WO2012005152A1 - Séparateur pour batterie non aqueuse et batterie non aqueuse - Google Patents

Séparateur pour batterie non aqueuse et batterie non aqueuse Download PDF

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Publication number
WO2012005152A1
WO2012005152A1 PCT/JP2011/064925 JP2011064925W WO2012005152A1 WO 2012005152 A1 WO2012005152 A1 WO 2012005152A1 JP 2011064925 W JP2011064925 W JP 2011064925W WO 2012005152 A1 WO2012005152 A1 WO 2012005152A1
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Prior art keywords
heat
fine particles
resistant porous
separator
porous membrane
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PCT/JP2011/064925
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English (en)
Japanese (ja)
Inventor
片山秀昭
松本修明
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日立マクセル株式会社
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Priority to JP2012502371A priority Critical patent/JPWO2012005152A1/ja
Publication of WO2012005152A1 publication Critical patent/WO2012005152A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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 heat-resistant porous membrane suitable for application to a separator separating a positive electrode and a negative electrode in a non-aqueous battery, a separator for a non-aqueous battery using the heat-resistant porous membrane, and the heat-resistant porous membrane.
  • the present invention relates to a nonaqueous battery having a membrane or the separator for a nonaqueous battery and having excellent output characteristics and safety.
  • a lithium secondary battery which is a type of non-aqueous battery, is widely used as a power source for portable devices such as mobile phones and notebook personal computers because of its high energy density.
  • portable devices such as mobile phones and notebook personal computers
  • an in-vehicle power source such as an electric assist bicycle, an electric motorcycle, an electric vehicle, and a hybrid vehicle
  • Since such a power source for in-vehicle use has a larger capacity than a power source for portable devices, it is important to ensure further safety.
  • the required output is larger than the power supply of the portable device, a safety technology that does not deteriorate the output characteristics is required.
  • a polyolefin microporous film having a thickness of about 20 to 30 ⁇ m is used as a separator interposed between a positive electrode and a negative electrode.
  • separator material the constituent resin of the separator is melted below the abnormal heat generation temperature of the battery to close the pores, thereby increasing the internal resistance of the battery and improving the safety of the battery in the event of a short circuit.
  • a material having a low melting point may be used among polyolefins such as polyethylene.
  • a separator for example, a uniaxially stretched film or a biaxially stretched film is used for increasing the porosity and improving the strength. Since such a separator is supplied as a single film, a certain strength is required in terms of workability and the like, and this is secured by the stretching. However, such a stretched film has increased crystallinity, and the shutdown temperature has increased to a temperature close to the abnormal heat generation temperature of the battery, so that the margin for ensuring the safety of the battery is not sufficient. hard.
  • the film is distorted by the stretching, and when it is exposed to high temperature, there is a problem that shrinkage occurs due to residual stress.
  • the shrinkage temperature is very close to the melting point, ie the shutdown temperature.
  • the current must be immediately reduced to prevent the battery temperature from rising. This is because if the pores are not sufficiently closed and the current cannot be reduced immediately, the battery temperature easily rises to the shrinkage temperature of the separator, and there is a risk of abnormal heat generation due to an internal short circuit.
  • Patent Documents 1 to 3 As a technique for preventing such a short circuit due to thermal contraction of the separator and improving the reliability of the battery, for example, a porous base material having good heat resistance, filler particles, and a resin component for ensuring a shutdown function It has been proposed to form an electrochemical element with a separator having the above (Patent Documents 1 to 3).
  • Patent Documents 4 to 6 it has been proposed to increase heat resistance by forming a heat-resistant layer mainly composed of heat-resistant resin or inorganic fine particles on a polyolefin porous film.
  • Patent Documents 1 to 6 it is possible to provide a battery with excellent safety that is unlikely to generate abnormal heat even when the battery is abnormal.
  • the present invention has been made in view of the above circumstances, and can be used as a nonaqueous battery having high safety and high output characteristics, a separator between a positive electrode and a negative electrode, and heat resistance capable of constituting the nonaqueous battery.
  • a porous membrane and a separator capable of constituting the nonaqueous battery are provided.
  • the separator for a non-aqueous battery according to the present invention is a separator for a non-aqueous battery in which a porous substrate and a heat-resistant porous membrane are integrated, and the heat-resistant porous membrane has a heat-resistant temperature of 150 ° C.
  • the fine particles Including the fine particles and an organic binder, the fine particles have an average particle diameter of 0.01 to 10 ⁇ m, and the proportion of the organic binder in the total solid content of the heat-resistant porous film is 7% by volume. It is characterized by the following.
  • the first nonaqueous battery of the present invention is a nonaqueous battery including a positive electrode, a negative electrode, a heat resistant porous membrane and a nonaqueous electrolyte, and is selected from the heat resistant porous membrane, the positive electrode and the negative electrode.
  • the heat-resistant porous membrane contains fine particles having a heat-resistant temperature of 150 ° C. or higher and an organic binder, and the average particle diameter of the fine particles is 0.01 to 10 ⁇ m.
  • the ratio of the organic binder in the total solid content of the heat-resistant porous membrane is 7% by volume or less.
  • the second non-aqueous battery of the present invention is a non-aqueous battery including a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, wherein the separator is formed by integrating a porous substrate and a heat-resistant porous film.
  • the heat-resistant porous film includes fine particles having a heat-resistant temperature of 150 ° C. or more and an organic binder, and the fine particles have an average particle diameter of 0.01 to 10 ⁇ m, and the heat-resistant porous film
  • the ratio of the organic binder in the total solid content of is 7% by volume or less.
  • a non-aqueous battery having high safety and high output characteristics a heat-resistant porous membrane capable of functioning as a separator between a positive electrode and a negative electrode and constituting the non-aqueous battery, and the non-aqueous battery Can be provided.
  • FIG. 1 is a cross-sectional view showing an example of the lithium secondary battery of the present invention.
  • the heat-resistant porous membrane of the present invention contains at least a fine particle having a heat-resistant temperature of 150 ° C. or higher and an organic binder, and is suitable as a separator for partitioning the positive electrode and the negative electrode in a non-aqueous battery. .
  • the heat-resistant porous membrane of the present invention acts as a separator that separates the positive electrode and the negative electrode in the non-aqueous battery, for example, by being integrated with at least one of the positive electrode and the negative electrode of the non-aqueous battery.
  • a non-aqueous battery separator as an independent film by being integrated with a porous substrate.
  • the total volume of all solids (total volume of components of the heat resistant porous membrane excluding the voids. The same applies to the “total volume of the minute.”)
  • the ratio of the volume of the organic binder in the volume is 7% by volume or less.
  • the proportion of the organic binder in the total solid content of the heat-resistant porous membrane is preferably 5% by volume or less, more preferably 3% by volume or less. More preferably, it is 1 volume% or less.
  • an organic binder having an amide group in the molecule, which will be described later, especially a homopolymer or copolymer of N-vinylacetamide a porous film is formed when the proportion of the fine particles is large. Therefore, it is desirable to reduce the proportion of the organic binder as much as possible from the viewpoint of imparting flexibility to the heat-resistant porous film.
  • the proportion of the organic binder in the heat-resistant porous film is too small, for example, the force for binding fine particles having a heat-resistant temperature of 150 ° C. or higher becomes weak, and the fine particles are likely to fall off from the heat-resistant porous film.
  • the heat-resistant porous film may be easily peeled off from the electrode and the porous substrate. Therefore, the proportion of the organic binder in the total solid content of the heat resistant porous membrane is preferably 0.5% by volume or more.
  • the components in the heat-resistant porous film, the heat-resistant porous film and the porous substrate or electrode can be satisfactorily bonded, and are electrochemically stable and non-aqueous
  • electrolyte non-aqueous electrolyte
  • tensile strength and tensile modulus it has good adhesion to fine particles with a heat resistant temperature of 150 ° C or higher. Therefore, those having an amide group (amide bond) in the molecule are preferred, and those containing a structural unit derived from a monomer represented by the following general formula (1) are more preferred.
  • the organic binder containing a structural unit derived from a monomer represented by the following general formula (1) has a side chain containing a moiety [—NR 3 — (C ⁇ O) —R 2 ] containing an amide group. Become.
  • R 1 is hydrogen or a methyl group
  • R 2 and R 3 are R 2 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 3 is hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • R 2 and R 3 are bonded to each other to form a ring, and the total number of carbon atoms in R 2 and R 3 of the ring is 2 to 10.
  • the alkyl group having 1 to 6 carbon atoms in R 2 includes all alkyl groups having 1 to 6 carbon atoms such as a linear alkyl group, a branched alkyl group, and a cyclic alkyl group.
  • the alkyl group having 1 to 4 carbon atoms in R 3 includes all alkyl groups having 1 to 4 carbon atoms such as a linear alkyl group, a branched alkyl group, and a cyclic alkyl group.
