、例えば、ビスコースレーヨン、天然セルロース等の抄紙;セルロース、ポリエステル等の繊維を抄紙して得られる混抄紙;電解紙;クラフト紙;マニラ紙;ポリエチレン不織布、ポリプロピレン不織布、ポリエステル不織布、ガラス繊維、多孔質ポリオレフィン(例えば、多孔質ポリエチレン、多孔質ポリプロピレン)、多孔質ポリエステル、アラミド繊維、ポリブチレンテレフタレート不織布、パラ系全芳香族ポリアミド、ポリフッ化ビニリデン、テトラフルオロエチレン、フッ化ビニリデンと6フッ化プロピレンとの共重合体、フッ素ゴム等の含フッ素樹脂等の不織布又は多孔質膜;プロトン伝導型ポリマー;等の膜が挙げられる。好ましくはポリオレフィンからなる多孔質膜(以下、ポリオレフィン膜ということがある)である。
多孔質膜の水分含有量が0.15質量%以上だと電池の充放電サイクル特性を損なう恐れがある。
ポリオレフィン膜に含まれるポリオレフィンとしては、例えば、エチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン、又は1-ヘキセン等を重合して得られる高分子量の単独重合体、又は共重合体が挙げられる。好ましくは、高分子量ポリエチレンである。これらのポリオレフィンは、単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
空隙率が20体積%未満では電解液の保持量が少なくなる恐れがあり、80体積%を超えるとシャットダウンが生じる高温における無孔化が不十分となる恐れがある、すなわち電池が激しく発熱したときに電流が遮断できなくなる恐れがある。
本多孔質膜の製造方法としては、本化合物と、無機粉末と、バインダー樹脂とを含有する塗工液(以下、本塗工液ということがある)を基材に塗工して本多孔質膜を形成し、その後、基材を除去することによって形成する方法、及び、本塗工液を基材に塗工した後、本塗工液と混合可能でバインダー樹脂を溶解しない溶媒中に浸漬させ、乾燥することによって多孔質膜を形成し、その後、基材を除去する方法等が挙げられる。
その他の多孔質膜は、公知の方法によって製造してもよいし、市販品を用いてもよい。
ポリオレフィン膜には、ポリオレフィンを用いて形成したフィルムやシートに、一軸または二軸延伸を施して微細な空孔を形成したもの等を用いることができる。ポリオレフィン膜の製造方法としては、例えば、特開平7-29563号公報に記載されたように、熱可塑性樹脂に可塑剤を加えてフィルム成形した後、該可塑剤を適当な溶媒で除去する方法が挙げられる。例えば、ポリオレフィン膜が、重量平均分子量が100万を超える高分子量ポリエチレンと重量平均分子量が1万以下の低分子量ポリオレフィンとを含むポリオレフィン樹脂から形成される場合には、製造コストの点から、以下の各工程を含む方法により製造することが好ましい。
(a)高分子量ポリエチレン100質量部と、低分子量ポリオレフィン5~200質量部と、炭酸カルシウム等の無機充填剤100~400質量部とを混練してポリオレフィン樹脂組成物を得る。
(b)前記ポリオレフィン樹脂組成物を用いてシートを成形する。
(c)工程(b)で得られたシート中から無機充填剤を除去する。
(d)工程(c)で得られたシートを延伸してポリオレフィン膜を得る。
を含む方法である。
本多孔質膜とその他の多孔質膜とを積層する方法としては、その他の多孔質膜と本多孔質膜とを別々に製造してそれぞれを積層する方法、並びに、その他の多孔質膜に、本塗工液を塗工して本多孔質膜を形成する方法等が挙げられ、より簡便であることから後者の方法が好ましい。
(a)本化合物及びバインダー樹脂が溶媒に溶解した溶液に、無機粉末が分散した塗工液を調製する。
(b)該塗工液をその他の多孔質膜に塗工し、塗工膜を形成する。
(c)溶媒除去、又はバインダー樹脂を溶解しない溶媒への浸漬等の手段で、前記塗工膜からバインダー樹脂を析出させ、必要に応じて乾燥する。
その他の多孔質膜の親水化処理は、いかなる方法でもよく、具体的には酸やアルカリ等による薬剤処理、コロナ処理、プラズマ処理等が挙げられる。
ここで、コロナ処理は、比較的短時間でその他の多孔質膜を親水化できることに加え、コロナ放電による改質が、その他の多孔質膜の表面近傍のみに限られ、その他の多孔質膜内部の性質を変化させることなく、高い塗工性を確保できるという利点がある。
