[go: up one dir, main page]

WO2018180714A1 - Membrane microporeuse en polyoléfine, séparateur pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux - Google Patents

Membrane microporeuse en polyoléfine, séparateur pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux Download PDF

Info

Publication number
WO2018180714A1
WO2018180714A1 PCT/JP2018/010834 JP2018010834W WO2018180714A1 WO 2018180714 A1 WO2018180714 A1 WO 2018180714A1 JP 2018010834 W JP2018010834 W JP 2018010834W WO 2018180714 A1 WO2018180714 A1 WO 2018180714A1
Authority
WO
WIPO (PCT)
Prior art keywords
microporous membrane
polyolefin microporous
tensile strength
polyolefin
tensile elongation
Prior art date
Application number
PCT/JP2018/010834
Other languages
English (en)
Japanese (ja)
Inventor
勝彦 松下
亘祐 春本
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2019509353A priority Critical patent/JP6665966B2/ja
Priority to KR1020197019996A priority patent/KR102126212B1/ko
Priority to CN201880020119.1A priority patent/CN110431176B/zh
Publication of WO2018180714A1 publication Critical patent/WO2018180714A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • H01M50/494—Tensile strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • 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 polyolefin microporous membrane, a separator for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery.
  • Microporous membranes are used in various fields such as filters such as filtration membranes and dialysis membranes, separators for batteries and separators for electrolytic capacitors.
  • filters such as filtration membranes and dialysis membranes
  • separators for batteries and separators for electrolytic capacitors.
  • a polyolefin microporous film using polyolefin as a resin material is excellent in chemical resistance, insulation, mechanical strength, etc., and has shutdown characteristics, and thus has been widely used as a battery separator in recent years.
  • Secondary batteries such as lithium ion secondary batteries, are widely used as batteries for personal computers, mobile phones and the like because of their high energy density. Secondary batteries are also used as motor drive power sources for electric vehicles and hybrid vehicles.
  • the porosity is 10% or more and less than 55%
  • the tensile strength of MD and TD is 50 to 300 MPa
  • the total of MD tensile strength and TD tensile strength is 100 to 600 MPa
  • the tensile elongation of MD and TD is 10
  • a polyolefin microporous membrane is described that is ⁇ 200% and the sum of MD tensile elongation and TD tensile elongation is 20 to 250%. According to Patent Document 1, this polyolefin microporous membrane is said to be difficult to deform and excellent in film resistance and stress relaxation properties.
  • Patent Document 2 a ratio of the tensile strength in the length direction to the tensile strength in the width direction is 0.75 to 1.25, and the thermal shrinkage in the width direction at 120 ° C. is less than 10%.
  • a porous membrane is described. According to Patent Document 2, this polyolefin microporous film is said to have good resistance to foreign matters and the like.
  • Patent Document 3 includes polypropylene, has a transverse breaking strength of 100 to 230 MPa, a transverse tensile breaking elongation of 10 to 110%, and a longitudinal tensile breaking strength with respect to the transverse tensile breaking strength of 0.8.
  • Polyolefin microporous membranes of ⁇ 1.3 are described.
  • the bubble point is 500 to 700 kPa
  • the ratio of length direction (MD) tensile strength / width direction (TD) tensile strength is 1.0 to 5.5
  • the shutdown temperature is 130 to 140.
  • a polyolefin microporous membrane at 0 ° C. is described. According to Patent Document 4, this polyolefin microporous membrane is said to achieve both good cycle characteristics and high voltage resistance characteristics.
  • JP 2006-124652 A International Publication No. 2010/070930 International Publication No. 2009/123015 JP 2013-234263 A
  • Patent Documents 1 to 4 describe polyolefin microporous membranes that have improved tensile strength and tensile elongation while maintaining battery characteristics. However, with the recent improvement in battery performance, further improvement in impact resistance is described. Is required. In addition, it is more difficult to achieve both strength and elongation and battery performance such as output characteristics and cycle characteristics, and there is a need for a separator that has both impact resistance and battery characteristics such as output characteristics. Yes.
  • an object of the present invention is to provide a microporous polyolefin membrane that is extremely excellent in impact resistance.