  • Examples of the organic binder containing a structural unit derived from the monomer represented by the general formula (1) include a homopolymer and a copolymer of the monomer represented by the general formula (1).
  • Examples of the monomer represented by the general formula (1) include N-vinylacetamide, N-vinylformamide, N-methyl, N-vinylformamide, N-vinylpyrrolidone, N-vinyl-2-caprolactam and the like. It is done.
  • poly N-vinylacetamide for example, poly N-vinylformamide, poly N-methyl, N-vinylformamide, poly N-vinylpyrrolidone, Examples thereof include poly N-vinyl-2-caprolactam.
  • Examples of the copolymer of the monomer represented by the general formula (1) include a copolymer of N-vinylacetamide and an ethylenically unsaturated monomer other than N-vinylacetamide; N-vinylformamide, N -Copolymer of ethylenically unsaturated monomers other than vinylformamide; Copolymer of N-methyl, N-vinylformamide and ethylenically unsaturated monomers other than N-methyl, N-vinylformamide; N-vinyl And a copolymer of pyrrolidone and an ethylenically unsaturated monomer other than N-vinylpyrrolidone.
  • the copolymer using the monomer represented by the said General formula (1) is also contained in the copolymer of the monomer represented by the said General formula (1).
  • Examples of the ethylenically unsaturated monomer [ethylenically unsaturated monomer other than the monomer represented by the general formula (1)] that can be used for forming the copolymer include acrylic acid, methacrylic acid, methyl acrylate, and ethyl.
  • the copolymerization ratio (mass ratio) in the copolymer of the monomer represented by the general formula (1) and the ethylenically unsaturated monomer other than the monomer represented by the general formula (1) is the latter ethylenic property.
  • the unsaturated monomer is preferably 2 to 50% by mass.
  • the molecular weight of an organic binder having an amide group in the molecule is a number average measured using gel permeation chromatography.
  • the molecular weight (in terms of polystyrene) is preferably 1000 or more, more preferably 4000 or more, and preferably 1000000 or less, more preferably 700000 or less, and 500000 or less. Further preferred.
  • heat-resistant porous membranes include ethylene-vinyl acetate copolymer (EVA, having a structural unit derived from vinyl acetate of 20 to 35 mol%), (meth) acrylate polymer [What is “(meth) acrylate”? , And acrylate and methacrylate. same as below. ], Fluorine type rubber, styrene butadiene rubber (SBR), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), one or more types of resins such as polyurethane may be used as the organic binder.
  • SBR styrene butadiene rubber
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • resins such as polyurethane
  • the fine particles having a heat resistant temperature of 150 ° C. or more related to the heat resistant porous film are used as a main component of the heat resistant porous film or fill a void formed between fibrous materials to be described later. It has the effect of suppressing the occurrence of the short circuit.
  • the term “heat-resistant temperature is 150 ° C. or higher” in fine particles having a heat-resistant temperature of 150 ° C. or higher and fibrous materials having a heat-resistant temperature of 150 ° C. or higher (described later) refers to deformation at least at 150 ° C. This means that no shape change is visually confirmed.
  • the fine particles having a heat-resistant temperature of 150 ° C. or higher have electrical insulation properties, are electrochemically stable, and further have a non-aqueous electrolyte (non-aqueous electrolyte solution) or a composition for forming a heat-resistant porous film. If it is stable with respect to the solvent used for a thing (composition containing a solvent), there will be no restriction
  • “stable with respect to the non-aqueous electrolyte” means that no deformation or chemical composition change occurs in the non-aqueous electrolyte of the non-aqueous battery.
  • electrochemically stable as used in the present specification means that no chemical change occurs during charging / discharging of the battery.
  • Such fine particles having a heat-resistant temperature of 150 ° C. or more include, for example, oxide fine particles such as iron oxide, SiO 2 , Al 2 O 3 , TiO 2 , BaTiO 3 , ZrO 2 ; aluminum nitride, silicon nitride, etc.
  • Nitride fine particles Calcium fluoride, barium fluoride, barium sulfate and other poorly soluble ionic crystal fine particles; silicon, diamond and other covalently bonded crystal fine particles; talc, montmorillonite and other clay fine particles; boehmite, zeolite, apatite, kaolin Inorganic fine particles such as mullite, spinel, olivine, sericite, bentonite, hydrotalcite, and other mineral resource-derived substances or artificial products thereof.
  • the surface of conductive fine particles such as metal fine particles; oxide fine particles such as SnO 2 and tin-indium oxide (ITO); carbonaceous fine particles such as carbon black and graphite; It may be fine particles that have been made electrically insulating by surface treatment with the above-mentioned materials constituting the electrically insulating fine particles.
  • organic fine particles can be used for the fine particles having a heat resistant temperature of 150 ° C. or higher.
  • organic fine particles include polyimide, melamine resin, phenol resin, crosslinked polymethylmethacrylate (crosslinked PMMA), crosslinked polystyrene (crosslinked PS), polydivinylbenzene (PDVB), benzoguanamine-formaldehyde condensate, etc.
  • Molecular fine particles; heat-resistant polymer fine particles such as thermoplastic polyimide;
  • the organic resin (polymer) constituting these organic fine particles is a mixture, modified body, derivative, copolymer (random copolymer, alternating copolymer, block copolymer, graft copolymer) of the materials exemplified above. ) Or a crosslinked product (in the case of the heat-resistant polymer).
  • the various fine particles exemplified above may be used alone or in combination of two or more.
  • the fine particles having a heat resistant temperature of 150 ° C. or higher may be particles containing two or more kinds of materials constituting the various fine particles exemplified above.
  • inorganic oxide fine particles are preferable, and alumina, silica, and boehmite are more preferable because, for example, the oxidation resistance of the heat-resistant porous film can be further improved.
  • the form of the fine particles having a heat resistant temperature of 150 ° C. or higher may be any form such as a spherical shape, a particle shape, or a plate shape, but a plate shape is preferable.
  • the plate-like particles include various commercially available products. For example, “Sun Green” (SiO 2 ) manufactured by Asahi Glass Stech Co., Ltd., “NST-B1” pulverized product (TiO 2 ) manufactured by Ishihara Sangyo Co., Ltd., Sakai Chemical Industry Co., Ltd.
  • the fine particles having a heat-resistant temperature of 150 ° C. or higher are plate-like, the fine particles are oriented in the heat-resistant porous film so that the flat plate surface is substantially parallel to the surface of the heat-resistant porous film.
  • the use of such a heat-resistant porous membrane can better suppress the occurrence of short circuits in the battery. This is because the fine particles having a heat-resistant temperature of 150 ° C. or more are oriented as described above, and the fine particles are arranged so as to overlap each other on a part of the flat plate surface, so that the heat-resistant porous film is directed from one side to the other side.
  • the aspect ratio (maximum length in the plate-like particles / thickness of the plate-like particles) is preferably 5 or more as the form when the fine particles having a heat resistant temperature of 150 ° C. or higher are plate-like particles. 10 or more is more preferable, 100 or less is preferable, and 50 or less is more preferable.
  • the average value of the ratio of the length in the major axis direction to the length in the minor axis direction (length in the minor axis direction / length in the major axis direction) of the tabular surface of the grain is preferably 0.3 or more, 0.5 It is more preferable that the number is 1 (that is, the length in the major axis direction and the length in the minor axis direction may be the same).
  • the fine particles having a heat resistant temperature of 150 ° C. or higher are plate-like particles having the aspect ratio and the average value of the ratio of the long axis direction length to the short axis direction of the flat plate surface, the above-mentioned short circuit prevention The effect is exhibited more effectively.
  • the average value of the ratio of the length in the major axis direction to the length in the minor axis direction of the flat plate surface when the fine particles having a heat resistant temperature of 150 ° C. or higher are plate-like for example, an image taken with a scanning electron microscope (SEM) Can be obtained by image analysis. Further, the aspect ratio in the case where the fine particles having a heat resistant temperature of 150 ° C. or higher are plate-like can also be obtained by image analysis of an image taken by SEM.
  • the average particle size of the fine particles having a heat resistant temperature of 150 ° C. or higher is too small, the amount of the organic binder may not be sufficient to bind the fine particles. It is preferably 1 ⁇ m or more. However, if the average particle size of the fine particles having a heat resistant temperature of 150 ° C. or higher is too large, the heat resistant porous membrane becomes too thick, and there is a risk that the energy density of a battery using this will decrease. Therefore, the average particle diameter of the fine particles having a heat resistant temperature of 150 ° C. or higher is 10 ⁇ m or less, and preferably 5 ⁇ m or less. As used herein, the average particle size of the fine particles having a heat resistance temperature of 150 ° C.
  • a laser scattering particle size distribution meter for example, “LA-920” manufactured by HORIBA
  • LA-920 manufactured by HORIBA
  • It can be defined as a number average particle diameter measured by dispersing fine particles having a heat resistant temperature of 150 ° C. or higher in a medium in which the fine particles are not dissolved or fine particles having a heat resistant temperature of 150 ° C. or higher are not swollen.