非水電解液二次電池は、正極と、負極と、該正極と該負極の対向面間に挟まれた非水電解液二次電池用セパレータと、非水電解液とを備える。
(1)カール測定:積層多孔質フィルムを8cm×8cm角の正方形に切り出し、室温下、露点-30℃で1日保持した後、端部の持ち上がった高さを測定した。
また、外観を以下の基準で判断を行った。Cは完全にカールした状態を示し、A、Bの状態が好ましく、Aがより好ましい。
A:端部の持ち上がりなし。
B:端部のみ持ち上がるが、端部以外の大部分は持ち上がりなく平坦な状態でいる。
C:両端が近づき、筒状に巻き込んでいる。
(2)寸法保持率:積層多孔質フィルムを5cm×5cm角の正方形に切り出し、中央に4cm角で正方形の罫書き線を描き、紙2枚の間に挟み、150℃のオーブンで1時間保持した後、取り出して正方形の寸法を測定し、寸法保持率を計算した。寸法保持率の計算方法は次の通りである。
垂直方向(TD)の加熱前の罫書き線の長さ:W1
垂直方向(TD)の加熱後の罫書き線の長さ:W2
垂直方向(TD)の寸法保持率(%)=W2/W1×100
(3)透気度:JIS P8117に準拠して測定した。
アルミナ微細粒子(住友化学株式会社製;商品名「AKP3000」)100質量部、カルボキシメチルセルロース(ダイセルファインケム株式会社製、品番1110)3質量部、ポリオキシエチレンアルキルエーテル(三洋化成工業株式会社製;サンモリン(登録商標)11)0.5質量部の混合物に、固形分が29重量%となるように水を添加し、得られた混合物を自転・公転ミキサー「あわとり練太郎」(株式会社シンキー製;登録商標)で室温下、2000rpm、30秒の条件で2回攪拌・混合した。得られた混合物にイソプロピルアルコール14質量部を加え、固形分が28重量%となるような均一なスラリーとして塗工液を得た。得られた塗工液を、コロナ処理20W/(m2/分)を施したポリエチレンからなる多孔質膜(厚さ12μm、空隙率41%)上に、ドクターブレード法により塗布し、得られた塗布物である積層体を65℃で5分間乾燥させて、本多孔質膜と、ポリエチレンからなる多孔質膜と、が積層された積層多孔質フィルム(1)を得た。積層多孔質フィルム(1)における本多孔質膜の目付は6.2g/m2であった。積層多孔質フィルム(1)の各物性を表1に示す。
実施例1におけるポリオキシエチレンアルキルエーテル0.5質量部を、1質量部とした以外は実施例1と同様にして積層多孔質フィルム(2)を得た。積層多孔質フィルム(2)における本多孔質膜の目付は6.6g/m2であった。積層多孔質フィルム(2)の各物性を表1に示す。
実施例1におけるポリオキシエチレンアルキルエーテル0.5質量部を、加えなかった以外は実施例1と同様にして積層多孔質フィルム(3)を得た。積層多孔質フィルム(3)における本多孔質膜の目付は6.9g/m2であった。積層多孔質フィルム(3)の各物性を表1に示す。
Claims (11)
- 疎水性基及びノニオン性の親水性基を有する化合物と、無機粉末と、バインダー樹脂と、を含む多孔質膜。
- 疎水性基及びノニオン性の親水性基を有する化合物がノニオン性界面活性剤である請求項1に記載の多孔質膜。
- 無機粉末が、金属酸化物、金属水酸化物、又は金属炭酸化物である請求項1又は2に記載の多孔質膜。
- ノニオン性の親水性基が、ポリオキシエチレン構造を有する請求項1~3のいずれかに記載の多孔質膜。
- バインダー樹脂が、水溶性の樹脂である請求項1~4のいずれかに記載の多孔質膜。
- 請求項1~5のいずれかに記載の多孔質膜と、請求項1~5のいずれかに記載の多孔質膜とは異なるその他の多孔質膜と、が積層された積層多孔質フィルム。
- 疎水性基及びノニオン性の親水性基を有する化合物と、無機粉末と、バインダー樹脂と、溶媒と、を含む塗工液。
- 請求項1~5のいずれかに記載の多孔質膜を含む非水電解液二次電池用セパレータ。
- 請求項8に記載の非水電解液二次電池用セパレータを用いた非水電解液二次電池。
- 請求項6に記載の積層多孔質フィルムを含む非水電解液二次電池用セパレータ。
- 請求項10に記載の非水電解液二次電池用セパレータを用いた非水電解液二次電池。