  • Another object of the present invention is to provide a polyolefin microporous membrane that, when used as a battery separator, has both high impact resistance and battery characteristics (output characteristics, dendrite resistance, etc.).
  • the present invention is a polyolefin microporous membrane having the following characteristics (1) to (5).
  • (1) The tensile strength (MPa) and tensile elongation (%) in the MD direction and TD direction satisfy the following relational expression (I). [(Tensile strength in MD direction ⁇ tensile elongation in MD direction / 100) 2 + (tensile strength in TD direction ⁇ tensile elongation in TD direction / 100) 2 ] 1/2 ⁇ 300 Formula (I)
  • the tensile strength in the MD direction and the TD direction is 196 MPa or more.
  • the maximum pore diameter measured using a palm porometer is 60 nm or less.
  • (4) The average flow pore diameter measured using a palm porometer is 40 nm or less.
  • the porosity is 40% or more.
  • the polyolefin microporous membrane of the present invention may have the following property (6).
  • (6) Ratio of tensile strength in MD direction and TD direction (tensile strength in MD direction / tensile strength in TD direction) is 0.8 or more and 1.2 or less.
  • the polyolefin microporous film of the present invention may have the following property (7).
  • Ratio of tensile elongation in MD direction and TD direction is 0.75 or more and 1.25 or less.
  • the polyolefin microporous film of the present invention may have the following property (8).
  • the tensile elongation in the MD direction and the TD direction is 90% or more, respectively.
  • the polyolefin microporous membrane may have a puncture strength converted to a film thickness of 12 ⁇ m of 5N or more.
  • membrane may satisfy
  • the present invention is also a separator for a non-aqueous electrolyte secondary battery using the polyolefin microporous membrane of the present invention.
  • the present invention is also a non-aqueous electrolyte secondary battery including the separator for a non-aqueous electrolyte secondary battery of the present invention.
  • the polyolefin microporous membrane of the present invention is extremely excellent in impact resistance and, when used as a battery separator, achieves both impact resistance and battery characteristics (output characteristics, dendrite resistance, cycle characteristics) at a high level. Can do.
  • polyolefin microporous membrane refers to a microporous membrane containing polyolefin as a main component, for example, a microporous membrane containing 90% by mass or more of polyolefin with respect to the total amount of the microporous membrane.
  • a microporous membrane containing 90% by mass or more of polyolefin with respect to the total amount of the microporous membrane.
  • the polyolefin microporous membrane of this embodiment satisfies the following formula (I) in relation to the tensile strength (MPa) and the tensile elongation (%) in the MD direction and the TD direction.
  • the polyolefin microporous membrane satisfies the following formula (I)
  • impact resistance can be improved. [(Tensile strength in MD direction ⁇ tensile elongation in MD direction / 100) 2 + (tensile strength in TD direction ⁇ tensile elongation in TD direction / 100) 2 ] 1/2 ⁇ 300 Formula (I).
  • the polyolefin microporous membrane of the present embodiment has a relationship between the tensile strength (MPa) and the tensile elongation (%) in the MD direction and the TD direction, from the viewpoint of further improving the impact resistance. ) Is more preferable, and (III) is more preferable.
  • the upper limit of the value of [(tensile strength in MD direction ⁇ tensile elongation in MD direction / 100) 2 + (tensile strength in TD direction ⁇ tensile elongation in TD direction / 100) 2 ] 1/2 is, for example, 1000 or less, preferably 800 or less, more preferably 600 or less.
  • the polyolefin microporous membrane of this embodiment has a tensile strength in the MD direction and TD direction of 196 MPa or more, preferably 200 MPa or more, and more preferably 230 MPa or more.
  • the tensile strength is in the above range, the film strength is excellent, a high tension can be applied when the electrode body is wound in the battery manufacturing process, and film breakage due to foreign matter or impact is suppressed in the battery.
  • the upper limit of the tensile strength in the MD direction and the TD direction is preferably 500 MPa or less, more preferably 450 MPa or less, and further preferably 400 MPa or less, from the viewpoint of shrinkage resistance.
  • about tensile strength it can measure by the method based on ASTMD882 using a strip-shaped test piece of width 10mm.