  • the specific surface area of the fine particles having a heat resistant temperature of 150 ° C. or higher is preferably 100 m 2 / g or less, more preferably 50 m 2 / g or less, and further preferably 30 m 2 / g or less.
  • the specific surface area of the fine particles having a heat-resistant temperature of 150 ° C. or higher is increased, generally, the amount of the organic binder required to bind the fine particles to each other well, and the fine particles to the base material and the electrode tends to increase. There is a possibility that it is difficult to adjust the ratio of the organic binder in the heat-resistant porous film to the above value.
  • the specific surface area of the fine particles having a heat resistant temperature of 150 ° C. or higher is preferably 1 m 2 / g or higher.
  • the specific surface area of fine particles having a heat resistant temperature of 150 ° C. or higher is a value measured by a BET method using nitrogen gas.
  • the heat-resistant porous film of the present invention uses fine particles having high heat resistance such as a heat-resistant temperature of 150 ° C. or higher, the action prevents thermal shrinkage at high temperatures and has high dimensional stability. is doing. Furthermore, when such a heat-resistant porous film having high heat resistance is integrated with the electrode (positive electrode and / or negative electrode), the overall dimensional stability of the heat-resistant porous film at high temperatures is further improved.
  • the separator for a non-aqueous battery of the present invention in which the porous substrate and the heat-resistant porous membrane of the present invention are integrated is a porous substrate whose temperature is high, such as a polyolefin microporous membrane.
  • the non-aqueous battery having the heat-resistant porous membrane of the present invention integrated with the electrode and the non-aqueous battery having the non-aqueous battery separator of the present invention are composed of, for example, only a conventional polyethylene microporous membrane. Since the occurrence of a short circuit due to the thermal contraction of the separator that has occurred in the battery using the separator can be prevented, the reliability and safety when the inside of the battery is abnormally overheated can be further increased.
  • nonaqueous battery having the heat resistant porous membrane of the present invention prevention of a short circuit due to the thermal contraction of the separator at a high temperature is achieved with a configuration other than increasing the thickness of the separator, for example. Therefore, it is possible to make the thickness of the separator (the heat-resistant porous membrane of the present invention or the separator for a non-aqueous battery of the present invention) that separates the positive electrode and the negative electrode relatively thin, thereby reducing the energy density. Can be suppressed as much as possible.
  • the amount of fine particles having a heat resistant temperature of 150 ° C. or higher in the heat resistant porous membrane is from the viewpoint of more effectively exerting the effect of using the fine particles, in the total volume of the total solid content of the heat resistant porous membrane, It is preferably 10% by volume or more, more preferably 30% by volume or more, and still more preferably 40% by volume or more.
  • the heat-resistant porous film does not contain a fibrous material, which will be described later, and contains a heat-meltable fine particle or a swellable fine particle, which will be described later, and has a shutdown function
  • the heat resistance of the fine particles having a heat-resistant temperature of 150 ° C. or higher is preferably 80% by volume or less in the total volume of the total solid content of the heat resistant porous membrane, for example.
  • the heat-resistant porous film does not contain a fibrous material described later and does not have a shutdown function
  • the amount of fine particles having a heat-resistant temperature of 150 ° C. or higher in the heat-resistant porous film is much larger. Specifically, there is no problem if it is 99.5% by volume or less in the total volume of the total solid content of the heat-resistant porous membrane.
  • fine particles having a heat-resistant temperature of 150 ° C. or higher The amount in the heat resistant porous membrane is preferably 70% by volume or less in the total volume of the total solid content of the heat resistant porous membrane, for example.
  • the amount of fine particles having a heat-resistant temperature of 150 ° C. or higher in the heat-resistant porous film may be larger. Specifically, there is no problem as long as it is 80% by volume or less in the total volume of the total solid content of the heat-resistant porous membrane.
  • the heat resistant porous membrane may contain a fibrous material.
  • a fibrous material By containing a fibrous material, the strength of the heat-resistant porous film can be increased.
  • the “fibrous material” in the present specification means that having an aspect ratio [length in the longitudinal direction / width (diameter) in a direction perpendicular to the longitudinal direction] of 4 or more.
  • the aspect ratio of the fibrous material is preferably 10 or more.
  • the fibrous material preferably has a heat resistant temperature of 150 ° C. or higher.
  • a material that can be melted at a temperature of 140 ° C. or less to block the pores of the heat-resistant porous film and provide a function of blocking the movement of ions in the heat-resistant porous film (so-called shutdown function)
  • shutdown function a function of blocking the movement of ions in the heat-resistant porous film
  • a fibrous material having a heat-resistant temperature of 150 ° C. or higher is also contained in the porous membrane, so that a shutdown occurs due to heat generation in the battery, and then 10 Even if the temperature of the separator rises by more than 0 ° C., the shape can be kept more stable.
  • the deformation can be substantially eliminated.
  • the fibrous material preferably has a heat-resistant temperature of 150 ° C. or higher, and has an electrical insulating property, is electrochemically stable, and further has a non-aqueous electrolyte (non-aqueous electrolyte) included in a non-aqueous battery, It is more preferable if the solvent used in the heat-resistant porous film-forming composition is stable.
  • constituent materials of the fibrous material include, for example, cellulose, modified cellulose (such as carboxymethyl cellulose), polypropylene (PP), polyester [polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT). And the like], resins such as polyacrylonitrile (PAN), aramid, polyamideimide, and polyimide; inorganic materials (inorganic oxides) such as glass, alumina, and silica; and the like.
  • the fibrous material may contain one kind of these constituent materials, or may contain two or more kinds.
  • the fibrous material may contain various known additives (for example, an antioxidant in the case of a resin) as necessary. Absent.
  • the fibrous material may be subjected to a surface treatment such as a corona treatment or a surfactant treatment in order to enhance adhesion with fine particles having a heat resistant temperature of 150 ° C. or higher.
  • a surface treatment such as a corona treatment or a surfactant treatment in order to enhance adhesion with fine particles having a heat resistant temperature of 150 ° C. or higher.
  • the diameter of the fibrous material may be equal to or less than the thickness of the heat resistant porous membrane, but is preferably 0.01 to 5 ⁇ m, for example. If the diameter is too large, the entanglement between the fibrous materials will be insufficient, and for example, the effect of improving the strength of the heat-resistant porous membrane by using the fibrous materials may be reduced. On the other hand, if the diameter is too small, the pores of the heat-resistant porous membrane become too small and the ion permeability tends to decrease, and the effect of improving the output characteristics of the battery may be reduced.
  • the state of the presence of the fibrous material in the heat resistant porous membrane is, for example, preferably that the angle of the long axis (long axis) with respect to the heat resistant porous membrane surface is 30 ° or less on average, 20 More preferably, it is not more than 0 °.
  • the content of the fibrous material in the heat-resistant porous membrane is from the viewpoint of more effectively exerting the action due to the use of the fibrous material.
  • the total volume of the total solid content of the membrane is preferably 10% by volume or more, and more preferably 30% by volume or more.
  • the content of the fibrous material is preferably 85% by volume or less, and 70% by volume or less in the total volume of the total solid content of the heat-resistant porous membrane. It is more preferable that
  • the shutdown function can be imparted to the heat resistant porous membrane of the present invention.
  • a heat-resistant porous film having a shutdown function for example, hot-melt fine particles that melt at 80 to 150 ° C., or swellable fine particles that swell by absorbing a nonaqueous electrolyte at a temperature of 80 to 150 ° C.
  • the method of containing can be adopted.
  • the shutdown function in the heat resistant porous membrane can be evaluated by, for example, an increase in resistance due to the temperature of the model cell. That is, a model cell including a positive electrode, a negative electrode, a heat-resistant porous membrane (integrated with one of the positive electrode and the negative electrode), and a non-aqueous electrolyte is manufactured, and the model cell is placed in a thermostatic bath. Hold and measure the internal resistance value of the model cell while raising the temperature at a rate of 5 ° C./minute, and measure the temperature at which the measured internal resistance value is at least 5 times that before heating (resistance value measured at room temperature). By measuring, this temperature can be evaluated as the shutdown temperature of the heat resistant porous membrane.
  • Heat-melting fine particles that melt at 80 to 150 ° C. that is, fine particles having a melting temperature of 80 to 150 ° C. measured using a differential scanning calorimeter (DSC) in accordance with the provisions of Japanese Industrial Standard (JIS) K 7121
  • DSC differential scanning calorimeter
  • JIS Japanese Industrial Standard
  • the shutdown temperature of the separator evaluated by the increase in internal resistance is not less than the melting point of the heat-meltable fine particles and not more than 150 ° C.
  • the melting point (the melting temperature) of the heat-meltable fine particles is more preferably 140 ° C. or lower.
