WO2016043142A1 - Séparateur d'élément électrochimique et élément électrochimique obtenu en l'utilisant - Google Patents

Séparateur d'élément électrochimique et élément électrochimique obtenu en l'utilisant Download PDF

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Publication number
WO2016043142A1
WO2016043142A1 PCT/JP2015/075915 JP2015075915W WO2016043142A1 WO 2016043142 A1 WO2016043142 A1 WO 2016043142A1 JP 2015075915 W JP2015075915 W JP 2015075915W WO 2016043142 A1 WO2016043142 A1 WO 2016043142A1
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WIPO (PCT)
Prior art keywords
particle layer
inorganic particle
separator
nonwoven fabric
electrochemical element
Prior art date
Application number
PCT/JP2015/075915
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English (en)
Japanese (ja)
Inventor
友洋 佐藤
鬼頭　昌利
Original Assignee
三菱製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015158617A external-priority patent/JP6033933B2/ja
Application filed by 三菱製紙株式会社 filed Critical 三菱製紙株式会社
Priority to CN201580049941.7A priority Critical patent/CN106716680B/zh
Priority to EP15843044.7A priority patent/EP3196960B1/fr
Priority to US15/511,872 priority patent/US20170294637A1/en
Publication of WO2016043142A1 publication Critical patent/WO2016043142A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an electrochemical element separator and an electrochemical element using the same.
  • the electrochemical element has a built-in electrochemical element separator.
  • the separator for electrochemical elements plays a role of preventing direct contact between the positive electrode and the negative electrode in the electrochemical element.
  • the separator for electrochemical elements separates the positive electrode and the negative electrode so as not to cause an internal short circuit (internal short circuit).
  • an internal short circuit internal short circuit
  • the separator for electrochemical elements needs to be porous.
  • a resin porous film made of a polyolefin resin such as polyethylene or polypropylene has been conventionally used.
  • a resin porous membrane is used as a separator for a lithium ion secondary battery, the function of isolating the positive and negative electrodes is lost due to melting and shrinkage when the battery abnormally generates heat, resulting in a significant internal short circuit. There was a problem that caused.
  • a lithium ion secondary comprising an inorganic particle layer formed by applying inorganic particles such as alumina, boehmite, magnesium oxide, magnesium hydroxide to a nonwoven fabric substrate made of highly heat-resistant fibers.
  • Battery separators have been proposed (see, for example, Patent Documents 1 to 4).
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • such lithium-ion secondary battery separators are designed to reduce the thickness of the entire lithium-ion secondary battery separator by reducing the thickness of the nonwoven fabric substrate or inorganic particle layer in order to reduce the internal resistance.
  • pinholes are easily generated, and internal short circuit is easily caused.
  • a capacitor which is another electrochemical element, has a large electric capacity and has high stability against repeated charge and discharge, and is therefore widely used in applications such as a power supply used in vehicles and electrical equipment.
  • a capacitor separator used in a capacitor conventionally, a paper mainly composed of a beaten product of solvent-spun cellulose fiber and regenerated cellulose fiber (for example, see Patent Documents 5 to 7) and a nonwoven fabric containing synthetic fibers (for example, Patent Document 8) is used.
  • a separator for example, see Patent Document 9 made of a nonwoven fabric base material and inorganic particles has been disclosed.
  • the capacitor separators described in Patent Documents 5 to 9 have a problem that, when the thickness is reduced in order to reduce the internal resistance, pinholes are likely to occur and internal short-circuiting is likely to occur. .
  • An object of the present invention is to provide a separator for an electrochemical element having excellent production stability, few pinholes and low internal resistance, and an electrochemical element using the same.
  • the present inventors have found the following invention as a means for solving the above problems.
  • the nonwoven fabric substrate is a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m;
  • an inorganic particle layer As the inorganic particle layer, an inorganic particle layer A containing magnesium hydroxide having an average particle size of 2.0 to 4.0 ⁇ m, an inorganic particle layer B containing magnesium hydroxide having an average particle size of 0.5 ⁇ m or more and less than 2.0 ⁇ m,
  • a separator for an electrochemical element having a configuration in which an inorganic particle layer A and an inorganic particle layer B are laminated in this order on one surface of the nonwoven fabric substrate.
  • the nonwoven fabric substrate is a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m;
  • an inorganic particle layer containing magnesium hydroxide having an average particle size of 2.0 to 4.0 ⁇ m
  • a separator for an electrochemical element characterized in that an inorganic particle layer A is provided on one side of the nonwoven fabric substrate and an inorganic particle layer B is provided on the other side.
  • the nonwoven fabric base material mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m has high strength, when an inorganic particle layer containing magnesium hydroxide is provided as inorganic particles, a coating containing inorganic particles is provided.
  • the liquid can be given sufficient strength to be applied to the nonwoven fabric substrate.
  • the inorganic particle layer A contains magnesium hydroxide having an average particle diameter of 2.0 to 4.0 ⁇ m as inorganic particles, and the inorganic particle layer B is water having an average fiber diameter of 0.5 ⁇ m or more and less than 2.0 ⁇ m as inorganic particles.
  • the average particle diameter of magnesium hydroxide contained in the inorganic particle layer A is larger than the average particle diameter of magnesium hydroxide contained in the inorganic particle layer B. Therefore, compared with the inorganic particle layer B, the inorganic particle layer A is less likely to permeate into the nonwoven fabric base material and pinholes are less likely to occur, but the thickness tends to be slightly thicker.
  • the inorganic particle layer B tends to permeate into the nonwoven fabric substrate, and compared to the inorganic particle layer A, pinholes are likely to occur, but the thickness tends to be thin.
