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WO2014069410A1 - Film poreux multicouches et procédé de fabrication correspondant, et séparateur pour une cellule d'électrolyte non-aqueuse - Google Patents

Film poreux multicouches et procédé de fabrication correspondant, et séparateur pour une cellule d'électrolyte non-aqueuse Download PDF

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Publication number
WO2014069410A1
WO2014069410A1 PCT/JP2013/079155 JP2013079155W WO2014069410A1 WO 2014069410 A1 WO2014069410 A1 WO 2014069410A1 JP 2013079155 W JP2013079155 W JP 2013079155W WO 2014069410 A1 WO2014069410 A1 WO 2014069410A1
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Prior art keywords
porous membrane
mass
parts
dispersant
multilayer porous
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PCT/JP2013/079155
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English (en)
Japanese (ja)
Inventor
健 片桐
主隼 熊添
Original Assignee
旭化成イーマテリアルズ株式会社
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Application filed by 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to CN201380057208.0A priority Critical patent/CN104812579B/zh
Priority to JP2014544500A priority patent/JP6279479B2/ja
Priority to KR1020177016360A priority patent/KR102053259B1/ko
Priority to KR1020157010852A priority patent/KR20150063119A/ko
Publication of WO2014069410A1 publication Critical patent/WO2014069410A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a multilayer porous membrane, a method for producing the same, and a separator for a nonaqueous electrolyte battery.
  • Patent Document 1 discloses a battery in which a porous film containing an inorganic filler mainly composed of plate-like particles and a porous film mainly composed of polyolefin are integrated so that a shutdown state can be maintained even at high temperatures.
  • a separator for use is disclosed.
  • Patent Document 1 Although the battery separator described in Patent Document 1 is considered to have improved heat resistance as compared with a normal separator having no heat-resistant layer, it is desirable that the porous film containing the inorganic filler is made thinner. However, there is still room for improvement from the viewpoint of not being able to obtain the heat resistance.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a multilayer porous membrane having a low thermal shrinkage rate, a method for producing the same, and a separator for a nonaqueous electrolyte battery including the multilayer porous membrane.
  • the present inventors diligently studied the above problems. As a result, it has been found that the above-mentioned problems can be solved by forming a predetermined porous layer on one or both surfaces of the polyolefin porous membrane, and the present invention has been completed.
  • the present invention is as follows. [1] A polyolefin porous membrane, A porous layer containing an inorganic filler, a resin binder, and an ion dissociable inorganic dispersant, disposed on one or both sides of the polyolefin porous membrane; A multilayer porous membrane. [2] The multilayer porous membrane according to [1] above, wherein the porous layer further contains an ion dissociative organic dispersant. [3] The content of the ionic dissociable inorganic dispersant is 20 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the total content of the ionic dissociative inorganic dispersant and the ionic dissociative organic dispersant.
  • the present invention it is possible to provide a multilayer porous membrane having a low thermal shrinkage rate, a method for producing the same, and a separator for a nonaqueous electrolyte battery provided with the multilayer porous membrane.
  • the present embodiment a mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be described in detail.
  • this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
  • the multilayer porous membrane of this embodiment is A polyolefin porous membrane, It has a porous layer (hereinafter also simply referred to as “porous layer”) containing an inorganic filler, a resin binder, and an ion dissociating inorganic dispersant, which is disposed on one or both surfaces of the polyolefin porous membrane.
  • a porous layer hereinafter also simply referred to as “porous layer” containing an inorganic filler, a resin binder, and an ion dissociating inorganic dispersant, which is disposed on one or both surfaces of the polyolefin porous membrane.
  • the polyolefin porous film is not particularly limited, and a porous film containing a polyolefin resin can be used.
  • the content of the polyolefin resin in the polyolefin porous membrane is not particularly limited, but is preferably 50% by mass or more, and more preferably 70 to 100% by mass. When the content of the polyolefin resin in the polyolefin porous membrane is within the above range, the shutdown performance when used as a battery separator tends to be further improved.
  • the polyolefin resin is not particularly limited, and for example, a polyolefin resin used for normal extrusion, injection, inflation, blow molding and the like can be used.
  • polyolefin resins include homopolymers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene, copolymers thereof, and these And a multistage polymer. More specifically, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and ultrahigh molecular weight polyethylene, isotactic polypropylene, atactic polypropylene, ethylene-propylene random copolymer, polybutene, and Examples include ethylene propylene rubber.
  • polyolefin resin may be used individually by 1 type, or may use 2 or more types together.
  • the polyolefin resin preferably contains polypropylene.
  • the content of polypropylene in the polyolefin resin is not particularly limited, but is preferably 1 to 35% by mass, more preferably 3 to 20% by mass, and further preferably 4 to 10% by mass.
  • the content of polypropylene is 1% by mass or more, the heat resistance of the porous membrane tends to be further improved.
  • the content of polypropylene having a relatively high melting point is 35% by mass or less, when the multilayer porous membrane of this embodiment is used as a battery separator, the membrane is more thermally melted at the shutdown temperature. It tends to block (shutdown property) and tends to cause shutdown at a lower temperature.
  • the viscosity average molecular weight (Mv) of the polyolefin resin is not particularly limited, but is preferably 50,000 to 3,000,000, more preferably 100,000 to 1,000,000, still more preferably 200, 000 to 800,000.
  • Mv the mechanical strength of the resulting polyolefin porous film tends to be further improved.
  • Mv of the polyolefin resin is 3,000,000 or less, the moldability during production tends to be further improved.
  • Mv is 1,000,000 or less
  • the hole tends to be blocked when the temperature rises, and the shutdown function tends to be further improved.
  • a mixture of two or more polyolefin resins having different Mvs may be used.
  • the viscosity average molecular weight (Mv) of polyolefin resin can be measured by the method as described in an Example.
  • Polyolefin porous membranes are made of antioxidants such as phenolic compounds, phosphorus compounds, or sulfur compounds, metal soaps such as calcium stearate and zinc stearate, UV absorbers, light stabilizers, and antistatics as necessary.