  • the polyolefin microporous membrane of this embodiment preferably has a tensile elongation in the MD direction and TD direction of 90% or more, respectively.
  • the tensile elongation is in the above range, when a shock is applied in the battery, the film breakage of the separator and the occurrence of a short circuit (short circuit) are suppressed due to its flexibility.
  • the upper limit of the tensile elongation of MD direction and TD direction is not specifically limited, For example, it is 400% or less, Preferably it is 300% or less, More preferably, it is 200% or less.
  • the tensile elongation is in the above range, the winding property is good without winding and deforming the separator when the electrode is wound.
  • the tensile elongation can be measured by a method based on ASTM D-882A.
  • the polyolefin microporous membrane of the present embodiment preferably has a ratio of tensile strength in the MD direction and TD direction (tensile strength in the MD direction / tensile strength in the TD direction) of 0.8 or more and 1.2 or less.
  • the ratio of the tensile strength is within the above range, the force is applied more uniformly to the impact in all directions, so that the impact resistance is improved and the film breakage and the short circuit (short circuit) can be more stably suppressed. it can.
  • the ratio of the tensile elongation in the MD direction and the TD direction is preferably 0.75 or more and 1.25 or less. .
  • the ratio of tensile elongation is in the above range, the force is applied more uniformly to impacts in all directions, so impact resistance is improved, and film breakage and short-circuiting (short-circuiting) are suppressed more stably. Can do.
  • the ratio between the tensile strength and the tensile elongation is preferably close to 1 from the viewpoint of more stably suppressing film breakage against impact in all directions. Further, when the tensile strength in the MD direction is too large, tearing in the MD direction may occur. If the tensile strength in the TD direction is too high, the TD direction tears or the electrode tab bonding part may be disconnected, and short-circuiting may occur easily.
  • the puncture strength of the polyolefin microporous membrane is preferably 5N or more, more preferably 5.2N or more, and further preferably 6N or more, when converted to a film thickness of 12 ⁇ m.
  • the upper limit of puncture strength is not specifically limited, For example, it is 10 N or less.
  • the puncture strength is in the above range, the polyolefin microporous membrane is excellent in membrane strength and can exhibit a good balance of physical properties.
  • a secondary battery using the polyolefin microporous membrane as a separator is excellent in resistance to unevenness and impact of the electrode, and the occurrence of a short circuit of the electrode is suppressed.
  • the puncture strength is the maximum load (N when a polyolefin microporous film having a film thickness T 1 ( ⁇ m) is punctured at a speed of 2 mm / sec with a needle having a spherical surface (curvature radius R: 0.5 mm) and a diameter of 1 mm. ) Is a measured value. Further, for a polyolefin microporous film having a film thickness T 1 ( ⁇ m), the puncture strength (N / 12 ⁇ m) in terms of a film thickness of 12 ⁇ m can be obtained by the following formula.
  • Puncture strength (12 ⁇ m conversion) Measured puncture strength (N) ⁇ 12 ( ⁇ m) / film thickness T 1 ( ⁇ m) [Film thickness]
  • the upper limit of the film thickness of the polyolefin microporous membrane is not particularly limited, but is, for example, 20 ⁇ m or less, preferably 17 ⁇ m or less, more preferably 13 ⁇ m or less. When the film thickness is within the above range, the permeability and film resistance are excellent, and the battery capacity can be improved by thinning the film.
  • the lower limit of the film thickness is not particularly limited, but is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 4 ⁇ m or more. When the film thickness is in the above range, the film strength is further improved.
  • the porosity of the polyolefin microporous membrane is preferably 40% or more, more preferably 40% or more and 70% or less. Further, the upper limit of the porosity is more preferably 60% or less, and further preferably 55% or less, from the viewpoint of film forming property, mechanical strength, and insulation. When the porosity is within the above range, the amount of electrolyte retained can be increased, high ion permeability can be ensured, and the output characteristics are excellent.
  • the output characteristics When the porosity is low, when used as a battery separator, the output characteristics may be inferior due to an increase in fibrils that impede ion permeation and a decrease in the electrolyte content, and due to by-products generated during the battery reaction. Clogging may increase and cycle characteristics may deteriorate rapidly.