  • the inorganic particle layer B bleeds into the nonwoven fabric substrate.
  • the inorganic particle layer A can prevent the formation of a uniform inorganic particle layer on the surface of the separator for electrochemical devices. As a result, even when the electrochemical element separator is thin, the generation of pinholes can be suppressed, and the internal resistance can be lowered.
  • the generation of pinholes can be similarly suppressed, and the thickness is thin.
  • the internal resistance can be lowered.
  • the inorganic particle layer A and the inorganic particle layer B are easy to adhere to the nonwoven fabric base material and the layer strength becomes strong, there is an effect that the defect is hardly generated during the manufacture of the separator and the manufacturing stability is excellent.
  • the separator for electrochemical devices (1) of the present invention comprises magnesium hydroxide having an average particle diameter of 2.0 to 4.0 ⁇ m on one side of a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m.
  • a separator for an electrochemical element characterized in that an inorganic particle layer A containing and an inorganic particle layer B containing magnesium hydroxide having an average particle diameter of 0.5 ⁇ m or more and less than 2.0 ⁇ m are laminated in this order. is there.
  • the separator for electrochemical devices (2) of the present invention contains magnesium hydroxide having an average particle diameter of 2.0 to 4.0 ⁇ m on one surface of a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m.
  • An electrochemical device comprising an inorganic particle layer A and an inorganic particle layer B containing magnesium hydroxide having an average particle size of 0.5 ⁇ m or more and less than 2.0 ⁇ m on the other surface Separator.
  • the nonwoven fabric substrate used in the separator for electrochemical devices of the present invention is a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m.
  • the content of the synthetic resin fiber having an average fiber diameter of 1 to 20 ⁇ m is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass with respect to all fibers constituting the nonwoven fabric substrate. It is at least mass%.
  • the strength of the nonwoven fabric substrate may be weakened.
  • the synthetic resin fiber having an average fiber diameter of 1 to 20 ⁇ m is a fiber that does not have fibrils, and is a so-called staple fiber (short fiber).
  • the average fiber diameter of the synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m is 1 to 20 ⁇ m, more preferably 1 to 15 ⁇ m, and further preferably 1 to 10 ⁇ m.
  • the average fiber diameter is less than 1 ⁇ m, the fibers are too thin and the inorganic particle layer is less likely to penetrate into the nonwoven fabric substrate, making it difficult to reduce the thickness of the separator.
  • the average fiber diameter is larger than 20 ⁇ m, it is difficult to reduce the thickness of the nonwoven fabric substrate itself, and it is difficult to reduce the thickness of the separator.
  • the nonwoven fabric base material can contain synthetic resin fibers having an average fiber diameter of less than 1 ⁇ m, synthetic resin fibers having an average fiber diameter of more than 20 ⁇ m, fibrillated products of synthetic resins and synthetic resin fibers, fibrils or pulped products, In order to obtain the effect of reducing the thickness of the separator, synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m are the main component of the nonwoven fabric substrate.
  • the average fiber diameter in the present invention refers to 30 fibers having a cross section perpendicular to or approximately perpendicular to the length direction of the fibers of the fibers forming the nonwoven fabric substrate, based on a scanning electron micrograph of the cross section of the nonwoven fabric substrate. It is the average value which selected this and measured the fiber diameter.
  • Synthetic resin fibers may be melted or deformed by heat or pressure. In that case, the cross-sectional area is measured, and the fiber diameter in terms of a perfect circle is calculated.
  • the fiber length of the synthetic resin fiber having an average fiber diameter of 1 to 20 ⁇ m is preferably 1 to 15 mm, more preferably 2 to 10 mm, and further preferably 2 to 5 mm. If the fiber length is shorter than 1 mm, it may fall off from the nonwoven fabric substrate. If the length is longer than 15 mm, the fibers may become tangled and become lumpy, which may cause uneven thickness.
  • the resin constituting the synthetic fiber examples include polyolefin (polyolefin), polyester (polyester), polyvinyl acetate, ethylene-vinyl acetate copolymer, polyamide (polyamide). ) Series, acrylic series, polyvinyl chloride series, polyvinylidene chloride series, polyvinyl ether series, polyvinyl ketone series, polyether ether series Alcohol (polyvinyl alc hol), diene, polyurethane (polyurethane), phenol, melamine, furan, urea, aniline, unsaturated polyester (Unsaturated polymer), Alkyd, Fluorocarbon, Silicone, Polyamideimide, Polyphenylenesulfide, Polyimidepolyimide, Polyimidepolyimide, Polyimidepolyimide, Polyimidepolyimide, Polyimidepolyimide, Polyimidepolyimide Polyazomethine (polyazomethine) ) Series, polyesteramide series,
  • derivatives of these resins can also be used.
  • these resins it is preferable to use a polyester resin, an acrylic resin, or a polyolefin resin in order to increase the adhesiveness with the inorganic particle layer.
  • a polyester resin, an acrylic resin, or a polyamide resin it is preferable to use a polyester resin, an acrylic resin, or a polyamide resin.
  • polyester resin examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polyethylene phthalate (PTT).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT polytrimethylene terephthalate
  • PTT polyethylene phthalate
  • Resin polybutylene naphthalate
  • polyethylene isophthalate wholly aromatic polyester, and the like. It is.
  • derivatives of these resins can also be used.
  • a polyethylene terephthalate resin is preferable in order to improve heat resistance, resistance to electrolytic solution, and adhesion to the inorganic particle layer.
  • acrylic resins include those made of a 100% acrylonitrile polymer, acrylic acid, methacrylic acid, acrylic ester, acrylate, and methacrylic acid.
  • acrylic acid derivatives such as esters (methacrylic ester), copolymers of vinyl acetate and the like.