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US10601011B2 (en) | 2015-06-29 | 2020-03-24 | Zeon Corporation | Composition for secondary battery porous membrane, porous membrane for secondary battery, and secondary battery |
KR20180030666A (ko) * | 2015-07-15 | 2018-03-23 | 미쯔비시 케미컬 주식회사 | 적층 다공 필름, 비수 전해액 이차 전지용 세퍼레이터, 비수 전해액 이차 전지, 및 적층 다공 필름의 제조 방법 |
CN105742551A (zh) * | 2016-03-23 | 2016-07-06 | 上海恩捷新材料科技股份有限公司 | 一种电化学装置隔离膜及其制备方法和用途 |
CN110352514B (zh) | 2017-11-28 | 2023-02-03 | 旭化成株式会社 | 蓄电装置用分隔件及其制造方法、以及蓄电装置及其制造方法 |
CN108123089A (zh) * | 2017-12-12 | 2018-06-05 | 上海恩捷新材料科技股份有限公司 | 隔离膜及电化学装置 |
JP7034842B2 (ja) * | 2018-06-08 | 2022-03-14 | 旭化成株式会社 | 多層セパレータ |
CN112635916A (zh) * | 2020-12-26 | 2021-04-09 | 宁德卓高新材料科技有限公司 | 一种陶瓷复合隔膜及其制备方法及电池 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011018590A (ja) * | 2009-07-10 | 2011-01-27 | Hitachi Maxell Ltd | 絶縁層形成用スラリー、リチウムイオン二次電池用セパレータおよびその製造方法、並びにリチウムイオン二次電池 |
WO2012014616A1 (ja) * | 2010-07-30 | 2012-02-02 | 三洋電機株式会社 | 非水電解質二次電池 |
WO2012165624A1 (ja) * | 2011-06-03 | 2012-12-06 | 富士シリシア化学株式会社 | セパレータ、電気化学素子、及びセパレータの製造方法 |
JP2014056843A (ja) * | 2008-01-29 | 2014-03-27 | Hitachi Maxell Ltd | 電気化学素子用セパレータおよび電気化学素子 |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007188777A (ja) * | 2006-01-13 | 2007-07-26 | Sony Corp | セパレータおよび非水電解質電池 |
JP5015474B2 (ja) | 2006-02-24 | 2012-08-29 | 帝人株式会社 | 電池用セパレータ及びリチウムイオン二次電池、電気二重層キャパシタ |
JP4958484B2 (ja) | 2006-03-17 | 2012-06-20 | 三洋電機株式会社 | 非水電解質電池及びその製造方法 |
JP2007273123A (ja) * | 2006-03-30 | 2007-10-18 | Matsushita Electric Ind Co Ltd | 非水電解質二次電池とその製造方法 |
JP5095121B2 (ja) | 2006-04-28 | 2012-12-12 | パナソニック株式会社 | 非水電解質二次電池用セパレータおよび非水電解質二次電池 |
JP2008016238A (ja) | 2006-07-04 | 2008-01-24 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池 |
JP5657856B2 (ja) | 2007-01-29 | 2015-01-21 | 日立マクセル株式会社 | 多孔質膜、電池用セパレータおよびリチウム二次電池 |
JP2008186721A (ja) | 2007-01-30 | 2008-08-14 | Asahi Kasei Chemicals Corp | 高耐熱性と高透過性を兼ね備えた多孔膜およびその製法 |