  • the porosity can be in the above range by adjusting the composition of the polyolefin resin, the draw ratio and the like in the production process.
  • the porosity is measured by the following formula (1), which compares the weight w 1 of the microporous membrane with the weight w 2 of the polymer without pores equivalent to the weight (a polymer having the same width, length and composition). it can.
  • Porosity (%) (w 2 ⁇ w 1 ) / w 2 ⁇ 100 (1).
  • the average pore size (average flow pore size) of the polyolefin microporous membrane is 40 nm or less, preferably 10 nm or more and 40 nm or less.
  • the average pore diameter is in the above range, the balance between strength and permeability is excellent, and at the same time, self-discharge derived from coarse pores is suppressed.
  • the average pore diameter exceeds 40 nm, the ion permeation channel selectively concentrates on the coarse pores, which causes an increase in electrical resistance and a deterioration in cycle characteristics due to local clogging of electrolyte decomposition byproducts. Sometimes.
  • the average pore diameter is a value measured by a method (half dry method) based on ASTM E1294-89.
  • a palm porometer manufactured by PMI (model number: CFP-1500A) can be used as a measuring instrument, and Galwick (15.9 dyn / cm) can be used as a measuring liquid.
  • the maximum pore diameter (bubble point diameter: BP diameter) is preferably 60 nm or less, and more preferably 30 nm or more and 60 nm or less.
  • the maximum pore diameter exceeds 60 nm, the positive electrode and the negative electrode may contact each other (minute short circuit), or may be destroyed by lithium dendrites (dendrites), resulting in a short circuit.
  • the maximum hole diameter is too small, the electric resistance of the battery becomes high, the cycle performance becomes insufficient, and the capacity retention during high-speed discharge may be low.
  • the upper limit of the air permeability resistance in terms of the film thickness of 12 ⁇ m of the polyolefin microporous film is not particularly limited, but is, for example, 300 seconds / 100 cm 3 Air / 12 ⁇ m or less, preferably 200 seconds / 100 cm 3 Air / 12 ⁇ m or less. .
  • the lower limit of the air resistance is, for example, 50 seconds / 100 cm 3 Air or more.
  • the air resistance is a value P 1 (seconds / 100 cm 3 ) that can be measured with an air permeability meter (manufactured by Asahi Seiko Co., Ltd., EGO-1T) in accordance with JIS P-8117 Oken type testing machine method. Air).
  • the air resistance P 2 (second / 100 cm 3 Air / 12 ⁇ m) converted to a film thickness of 12 ⁇ m is a value that can be obtained by the following equation. .
  • Formula: P 2 P 1 (second / 100 cm 3 Air) ⁇ 12 ( ⁇ m) / film thickness T 1 ( ⁇ m) 2.
  • the production method of the polyolefin microporous membrane is not particularly limited as long as the polyolefin microporous membrane having the above-described characteristics can be obtained, and known production methods of polyolefin microporous membrane can be used.
  • a manufacturing method of the polyolefin microporous film of this embodiment a wet film forming method is preferable from the viewpoint of easy control of the structure and physical properties of the film.
  • a wet film forming method for example, the methods described in the specifications of Japanese Patent No. 2132327 and Japanese Patent No. 3347835, International Publication No. 2006/137540, and the like can be used.
  • melt-kneading method for example, a method using a twin-screw extruder described in the specifications of Japanese Patent No. 2132327 and Japanese Patent No. 3347835 can be used. Since the melt-kneading method is well-known, description is abbreviate
  • Polyolefin resin examples of the polyolefin resin used as a raw material include polyethylene and polypropylene.
  • the polyethylene is not particularly limited, and various polyethylenes can be used. For example, ultrahigh molecular weight polyethylene (UHMwPE), high density polyethylene (HDPE), medium density polyethylene, branched low density polyethylene, linear low density. Polyethylene or the like is used.
  • UHMwPE ultrahigh molecular weight polyethylene
  • HDPE high density polyethylene
  • medium density polyethylene medium density polyethylene
  • branched low density polyethylene linear low density.
  • Polyethylene or the like is used.
  • the polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another ⁇ -olefin.