  • polystyrene resin examples include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl alcohol copolymer, olefin copolymer, and the like. From the viewpoint of heat resistance, polypropylene, polymethylpentene, ethylene-vinyl alcohol copolymer, olefin copolymer and the like can be mentioned.
  • polyamide resin examples include aliphatic polyamides such as nylon, poly-p-phenylene terephthalamide, and copoly (para-phenylene-3,4′-oxydiphenylene terephthalamide). ) (Copoly (para-phenylene-3,4'-oxydiphenylene terephthalic amide)), poly-m-phenylene isophthalamide (poly-m-phenylene isophthalamide), wholly aromatic polyamides, wholly aromatic polyamides Have a fatty chain as part of the main chain That semi-aromatic polyamide (semi-aromatic polyamide) can be mentioned.
  • aliphatic polyamides such as nylon, poly-p-phenylene terephthalamide, and copoly (para-phenylene-3,4′-oxydiphenylene terephthalamide).
  • poly-m-phenylene isophthalamide poly-m-phenylene isophthalamide
  • wholly aromatic polyamides wholly aromatic polyamides Have a
  • Semi-aromatic refers to a substance having, for example, a fatty chain as a part of the main chain.
  • the wholly aromatic polyamide may be either a para type or a meta type.
  • the synthetic resin fiber may be a fiber (single fiber) made of a single resin, or may be a fiber (composite fiber) made of two or more kinds of resins.
  • the synthetic resin fiber contained in the nonwoven fabric substrate may be one type or a combination of two or more types. Examples of the composite fiber include a core-sheath type, an eccentric type, a side-by-side type, a sea-island type, an orange type, and a multiple bimetal type. You may use the fiber which divided
  • the non-woven fabric substrate may contain fibers other than synthetic resin fibers.
  • fibers other than synthetic resin fibers For example, solvent-spun cellulose or regenerated cellulose short fibers, fibrillated products, natural cellulose fibers, natural cellulose fiber pulped products, fibrillated products, inorganic fibers, and the like may be contained.
  • the basis weight of the nonwoven fabric substrate is preferably 6 to 20 g / m 2 , more preferably 7 to 18 g / m 2 , and still more preferably 8 to 15 g / m 2 .
  • the basis weight is measured based on the method defined in JIS P 8124 (paper and paperboard—basis weight measurement method).
  • the thickness of the nonwoven fabric substrate is preferably 9 to 30 ⁇ m, more preferably 10 to 27 ⁇ m, and still more preferably 11 to 24 ⁇ m. When the thickness is less than 9 ⁇ m, sufficient strength of the nonwoven fabric substrate may not be obtained. If the thickness exceeds 30 ⁇ m, it may be difficult to reduce the thickness of the separator.
  • thickness means the value measured based on the method prescribed
  • a production method in which a nonwoven fabric is obtained by forming a fiber web and bonding, fusing and entanglement of fibers in the fiber web can be used.
  • the obtained nonwoven fabric may be used as it is as a nonwoven fabric substrate, or may be used as a laminate comprising a plurality of nonwoven fabrics.
  • the method for producing the fiber web include dry methods such as a carding method, an airlay method, a spunbond method, and a meltblow method; wet methods such as a wet papermaking method; (Electrospinning) method and the like.
  • the web obtained by a wet method is homogeneous and dense, and can be suitably used as a nonwoven fabric substrate.
  • fibers are dispersed in water to form a uniform papermaking slurry, and this papermaking slurry is made into a fiber web using a papermaking machine having at least one of a papermaking system such as a circular net type, a long net type, and an inclined type. How to get.
  • a papermaking system such as a circular net type, a long net type, and an inclined type. How to get.
  • a hydroentangled (spun lace) method As a method for producing a nonwoven fabric substrate from a fiber web, a hydroentangled (spun lace) method, a needle punch method, a binder bonding method (thermal bond, thermal bond), or the like can be used.
  • a binder synthetic resin fiber when the wet method is used with emphasis on uniformity, it is preferable to bond a binder synthetic resin fiber by performing a binder bonding method.
  • a uniform nonwoven fabric is formed from a uniform web by the binder bonding method. It is preferable to adjust the thickness or make the thickness uniform by applying pressure to the wet nonwoven fabric produced in this way with a calendar or the like. However, it is preferable to apply pressure at a temperature at which the synthetic resin fiber for binder does not form a film (temperature lower by 20 ° C. or more than the melting point or softening point of the synthetic resin fiber for binder).
  • the inorganic particle layer A is formed by applying a coating liquid a containing magnesium hydroxide having an average particle size of 2.0 to 4.0 ⁇ m on one side of the nonwoven fabric substrate. It is obtained by the method of coating on.
  • the average particle diameter is a volume average particle diameter (D50) obtained from a particle size distribution measurement by a laser diffraction method.
  • the average particle diameter of magnesium hydroxide in the inorganic particle layer A is more preferably 2.2 to 3.7 ⁇ m, still more preferably 2.5 to 3.5 ⁇ m.
  • the coating amount (absolute dryness) of the inorganic particle layer A is preferably 2.0 to 8.0 g / m 2 , more preferably 2.5 to 7.0 g / m 2 , and still more preferably 3. 0 to 6.0 g / m 2 .
  • the coating amount exceeds 8.0 g / m 2 , the electrochemical element separator may be too thick.
  • the coating amount is less than 2.0 g / m 2 , pinholes are likely to occur.
  • the inorganic particle layer B layer is formed by coating the inorganic particle layer A with a coating liquid b containing magnesium hydroxide having an average particle size of 0.5 ⁇ m or more and 2.0 ⁇ m or less. It is obtained by the method.