CN101600571A (zh) | 2007-01-30 | 2009-12-09 | 旭化成电子材料株式会社 | 多层多孔膜及其制造方法 |
KR100754746B1 (ko) * | 2007-03-07 | 2007-09-03 | 주식회사 엘지화학 | 다공성 활성층이 코팅된 유기/무기 복합 분리막 및 이를구비한 전기화학소자 |
KR100971110B1 (ko) * | 2007-06-06 | 2010-07-20 | 데이진 가부시키가이샤 | 비수계 2 차 전지용 세퍼레이터 및 비수계 2 차 전지 |
JP2008305662A (ja) * | 2007-06-07 | 2008-12-18 | Sony Corp | 非水電解質二次電池 |
JP4748136B2 (ja) * | 2007-10-03 | 2011-08-17 | ソニー株式会社 | 耐熱絶縁層付きセパレータ及び非水電解質二次電池 |
JP5361207B2 (ja) | 2008-02-20 | 2013-12-04 | 住友化学株式会社 | 多孔性フィルムを有するセパレータ |
CN102089901B (zh) * | 2008-07-16 | 2015-07-01 | 东丽株式会社 | 蓄电装置用隔膜 |
JP4685974B2 (ja) | 2009-02-24 | 2011-05-18 | 帝人株式会社 | 非水系二次電池用多孔膜、非水系二次電池用セパレータ、非水系二次電池用吸着剤および非水系二次電池 |
JP5412937B2 (ja) * | 2009-04-27 | 2014-02-12 | ソニー株式会社 | 非水電解質組成物及び非水電解質二次電池 |
WO2010134585A1 (ja) * | 2009-05-21 | 2010-11-25 | 旭化成イーマテリアルズ株式会社 | 多層多孔膜 |
JP5226128B2 (ja) * | 2009-06-30 | 2013-07-03 | パナソニック株式会社 | 非水電解質二次電池用負極及びその製造方法並びに非水電解質二次電池 |
KR101679451B1 (ko) | 2009-08-06 | 2016-11-24 | 스미또모 가가꾸 가부시끼가이샤 | 다공질 필름, 전지용 세퍼레이터 및 전지 |
JP5399190B2 (ja) | 2009-09-29 | 2014-01-29 | 古河電池株式会社 | 非水電解質二次電池用セパレータの製造方法 |
JP2011108443A (ja) * | 2009-11-16 | 2011-06-02 | Teijin Ltd | 非水系二次電池用セパレータおよび非水系二次電池 |
US10312491B2 (en) * | 2009-12-04 | 2019-06-04 | Murata Manufacturing Co., Ltd. | Separator and battery |
CN101789499B (zh) * | 2010-01-19 | 2012-04-25 | 中国海诚工程科技股份有限公司 | 一种锂离子电池隔膜的涂层组合物及泡沫施胶方法 |
KR101251437B1 (ko) * | 2010-03-23 | 2013-04-05 | 데이진 가부시키가이샤 | 폴리올레핀 미다공막, 비수계 2차 전지용 세퍼레이터, 비수계 2차 전지 및 폴리올레핀 미다공막의 제조 방법 |
WO2011129169A1 (ja) | 2010-04-16 | 2011-10-20 | 日立マクセル株式会社 | 電気化学素子用セパレータおよびそれを用いた電気化学素子、並びにその電気化学素子用セパレータの製造方法 |
KR101921659B1 (ko) | 2010-09-30 | 2018-11-26 | 제온 코포레이션 | 이차 전지 다공막 슬러리, 이차 전지 다공막, 이차 전지 전극, 이차 전지 세퍼레이터, 이차 전지, 및 이차 전지 다공막의 제조 방법 |
CN103328209B (zh) | 2011-01-20 | 2015-05-06 | 东丽株式会社 | 多孔质层合膜、蓄电装置用隔板及蓄电装置 |
CN103403919B (zh) | 2011-02-25 | 2016-10-26 | 日本瑞翁株式会社 | 二次电池用多孔膜、二次电池多孔膜用浆料及二次电池 |