  • antioxidants such as phenolic compounds, phosphorus compounds, or sulfur compounds
  • metal soaps such as calcium stearate and zinc stearate
  • UV absorbers such as calcium stearate and zinc stearate
  • UV absorbers such as calcium stearate and zinc stearate
  • light stabilizers such as an additive
  • An additive such as an agent, an antifogging agent, and a color pigment may be included.
  • the film thickness of the polyolefin porous membrane is not particularly limited, but is preferably 0.10 ⁇ m or more and 25 ⁇ m or less, more preferably 1.0 ⁇ m or more and 20 ⁇ m or less, further preferably 3.0 ⁇ m or more and 18 ⁇ m or less, and particularly preferably. Is 5.0 ⁇ m or more and 16 ⁇ m or less.
  • the film thickness of the polyolefin porous membrane is 0.10 ⁇ m or more, the mechanical strength of the resulting multilayer porous membrane tends to be further improved.
  • the film thickness of the polyolefin porous membrane is 25 ⁇ m or less, the battery tends to have a higher capacity.
  • the film thickness of a polyolefin porous membrane can be measured by the method as described in an Example.
  • the average pore diameter of the polyolefin porous membrane is not particularly limited, but is preferably 0.030 ⁇ m or more and 0.20 ⁇ m or less, more preferably 0.040 ⁇ m or more and 0.10 ⁇ m or less, and further preferably 0.050 ⁇ m or more and 0.090 ⁇ m or less. Or less, and particularly preferably 0.060 ⁇ m or more and 0.090 ⁇ m or less.
  • the porosity of the polyolefin porous membrane is not particularly limited, but is preferably 25% or more and 65% or less, more preferably 30% or more and 60% or less, and further preferably 35% or more and 55% or less.
  • the porosity of the polyolefin porous membrane is 25% or more, an increase in the air permeability after applying the inorganic filler-containing dispersion described later tends to be further suppressed.
  • the porosity of a polyolefin porous membrane can be measured by the method as described in an Example.
  • the maximum value of the heat shrinkage stress of the polyolefin porous film is not particularly limited, but is preferably 10 g or less in both the drawing direction (hereinafter also referred to as “MD”) and the width direction (hereinafter also referred to as “TD”). More preferably, it is 8 g or less, More preferably, it is 6 g or less, Especially preferably, it is 4 g or less.
  • MD drawing direction
  • TD width direction
  • the multilayer porous membrane of this embodiment has a porous layer containing an inorganic filler, a resin binder, and an ion dissociative inorganic dispersant, which are disposed on one or both sides of a polyolefin porous membrane.
  • a porous layer containing an inorganic filler, a resin binder, and an ion dissociative inorganic dispersant, which are disposed on one or both sides of a polyolefin porous membrane.
  • the heat resistance is further improved.
  • the ion dissociable inorganic dispersant has a strong affinity with the surface of the inorganic filler, and in the slurry used when forming the porous layer, the affinity of the inorganic filler to the slurry solvent can be increased, and charge repulsion can be achieved. This is considered to be because the dispersibility of the inorganic filler in the slurry solvent can be improved.
  • the reason why the heat resistance is improved is not limited to these.
  • the ion dissociable inorganic dispersant is not particularly limited, and examples thereof include inorganic acid salts.
  • inorganic acid salts include orthophosphates, condensed phosphates, and aluminates. Among them, it has multiple phosphate groups in one molecule and is considered to exhibit strong affinity with the inorganic filler surface.
  • a condensed phosphate is preferred.
  • the condensed phosphate is not particularly limited, and examples thereof include polyphosphate, metaphosphate, and ultraphosphate. Among these, polyphosphate and metaphosphate are preferable.
  • polyphosphate has a structure in which orthophosphoric acid is linked in a chain
  • metaphosphate has a structure linked in a ring
  • ultraphosphate has a structure linked in a network.
  • polyphosphate and metaphosphate are particularly preferable.
  • the polyphosphates are not particularly limited, for example, a compound represented by the formula (M n + 2 P n O 3n + 1) and the like.
  • the degree of condensation n in the formula is not particularly limited, but is preferably 2 to 30, more preferably 2 to 10, and further preferably 2 to 6.
  • M is a cation.
  • the polyphosphate is not particularly limited, and examples thereof include pyrophosphate, tripolyphosphate, tetrapolyphosphate, pentapolyphosphate, and hexapolyphosphate.
  • the metaphosphate is not particularly limited, for example, a compound represented by the formula (MPO 3) n and the like.
  • the degree of condensation n in the formula is not particularly limited, but is preferably 3 to 200, more preferably 3 to 25, and further preferably 3 to 6.
  • M is a cation.
  • a metaphosphate For example, a trimetaphosphate, a tetrametaphosphate, a pentametaphosphate, and a hexametaphosphate are mentioned. By using such a metaphosphate, adsorption to the inorganic filler becomes faster, stable dispersibility can be maintained, and aggregation of a resin binder or the like tends not to occur.
  • a cation which comprises an ion dissociable inorganic dispersing agent for example, an inorganic cation or an organic cation is mentioned.
  • the inorganic cation is not particularly limited, and examples thereof include alkali metal ions or alkaline earth metal ions such as potassium ions and sodium ions.
  • an organic cation For example, an amine ion, an ammonium ion, etc. are mentioned.
  • the cation constituting the ion dissociable inorganic dispersant is preferably an amine ion or an ammonium ion from the viewpoint of affinity with the resin binder.
  • condensed phosphate As the condensed phosphate, commercially available products such as those manufactured by Taiyo Chemical Industry Co., Ltd., phosphorus chemical industry Co., Ltd., San Nopco Co., Ltd., and Kirin Kyowa Foods Co., Ltd. can be used.
  • An ion dissociative inorganic dispersing agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the ion dissociable inorganic dispersant in the porous layer is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 100 parts by mass of the inorganic filler. 0.3 parts by mass or more.
  • the content of the ion dissociable inorganic dispersant in the porous layer is 0.05 parts by mass or more, the heat resistance of the multilayer porous membrane tends to be further improved.