  • the inorganic particle layer B is coated with the coating liquid b on the other surface of the nonwoven fabric substrate opposite to the surface on which the inorganic particle layer A is provided. It is obtained by the method of crafting.
  • the average particle diameter of magnesium hydroxide in the inorganic particle layer B is more preferably 0.5 to 1.5 ⁇ m, still more preferably 0.5 to 1.3 ⁇ m, and particularly preferably 0.5 to 1.0 ⁇ m. It is.
  • the coating amount (absolute dryness) of the inorganic particle layer B is preferably 2.0 to 8.0 g / m 2 , more preferably 2.5 to 7.0 g / m 2 , and still more preferably 3. 0 to 6.0 g / m 2 .
  • the coating amount exceeds 8.0 g / m 2 , the electrochemical element separator may be too thick.
  • the coating amount is less than 2.0 g / m 2 , pinholes are likely to occur.
  • the medium for preparing the coating liquid containing magnesium hydroxide is not particularly limited as long as it can uniformly dissolve or disperse the binder and magnesium hydroxide.
  • aromatic hydrocarbons such as toluene, tetrahydrofuran (cyclic ethers such as tetrahydrofuran (THF), ketones such as methyl ethyl ketone (MEK), alcohols such as isopropanol, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (N, N-Dimethylacetamide, DMAc), N, N-dimethylformamide (N, N-dimethylformamide, DMF), dimethyl sulfoxide (Dimet) yl sulfoxide, DMSO), can be used, such as optionally water. Moreover, you may mix and use these media as needed.
  • the medium to be used is preferably a medium that does not expand or dissolve the nonwoven fabric substrate.
  • Examples of the method for applying the coating liquid include a blade, a rod, a reverse roll, a lip, a die, a curtain, an air knife, and the like.
  • Various coating methods, flexographic, screen, offset, gravure, ink jet, and other printing methods, transfer methods such as roll transfer and film transfer are required. It can be selected and used accordingly.
  • the basis weight of the separator for electrochemical devices of the present invention is preferably 10 to 36 g / m 2 , more preferably 12 to 32 g / m 2 , and further preferably 14 to 27 g / m 2 .
  • the basis weight exceeds 36 g / m 2 , the internal resistance may become too high.
  • the basis weight is less than 10 g / m 2 , pinholes are likely to occur or it may be difficult to obtain sufficient strength.
  • the thickness of the separator for an electrochemical element of the present invention is preferably 10 to 40 ⁇ m, more preferably 11 to 30 ⁇ m, and further preferably 12 to 25 ⁇ m.
  • the thickness exceeds 40 ⁇ m, the electrochemical element separator becomes too thick, and the internal resistance may increase. If the thickness is less than 10 ⁇ m, pinholes are likely to occur or it may be difficult to obtain sufficient strength.
  • the separator for electrochemical elements of the present invention is particularly suitably used for electrochemical elements such as lithium ion secondary batteries and capacitors.
  • Lithium ion secondary battery As the negative electrode active material of the lithium ion secondary battery in the present invention, carbon materials such as graphite and coke, metallic lithium, aluminum (Al), silicon (Si), tin (Sn), nickel (Ni), lead (Pb) Metals such as alloys of one or more (semi) metals and lithium (Li) selected from: SiO, SnO, Fe 2 O 3 , WO 2 , Nb 2 O 5 , Li 4/3 Ti 5/3 O 4 Oxides and nitrides such as Li 0.4 CoN are used.
  • carbon materials such as graphite and coke, metallic lithium, aluminum (Al), silicon (Si), tin (Sn), nickel (Ni), lead (Pb) Metals such as alloys of one or more (semi) metals and lithium (Li) selected from: SiO, SnO, Fe 2 O 3 , WO 2 , Nb 2 O 5 , Li 4/3 Ti 5/3 O 4 Oxides and n
  • Examples of the positive electrode active material include lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium titanium oxide (LTO), lithium nickel manganese oxide (LTO), lithium nickel manganese oxide (LTO), lithium nickel manganese oxide (LTO), lithium nickel manganese oxide (LTO), lithium nickel manganese oxide (LTO), and lithium nickel manganese oxide (LTO).
  • Lithium-nickel-manganese oxide) and lithium iron phosphate are used.
  • Lithium iron phosphate further includes manganese (Mn), chromium (Cr), cobalt (Co), copper (Cu), nickel, vanadium (V), molybdenum (Mo), titanium (Ti), zinc (Zn), It may be a composite with one or more metals selected from aluminum (Al), gallium (Ga), magnesium (Mg), boron (B), and niobium (Nb).
  • Examples of the electrolyte of the lithium ion secondary battery include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, dimethoxymethane, and dimethoxymethane.
  • a solution obtained by dissolving a lithium salt in an organic solvent such as a mixed solvent thereof is used.
  • Examples of the lithium salt include lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ).
  • the capacitor in the present invention means an electric double layer capacitor, a lithium ion capacitor, a hybrid capacitor, or a redox capacitor.
  • the electric double layer capacitor is charged with an electric double layer formed at the interface between the electrode and the electrolyte.
  • the electrode active material carbon materials such as activated carbon, carbon black, carbon aerogel, carbon nanotube, and non-porous carbon are mainly used.
  • the electrolytic solution include an aqueous solution in which an ion dissociable salt is dissolved, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, acetonitrile, ⁇ -butyrolactone, N, N-dimethylformamide, tetrahydrofuran.
  • Ion-dissociable salts in organic solvents such as dimethoxyethane, dimethoxymethane, sulfolane, dimethyl sulfoxide, ethylene glycol, propylene glycol, methyl cellosolve, and mixed solvents thereof Ionic liquid (solid molten salt), etc. It is not limited.