  • the constituent material of the heat-meltable fine particles include polyethylene (PE), copolymerized polyolefin having a structural unit derived from ethylene of 85 mol% or more, PP, or a polyolefin derivative (chlorinated polyethylene, chlorinated polypropylene, etc.), polyolefin Examples thereof include wax, petroleum wax, carnauba wax and the like.
  • the copolymer polyolefin include an ethylene-vinyl monomer copolymer, more specifically, an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer, or an ethylene-ethyl acrylate copolymer. it can.
  • the heat-meltable fine particles may have only one kind of these constituent materials, or may have two or more kinds.
  • PE polyolefin wax, or EVA having a structural unit derived from ethylene of 85 mol% or more is preferable.
  • the heat-meltable fine particles may contain various known additives (for example, antioxidants) added to the resin as necessary, in addition to the above-described constituent materials. Absent.
  • the particle diameter of the heat-meltable fine particles is a number average particle diameter measured by the same measurement method as that of the fine particles having the heat-resistant temperature of 150 ° C. or more, and is preferably 0.001 ⁇ m or more, for example, 0.1 ⁇ m or more. More preferably, it is preferably 15 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • a heat-resistant porous membrane having swellable fine particles that swell by absorbing a non-aqueous electrolyte at a temperature of 80 to 150 ° C. the swellable fine particles do not form a non-aqueous electrolyte when exposed to high temperatures in the battery.
  • Li ion in the heat-resistant porous membrane by absorbing and expanding greatly hereinafter referred to as “heat-swelling”. Therefore, the internal resistance of the battery is increased, and the shutdown function can be reliably ensured.
  • swellable fine particles having thermal swellability examples include crosslinked polystyrene (PS), crosslinked acrylic resin [for example, crosslinked polymethyl methacrylate (PMMA)], and crosslinked fluororesin [for example, crosslinked polyvinylidene fluoride (PVDF). ] Is preferred, and cross-linked PMMA is particularly preferred.
  • the particle diameter of the swellable fine particles is a number average particle diameter measured by dispersing the fine particles in a non-swelling medium (for example, water) using a laser scattering particle size distribution analyzer (for example, “LA-920” manufactured by HORIBA). It is preferably 1 to 20 ⁇ m.
  • cross-linked PMMA As commercially available products of swellable fine particles, for example, cross-linked PMMA “Gantz Pearl (product name)” manufactured by Ganz Kasei Co., Ltd., and cross-linked PMMA “RSP1079 (product name)” manufactured by Toyo Ink Co., Ltd. are available.
  • the heat-resistant porous membrane may contain only hot-melt fine particles, may contain only swellable fine particles, or contain both hot-melt fine particles and swellable fine particles. May be. Also, composite fine particles of a constituent material of a heat-fusible fine particle and a constituent material of a swellable fine particle such as a core-shell type fine particle having a swellable fine particle as a core and the surface thereof covered with the constituent material of a heat-fusible fine particle You may make it contain in a heat resistant porous membrane.
  • a heat-resistant porous film contains a heat-meltable fine particle or a swellable fine particle to provide a shutdown function
  • the heat-meltable fine particle or swelling in the heat-resistant porous film is required to ensure a good shutdown function.
  • Content of heat-soluble fine particles (when the heat-resistant porous film contains both heat-meltable fine particles and swellable fine particles, the total amount thereof is obtained.
  • the amount of the heat-meltable fine particles or the swellable fine particles in the heat-resistant porous membrane is the same hereinafter.) Is the total solid content of the heat-resistant porous membrane.
  • the total volume is preferably 5 to 70% by volume.
  • the content of these fine particles is too small, the shutdown effect due to the inclusion of these may be reduced, and if too large, the heat resistant temperature in the heat-resistant porous membrane is fine particles or fibrous materials having a heat resistance temperature of 150 ° C. or higher. Therefore, the effect secured by these may be reduced.
  • heat resistant porous membrane of the present invention include the following embodiments (a), (b) and (c).
  • B Sheet-like heat-resistant formed by uniformly dispersing fine particles having a heat-resistant temperature of 150 ° C. or more and fibrous materials (and, if necessary, other fine particles) and binding them with an organic binder. Porous membrane.
  • C A material in which a large number of fibrous materials are aggregated to form a sheet-like material only, for example, a woven fabric or a nonwoven fabric (including paper) is used. Heat-resistant porous material composed of a single layer composed of fine particles having a temperature of 150 ° C. or higher and other fine particles as necessary, and binding the fibrous material related to the sheet-like material and various fine particles with an organic binder film.
  • Such a heat-resistant porous membrane is integrated with an electrode (positive electrode and / or negative electrode) used in a nonaqueous battery, and used as a separator for separating the positive electrode and the negative electrode.
  • the heat-resistant temperature is 150 ° C. or more.
  • an organic binder and, if necessary, a fibrous material and other fine particles are dispersed in a solvent (including a dispersion medium; the same shall apply hereinafter) to prepare a heat-resistant porous film-forming composition.
  • the organic binder may be dissolved in a solvent may be used), and this may be applied to the electrode surface and dried to directly form a heat resistant porous film on the electrode surface.
  • the heat-resistant porous film-forming composition is applied to a substrate such as a PET film or a metal plate, and dried to form the heat-resistant porous film of the aspect (a) or (b). After being peeled from the substrate, it may be superposed on the electrode and integrated with the electrode by a roll press or the like.
  • a fibrous sheet-like material is impregnated with the heat-resistant porous film-forming composition, and an unnecessary composition is passed through a certain gap. After removing the matter, it can be dried to obtain an independent heat-resistant porous membrane.
  • the heat-resistant porous film is then overlapped with the electrode and integrated with the electrode by a roll press or the like.
  • Examples of the fibrous sheet used in the heat-resistant porous membrane of the aspect (c) include a woven fabric composed of at least one fibrous substance containing the above-mentioned exemplified materials as constituent components, and these Examples thereof include a porous sheet such as a nonwoven fabric having a structure in which fibrous materials are entangled with each other. More specifically, non-woven fabrics such as paper, PP non-woven fabric, polyester non-woven fabric (PET non-woven fabric, PEN non-woven fabric, PBT non-woven fabric, etc.) and PAN non-woven fabric can be exemplified.
  • non-woven fabrics such as paper, PP non-woven fabric, polyester non-woven fabric (PET non-woven fabric, PEN non-woven fabric, PBT non-woven fabric, etc.) and PAN non-woven fabric can be exemplified.
  • the solvent used in the composition for forming a heat-resistant porous film can uniformly disperse fine particles having a heat-resistant temperature of 150 ° C. or more, heat-meltable fine particles, swellable fine particles, and can uniformly dissolve or disperse the organic binder.
  • Any organic solvent may be used, for example, aromatic hydrocarbons such as toluene; furans such as tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone;
  • alcohols ethylene glycol, propylene glycol, etc.
  • various propylene oxide glycol ethers such as monomethyl acetate may be appropriately added to these solvents.
  • the binder when the binder is water-soluble or used as an emulsion, water may be used as a solvent.
  • an alcohol methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, etc.
  • the tension can also be controlled.
  • the solid content including fine particles having an heat resistant temperature of 150 ° C. or higher, an organic binder, hot melt fine particles, swellable fine particles, fibrous materials, etc., for example, 10 to 80 mass. % Is preferable.
  • the composition for forming a heat-resistant porous film is applied to the electrode surface or other
  • a coated film (coated film before drying) applied to the substrate surface or a sheet-like material impregnated with a heat-resistant porous film-forming composition these compositions may be shared.
  • a certain gap is passed through.
  • a high solid content concentration for example, 50-80 Mass% heat-resistant porous film-forming composition
  • fine particles having a heat-resistant temperature of 150 ° C. or higher various mixing / stirring devices such as dispersers, agitators, homogenizers, ball mills, attritors, jet mills, dispersions
  • Heat-resistant porous material prepared by dispersing in an organic solvent using an apparatus and adding and mixing organic binders (further, if necessary, fibrous materials, heat-meltable fine particles, swellable fine particles, etc.).
  • a method of using a composition for forming a membrane; using fine particles having a heat resistance of 150 ° C. or higher, which is modified by applying a dispersing agent such as fats and oils, surfactants, and silane coupling agents on the surface Using a composition for forming a heat-resistant porous film prepared by using a composition for forming a heat-resistant porous film prepared using a combination of fine particles having a heat-resistant temperature of 150 ° C.
  • Method for controlling the drying conditions after impregnating the composition for forming a heat-resistant porous film into a sheet or coating on a substrate; pressurizing or heat-pressing the heat-resistant porous film A method of pressing; a method of impregnating a heat-resistant porous film-forming composition into a sheet-like material, or applying a magnetic field before drying after coating on a substrate; and the like can be employed. It may be carried out alone or in combination of two or more methods.