  • the content of the ion dissociable inorganic dispersant in the porous layer is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass with respect to 100 parts by mass of the inorganic filler. Or less.
  • the content of the ion dissociable inorganic dispersant in the porous layer is 5 parts by mass or less, the content ratio of the other components in the porous layer is reduced, and the effect of the other components is further suppressed from being reduced. There is a tendency.
  • the content of the ion dissociable inorganic dispersant in the porous layer is the total content of the ion dissociable inorganic dispersant and the ion dissociable organic dispersant. Preferably it is 20 to 95 mass parts with respect to 100 mass parts, More preferably, it is 30 to 93 mass parts, More preferably, it is 50 to 90 mass parts.
  • the content of the ion dissociable inorganic dispersant in the porous layer is within the above range, the heat resistance tends to be further improved.
  • the porous layer of this embodiment contains an inorganic filler
  • the heat resistance of a multilayer porous membrane improves.
  • the inorganic filler contained in the porous layer has a melting point of 200 ° C. or higher, high electrical insulation, and under the conditions for use as a separator. Those that are electrochemically stable are preferred.
  • the inorganic filler is not particularly limited.
  • alumina aluminum hydroxide oxide (boehmite), silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, and other oxide ceramics and hydration thereof.
  • Nitride ceramics such as silicon nitride, titanium nitride, boron nitride; ceramics such as silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, barium titanate; talc, kaolinite, dickite, nacrite, halloysite, pyrophyll Layered silicate minerals such as light, montmorillonite, sericite, mica, and amesite; glass fibers and the like.
  • An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
  • aluminum oxide ceramics such as alumina and aluminum hydroxide oxide (boehmite) and hydrates thereof; layered silicates having no ion exchange ability such as kaolinite, dickite, nacrite, halloysite, and pyrophyllite Minerals are preferred.
  • layered silicates having no ion exchange ability such as kaolinite, dickite, nacrite, halloysite, and pyrophyllite Minerals are preferred.
  • the aluminum oxide ceramics and their hydrates are not particularly limited, but for example, aluminum hydroxide oxide is more preferable.
  • kaolin mainly composed of kaolinite is more preferable.
  • Kaolin includes wet kaolin and calcined kaolin, which is calcined. However, calcined kaolin releases crystal water during the calcining process and removes impurities. Particularly preferred.
  • the average particle size of the inorganic filler is not particularly limited, but is preferably from 0.10 ⁇ m to 3.0 ⁇ m, more preferably from 0.20 ⁇ m to 2.0 ⁇ m, still more preferably from 0.50 ⁇ m to 1. It is 2 ⁇ m or less, more preferably 0.50 ⁇ m or more and 0.80 ⁇ m or less.
  • the average particle size of the inorganic filler is 0.10 ⁇ m or more, the short temperature when used as a battery separator tends to be higher.
  • the average particle size of the inorganic filler can be obtained as a value of a particle size at which the cumulative frequency of the number of particles is 50% by measuring the particle size distribution using water as a dispersion medium and using a laser particle size distribution measuring device.
  • the content of the inorganic filler in the porous layer is not particularly limited, but is preferably 50% or more and less than 100%, more preferably 55% or more and 99.99% or less, and further preferably 60% or more and 99.9%. % Or less, particularly preferably 65% or more and 99% or less, and most preferably 90% or more and 99% or less.
  • the heat resistance and the like tend to be further improved.
  • the resin binder contained in the porous layer has a function for binding the inorganic filler onto the porous film.
  • the resin binder contained in the porous layer is insoluble in the electrolyte solution of the lithium ion secondary battery, and the use of the lithium ion secondary battery It is preferable to use one that is electrochemically stable within a range.
  • Such a resin binder is not particularly limited, but examples thereof include polyolefin resins such as polyethylene, polypropylene, and ⁇ -polyolefin; fluorine-based polymers such as polyvinylidene fluoride and polytetrafluoroethylene and copolymers containing them; butadiene, isoprene, and the like A diene polymer containing a conjugated diene as a monomer unit or a copolymer thereof and a hydride thereof; an acrylic polymer containing an acrylate ester, a methacrylic acid ester or the like as a monomer unit or a copolymer containing the same and a hydride thereof; ethylene propylene Rubbers such as rubber, polyvinyl alcohol and polyvinyl acetate; cellulose derivatives such as ethyl cellulose, methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose ; Polyphenylene ether, polysulfone, poly
  • a resin binder may be used individually by 1 type, or may use 2 or more types together.
  • a fluorine polymer, a diene polymer, and an acrylic polymer are preferable, and an acrylic polymer is more preferable.
  • the binding property, heat resistance, and permeability tend to be further improved.
  • oxidation resistance tends to be further improved by using an acrylic polymer.
  • electrochemical stability tends to be improved by using a fluorine-based polymer.
  • the fluorine-based polymer is not particularly limited, and examples thereof include a homopolymer of vinylidene fluoride and a copolymer with a monomer copolymerizable with vinylidene fluoride.
  • the content of the vinylidene fluoride monomer unit in the fluoropolymer is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more.
  • the monomer copolymerizable with vinylidene fluoride is not particularly limited.
  • the fluorine-based polymer is not particularly limited, but a homopolymer of vinylidene fluoride, a vinylidene fluoride / tetrafluoroethylene copolymer, a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, or the like is preferable. Among these, a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer is more preferable.
  • the monomer composition of the vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer is not particularly limited.
  • a fluorine-type polymer may be used individually by 1 type, or may use 2 or more types together.
  • the diene polymer is not particularly limited as long as it contains a diene monomer unit having two double bonds as a repeating unit.
  • a diene monomer homopolymer or a copolymer of a diene monomer and a copolymerizable monomer can be used. Can be mentioned.
  • the diene monomer is not particularly limited, and examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2- Examples include methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.
  • a diene monomer may be used individually by 1 type, or may use 2 or more types together.
  • the content of the diene monomer unit in the diene polymer is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% with respect to the total amount of the diene polymer. It is at least mass%.