  • ⁇ -olefin examples include propylene, butene-1, hexene-1, pentene-1, 4-methylpentene-1, octene, vinyl acetate, methyl methacrylate, styrene and the like.
  • the polyolefin resin preferably contains ultra high molecular weight polyethylene (UHMwPE).
  • UHMwPE ultra high molecular weight polyethylene
  • strength of the polyolefin fine porous film obtained can be improved.
  • the fibrils of the polyolefin microporous membrane can be refined (densified), and a membrane having a small pore diameter can be expressed uniformly over the entire membrane.
  • ultra high molecular weight polyethylene can be used individually by 1 type or in combination of 2 or more types, For example, 2 or more types of ultra high molecular weight polyethylene from which Mw differs may be mixed and used.
  • the weight average molecular weight (Mw) of the ultrahigh molecular weight polyethylene is 1 ⁇ 10 6 or more (100,000 or more), preferably 2 ⁇ 10 6 or more and less than 4 ⁇ 10 6 .
  • Mw is in the above range, the film forming property is good.
  • Mw of the ultra high molecular weight polyethylene is 4 ⁇ 10 6 or more, the viscosity of the melt becomes too high, so that there may be a problem in the film forming process such that the resin cannot be extruded from the die.
  • Mw is a value measured by gel permeation chromatography (GPC).
  • the content of ultrahigh molecular weight polyethylene is preferably 10% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the entire polyolefin resin.
  • the upper limit of content of ultra high molecular weight polyethylene is not specifically limited, For example, it is 50 mass% or less.
  • the film strength and the air resistance can be made compatible at a high level by adjusting the stretching conditions described later.
  • Polyolefin resin high density polyethylene (HDPE, density: 0.942 g / cm 3 or higher) can contain.
  • the polyolefin resin preferably contains ultra high molecular weight polyethylene and high density polyethylene.
  • the melt extrusion characteristics are excellent, and the uniform stretch processing characteristics are excellent.
  • the high density polyethylene include those having a weight average molecular weight (Mw) of 1 ⁇ 10 4 or more and less than 1 ⁇ 10 6 .
  • Mw is a value measured by gel permeation chromatography (GPC).
  • the content of the high-density polyethylene is preferably 50% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less, with respect to 100% by mass of the entire polyolefin resin.
  • the polyolefin resin may include polypropylene.
  • the polypropylene is not particularly limited, and a propylene homopolymer, a copolymer of propylene and another ⁇ -olefin and / or diolefin (propylene copolymer), or a mixture thereof can be used.
  • the content of polypropylene is, for example, from 0% by mass to less than 10% by mass, and preferably from 0% by mass to 5% by mass with respect to 100% by mass of the total polyolefin resin.
  • the pore diameter of the resulting polyolefin microporous membrane tends to increase.
  • the polyolefin resin can contain other resin components other than polyethylene and polypropylene as necessary.
  • resin components for example, a heat resistant resin or the like can be used.
  • the polyolefin microporous membrane is an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, an antiblocking agent, a filler, a crystal nucleating agent, and a crystallization retarder as long as the effects of the present invention are not impaired.
  • Various additives such as these may be contained.
  • the solvent for film formation any solvent that can sufficiently dissolve the polyolefin resin can be used without particular limitation.
  • the solvent for film formation is preferably a liquid at room temperature in order to enable stretching at a relatively high magnification.
  • the film-forming solvent include aliphatic, cycloaliphatic or aromatic hydrocarbons such as nonane, decane, decalin, paraxylene, undecane, dodecane, and liquid paraffin, and mineral oil fractions having boiling points corresponding to these.
  • phthalic acid esters which are liquid at room temperature such as dibutyl phthalate and dioctyl phthalate. Among these, it is preferable to use a non-volatile liquid solvent such as liquid paraffin.
  • a solid solvent and the film-forming solvent may be mixed and used.
  • a solid solvent include stearyl alcohol, seryl alcohol, and paraffin wax.
  • the blending ratio of the polyolefin resin and the film-forming solvent in the polyolefin solution is not particularly limited, but is preferably 20 to 35 parts by mass with respect to 100 parts by mass of the polyolefin resin solution.