  • the thickness of the heat-resistant porous membrane thus obtained is preferably 3 ⁇ m or more, for example, from the viewpoint of further enhancing the short-circuit prevention effect of the battery in which it is used and increasing the strength of the heat-resistant porous membrane. More preferably.
  • the thickness of the heat-resistant porous film is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the porosity of the heat resistant porous membrane is preferably 20% or more in a dry state in order to secure the liquid retention amount of the nonaqueous electrolyte and improve the ion permeability, and preferably 30% More preferably.
  • the porosity of the heat resistant porous membrane is preferably 70% or less in a dry state, and is 60% or less. More preferably.
  • the porosity of the heat-resistant porous membrane: P (%) is calculated from the thickness of the heat-resistant porous membrane, the mass per area, and the density of the constituent components for each component i using the following formula (2). It can be calculated by calculating the sum.
  • the heat shrinkage rate at 150 ° C. (heat shrinkage rate in an integrated state with the electrode) of the heat-resistant porous membrane obtained by the method described in the examples below is preferably 5% or less.
  • the strength of the heat resistant porous membrane is desirably 50 g or more in terms of puncture strength using a needle having a diameter of 1 mm. If the piercing strength is too small, there is a possibility that a short circuit occurs due to the piercing of the heat-resistant porous film when lithium dendrite crystals are generated.
  • the air permeability of the heat-resistant porous membrane is measured by a method according to JIS P 8117, and is a Gurley value indicated by the number of seconds that 100 ml of air permeates the membrane under a pressure of 0.879 g / mm 2. 10 to 300 sec is desirable. If the air permeability is too high, the ion permeability is reduced, and if it is too low, the strength of the heat resistant porous membrane may be reduced.
  • the heat shrinkage rate, strength, and air permeability described above can be ensured by using the heat-resistant porous membrane having the configuration described so far.
  • the separator for non-aqueous batteries of the present invention is a separator having a multilayer structure in which a porous substrate and the heat-resistant porous membrane of the present invention are integrated.
  • porous base material related to the separator a resin nonwoven fabric, woven fabric, microporous film, or the like can be used.
  • thermoplastic resin having a melting point of 80 to 150 ° C. As the constituent resin of the porous substrate, thermoplastic resin having a melting point of 80 to 150 ° C. include various thermoplastic resins exemplified above as the constituent resin of the heat-meltable fine particles.
  • porous substrates composed of such thermoplastic resins microporous membranes made of polyolefin (PE, ethylene-propylene copolymer, etc.) are preferable.
  • the shutdown function in the separator of the present invention can also be evaluated by the resistance increase due to the temperature of the model cell, similar to the shutdown function of the heat-resistant porous film. That is, a model cell including a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte is prepared, and the model cell is held in a thermostatic bath, and the internal resistance value of the model cell is set while increasing the temperature at a rate of 5 ° C./min. By measuring and measuring the temperature at which the measured internal resistance value is at least five times that before heating (resistance value measured at room temperature), this temperature can be evaluated as the shutdown temperature of the separator.
  • a porous substrate made of a heat resistant resin can be used.
  • a heat-resistant resin any resin that has a heat-resistant temperature of 150 ° C. or more, is stable with respect to the nonaqueous electrolyte used in the battery, and is stable with respect to the oxidation-reduction reaction inside the battery. Good. More specifically, heat-resistant resins such as polyimide, polyamideimide, aramid, polytetrafluoroethylene, polysulfone, polyurethane, PAN, polyester (PET, PBT, PEN, etc.) can be mentioned.
  • an ion-permeable porous film produced by a solvent extraction method, a dry or wet stretching (uniaxial or biaxial stretching) method, or the like can be used.
  • a film microporous by a foaming method using a drug, supercritical CO 2 or the like can also be used.
  • the step of applying the heat-resistant porous film forming composition used in the formation of the heat-resistant porous film to the surface of the porous substrate and drying it is performed. Then, the method of forming the layer which consists of a heat resistant porous film on the surface of a porous base material is employable. Further, the heat-resistant porous film obtained by the method for forming the heat-resistant porous film of the independent film exemplified above and the porous base material may be stacked and integrated by a roll press or the like.
  • the orientation of the plate-like particles is increased in the heat-resistant porous film.
  • various methods exemplified above can be used.
  • the heat-resistant porous membrane and the porous substrate do not have to be one each, and a plurality of separators may be configured.
  • positioned the porous base material on both surfaces of a heat resistant porous film or the structure which has arrange
  • the thickness of the separator is increased, which may increase the internal resistance of the battery and decrease the energy density.
  • the total number of the heat-resistant porous membrane and the porous substrate is preferably 5 or less.
  • the thickness is, for example, 5.5 ⁇ m or more from the viewpoint of further enhancing the short-circuit preventing effect of the battery, ensuring the strength of the separator, and improving its handleability.
  • the thickness is 10 ⁇ m or more.
  • the thickness of the separator is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the thickness of the heat-resistant porous film is X ( ⁇ m) and the thickness of the porous substrate is Y ( ⁇ m)
  • the ratio Y / X of X to Y is 1 to 20
  • Y / X is too large, the heat-resistant porous film becomes too thin, and, for example, when a porous substrate having poor dimensional stability at high temperatures is used, the effect of suppressing the thermal shrinkage becomes small. There is a fear.
  • the thickness X is the total thickness
  • the thickness Y is the total thickness
  • the thickness of the porous substrate is preferably 5 ⁇ m or more, and 30 ⁇ m or less. Is preferred.
  • the thickness of the heat resistant porous membrane is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, More preferably, it is 2 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 3 ⁇ m or less.
  • the porosity of the separator obtained by using the above formula (2), where m is the mass per unit area (g / cm 2 ) of the separator and t is the thickness (cm) of the separator, is the retention of the non-aqueous electrolyte.
  • m is the mass per unit area (g / cm 2 ) of the separator and t is the thickness (cm) of the separator
  • the porosity of the separator obtained by the above method is preferably 70% or less and more preferably 60% or less in a dry state. .
  • m is the mass per unit area (g / cm 2 ) of the porous substrate
  • t is the porous substrate according to the separator that is required as the thickness (cm) of the porous substrate.
  • the porosity of the material is preferably 30 to 70%.
  • the porosity of the heat-resistant porous film related to the separator obtained by the above formula (2) is 20% or more (more preferably 30%) as in the case of the heat-resistant porous film integrated with the electrode. Above), 70% or less (more preferably 60% or less).
  • the thermal shrinkage rate at 150 ° C. of the separator obtained by the method shown in the examples below is 5% or less.
  • the strength of the separator is preferably 50 g or more in terms of piercing strength using a needle having a diameter of 1 mm. If the piercing strength is too low, a short circuit may occur due to the breakthrough of the separator when lithium dendrite crystals are generated.
  • the air permeability of the separator is measured by a method according to JIS P 8117, and is 100 to 300 sec as a Gurley value indicated by the number of seconds that 100 ml of air passes through the membrane under a pressure of 0.879 g / mm 2. Is desirable. If the air permeability is too high, the ion permeability is reduced, and if it is too low, the strength of the separator may be reduced.
  • the Gurley value of the separator satisfies the relationship of the following formula (3).
  • Gs Gurley value of the separator
  • Ga Gurley value of the porous substrate
  • Gb Gurley value of the heat-resistant porous film
  • max ⁇ Ga, Gb ⁇ whichever is greater of Ga and Gb.
  • Gb is calculated
  • Gb Gs-Ga (4)
  • the 180 ° peel strength of the heat-resistant porous membrane is 0.6 N / It is preferably at least cm, and more preferably at least 1.0 N / cm.
  • the peel strength is a value measured by the following method.
  • a test piece having a width of 2 cm and a length of 5 cm is cut out from an integrated product of the heat-resistant porous membrane and the electrode, or a separator, and an adhesive tape is attached to a 2 cm ⁇ 2 cm region on the surface of the heat-resistant porous membrane.
  • the pressure-sensitive adhesive tape has a width of 2 cm and a length of about 5 cm, and is attached so that one end of the pressure-sensitive adhesive tape and one end of the heat-resistant porous membrane are aligned.
  • the end of the test piece opposite to the side where the adhesive tape was affixed and the end of the adhesive tape affixed to the test piece opposite the end affixed to the test piece Gripping and pulling at a pulling speed of 10 mm / min to measure the strength when the heat-resistant porous film is peeled off.
  • the nonaqueous battery of the present invention the heat-resistant porous membrane of the present invention is integrated with at least one of the positive electrode and the negative electrode and used as a separator to separate the counter electrode, or the separator of the present invention has a positive electrode and a negative electrode.
  • Any other configuration and structure may be used as long as it is used as a separating material, and non-aqueous batteries using a conventionally known non-aqueous electrolyte (non-aqueous primary batteries such as lithium primary batteries, lithium Various configurations and structures employed in non-aqueous secondary batteries such as secondary batteries can be applied. Below, the lithium secondary battery which is especially a main form among the non-aqueous batteries of this invention is demonstrated in detail.