  • the monomer copolymerizable with the diene monomer is not particularly limited, and examples thereof include a (meth) acrylate monomer described below and the following monomers (hereinafter also referred to as “other monomers”).
  • Other monomers are not particularly limited, and examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid; styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, and vinyl benzoic acid.
  • Styrene monomers such as methyl, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, ⁇ -methylstyrene, divinylbenzene; olefins such as ethylene and propylene; halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; vinyl acetate, propion Vinyl esters such as vinyl acid vinyl, vinyl butyrate, vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hex Vinyl ketones such as ruvinyl ketone and isopropenyl vinyl ketone; heterocycle-containing vinyl compounds such as N-vinyl pyrrolidone, vinyl pyridine and vinyl imidazole; amide monomers such as acrylamide, N-methylol acrylamide and acrylamide-2-methyl
  • the acrylic polymer is not particularly limited as long as it is a polymer containing a (meth) acrylate monomer unit, and examples thereof include a homopolymer of a (meth) acrylate monomer and a copolymer of a monomer copolymerizable with a (meth) acrylate monomer.
  • (meth) acrylic acid means “acrylic acid or methacrylic acid”
  • (meth) acrylate” means “acrylate or methacrylate”.
  • the acrylic polymer is not particularly limited, but is preferably latex.
  • the (meth) acrylate monomer is not particularly limited.
  • the content of the (meth) acrylate monomer unit in the acrylic polymer is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total amount of the acrylic polymer. Preferably it is 60 mass% or more.
  • the monomer copolymerizable with the (meth) acrylate monomer is not particularly limited, and examples thereof include other monomers listed in the item of the diene polymer.
  • the monomer copolymerizable with the (meth) acrylate monomer may be used alone or in combination of two or more.
  • unsaturated carboxylic acids it is preferable to use unsaturated carboxylic acids.
  • Unsaturated carboxylic acids are not particularly limited.
  • monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid half ester, maleic acid half ester, fumaric acid half ester; itaconic acid, fumaric acid, maleic acid.
  • dicarboxylic acids such as acids. Of these, acrylic acid, methacrylic acid and itaconic acid are preferred, and acrylic acid and methacrylic acid are more preferred.
  • the saponification degree is preferably 85% or more and 100% or less, more preferably 90% or more and 100% or less, and further preferably 95% or more and 100%. Or less, particularly preferably 99% or more and 100% or less.
  • the saponification degree is 85% or more, when the multilayer porous membrane is used as a battery separator, the temperature at which a short circuit occurs (short temperature) is improved, and the safety performance tends to be further improved.
  • the polymerization degree of polyvinyl alcohol is preferably 200 or more and 5000 or less, more preferably 300 or more and 4000 or less, and particularly preferably 500 or more and 3500 or less.
  • the polymerization degree is 200 or more, the inorganic filler can be firmly bound with a small amount of polyvinyl alcohol, and the increase in the air permeability of the multilayer porous film due to the formation of the porous layer can be suppressed while maintaining the mechanical strength of the porous layer. It tends to be possible.
  • content of the resin binder in a porous layer is not specifically limited, Preferably it is 0.5 mass part or more with respect to 100 mass parts of inorganic fillers, More preferably, it is 0.7 mass part or more, More preferably Is 1.2 parts by mass or more, particularly preferably 1.5 parts by mass or more.
  • the content of the resin binder in the porous layer is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 7 parts by mass or less.
  • the content of the resin binder in the porous layer is 10 parts by mass or less, the ion permeability tends to be further improved.
  • the porous layer may contain other additives other than the inorganic filler, the resin binder, and the ion dissociable inorganic dispersant.
  • Other additives are not particularly limited, and examples thereof include ion dissociable organic dispersants.
  • the porous layer of the present embodiment it is preferable that the porous layer further contains an ion dissociative organic dispersant from the viewpoint of heat resistance of the multilayer porous membrane.
  • the reason why heat resistance is improved by including an ion dissociable organic dispersant is that the dispersion stability of the inorganic filler and resin binder in the slurry is further improved by using a dispersant other than the ion dissociable inorganic dispersant. Although it is thought that it is because it can be made, it is not specifically limited.
  • Organic acid salt can be mentioned.
  • the organic acid salt for example, various anionic or cationic polymer surfactants can be used.
  • the ion dissociable organic dispersant is an ion dissociable acid group (carboxyl group, sulfonic acid group, amino acid group, maleic acid group, etc.) or ion dissociable acid base (carboxylic acid group, sulfonic acid). Those containing a plurality of bases, maleate bases, etc.) are preferred.
  • polycarboxylate, polyacrylate, and polymethacrylate are more preferable.
  • An ion dissociative organic dispersing agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the ion dissociable organic dispersant in the porous layer is not particularly limited, but is preferably 20 parts by mass or more with respect to 100 parts by mass of the total content of the ion dissociable inorganic dispersant and the ion dissociable organic dispersant. 95 parts by mass or less, more preferably 30 parts by mass or more and 93 parts by mass or less, and further preferably 50 parts by mass or more and 90 parts by mass or less.
  • the content of the ion dissociable inorganic dispersant in the porous layer is 20 parts by mass or more and 95 parts by mass or less, the heat resistance tends to be further improved.
  • the layer thickness of the porous layer in the present embodiment is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.5 ⁇ m or more and 8 ⁇ m or less, further preferably 1 ⁇ m or more and 6 ⁇ m or less, and particularly preferably 1.5 ⁇ m. It is 5 ⁇ m or less.
  • the thickness of the porous layer is 0.1 ⁇ m or more, the heat resistance tends to be further improved.
  • the layer thickness of the porous layer is 10 ⁇ m or less, the battery has a higher capacity, the ion permeability of the separator is further improved, and the powder of the inorganic filler during use tends to be further suppressed.
  • the porous layer has a permeability that does not significantly impair the permeability of the polyolefin porous membrane in the state of the multilayer porous membrane, but the air permeability of the multilayer porous membrane due to the formation of the porous layer is sufficient.