WO2013005796A1 (ja) | 2011-07-06 | 2013-01-10 | 日本ゼオン株式会社 | 二次電池用多孔膜、二次電池用セパレーター及び二次電池 |
KR101488918B1 (ko) * | 2012-02-29 | 2015-02-03 | 제일모직 주식회사 | 밀도가 조절된 코팅층을 포함하는 분리막 및 이를 이용한 전지 |
JP6179507B2 (ja) | 2012-04-13 | 2017-08-16 | 東レ株式会社 | 積層多孔質膜、電池用セパレーター及び電池 |
CN103000848B (zh) | 2012-11-29 | 2016-09-07 | 东莞新能源科技有限公司 | 复合多孔性隔膜及其制备方法 |
JP6186852B2 (ja) | 2013-04-30 | 2017-08-30 | 日本ゼオン株式会社 | 二次電池多孔膜用スラリー組成物、二次電池用電極、二次電池用セパレータおよび二次電池 |
-
2014
- 2014-07-29 JP JP2014153627A patent/JP6094542B2/ja active Active
-
2015
- 2015-07-02 US US14/787,971 patent/US10062888B2/en active Active
- 2015-07-02 KR KR1020157030944A patent/KR101826793B1/ko active IP Right Review Request
- 2015-07-02 WO PCT/JP2015/069109 patent/WO2016017366A1/ja active Application Filing
- 2015-07-02 KR KR1020187003239A patent/KR20180015296A/ko active Application Filing
- 2015-07-02 CN CN201580000673.XA patent/CN105493313B/zh active Active
-
2018
- 2018-07-25 US US16/044,779 patent/US20180331339A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014056843A (ja) * | 2008-01-29 | 2014-03-27 | Hitachi Maxell Ltd | 電気化学素子用セパレータおよび電気化学素子 |
JP2011018590A (ja) * | 2009-07-10 | 2011-01-27 | Hitachi Maxell Ltd | 絶縁層形成用スラリー、リチウムイオン二次電池用セパレータおよびその製造方法、並びにリチウムイオン二次電池 |
WO2012014616A1 (ja) * | 2010-07-30 | 2012-02-02 | 三洋電機株式会社 | 非水電解質二次電池 |
WO2012165624A1 (ja) * | 2011-06-03 | 2012-12-06 | 富士シリシア化学株式会社 | セパレータ、電気化学素子、及びセパレータの製造方法 |
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US20180331339A1 (en) | 2018-11-15 |
KR20180015296A (ko) | 2018-02-12 |
KR101826793B1 (ko) | 2018-02-07 |
US10062888B2 (en) | 2018-08-28 |
JP2016031833A (ja) | 2016-03-07 |
CN105493313B (zh) | 2019-05-03 |
CN105493313A (zh) | 2016-04-13 |
US20170149037A1 (en) | 2017-05-25 |
JP6094542B2 (ja) | 2017-03-15 |
KR20160117154A (ko) | 2016-10-10 |
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