  • Examples of the form of the lithium secondary battery include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
  • the positive electrode is not particularly limited as long as it is a positive electrode used in a conventionally known lithium secondary battery, that is, a positive electrode containing an active material capable of occluding and releasing Li ions.
  • an active material lithium-containing transition metal oxide represented by Li 1 + x MO 2 ( ⁇ 0.1 ⁇ x ⁇ 0.1, M: Co, Ni, Mn, etc.); lithium manganese such as LiMn 2 O 4 Oxide; LiMn x M (1-x) O 2 in which part of Mn of LiMn 2 O 4 is substituted with another element; olivine type LiMPO 4 (M: Co, Ni, Mn, Fe); LiMn 0.5 Ni 0.5 O 2 ; Li (1 + a) Mn x Ni y Co (1-xy) O 2 ( ⁇ 0.1 ⁇ a ⁇ 0.1, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.
  • a known conductive additive carbon material such as carbon black
  • PVDF polyvinylidene fluoride
  • a metal foil such as aluminum, a punching metal, a net, an expanded metal, or the like can be used, but an aluminum foil having a thickness of 10 to 30 ⁇ m is usually preferably used.
  • the lead part on the positive electrode side is usually provided by leaving the exposed part of the current collector without forming the positive electrode mixture layer on a part of the current collector and forming the lead part at the time of producing the positive electrode.
  • the lead portion is not necessarily integrated with the current collector from the beginning, and may be provided by connecting an aluminum foil or the like to the current collector later.
  • the negative electrode is not particularly limited as long as it is a negative electrode used in a conventionally known lithium secondary battery, that is, a negative electrode containing an active material capable of occluding and releasing Li ions.
  • an active material capable of occluding and releasing Li ions for example, carbon that can occlude and release lithium, such as graphite, pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesocarbon microbeads (MCMB), and carbon fibers as active materials
  • MCMB mesocarbon microbeads
  • elements such as Si, Sn, Ge, Bi, Sb, In and alloys thereof, lithium-containing nitrides, compounds that can be charged and discharged at a low voltage close to lithium metal such as lithium-containing oxides, or lithium metal or lithium / An aluminum alloy can also be used as the negative electrode active material.
  • a negative electrode mixture obtained by appropriately adding a conductive additive (carbon material such as carbon black) or a binder such as PVDF to these negative electrode active materials, and a molded body (negative electrode mixture layer) using a current collector as a core material
  • a conductive additive carbon material such as carbon black
  • a binder such as PVDF
  • the current collector When a current collector is used for the negative electrode, a copper or nickel foil, a punching metal, a net, an expanded metal, or the like can be used as the current collector, but a copper foil is usually used.
  • the upper limit of the thickness is preferably 30 ⁇ m, and the lower limit is preferably 5 ⁇ m.
  • the negative electrode layer (including a layer having a negative electrode active material and a negative electrode mixture layer) is usually formed on a part of the current collector during the preparation of the negative electrode. Without leaving the exposed portion of the current collector, it is provided as a lead portion.
  • the lead portion on the negative electrode side is not necessarily integrated with the current collector from the beginning, and may be provided by connecting a copper foil or the like to the current collector later.
  • the electrode is formed by laminating the positive electrode and the negative electrode via the separator of the present invention, or integrating at least one of the positive electrode and the negative electrode with the heat-resistant porous membrane of the present invention, It can be used in the form of an electrode group having a laminated structure in which a positive electrode and a negative electrode are laminated so that this heat-resistant porous film is interposed, or an electrode group having a wound structure in which these are wound.
  • a separate separator for example, a conventionally known lithium secondary battery
  • the microporous membrane separator made of polyolefin used in the battery of (1) may be used, but since the heat-resistant porous membrane of the present invention functions as a separator (that is, a separator) separating the positive electrode and the negative electrode, There is no need to use a separator.
  • non-aqueous electrolyte a solution (non-aqueous electrolyte) in which a lithium salt is dissolved in an organic solvent is used.
  • the lithium salt is not particularly limited as long as it dissociates in a solvent to form Li + ions and does not cause a side reaction such as decomposition in a voltage range used as a battery.
  • inorganic lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (2 ⁇ n ⁇ 7), LiN (R f OSO 2 ) 2 [where R f is a fluoroalkyl group]; Etc. can be used.
  • inorganic lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (2 ⁇
  • the organic solvent used in the non-aqueous electrolyte is not particularly limited as long as it dissolves the lithium salt and does not cause side reactions such as decomposition in the voltage range used as a battery.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate
  • chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate
  • chain esters such as methyl propionate
  • cyclic esters such as ⁇ -butyrolactone
  • Chain ethers such as ethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme
  • cyclic ethers such as dioxane, tetrahydrofuran and 2-methyltetrahydrofuran
  • nitriles such as acetonitrile, propionitrile and methoxypropionitrile
  • Sulfites such as
  • ⁇ may be used in combination of two or more thereof.
  • a combination that can obtain high conductivity such as a mixed solvent of ethylene carbonate and chain carbonate.
  • vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, biphenyl, and fluorobenzene are used for the purpose of improving the safety, charge / discharge cycleability, and high-temperature storage properties of these non-aqueous electrolytes.
  • Additives such as t-butylbenzene can also be added as appropriate.
  • the concentration of this lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, more preferably 0.9 to 1.25 mol / l.
  • melting at room temperature such as ethyl-methylimidazolium trifluoromethylsulfonium imide, heptyl-trimethylammonium trifluoromethylsulfonium imide, pyridinium trifluoromethylsulfonium imide, guanidinium trifluoromethylsulfonium imide A salt can also be used.
  • a polymer material that gels the non-aqueous electrolyte may be added, and the non-aqueous electrolyte may be gelled and used for a battery.
  • Polymer materials for making non-aqueous electrolyte into a gel include PVDF, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), PAN, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer
  • a known host polymer capable of forming a gel electrolyte such as a crosslinked polymer having an ethylene oxide chain in the main chain or side chain, and a crosslinked poly (meth) acrylate.
  • FIG. 1 is a cross-sectional view showing an example of the lithium secondary battery of the present invention.
  • a lithium secondary battery of the present invention includes a positive electrode 1 having a positive electrode mixture layer containing the positive electrode active material described above, a negative electrode 2 having a negative electrode mixture layer containing a negative electrode active material, and A separator 3 and a non-aqueous electrolyte 4 are provided.
  • the positive electrode 1 and the negative electrode 2 are spirally wound via a separator 3 and are housed in a cylindrical battery can 5 together with a nonaqueous electrolyte solution 4 as an electrode group having a wound structure.
  • the metal foil which is a current collector used for manufacturing the positive electrode 1 and the negative electrode 2 is not illustrated.
  • the separator 3 shows the cut surface, it does not attach
  • the battery can 5 is made of, for example, iron and nickel-plated on the surface, and an insulator 6 made of, for example, polypropylene is disposed at the bottom of the battery can 5 prior to the insertion of the electrode group having the wound structure.
  • the sealing plate 7 is made of, for example, aluminum and has a disk shape.
  • a thin portion 7a is provided at the center of the sealing plate 7, and a pressure introduction port 7b for allowing the battery internal pressure to act on the explosion-proof valve 9 around the thin portion 7a.
  • the protrusion part 9a of the explosion-proof valve 9 is welded to the upper surface of the thin part 7a, and the welding part 11 is comprised.
  • the thin-walled portion 7a provided on the sealing plate 7 and the protruding portion 9a of the explosion-proof valve 9 are shown only on the cut surface for easy understanding on the drawing, and the contour line behind the cut surface is not shown. is doing.
  • the welded portion 11 between the thin-walled portion 7a of the sealing plate 7 and the protruding portion 9a of the explosion-proof valve 9 is also shown in an exaggerated state so as to facilitate understanding on the drawing.
  • the terminal plate 8 is made of, for example, rolled steel, has a nickel-plated surface, has a hat-like shape with a peripheral edge portion, and the terminal plate 8 is provided with a gas discharge port 8a.
  • the explosion-proof valve 9 is made of, for example, aluminum and has a disk shape.
  • a projecting portion 9a having a tip portion is provided on the power generation element side (lower side in FIG. 1) at the center, and the thin-walled portion 9b As described above, the lower surface of the protruding portion 9a is welded to the upper surface of the thin-walled portion 7a of the sealing plate 7 to form the welded portion 11.
  • the insulating packing 10 is made of, for example, polypropylene and has an annular shape.
  • the insulating packing 10 is arranged at the upper part of the peripheral edge of the sealing plate 7, and the explosion-proof valve 9 is arranged at the upper part thereof, so that the sealing plate 7 and the explosion-proof valve 9 are insulated. At the same time, the gap between the two is sealed so that the electrolyte does not leak from between them.