  • the rate of increase in the degree is preferably 0% or more and 200% or less, more preferably 0% or more and 100% or less, and further preferably 0% or more and 70% or less.
  • the rate of increase in the air permeability of the multilayer porous membrane after forming the porous layer is preferably 0% or more and 500% or less. is there.
  • the multilayer porous membrane of this embodiment has a polyolefin porous membrane and a porous layer disposed on one side or both sides of the polyolefin porous membrane.
  • the air permeability of the multilayer porous membrane of the present embodiment is not particularly limited, but is preferably 10 seconds / 100 cc to 650 seconds / 100 cc, more preferably 20 seconds / 100 cc to 500 seconds / 100 cc, It is preferably 30 seconds / 100 cc or more and 450 seconds / 100 cc or less, particularly preferably 50 seconds / 100 cc or more and 400 seconds / 100 cc or less.
  • the air permeability of the multilayer porous membrane is 10 seconds / 100 cc or more, the self-discharge resistance tends to be further improved. Moreover, when the air permeability of the multilayer porous membrane is 650 seconds / 100 cc or less, the charge / discharge characteristics tend to be further improved.
  • the final film thickness of the multilayer porous membrane of the present embodiment is not particularly limited, but is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 5 ⁇ m or more and 19 ⁇ m or less, and further preferably 7 ⁇ m or more and 18 ⁇ m or less. Preferably they are 9 micrometers or more and 17 micrometers or less.
  • the final film thickness of the multilayer porous membrane is 2 ⁇ m or more, the mechanical strength tends to be further improved.
  • the final film thickness of the multilayer porous membrane is 20 ⁇ m or less, the battery tends to have a higher capacity.
  • the heat shrinkage rate at 150 ° C. of the multilayer porous membrane of the present embodiment is not particularly limited, but both MD and TD are preferably 0% or more and 15% or less, more preferably 0% or more and 10% or less, More preferably, it is 0% or more and 5% or less. Since the thermal contraction rate at 150 ° C. in both the MD and TD directions is 15% or less, it is possible to prevent the separator from being broken even when the battery is abnormally heated. Good safety performance tends to be obtained.
  • the shutdown temperature of the multilayer porous membrane of this embodiment is not particularly limited, but is preferably 120 ° C. or higher and 160 ° C. or lower, more preferably 120 ° C. or higher and 150 ° C. or lower.
  • the shutdown temperature of the multilayer porous membrane is 160 ° C. or lower, even when the battery generates heat, current interruption is promptly promoted, and better safety performance tends to be obtained.
  • the shutdown temperature of the multilayer porous membrane is 120 ° C. or higher because, for example, use of a high temperature around 100 ° C., heat treatment, etc. can be carried out.
  • the short-circuit temperature of the multilayer porous membrane of the present embodiment is not particularly limited, but is preferably 180 ° C. or higher, preferably 190 ° C. or higher, and more preferably 200 ° C. or higher.
  • the multilayer porous membrane has a short-circuit temperature of 180 ° C. or higher, contact between the positive and negative electrodes can be suppressed until heat is dissipated even in abnormal battery heat generation, and thus better safety performance tends to be obtained.
  • the manufacturing method of the multilayer porous membrane of this embodiment has the application
  • the manufacturing method of a multilayer porous membrane may have the process of manufacturing a polyolefin porous membrane as needed.
  • the production method of the polyolefin porous film is not particularly limited.
  • the polyolefin resin and the plasticizer are melt-kneaded and formed into a sheet shape, and then the porous film is extracted by extracting the plasticizer.
  • Polyolefin resin is melt-kneaded and extruded at a high draw ratio, then the polyolefin crystal interface is peeled off by heat treatment and stretching, and polyolefin resin and inorganic filler are melt-kneaded and molded on a sheet After that, by making the interface by peeling the interface between the polyolefin resin and the inorganic filler by stretching, the polyolefin resin is dissolved and then immersed in a poor solvent for the polyolefin resin to solidify the polyolefin resin and simultaneously remove the solvent.
  • Well-known methods such as a method of making it porous, can be mentioned.
  • the inorganic filler-containing resin dispersion can be more uniformly applied and moreover, after the coating. Since the adhesiveness of an inorganic filler containing resin layer and the polyolefin porous membrane surface improves, it is preferable.
  • the surface treatment method is not particularly limited as long as the porous structure of the polyolefin porous membrane is not significantly impaired, and examples thereof include a corona discharge treatment method, a mechanical surface roughening method, a solvent treatment method, an acid treatment method, and an ultraviolet oxidation method. Can be mentioned.
  • a dispersion containing an inorganic filler, a resin binder, and an ion dissociating inorganic dispersant is applied to one or both sides of the polyolefin porous membrane.
  • the dispersion used in the production method of the present embodiment contains an ion dissociable inorganic dispersant in addition to the inorganic filler and the resin binder, the dispersion stability of the inorganic filler in the dispersion is further improved. Since the dispersion contains a resin binder, the binding property between the porous film, the inorganic filler, and the inorganic filler is further improved.
  • the inorganic filler is not particularly limited, and those described above can be used.
  • the resin binder is not particularly limited, and the above-mentioned ones can be used. Of these, aliphatic conjugated diene monomers and unsaturated carboxylic acid monomers and their copolymerization are possible because the ion permeability is less likely to decrease when the porous layer is laminated on at least one side of the porous membrane. It is preferable to use a latex obtained by emulsion polymerization of other monomers.
  • the resin binder is preferably an acrylic polymer, particularly an acrylic latex. In particular, depending on the inorganic filler used, aggregation is likely to occur when an acrylic polymer is added. However, in the manufacturing method of this embodiment, since a dispersant containing an ion dissociable inorganic dispersant is used, the aggregation of the resin binder is suppressed. Can do.
  • the ion dissociable inorganic dispersant is not particularly limited, and those described above can be used.
  • the solvent of the dispersion is not particularly limited, and examples thereof include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, water, ethanol, toluene, hot xylene, and hexane. Water is preferable from the viewpoint of dispersibility of the inorganic filler and the resin binder.