  • the negative electrode active material is a material capable of reversibly supporting lithium ions
  • the positive electrode active material is a material capable of reversibly supporting lithium ions and / or anions. This is a capacitor in which lithium ions are supported.
  • the negative electrode active material include graphite, non-graphitizable carbon, polyacene organic semiconductor, and lithium titanate.
  • the positive electrode active material include conductive polymers such as polypyrrole, polythiophene, polyaniline, polyacetylene, activated carbon, and polyacene organic semiconductor.
  • As the electrolytic solution an organic solvent in which a lithium salt is dissolved is used.
  • lithium salt examples include LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , and Li (C 2 F 5 SO 2 ) N.
  • organic solvent examples include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, acetonitrile, ⁇ -butyrolactone, N, N-dimethylformamide, tetrahydrofuran, dimethoxyethane, dimethoxymethane, sulfolane, dimethyl sulfoxide, ethylene glycol, propylene glycol, Examples thereof include methyl cellosolve and mixed solvents thereof.
  • a hybrid capacitor is a capacitor in which the reaction mechanism or electrode material of the positive electrode and the negative electrode are different.
  • the negative electrode is an oxidation-reduction reaction
  • the positive electrode is an electric double layer reaction.
  • the negative electrode active material of the hybrid capacitor include activated carbon, graphite, hard carbon, polyacene, metal oxide such as Li 4 Ti 5 O 12 , and n-type conductive polymer.
  • the positive electrode active material include activated carbon, metal oxides such as MnO 2 , LiCoO 2 , ruthenium oxide, graphite, and p-type conductive polymer.
  • a redox capacitor has a storage and discharge mechanism that uses all or part of oxidation / reduction of an electrode active material, adsorption / desorption of ions on an electrode surface, and charge / discharge in an electric double layer.
  • electrode active materials of redox capacitors include metal oxides such as ruthenium oxide, iridium oxide, titanium oxide, zirconium oxide, nickel oxide, vanadium oxide, tungsten oxide, manganese oxide, and cobalt oxide, and composites of these metal oxides.
  • lithium metal oxides such as LiFePO 4 , polypyrrole, polyaniline, polythiophene, polyacene, derivatives thereof, polyfluorene derivatives, polyquinoxaline derivatives, polyindole, polyindole, cyclic Examples include quindole polymers, 1,5-diaminoanthraquinone, 1,4-benzoquinone, complexes of graphite with these quinone compounds, and metal complex polymers.
  • the electrolytic solution examples include an aqueous solution in which an ion dissociable salt is dissolved, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, acetonitrile, ⁇ -butyrolactone, N, N-dimethylformamide, tetrahydrofuran, dimethoxyethane, dimethoxymethane, and sulfolane. , Dimethyl sulfoxide, ethylene glycol, propylene glycol, methyl cellosolve, ionic liquid (solid molten salt), etc., in which an ionic dissociable salt is dissolved in an organic solvent such as a mixed solvent thereof. Is not to be done.
  • PET1 Oriented crystallized polyethylene terephthalate fiber with average fiber diameter of 2.5 ⁇ m and fiber length of 3 mm
  • PET2 Oriented crystallized polyethylene terephthalate fiber with average fiber diameter of 3.2 ⁇ m and fiber length of 3 mm
  • PET3 Average fiber diameter of 4.3 ⁇ m, fiber length of 3 mm
  • PA1 Total aromatic polyamide fiber (copoly (para-phenylene-3,4'-oxydiphenylene terephthalamide), Copoly (p-phenylene-3,4'-oxydiphenylene terephthalamide) having an average fiber diameter of 8.1 ⁇ m and a fiber length of 5 mm. ))
  • Nonwoven fabric substrate 1-5 Slurries 1 to 3 were subjected to wet paper making using a circular net / tilted combination paper machine to produce nonwoven substrates 1 to 5 shown in Table 2.
  • the thickness was determined by using a heat calender device having a configuration of metal roll-resin roll (Shore hardness D92) under the conditions of a metal roll temperature of 195 ° C., a linear pressure of 200 kN / m, a processing speed of 10 m / min, and a nip (nip). Adjustment was performed by performing a thermal calendar process.
  • a coating liquid a2 was prepared in the same manner as the coating liquid a1, except that magnesium hydroxide having an average particle diameter of 2.0 ⁇ m was changed to magnesium hydroxide having an average particle diameter of 3.0 ⁇ m.
  • a coating liquid a3 was prepared in the same manner as the coating liquid a1, except that magnesium hydroxide having an average particle diameter of 2.0 ⁇ m was changed to magnesium hydroxide having an average particle diameter of 4.0 ⁇ m.
  • a coating solution b2 was prepared in the same manner as the coating solution b1, except that magnesium hydroxide having an average particle size of 0.5 ⁇ m was changed to magnesium hydroxide having an average particle size of 1.0 ⁇ m.
  • a coating solution b3 was prepared in the same manner as the coating solution b1, except that magnesium hydroxide having an average particle size of 0.5 ⁇ m was changed to magnesium hydroxide having an average particle size of 1.5 ⁇ m.
  • a coating solution c2 was prepared in the same manner as the coating solution c1 except that the alumina hydrate having an average particle size of 2.0 ⁇ m was changed to alumina hydrate having an average particle size of 0.5 ⁇ m.
  • Example 1-1 After coating and drying the coating liquid a1 on the nonwoven fabric substrate 1 with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 7.0 g / m 2 , On the same coated surface, the coating liquid b1 was coated and dried with a kiss reverse gravure coater so that the coating amount (absolutely dry) was 2.5 g / m 2 to obtain an electrochemical device separator.