  • the ratio of the polyolefin resin is within the above range, swell and neck-in can be prevented at the die exit when extruding the polyolefin solution, and the moldability and self-supporting property of the extruded molded body (gel-shaped molded body) are improved.
  • the polyolefin solution prepared above is fed from an extruder to a die, extruded into a sheet shape, and the obtained extruded product is cooled to form a gel-like sheet.
  • the cooling is preferably performed to 90 ° C., which is lower than the crystal dispersion temperature (Tcd) of the polyolefin resin, more preferably 50 ° C. or less, and even more preferably 40 ° C. or less.
  • Tcd crystal dispersion temperature
  • the polyolefin microphase separated by the film-forming solvent can be immobilized.
  • the cooling rate is within the above range, the crystallization degree is maintained in an appropriate range, and a gel-like sheet suitable for stretching is obtained.
  • a method of contacting with a cooling medium such as cold air or cooling water, a method of contacting with a cooling roll, or the like can be used, but it is preferable that the cooling is performed by contacting with a roll cooled with a cooling medium.
  • a plurality of polyolefin solutions having the same or different compositions may be fed from a plurality of extruders to a single die, laminated there in a layer form, and extruded into a sheet form.
  • a method for forming the gel-like sheet for example, the methods disclosed in Japanese Patent No. 2132327 and Japanese Patent No. 3347835 can be used.
  • the stretching of the gel sheet is also called wet stretching.
  • the stretching may be uniaxial stretching or biaxial stretching, but biaxial stretching is preferred.
  • biaxial stretching any of simultaneous biaxial stretching, sequential stretching and multistage stretching (for example, a combination of simultaneous biaxial stretching and sequential stretching) may be used, but sequential stretching is preferable, and stretching in the MD direction (machine direction, longitudinal direction).
  • TD direction width direction, transverse direction.
  • the MD direction and the TD direction are separately stretched, it is considered that the stretching tension is applied only in each direction during the stretching, and the molecular orientation easily proceeds.
  • the TD direction is a direction orthogonal to the MD direction when the microporous film is viewed in a plane.
  • the final area draw ratio (surface ratio) in the drawing process needs to be 30 times or more and 150 times or less.
  • the area stretching ratio is preferably 35 times or more and 120 times or less.
  • the ratio of the draw ratio in the MD direction and the TD direction (the draw ratio in the MD direction / the draw ratio in the TD direction) needs to be 0.7 or more and 1.0 or less.
  • the ratio of the draw ratio is in the above range, the MD and TD directions have a good balance with respect to the tensile strength and tensile elongation of the resulting polyolefin microporous membrane, the membrane strength can be further improved, and the impact resistance is improved. improves. From the viewpoint of further improving the film strength, it is preferable that the draw ratio in the TD direction is larger than the draw ratio in the MD direction.
  • the reason for this is not particularly limited, but when stretching in the TD direction after stretching in the MD direction, the molecular orientation once oriented in the MD direction is less likely to be oriented in the TD direction due to stretching in the MD direction. Therefore, it is considered that the molecular orientation can be advanced more uniformly in both directions by stretching in the TD direction at a larger magnification.
  • the draw ratio in this step means the draw ratio of the gel-like sheet immediately before being used for the next step on the basis of the gel-like sheet immediately before this step.
  • the ratio of the draw ratio in the MD direction and the TD direction (the draw ratio in the MD direction / the draw ratio in the TD direction) is preferably 0.75 or more and 1.0 or less.
  • the stretching temperature is preferably in the range of not less than the crystal dispersion temperature (Tcd) of the polyolefin resin and not more than the melting point of the polyolefin resin.
  • the melting point of the polyolefin resin refers to the melting point of the polyolefin resin in the gel sheet.
  • the stretching temperature when the stretching temperature is equal to or higher than the crystal dispersion temperature (Tcd) of the polyolefin resin, the polyolefin resin in the gel-like sheet can be sufficiently softened and the stretching tension can be lowered, so that the film forming property is improved and the stretching is performed. The film breakage at the time is suppressed, and stretching at a high magnification becomes possible.
  • the stretching temperature can be, for example, 100 ° C. or higher and 127 ° C. or lower.