  • the dispersion preferably further contains an ion dissociable organic dispersant.
  • the dispersion stability of the inorganic filler and the resin binder in the dispersion tends to be further improved. It does not specifically limit as an ion dissociative organic dispersing agent, The same thing as the above can be used.
  • the ion dissociable organic dispersant, together with the ion dissociable inorganic dispersant, serves as a dispersant in the dispersion of the production method of the present embodiment.
  • the content of the ion dissociable inorganic dispersant in the dispersion is not particularly limited, but is the total of the ion dissociable inorganic dispersant and the ion dissociable organic dispersant.
  • it is 20 mass parts or more and 95 mass parts or less with respect to 100 mass parts of content, More preferably, they are 30 mass parts or more and 93 mass parts or less, More preferably, they are 50 mass parts or more and 90 mass parts or less.
  • the content of the ion dissociable inorganic dispersant in the dispersion is 20 parts by mass or more and 95 parts by mass or less, the dispersibility of the inorganic filler and the resin binder in the slurry solvent tends to be further improved.
  • a dispersant such as a surfactant, a thickener, a wetting agent, an antifoaming agent, Various additives such as pH adjusting agents including acids and alkalis may be added. These additives are preferably those that can be removed upon solvent removal or plasticizer extraction. However, if they are electrochemically stable in the range of use of the lithium ion secondary battery and do not inhibit the battery reaction, May remain.
  • a method for dissolving or dispersing the inorganic filler, the resin binder, and the ion dissociable inorganic dispersant in a solvent is not particularly limited.
  • a ball mill, a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid examples thereof include a mill, an attritor, a roll mill, a high-speed impeller dispersion, a disperser, a homogenizer, a high-speed impact mill, ultrasonic dispersion, and mechanical stirring using a stirring blade.
  • the method for applying the dispersion to the polyolefin porous film is not particularly limited as long as it can realize the required layer thickness and application area.
  • gravure coater method small diameter gravure coater method, reverse roll coater method, transfer roll coater method, kiss coater method, dip coater method, knife coater method, air doctor coater method, blade coater method, rod coater method, squeeze coater method
  • examples thereof include a cast coater method, a die coater method, a screen printing method, and a spray coating method.
  • an inorganic filler containing resin dispersion liquid may be apply
  • the solvent after applying the dispersion.
  • a method for removing the solvent for example, a method of drying at a temperature below the melting point while fixing the polyolefin porous film, a method of drying under reduced pressure at a low temperature, and immersing in a poor solvent for the resin binder to solidify the resin binder The method of extracting a solvent simultaneously is mentioned.
  • the separator for nonaqueous electrolyte batteries of this embodiment includes the multilayer porous film.
  • the multilayer porous membrane has heat resistance and can be suitably used as a separator for nonaqueous electrolyte batteries.
  • the multilayer porous membrane of this embodiment can achieve both good heat resistance and ion permeability (air permeability). When such a multilayer porous membrane is used as a separator for a non-aqueous electrolyte battery, a non-aqueous electrolyte battery excellent in safety performance and output characteristics can be realized.
  • the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
  • the physical property in an Example was measured with the following method. Unless otherwise stated, various measurements and evaluations were performed under conditions of room temperature 23 ° C., 1 atm, and relative humidity 50%.
  • Thickness ( ⁇ m) of multilayer porous membrane and polyolefin porous membrane, and layer thickness ( ⁇ m) of porous layer The film thicknesses of the multilayer porous membrane and the polyolefin porous membrane were measured with a dial gauge (manufactured by Ozaki Seisakusho, trade name “PEACOCK No. 25”). Specifically, a sample having a dimension of 100 mm in the MD direction ⁇ 100 mm in the TD direction was cut out, and the local film thicknesses at 9 locations (3 points ⁇ 3 points) were measured in a lattice shape. The arithmetic average value was defined as the film thickness. The thickness of the porous layer was calculated from the difference between the thickness of the multilayer porous membrane and the thickness of the polyolefin porous membrane (measured by peeling the porous layer).
  • Air permeability (second / 100 cc), rate of increase in air permeability (%) of multilayer porous membrane and polyolefin porous membrane For measurement of the air permeability (second / 100 cc) of the multilayer porous membrane and the polyolefin porous membrane, a Gurley type air permeability meter (G-B2 (trademark) manufactured by Toyo Seiki Co.) conforming to JIS P-8117 was used. The inner cylinder weight was 567 g, and the time required for 100 mL of air to pass through an area of 28.6 mm in diameter and 645 mm 2 was measured as the air permeability.
  • Average particle size of inorganic filler The average particle size of the inorganic filler is measured by measuring the particle size distribution using a laser particle size distribution measuring device (Microtrack MT3300EX manufactured by Nikkiso Co., Ltd.) using water as a dispersion medium, and the cumulative frequency. was the average particle size.
  • Example 1 Manufacture of polyolefin porous membrane 47 parts by mass of polyethylene having an Mv of 700,000, 46 parts by mass of polyethylene having an Mv of 300,000, and 7 parts by mass of polypropylene having an Mv of 400,000 were dry blended using a tumbler blender. Next, 1 part by mass of pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added to 99 parts by mass of the obtained pure polymer mixture. Then, the mixture was made into 100 parts by mass in total, and dry blended again using a tumbler blender to obtain a polymer mixture.
  • the obtained mixture such as polymer was fed to the twin screw extruder by a feeder under a nitrogen atmosphere. Further, liquid paraffin (kinematic viscosity at 37.78 ° C .: 7.59 ⁇ 10 ⁇ 5 m 2 / s) was injected into the extruder cylinder by a plunger pump.
  • liquid paraffin kinematic viscosity at 37.78 ° C .: 7.59 ⁇ 10 ⁇ 5 m 2 / s
  • a mixture such as a polymer and liquid paraffin were melt-kneaded in a twin-screw extruder, and the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture to be extruded was 65 parts by mass.
  • the melt kneading conditions were a set temperature of 200 ° C., a screw rotation speed of 240 rpm, and a discharge rate of 12 kg / h. Subsequently, the melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a gel sheet having a thickness of 1600 ⁇ m.