  • Example 1-2 After coating and drying the coating liquid a2 on the nonwoven fabric substrate 2 with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 5.0 g / m 2 , the coating liquid a2 is further applied to the same coated surface.
  • the coating liquid b2 was coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) was 5.0 g / m 2 to obtain a separator for an electrochemical device.
  • Example 1-3 After coating and drying the coating liquid a3 on the nonwoven fabric substrate 3 with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 3.0 g / m 2 , the coating liquid a3 is further applied to the same coated surface.
  • the coating liquid b3 was coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) was 6.0 g / m 2 to obtain a separator for an electrochemical device.
  • Example 1-4 After coating and drying the coating liquid a1 on the nonwoven fabric substrate 4 with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 2.0 g / m 2 , the coating liquid a1 is further applied to the same coated surface.
  • the coating liquid b1 was coated and dried with a kiss reverse gravure coater so that the coating amount (absolutely dry) was 2.0 g / m 2 to obtain a separator for an electrochemical device.
  • Example 1-5 On the nonwoven fabric substrate 5, the coating liquid a1 is coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 8.0 g / m 2.
  • the coating liquid b1 was coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) was 8.0 g / m 2 to obtain a separator for an electrochemical device.
  • Example 2-1 After coating and drying the coating liquid a1 on the nonwoven fabric substrate 1 with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 7.0 g / m 2 , On the other surface, the coating liquid b1 is coated and dried with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 2.5 g / m 2 to obtain a separator for an electrochemical device. It was.
  • Example 2-2 After coating and drying the coating liquid a2 on the nonwoven fabric substrate 2 with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 5.0 g / m 2 , the nonwoven fabric substrate 2 is further coated. On the other surface, the coating liquid b2 is coated and dried with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 5.0 g / m 2, and an electrochemical element separator is formed. Obtained.
  • Example 2-3 After coating and drying the coating liquid a3 on the nonwoven fabric substrate 3 with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 3.0 g / m 2 , the nonwoven fabric substrate 3 is further coated. On the other surface, the coating liquid b3 is coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 7.0 g / m 2. Obtained.
  • Example 2-4 After coating and drying the coating liquid a1 on the nonwoven fabric substrate 4 with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 2.0 g / m 2 , the nonwoven fabric substrate 4 is further coated. On the other surface, the coating liquid b1 is coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 2.0 g / m 2, and an electrochemical element separator is formed. Obtained.
  • Example 2-5 After coating and drying the coating liquid a1 on the nonwoven fabric substrate 5 with a kiss reverse gravure coater so that the coating amount (absolute dryness) is 8.0 g / m 2 , the nonwoven fabric substrate 5 is further coated. On the other surface, the coating liquid b2 is coated and dried with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 8.0 g / m 2, and the electrochemical element separator is formed. Obtained.
  • Example 2-6 After coating and drying the coating liquid b1 on the nonwoven fabric substrate 2 with a kiss reverse gravure coater so that the coating amount (absolutely dry) is 3 g / m 2 , the nonwoven fabric substrate 2 is further coated. On one surface, the coating liquid a2 was coated and dried with a kiss reverse gravure coater so that the coating amount (absolute dryness) was 4 g / m 2 to obtain a separator for an electrochemical device.
  • a fiber C1 obtained by beating a solvent-spun cellulose fiber having an average fiber diameter of 10.0 ⁇ m and a fiber length of 4 mm using a refiner to a Canadian standard freeness (CSF) of 20 ml measured according to JIS P8121, and Manila hemp Then, using a refiner, the fiber C2 beaten until the CSF becomes 300 ml, a papermaking slurry prepared at a ratio of C1 / C2 70/30, and wet papermaking using a circular mesh / inclined combination papermaking machine.
  • a separator for an electrochemical device having an amount of 7.0 g / m 2 , a thickness of 20 ⁇ m, and a density of 0.35 g / cm 3 was produced.
  • A The occurrence of visual pinholes is not observed.
  • B There is a portion where transmitted light is observed slightly.
  • C Obviously many transmitted lights are observed.
  • A No damage is observed in the inorganic particle layer at the fold.
  • C Many cracks are seen in the inorganic particle layer in the crease portion.
  • Lithium ion secondary battery [Production of lithium ion secondary battery] Using each of the above-described separators for electrochemical devices, lithium manganate as the positive electrode, mesocarbon microbead as the negative electrode, and 1 mol / L diethyl carbonate (DEC) / lithium hexafluorophosphate (LiPF 6 ) as the electrolyte A lithium ion secondary battery having a design capacity of 30 mAh using a mixed solvent solution of ethylene carbonate (EC) (capacity ratio: 7/3) was produced.
  • EC ethylene carbonate
  • Electrode 0 10 parts by weight of polyvinylidene fluoride is dissolved in 90 parts by weight of N-methyl-2-pyrrolidone, and an average particle diameter of 5.0 ⁇ m using a phenol resin as a starting material, 80 parts by mass of powdered activated carbon having a specific surface area of 2000 m 2 / g, 10 parts by mass of acetylene black having an average particle diameter of 200 nm, and 300 parts by mass of N-methyl-2-pyrrolidone were added and mixed thoroughly with a mixing stirrer. An electrode slurry was obtained.
  • the electrode slurry is applied and dried using an applicator to an aluminum foil current collector having a thickness of 30 ⁇ m whose surface has been etched with hydrochloric acid, and then subjected to a press treatment using a roll press apparatus, and an electric double layer having a thickness of 150 ⁇ m.
  • An electrode for a capacitor was produced and designated as electrode 0.