  • the annular gasket 12 is made of, for example, polypropylene.
  • the lead body 13 is made of aluminum, for example, and connects the sealing plate 7 and the positive electrode 1.
  • An insulator 14 is disposed on the upper part of the electrode group having a wound structure, and the negative electrode 2 and the bottom of the battery can 5 are connected by a lead body 15 made of nickel, for example.
  • the thin-walled portion 7a of the sealing plate 7 and the protruding portion 9a of the explosion-proof valve 9 are in contact with each other at the welded portion 11, and the peripheral portion of the explosion-proof valve 9 and the peripheral portion of the terminal plate 8 are in contact.
  • 1 and the sealing plate 7 are connected by a lead body 13 on the positive electrode side. Therefore, in a normal state, the positive electrode 1 and the terminal plate 8 are connected to the lead body 13, the sealing plate 7, the explosion-proof valve 9 and their welded parts.
  • the electrical connection is obtained by 11 and functions normally as an electric circuit.
  • the explosion-proof valve 9 When an abnormal situation occurs in the battery, such as the battery is exposed to high temperature or generates heat due to overcharge, and gas is generated inside the battery and the internal pressure of the battery increases, the explosion-proof valve 9 The center part of the is deformed in the internal pressure direction (the upper direction in FIG. 1). Along with this, a shearing force is applied to the thin portion 7a of the sealing plate 7 integrated at the welded portion 11, and the thin portion 7a is broken, or the projection 9a of the explosion-proof valve 9 and the thin portion 7a of the sealing plate 7 are broken.
  • the thin-walled portion 9b provided in the explosion-proof valve 9 is cleaved to discharge the gas from the gas discharge port 8a of the terminal plate 8 to the outside of the battery, thereby preventing the battery from bursting. Designed to be able to.
  • the non-aqueous battery of the present invention can be applied to the same uses as various uses in which non-aqueous batteries such as lithium secondary batteries known in the art are used.
  • Example 1 Provide of electrode> The positive electrode was produced as follows. First, 90 parts by mass of LiCoO 2 (positive electrode active material), which is a lithium-containing composite oxide, is mixed with 5 parts by mass of carbon black as a conductive additive, and PVDF: 5 parts by mass as a binder is added to NMP as a binder. The dissolved solution was added and mixed to obtain a positive electrode mixture-containing slurry, which was passed through a 70-mesh net to remove large particles.
  • LiCoO 2 positive electrode active material
  • carbon black as a conductive additive
  • PVDF 5 parts by mass as a binder
  • the negative electrode was produced as follows. Artificial graphite was used as the negative electrode active material, PVDF was used as the binder, these were mixed at a mass ratio of 95: 5, and NMP was added and mixed to obtain a negative electrode mixture-containing paste.
  • This negative electrode mixture-containing paste was uniformly applied to both sides of a negative electrode current collector made of a copper foil having a thickness of 10 ⁇ m and dried, and then compression-molded with a roll press machine to a total thickness of 100 ⁇ m. It cut
  • PNVA poly N-vinylacetamide
  • a PE microporous film (thickness 16 ⁇ m, porosity 40%, PE melting point 135 ° C.) with a corona discharge treatment on one side was used as a porous substrate, and the slurry was applied to the treated surface with a microgravure coater.
  • the separator was dried to form a heat-resistant porous film, thereby obtaining a separator having a thickness of 20 ⁇ m.
  • the volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 7.0% by volume, and the porosity of the heat resistant porous membrane was 48%.
  • the separator obtained as described above was stacked while being interposed between the positive electrode and the negative electrode so that the heat-resistant porous membrane side was directed to the positive electrode side, and wound to form a wound body electrode group.
  • the obtained wound electrode group was put into an iron battery can having a diameter of 18 mm and a height of 65 mm, and after injecting an electrolytic solution, sealing was performed to produce a lithium secondary battery.
  • the lithium secondary battery includes an explosion-proof valve at the top of the can for releasing the pressure when the internal pressure increases.
  • the design electric capacity when charged to 4.2 V (the positive electrode potential is 4.3 V with respect to Li) is 1400 mAh.
  • Example 2 4000 g of the same boehmite powder used in Example 1 was added to 4000 g of water in four portions, and the mixture was stirred with a disper at 2800 rpm for 5 hours to prepare a uniform dispersion. 400 g of an aqueous solution of PNVA (concentration: 10% by mass) as an organic binder was added to this dispersion, and water was further added and stirred at room temperature until uniformly dispersed to prepare a slurry having a solid content ratio of 30% by mass.
  • PNVA concentration: 10% by mass
  • a fluorosurfactant perfluoroalkylethylene oxide adduct
  • a fluorosurfactant perfluoroalkylethylene oxide adduct
  • the slurry was applied using a micro gravure coater, and then dried to form a heat resistant porous membrane, resulting in a thickness of 20 ⁇ m.
  • a separator was obtained.
  • the volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 2.5% by volume, and the porosity of the heat resistant porous membrane was 52%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that this separator was used.
  • Example 3 The heat resistance was the same as in Example 2 except that the fine particles having a heat resistance temperature of 150 ° C. or higher were changed to secondary particulate boehmite (average particle diameter 0.6 ⁇ m, specific surface area 15 m 2 / g) in which primary particles were continuous.
  • a slurry for forming a porous film was prepared.
  • a three-layer polyolefin microporous membrane (thickness 16 ⁇ m, porosity 40%, PE melting point 135 ° C.
  • the slurry was dried to form a heat-resistant porous film, thereby obtaining a separator having a thickness of 18 ⁇ m.
  • the volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 2.5% by volume, and the porosity of the heat resistant porous membrane was 55%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that this separator was used.
  • Example 4 To fine particles having a heat resistant temperature of 150 ° C. or higher, 4000 g of secondary particulate boehmite with the same primary particles as used in Example 3 was added to 4000 g of water in four portions, and 5 times at 2800 rpm with a disper. A uniform dispersion was prepared by stirring for a period of time. In this dispersion, an aqueous dispersion (solid content ratio: 40% by mass) of crosslinked PMMA fine particles (average particle size 0.4 ⁇ m), which are swellable fine particles that swell by absorbing a nonaqueous electrolytic solution at a temperature of 80 to 150 ° C.
  • the slurry was applied using a micro gravure coater and then dried to form a heat-resistant porous film.
  • a 20 ⁇ m separator was obtained.
  • the volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 4.8% by volume, and the porosity of the heat resistant porous membrane was 50%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that this separator was used.
  • Example 5 Use 4000 g of secondary particulate boehmite (average particle size 0.06 ⁇ m, specific surface area 100 m 2 / g) in which primary particles are connected to fine particles having a heat-resistant temperature of 150 ° C. or more, and add them to 4000 g of water in four portions. The mixture was stirred for 5 hours at 2800 rpm with a disper to prepare a uniform dispersion.
  • an aqueous dispersion solid content ratio 40 mass% of PE fine particles (melting point 135 ° C.) and 2100 g of an aqueous solution of PNVA (concentration 10 mass%) are added as hot-melt fine particles, and water is further added to the solid content ratio.
  • a slurry for forming a heat resistant porous film A nonwoven fabric made of PET (weighing 8 g / m 2 , thickness 16 ⁇ m) is used as a porous substrate, and the slurry is dip coated on the porous substrate and dried to form a heat-resistant porous film, thereby obtaining a separator having a thickness of 20 ⁇ m. It was.
  • the volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 6.2% by volume, and the porosity of the heat resistant porous membrane was 38%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that this separator was used.
  • Example 6 4000 g of alumina fine particles (average particle size 0.4 ⁇ m, specific surface area 7 m 2 / g) are used as fine particles having a heat resistance temperature of 150 ° C. or higher, and this is added to 4000 g of water in four portions, and stirred at 2800 rpm for 5 hours with a disper. And a uniform dispersion was prepared. To this dispersion, 4000 g of an aqueous dispersion (solid content ratio: 40% by mass) of PE fine particles (melting point: 135 ° C.) and 1600 g of an aqueous solution of PNVA (concentration: 10% by mass) are added as heat-meltable fine particles. The mixture was added so that the ratio was 30% by mass, and stirred until uniform to obtain a heat-resistant porous film forming slurry.
  • alumina fine particles average particle size 0.4 ⁇ m, specific surface area 7 m 2 / g
  • the slurry was applied on both surfaces of the same negative electrode as that prepared in Example 1 using a micro gravure coater to form a heat-resistant porous film having a thickness of 20 ⁇ m.
  • the volume ratio of the organic binder in the total volume of the total solid content of the heat-resistant porous film was 4.5% by volume, and the porosity of the heat-resistant porous film was 50%.
  • the negative electrode integrated with the heat-resistant porous membrane and the same positive electrode as that prepared in Example 1 were superposed and wound in a spiral shape to produce a wound electrode group.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that this wound electrode group was used.