  • the stretching temperature is the temperature of the gel sheet, and when there is a temperature difference between the front and back surfaces such as roll stretching, it means the center temperature in the thickness direction.
  • the stretching temperature in the MD direction is 100 ° C. or higher and 110 ° C. or lower, preferably 103 ° C. or higher and 110 ° C. or lower.
  • the stretching temperature in the TD direction is 115 ° C. or higher and 127 ° C. or lower, preferably 115 ° C. or higher and 125 ° C.
  • the film forming solvent is removed from the stretched gel-like sheet to obtain a microporous film.
  • the removal of the solvent is performed using a cleaning solvent. Since the polyolefin phase is phase-separated from the film-forming solvent phase, removing the film-forming solvent consists of fibrils that form a fine three-dimensional network structure, and pores (voids) that communicate irregularly in three dimensions. A porous membrane having the following is obtained. Since the cleaning solvent and the method for removing the film-forming solvent using the same are known, the description thereof is omitted. For example, the methods disclosed in Japanese Patent No. 2132327 and Japanese Patent Application Laid-Open No. 2002-256099 can be used.
  • the microporous membrane from which the film-forming solvent has been removed is dried by a heat drying method or an air drying method.
  • the drying temperature is preferably equal to or lower than the crystal dispersion temperature (Tcd) of the polyolefin resin, and particularly preferably 5 ° C. or more lower than Tcd. Drying is preferably carried out until the residual washing solvent is 5% by mass or less, more preferably 3% by mass or less, with the microporous membrane being 100% by mass (dry weight).
  • Tcd crystal dispersion temperature
  • the microporous membrane after drying may be subjected to heat treatment.
  • heat treatment method heat setting treatment and / or heat relaxation treatment can be used.
  • the heat setting treatment is a heat treatment in which heating is performed while keeping the dimension of the film in the TD direction unchanged.
  • the thermal relaxation treatment is a treatment for thermally contracting the film in the MD direction and / or TD direction during heating.
  • the heat setting treatment is preferably performed by a tenter method or a roll method.
  • a thermal relaxation treatment method a method disclosed in Japanese Patent Application Laid-Open No. 2002-256099 can be given.
  • the heat treatment temperature is preferably within the range of Tcd to Tm of the polyolefin resin, more preferably within the range of the second stretching temperature ⁇ 5 ° C of the microporous membrane, and within the range of the second stretching temperature ⁇ 3 ° C of the microporous membrane. Particularly preferred.
  • microporous membrane after drying may be re-stretched at a predetermined area stretch ratio in at least uniaxial direction. Stretching of the microporous membrane after drying is also referred to as dry stretching.
  • the obtained polyolefin microporous membrane may be subjected to a crosslinking treatment and a hydrophilic treatment.
  • the crosslinking treatment is performed by irradiating the polyolefin microporous film with ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, and electron beams.
  • ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, and electron beams.
  • electron beam irradiation an electron dose of 0.1 to 100 Mrad is preferable, and an acceleration voltage of 100 to 300 kV is preferable.
  • the meltdown temperature of the microporous membrane is increased by the crosslinking treatment.
  • the hydrophilic treatment can be performed by monomer grafting, surfactant treatment, corona discharge, or the like. Monomer grafting is preferably performed after the crosslinking treatment.
  • the polyolefin microporous membrane may be a single layer, or a layer composed of a polyolefin microporous membrane may be laminated.
  • the multilayer polyolefin microporous membrane can be made into two or more layers.
  • the composition of the polyolefin resin constituting each layer may be the same or different.
  • the polyolefin microporous membrane may be a laminated polyolefin porous membrane by laminating a porous layer other than the polyolefin resin on at least one surface thereof.
  • stack coating layers such as an inorganic particle layer containing a binder and an inorganic particle.
  • the binder component constituting the inorganic particle layer is not particularly limited, and known components can be used.
  • acrylic resin, polyvinylidene fluoride resin, polyamideimide resin, polyamide resin, aromatic polyamide resin, polyimide resin, etc. can be used.
  • the inorganic particles constituting the inorganic particle layer are not particularly limited, and known materials can be used.
  • the porous binder resin may be laminated on at least one surface of the polyolefin microporous membrane.