  • the separators for electrochemical devices produced in Examples 1-1 to 1-5 were provided with inorganic particles on one side of a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m. Since the layer A and the inorganic particle layer B have a structure laminated in this order, there are few pinholes in the separator for an electrochemical element, and the internal resistance of the lithium ion secondary battery and capacitor using the separator is low. It was excellent. In addition, since the layer strength is strong, defects are unlikely to occur during the production of the separator, and the production stability is excellent.
  • the separators for electrochemical devices produced in Examples 2-1 to 2-6 are provided with the inorganic particle layer A on one side of a nonwoven fabric substrate mainly composed of synthetic resin fibers having an average fiber diameter of 1 to 20 ⁇ m.
  • the inorganic particle layer B is provided on the other surface, there are few pinholes in the separator for electrochemical elements, and the internal resistance of the lithium ion secondary battery and capacitor using the separator is low, which is excellent It was.
  • the layer strength is strong, defects are unlikely to occur during the production of the separator, and the production stability is excellent.
  • the separator for an electrochemical element produced in Comparative Example 1-2 does not include the inorganic particle layer B, and the coating amount of the inorganic particle layer A is larger than that of the separator for electrochemical element produced in Comparative Example 1-1. Although it was further increased, although the generation of pinholes was suppressed, the inorganic particle layer became too thick, and the internal resistance of the lithium ion secondary battery and capacitor deteriorated.
  • the separator for an electrochemical element produced in Comparative Example 1-3 does not include the inorganic particle layer A, and the inorganic particle layer B soaks into the nonwoven fabric base material to form a uniform inorganic particle layer on the separator surface. Since it was not possible, the occurrence of pinholes was observed.
  • the separator for an electrochemical element produced in Comparative Example 1-4 has a configuration in which an inorganic particle layer B and an inorganic particle layer A layer are laminated in this order on one side of a nonwoven fabric substrate. Since the inorganic particle layer B soaked into the nonwoven fabric base material and a uniform inorganic particle layer could not be formed on the separator surface, generation of pinholes was observed.
  • the separator for an electrochemical element produced in Comparative Example 1-5 has an inorganic particle layer C containing an alumina hydrate having an average particle diameter of 2.0 ⁇ m and an alumina having an average particle diameter of 0.5 ⁇ m on one side of a nonwoven fabric substrate.
  • the inorganic particle layer D containing a hydrate has a structure in which the layers are laminated in this order, but the layer strength is weaker than the separators for electrochemical devices produced in Examples 1-1 to 1-5. The production stability of was poor.
  • the inorganic particle layer A is provided on both surfaces of the nonwoven fabric base material.
  • the electrochemical element separator becomes thicker. As a result, the internal resistance of the lithium ion secondary battery and the capacitor deteriorated.
  • the inorganic particle layer B layer is provided on both surfaces of the nonwoven fabric base material.
  • the inorganic particle layer A is not included, the inorganic particle layer B is not a nonwoven fabric base material. It was easy to seep into the interior and pinholes were observed.
  • the separator for an electrochemical element produced in Comparative Example 2-3 was provided with an inorganic particle layer C containing alumina hydrate having an average particle diameter of 2.0 ⁇ m on one side of a nonwoven fabric substrate, and on the other side.
  • the inorganic particle layer D containing alumina hydrate having an average particle diameter of 0.5 ⁇ m is provided, but the layer strength is the same as that of the separator for an electrochemical element produced in Examples 2-1 to 2-6.
  • the separator was weaker and the manufacturing stability of the separator was poor.
  • the separator for an electrochemical element produced in Comparative Example 3-1 is a paper separator made of solvent-spun cellulose fiber C1 and Manila hemp fiber C2. However, since the thickness was as thin as 20 ⁇ m, generation of pinholes was observed.
  • the separator for electrochemical elements produced in Example 4 has a slightly lower basis weight and a slightly thinner thickness. Compared with the separators prepared in -1 to 1-3 and 1-5, in the pinhole evaluation, there was a portion where transmitted light was slightly observed.
  • the separator for an electrochemical element produced in Example 5 has a slightly higher basis weight and a slightly thicker thickness. Therefore, compared with the separator for an electrochemical element produced in Examples 1-1 to 1-4, lithium ion The internal resistance of the secondary battery and capacitor became slightly high.
  • the separator for electrochemical elements produced in Example 2-4 has a slightly lower basis weight and a slightly thinner thickness. Compared with the separators for electrochemical devices produced in Examples 2-1 to 2-3, 2-5, and 2-6, in the pinhole evaluation, there was a portion where a slight amount of transmitted light was observed.
  • the separator for an electrochemical element produced in Example 2-5 has a slightly higher basis weight and a slightly thicker thickness. Therefore, the separator for an electrochemical element in Examples 2-1 to 2-4 and 2-6 was compared. As a result, the internal resistance of the lithium ion secondary battery and the capacitor was slightly increased.
  • the inorganic particle layer B layer was first coated on the nonwoven fabric substrate, but the inorganic particle layer A was first coated on the nonwoven fabric substrate. Similar to the separators for electrochemical devices of -1 to 2-5, no pinholes were observed, and the internal resistance of the lithium ion secondary battery and capacitor was low and excellent.