  • Example 7 The same heat-resistant porous film forming slurry as that prepared in Example 6 was applied on both surfaces of the same negative electrode as that prepared in Example 1 using a microgravure coater, and the heat-resistant porous film having a thickness of 10 ⁇ m. A membrane was formed. Further, the same heat-resistant porous film-forming slurry as that prepared in Example 6 was applied on both surfaces of the same positive electrode as that prepared in Example 1 using a microgravure coater, and the thickness was 10 ⁇ m. A porous film was formed.
  • a lithium secondary battery was produced in the same manner as in Example 6 except that the negative electrode integrated with the heat resistant porous membrane and the positive electrode integrated with the heat resistant porous membrane were used.
  • Example 1 A slurry for forming a heat-resistant porous film was prepared in the same manner as in Example 1 except that the amount of the aqueous solution of PNVA (concentration: 10% by mass) used as an organic binder was changed to 2000 g, and this slurry was used except that this slurry was used.
  • a separator was produced in the same manner as in Example 1. The volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 11% by volume, and the porosity of the heat resistant porous membrane was 42%.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that this separator was used.
  • Example 2 A slurry for forming a heat-resistant porous film prepared in the same manner as in Example 1 except that boehmite particles (average particle size 0.005 ⁇ m, specific surface area 250 m 2 / g) were used as fine particles having a heat-resistant temperature of 150 ° C. or higher.
  • a separator was prepared in the same manner as in Example 1. However, since the filler of the heat resistant porous membrane was peeled off immediately, the battery was not manufactured.
  • Comparative Example 3 Use 4000 g of the same boehmite particles as those used in Comparative Example 2 for fine particles having a heat-resistant temperature of 150 ° C. or higher, add them to 4000 g of water in four portions, and stir the mixture at 2800 rpm for 5 hours with uniform dispersion. A liquid was prepared. To this dispersion, 4000 g of an aqueous solution of PNVA (concentration: 10% by mass) as an organic binder was added and stirred at room temperature until uniformly dispersed to prepare a slurry for forming a heat resistant porous film. And the separator was produced like Example 1 except having used this slurry. The volume ratio of the organic binder in the total volume of the total solid content of the heat resistant porous membrane of this separator was 20% by volume, and the porosity of the heat resistant porous membrane was 38%.
  • PNVA concentration: 10% by mass
  • Example 2 Furthermore, a lithium secondary battery was produced in the same manner as in Example 1 except that this separator was used.
  • the MD direction and the TD direction are each 5 cm. A strip-shaped sample piece of 10 cm was cut out.
  • the MD direction is the machine direction when producing an integrated product of the separator or heat-resistant porous membrane and the negative electrode
  • the TD direction is a direction perpendicular to them.
  • the heat shrinkage rate of each separator and the heat resistant porous film was set to the larger one of the heat shrinkage rate in the long side direction and the heat shrinkage rate in the short side direction.
  • Table 1 shows the results of the above evaluations excluding safety evaluation.
  • the lithium secondary batteries of Examples 1 to 7 having a heat-resistant porous film with an appropriate organic binder volume ratio have good output characteristics.
  • the separators used in the lithium secondary batteries of Examples 1 to 5 and the heat-resistant porous membrane used in the lithium secondary batteries of Examples 6 and 7 have a low thermal shrinkage at 150 ° C.
  • the lithium secondary batteries of Examples 1 to 7 that use Pt suppress the occurrence of short circuits due to thermal contraction of separators and separators (heat-resistant porous membrane integrated with electrodes) even when the temperature inside the batteries becomes high. As shown in the safety evaluation, it has good safety.
  • the lithium secondary batteries of Comparative Examples 1 and 3 having a heat-resistant porous film in which the volume ratio of the organic binder is too large are inferior in output characteristics to the batteries of the examples.

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Abstract

L'invention concerne un séparateur pour batterie non aqueuse, caractérisé en ce qu'il comprend un matériau de base poreux et un film poreux résistant à la chaleur qui sont intégrés l'un à l'autre, lequel film poreux résistant à la chaleur comprend des microparticules ayant une limite supérieure en température de 150° C ou plus et un liant organique, et lesdites microparticules ayant un diamètre moyen de 0,01-10 μm ; le film poreux résistant à la chaleur contient le liant organique selon un rapport de composition de 7 % en volume ou moins par rapport à la quantité totale de contenu solide. L'invention concerne également une batterie non aqueuse qui est caractérisée en ce qu'elle comprend le film poreux résistant à la chaleur ou le séparateur.
PCT/JP2011/064925 2010-07-09 2011-06-29 Séparateur pour batterie non aqueuse et batterie non aqueuse WO2012005152A1 (fr)

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JP5165158B1 (ja) * 2012-03-13 2013-03-21 株式会社日立製作所 非水電解質二次電池及びその製造方法
JP5647378B1 (ja) * 2013-03-19 2014-12-24 帝人株式会社 非水系二次電池用セパレータ及び非水系二次電池
CN107925039A (zh) * 2015-08-31 2018-04-17 日本瑞翁株式会社 非水系二次电池功能层用组合物、非水系二次电池用功能层、以及非水系二次电池
WO2019235112A1 (fr) 2018-06-08 2019-12-12 旭化成株式会社 Séparateur multicouche
CN113574730A (zh) * 2019-03-20 2021-10-29 帝人株式会社 非水系二次电池用隔膜及非水系二次电池
CN114665227A (zh) * 2022-03-23 2022-06-24 哈尔滨工业大学无锡新材料研究院 一种高浸润性的锂离子电池隔膜及其制备方法
JP7567477B2 (ja) 2019-03-28 2024-10-16 東レ株式会社 多孔性フィルム、二次電池用セパレータおよび二次電池

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JP2009026733A (ja) * 2007-01-30 2009-02-05 Asahi Kasei Chemicals Corp 多層多孔膜及びその製造方法
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JP2008123996A (ja) * 2006-10-16 2008-05-29 Hitachi Maxell Ltd 非水電解質電池用セパレータおよび非水電解質電池
JP2008210782A (ja) * 2007-01-29 2008-09-11 Hitachi Maxell Ltd 電池用セパレータ、電池用セパレータの製造方法およびリチウム二次電池
JP2008210794A (ja) * 2007-01-30 2008-09-11 Asahi Kasei Chemicals Corp 多層多孔膜及びその製造方法
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Publication number Priority date Publication date Assignee Title
JP5165158B1 (ja) * 2012-03-13 2013-03-21 株式会社日立製作所 非水電解質二次電池及びその製造方法
WO2013136426A1 (fr) * 2012-03-13 2013-09-19 株式会社日立製作所 Pile secondaire à électrolyte non aqueux et procédé de fabrication correspondant
US8999586B2 (en) 2012-03-13 2015-04-07 Hitachi, Ltd. Electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for manufacturing the same
KR101519436B1 (ko) 2012-03-13 2015-05-12 가부시키가이샤 히타치세이사쿠쇼 비수 전해질 이차 전지용 전극, 비수 전해질 이차 전지 및 그 제조 방법
JP5647378B1 (ja) * 2013-03-19 2014-12-24 帝人株式会社 非水系二次電池用セパレータ及び非水系二次電池
JPWO2017038067A1 (ja) * 2015-08-31 2018-06-14 日本ゼオン株式会社 非水系二次電池機能層用組成物、非水系二次電池用機能層、及び非水系二次電池
CN107925039A (zh) * 2015-08-31 2018-04-17 日本瑞翁株式会社 非水系二次电池功能层用组合物、非水系二次电池用功能层、以及非水系二次电池
CN107925039B (zh) * 2015-08-31 2021-10-01 日本瑞翁株式会社 非水系二次电池功能层用组合物、非水系二次电池用功能层、以及非水系二次电池
WO2019235112A1 (fr) 2018-06-08 2019-12-12 旭化成株式会社 Séparateur multicouche
KR20210006951A (ko) 2018-06-08 2021-01-19 아사히 가세이 가부시키가이샤 다층 세퍼레이터
CN113574730A (zh) * 2019-03-20 2021-10-29 帝人株式会社 非水系二次电池用隔膜及非水系二次电池
CN113574730B (zh) * 2019-03-20 2023-06-02 帝人株式会社 非水系二次电池用隔膜及非水系二次电池
JP7567477B2 (ja) 2019-03-28 2024-10-16 東レ株式会社 多孔性フィルム、二次電池用セパレータおよび二次電池
CN114665227A (zh) * 2022-03-23 2022-06-24 哈尔滨工业大学无锡新材料研究院 一种高浸润性的锂离子电池隔膜及其制备方法
CN114665227B (zh) * 2022-03-23 2024-04-09 哈尔滨工业大学无锡新材料研究院 一种高浸润性的锂离子电池隔膜及其制备方法

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