  • the obtained gel sheet was guided to a simultaneous biaxial tenter stretching machine, and biaxial stretching was performed.
  • the set stretching conditions were an MD magnification of 7.0 times, a TD magnification of 7.0 times, and a preset temperature of 125 ° C.
  • the stretched gel sheet was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then methyl ethyl ketone was removed by drying.
  • the dried gel sheet was guided to a TD tenter and heat fixed.
  • the stretching temperature and magnification during heat setting were 128 ° C. and 2.0 times, and the temperature and relaxation rate during subsequent relaxation were 133 ° C. and 0.80.
  • the reaction vessel was charged from the tank.
  • the pH of the reaction system was maintained at 4 or lower.
  • the temperature of the reaction vessel was kept at 80 ° C. and stirring was continued for 120 minutes. Then, it cooled to room temperature.
  • Formation of porous layer 94 parts by mass of aluminum hydroxide oxide particles (average particle size: 1.0 ⁇ m) as inorganic filler, 6.0 parts by mass of acrylic polymer (solid content concentration: 45%) as resin binder, and ion dissociable inorganic dispersant Then, 1.0 part by mass of polyphosphate amine salt (dispersant) was uniformly dispersed in 100 parts by mass of water to prepare a dispersion for forming a porous layer. The prepared dispersion for forming a porous layer was applied to the surface of the polyolefin porous film using a gravure coater.
  • Example 2 The dispersant in the dispersion for forming the porous layer is 0.95 part by mass of polyphosphate amine salt, 0.05 part by mass of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco) that is an ion dissociative organic dispersant, A multilayer porous membrane was obtained in the same manner as in Example 1 except that the mixture was used. The results are listed in Table 1.
  • Example 3 Example 1 except that the dispersant in the porous layer-forming dispersion was a mixture of 0.8 parts by mass of polyphosphate amine salt and 0.2 parts by mass of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco). In the same manner, a multilayer porous membrane was obtained. The results are listed in Table 1.
  • Example 4 Example 1 except that the dispersant in the porous layer-forming dispersion was a mixture of 0.6 parts by mass of polyphosphate amine salt and 0.4 parts by mass of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco). In the same manner, a multilayer porous membrane was obtained. The results are listed in Table 1.
  • Example 5 Example 1 except that the dispersant in the dispersion for forming the porous layer was a mixture of 0.2 parts by mass of polyphosphate amine salt and 0.8 parts by mass of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco). In the same manner, a multilayer porous membrane was obtained. The results are listed in Table 1.
  • Example 6 Example 1 except that the dispersant in the dispersion for forming a porous layer was a mixture of 0.05 part by mass of a polyphosphate amine salt and 0.95 part by mass of ammonium polycarboxylate (SN Dispersant 5468 manufactured by San Nopco). In the same manner, a multilayer porous membrane was obtained. The results are listed in Table 1.
  • Example 7 A multilayer porous membrane was obtained in the same manner as in Example 3 except that the thickness of the porous layer was 5 ⁇ m. The results are listed in Table 1.
  • Example 8 A multilayer porous membrane was obtained in the same manner as in Example 3 except that the thickness of the porous layer was 7 ⁇ m. The results are listed in Table 1.
  • Example 9 A multilayer porous membrane was obtained in the same manner as in Example 3 except that the thickness of the porous layer was 10 ⁇ m. The results are listed in Table 1.
  • Example 10 Example except that the dispersant in the dispersion for forming the porous layer was a mixture of 0.8 parts by mass of polyphosphate amine salt and 0.2 parts by mass of sodium polyacrylate which is an ionic dissociative organic dispersant. In the same manner as in Example 3, a multilayer porous membrane was obtained. The results are listed in Table 1.
  • DOP dioctyl phthalate
  • the molded product was subjected to extraction removal of DOP with methylene chloride and silica with sodium hydroxide to form a porous film.
  • the porous membrane was heated to 118 ° C. and stretched 5.3 times in the longitudinal direction and then 1.8 times in the transverse direction.
  • a porous film having a film thickness of 11 ⁇ m, porosity of 48 volume%, air permeability of 55 seconds / 100 cc, MD maximum heat shrinkage stress of 8.7 g, and TD maximum heat shrinkage stress of 0.9 g was obtained.
  • a multilayer porous membrane was obtained in the same manner as in Example 3 except that the polyolefin porous membrane was used as a substrate. The results are listed in Table 1.
  • Example 12 A multilayer porous membrane was obtained in the same manner as in Example 1 except that calcined kaolin (average particle size: 1.0 ⁇ m) was used as the inorganic filler in the porous layer forming dispersion. The results are listed in Table 1.
  • Example 13 A multilayer porous membrane was obtained in the same manner as in Example 1 except that alumina (average particle size: 1.0 ⁇ m) was used as the inorganic filler in the dispersion for forming the porous layer. The results are listed in Table 1.
  • Example 14 A multilayer porous membrane was obtained in the same manner as in Example 1 except that ammonium polyphosphate was used as the dispersant in the dispersion for forming the porous layer. The results are also shown in Table 1.
  • Example 15 A multilayer porous membrane was obtained in the same manner as in Example 1 except that sodium polyphosphate was used as the dispersant in the dispersion for forming the porous layer. The results are also shown in Table 1.
  • Example 16 A multilayer porous membrane was obtained in the same manner as in Example 1 except that the dispersant in the dispersion for forming the porous layer was changed to 0.3 parts by mass of polyphosphate amine salt. The results are listed in Table 1.
  • Example 17 A multilayer porous membrane was obtained in the same manner as in Example 1 except that the dispersant in the dispersion for forming a porous layer was changed to 2.5 parts by mass of polyphosphate amine salt. The results are listed in Table 1.
  • Example 18 A multilayer porous membrane was obtained in the same manner as in Example 1 except that 90 parts by mass of the inorganic filler and 10 parts by mass of the resin binder in the dispersion for forming the porous layer were used. The results are listed in Table 1.