  • a separator for an electrochemical element and an electrochemical element are suitable.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention a pour but de fournir : un séparateur d'élément électrochimique qui possède une excellente stabilité de fabrication, qui est exempt de piqûres et possède une faible résistance interne ; un élément électrochimique qui est obtenu en l'utilisant. L'invention concerne un séparateur d'élément électrochimique comportant : un substrat non tissé ; une couche de particules inorganiques qui contient des particules inorganiques. Le séparateur d'élément électrochimique est caractérisé : en ce que des fibres de résine synthétique ayant un diamètre moyen de fibre de 1 à 20 μm sont un constituant principal du substrat non tissé ; en ce que la couche de particules inorganiques comprend une couche de particules inorganiques A qui contient de l'hydroxyde de magnésium ayant un diamètre moyen de particule de 2,0 à 4,0 μm, et une couche de particules inorganiques B qui contient de l'hydroxyde de magnésium ayant un diamètre moyen de particule supérieur ou égal à 0,5 μm et inférieur à 2,0 μm ; en ce que la couche de particules inorganiques A et la couche de particules inorganiques B sont empilées dans cet ordre sur une surface du substrat non tissé ou en ce que la couche de particules inorganiques A est disposée sur une surface du substrat non tissé et la couche de particules inorganiques B est disposée sur son autre surface. L'élément électrochimique est obtenu en utilisant le séparateur d'élément électrochimique.
PCT/JP2015/075915 2014-09-17 2015-09-11 Séparateur d'élément électrochimique et élément électrochimique obtenu en l'utilisant WO2016043142A1 (fr)

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EP15843044.7A EP3196960B1 (fr) 2014-09-17 2015-09-11 Séparateur d'élément électrochimique et élément électrochimique obtenu en l'utilisant
US15/511,872 US20170294637A1 (en) 2014-09-17 2015-09-11 Separator for electrochemical device and electrochemical device including the separator

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017218701A (ja) * 2016-06-09 2017-12-14 三菱製紙株式会社 耐熱性湿式不織布
WO2018047742A1 (fr) * 2016-09-08 2018-03-15 三菱製紙株式会社 Substrat pour séparateurs de batterie au lithium-ion, et séparateur de batterie au lithium-ion
JP2018170215A (ja) * 2017-03-30 2018-11-01 三菱製紙株式会社 リチウムイオン電池セパレータ
CN109328408A (zh) * 2016-06-27 2019-02-12 日本高度纸工业株式会社 电化学元件用分隔件和电化学元件、汽车、电子设备
WO2019146626A1 (fr) 2018-01-25 2019-08-01 三菱製紙株式会社 Liquide de revêtement pour séparateurs pour batteries au lithium-ion, et séparateur pour batteries au lithium-ion
CN110114911A (zh) * 2016-12-27 2019-08-09 三菱制纸株式会社 锂离子电池隔板和锂离子电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000003834A (ja) * 1998-06-16 2000-01-07 Nippon Kodoshi Corp 電気二重層コンデンサ
JP2012134024A (ja) * 2010-12-22 2012-07-12 Mitsubishi Paper Mills Ltd リチウム二次電池用セパレータ
JP2014038974A (ja) * 2012-08-20 2014-02-27 Jm Energy Corp 蓄電デバイス

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000003834A (ja) * 1998-06-16 2000-01-07 Nippon Kodoshi Corp 電気二重層コンデンサ
JP2012134024A (ja) * 2010-12-22 2012-07-12 Mitsubishi Paper Mills Ltd リチウム二次電池用セパレータ
JP2014038974A (ja) * 2012-08-20 2014-02-27 Jm Energy Corp 蓄電デバイス

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3196960A4 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017218701A (ja) * 2016-06-09 2017-12-14 三菱製紙株式会社 耐熱性湿式不織布
CN109328408A (zh) * 2016-06-27 2019-02-12 日本高度纸工业株式会社 电化学元件用分隔件和电化学元件、汽车、电子设备
CN109328408B (zh) * 2016-06-27 2021-06-29 日本高度纸工业株式会社 电化学元件用分隔件和电化学元件、汽车、电子设备
EP3512000A4 (fr) * 2016-09-08 2020-04-29 Mitsubishi Paper Mills Limited Substrat pour séparateurs de batterie au lithium-ion, et séparateur de batterie au lithium-ion
CN109661737A (zh) * 2016-09-08 2019-04-19 三菱制纸株式会社 锂离子电池隔板用基材和锂离子电池隔板
JPWO2018047742A1 (ja) * 2016-09-08 2019-10-10 三菱製紙株式会社 リチウムイオン電池セパレータ用基材及びリチウムイオン電池セパレータ
WO2018047742A1 (fr) * 2016-09-08 2018-03-15 三菱製紙株式会社 Substrat pour séparateurs de batterie au lithium-ion, et séparateur de batterie au lithium-ion
CN109661737B (zh) * 2016-09-08 2022-12-20 三菱制纸株式会社 锂离子电池隔板用基材和锂离子电池隔板
US11637349B2 (en) 2016-09-08 2023-04-25 Mitsubishi Paper Mills Limited Substrate for lithium ion battery separators and lithium ion battery separator
CN110114911A (zh) * 2016-12-27 2019-08-09 三菱制纸株式会社 锂离子电池隔板和锂离子电池
EP3565028A4 (fr) * 2016-12-27 2020-11-04 Mitsubishi Paper Mills Limited Séparateur de batterie au lithium-ion et batterie au lithium-ion
US11335972B2 (en) 2016-12-27 2022-05-17 Mitsubishi Paper Mills Limited Lithium ion battery separator and lithium ion battery
JP2018170215A (ja) * 2017-03-30 2018-11-01 三菱製紙株式会社 リチウムイオン電池セパレータ
WO2019146626A1 (fr) 2018-01-25 2019-08-01 三菱製紙株式会社 Liquide de revêtement pour séparateurs pour batteries au lithium-ion, et séparateur pour batteries au lithium-ion
US11735797B2 (en) 2018-01-25 2023-08-22 Mitsubishi Paper Mills Limited Coating solution for lithium ion battery separators and lithium ion battery separator
US11881595B2 (en) 2018-01-25 2024-01-23 Mitsubishi Paper Mills Limited Coating solution for lithium ion battery separators and lithium ion battery separator

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