  • Example 19 A multilayer porous membrane was obtained in the same manner as in Example 1 except that 98 parts by mass of the inorganic filler in the dispersion for forming the porous layer and 2 parts by mass of the resin binder were used. The results are listed in Table 1.
  • Example 2 A multilayer porous membrane was obtained in the same manner as in Example 1 except that the dispersant in the dispersion for forming the porous layer was 1 part by mass of ammonium polycarboxylate. The results are listed in Table 1.
  • Example 3 A multilayer porous membrane was obtained in the same manner as in Example 1 except that the dispersant in the dispersion for forming the porous layer was 1 part by mass of sodium polyacrylate. The results are listed in Table 1.
  • the multilayer porous membrane of the present invention has industrial applicability as a separator for batteries, particularly high capacity batteries.

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Abstract

La présente invention concerne un film poreux multicouches ayant un taux de rétrécissement thermique bas, un procédé de fabrication correspondant, et un séparateur pour une cellule d'électrolyte non-aqueuse comprenant le film poreux multicouches. Ledit film poreux multicouches comprend : un film poreux en polyoléfine ; et une couche poreuse contenant une charge inorganique, un liant de résine et un dispersant inorganique dissociatif, la couche poreuse étant ménagée sur un côté ou sur les deux côtés du film poreux en polyoléfine.
PCT/JP2013/079155 2012-10-31 2013-10-28 Film poreux multicouches et procédé de fabrication correspondant, et séparateur pour une cellule d'électrolyte non-aqueuse WO2014069410A1 (fr)

Priority Applications (4)

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CN201380057208.0A CN104812579B (zh) 2012-10-31 2013-10-28 多层多孔膜和其制造方法、以及非水电解液电池用分隔件
JP2014544500A JP6279479B2 (ja) 2012-10-31 2013-10-28 多層多孔膜及びその製造方法、並びに非水電解液電池用セパレータ
KR1020177016360A KR102053259B1 (ko) 2012-10-31 2013-10-28 다층 다공막 및 그의 제조 방법, 및 비수 전해액 전지용 세퍼레이터
KR1020157010852A KR20150063119A (ko) 2012-10-31 2013-10-28 다층 다공막 및 그의 제조 방법, 및 비수 전해액 전지용 세퍼레이터

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JP2015151445A (ja) * 2014-02-13 2015-08-24 三菱樹脂株式会社 積層多孔フィルム、非水電解液二次電池用セパレータ、及び非水電解液二次電池
JP2016033916A (ja) * 2014-07-30 2016-03-10 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
JP2016076323A (ja) * 2014-10-03 2016-05-12 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータの製造方法
WO2017038067A1 (fr) * 2015-08-31 2017-03-09 日本ゼオン株式会社 Composition pour couche fonctionnelle de pile rechargeable à électrolyte non aqueux, couche fonctionnelle pour pile rechargeable à électrolyte non aqueux et pile rechargeable à électrolyte non aqueux
JP2017107851A (ja) * 2015-11-30 2017-06-15 旭化成株式会社 蓄電デバイス用セパレータ
US20200144577A1 (en) * 2017-08-31 2020-05-07 Asahi Kasei Kabushiki Kaisha Polyolefin Microporous Membrane
JPWO2020105672A1 (ja) * 2018-11-22 2021-10-14 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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KR102787908B1 (ko) 2019-11-18 2025-03-26 주식회사 엘지에너지솔루션 전기화학소자용 분리막 및 이를 포함하는 전기화학소자
KR102287723B1 (ko) * 2019-12-06 2021-08-10 더블유스코프코리아 주식회사 분리막 코팅 조성물 및 이를 이용한 분리막의 제조방법
EP4089821A4 (fr) * 2020-01-08 2024-07-31 Asahi Kasei Kabushiki Kaisha Séparateur réticulé de couche de revêtement inorganique

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WO2008093575A1 (fr) * 2007-01-30 2008-08-07 Asahi Kasei E-Materials Corporation Membrane poreuse multicouche et son procédé de fabrication
WO2009096451A1 (fr) * 2008-01-29 2009-08-06 Hitachi Maxell, Ltd. Suspension épaisse pour former une couche isolante, séparateur pour dispositif électrochimique, procédé pour produire celui-ci et dispositif électrochimique
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015015096A (ja) * 2013-07-03 2015-01-22 旭化成株式会社 電池用セパレータ及び非水系電解液電池
JP2015151445A (ja) * 2014-02-13 2015-08-24 三菱樹脂株式会社 積層多孔フィルム、非水電解液二次電池用セパレータ、及び非水電解液二次電池
JP2016033916A (ja) * 2014-07-30 2016-03-10 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
JP2016076323A (ja) * 2014-10-03 2016-05-12 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータの製造方法
WO2017038067A1 (fr) * 2015-08-31 2017-03-09 日本ゼオン株式会社 Composition pour couche fonctionnelle de pile rechargeable à électrolyte non aqueux, couche fonctionnelle pour pile rechargeable à électrolyte non aqueux et pile rechargeable à électrolyte non aqueux
JP2017107851A (ja) * 2015-11-30 2017-06-15 旭化成株式会社 蓄電デバイス用セパレータ
US20200144577A1 (en) * 2017-08-31 2020-05-07 Asahi Kasei Kabushiki Kaisha Polyolefin Microporous Membrane
US11837693B2 (en) * 2017-08-31 2023-12-05 Asahi Kasei Kabushiki Kaisha Polyolefin microporous membrane with improved puncture elongation and thermomechanical properties and method for manufacturing the same
JPWO2020105672A1 (ja) * 2018-11-22 2021-10-14 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
JP7234941B2 (ja) 2018-11-22 2023-03-08 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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KR20150063119A (ko) 2015-06-08
TWI511353B (zh) 2015-12-01
CN104812579B (zh) 2017-05-31
KR20170073712A (ko) 2017-06-28
JPWO2014069410A1 (ja) 2016-09-08
TW201431158A (zh) 2014-08-01
KR102053259B1 (ko) 2019-12-09
CN104812579A (zh) 2015-07-29

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