  • the final area stretching ratio (surface ratio) in the stretching process described above, the ratio of the stretching ratio in the MD direction and the TD direction (stretching ratio in the MD direction / stretching ratio in the TD direction), the MD and TD directions By adjusting the stretching temperature as appropriate, it is extremely excellent in impact resistance, and when used as a battery separator, both impact resistance and battery characteristics (output characteristics, dendrite resistance, etc.) are compatible at a high level.
  • a polyolefin microporous membrane can be provided.
  • Measurement method and evaluation method [Film thickness] The film thickness at 5 points in the range of 95 mm ⁇ 95 mm of the microporous membrane was measured with a contact thickness meter (Lightmatic manufactured by Mitutoyo Corporation), and the average value was obtained.
  • d C ⁇ ⁇ / P
  • d ( ⁇ m) is the pore diameter of the microporous membrane
  • ⁇ (mN / m) is the surface tension of the liquid
  • P (Pa) is the pressure
  • C is a constant.
  • the weight average molecular weight (Mw) of the polyolefin microporous membrane was determined by gel permeation chromatography (GPC) method under the following conditions.
  • GPC gel permeation chromatography
  • ⁇ Measurement device GPC-150C manufactured by Waters Corporation Column: Shodex UT806M manufactured by Showa Denko KK -Column temperature: 135 ° C
  • Injection volume 500 ⁇ l
  • Detector Differential refractometer (RI detector) manufactured by Waters Corporation -Calibration curve: A polyethylene conversion constant (0.46) was used from a calibration curve obtained using a monodisperse polystyrene standard sample.
  • N -A slurry was prepared by dispersing in methylpyrrolidone (NMP). This slurry was applied to one side of an aluminum foil having a thickness of 20 ⁇ m serving as a positive electrode current collector with a die coater at an active material coating amount of 250 g / m 2 and an active material bulk density of 3.00 g / cm 3 . And after drying at 130 degreeC for 3 minute (s) and compression-molding with the roll press machine, it cut
  • NMP methylpyrrolidone
  • a slurry was prepared by dispersing 96.9% by mass of artificial graphite as an active material, 1.4% by mass of ammonium salt of carboxymethyl cellulose and 1.7% by mass of styrene-butadiene copolymer latex as a binder in purified water.
  • This slurry was coated with a die coater on one side of a 12 ⁇ m thick copper foil serving as a negative electrode current collector at a high packing density of 106 g / m 2 of active material and a bulk density of 1.55 g / cm 3 of active material. It was attached. And after drying at 120 degreeC for 3 minute (s) and compression-molding with the roll press machine, it cut
  • a strip-shaped negative electrode, a separator, a strip-shaped positive electrode, and a separator were stacked in this order, and the electrode plate laminate was fabricated by winding a plurality of times in a spiral shape with a winding tension of 250 gf.
  • the electrode plate laminate is housed in a stainless steel container having an outer diameter of 18 mm and a height of 65 mm, and an aluminum tab derived from the positive electrode current collector is provided on the container lid terminal part, and is made of nickel derived from the negative electrode current collector. The tab was welded to the container wall. And after drying for 12 hours at 80 degreeC under vacuum, the said nonaqueous electrolyte solution was inject
  • ⁇ Impact resistance test> The assembled battery is first charged with a constant current of 500 mA, and after each battery voltage reaches 4.20 V, the battery is fully charged by charging each constant voltage until the current value becomes 10 mA or less. It was. Next, a fully charged cylindrical battery was installed so that the long side lies sideways, and a rod having a diameter of 15.8 mm having a mass of 9.1 kg from a height of 61 cm was dropped on the central flat surface of the battery. Shocked. What caused the battery to ignite due to this shock even once in the 3 times test ⁇ ignited even if it did not ignite during the 3 times test, but caused smoke even once, ignited or smoked once during the 3 times test The case where was not confirmed was evaluated as “Good”.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the obtained sample cell was put in a thermostatic bath at 25 ° C. and allowed to stand for 3 hours, and then the resistance of the cell was measured at an amplitude of 20 mV using an AC impedance measuring device (manufactured by Hioki Electric Co., Ltd.).
  • the measured resistance component value of the cell (the real value when the imaginary axis value is 0) is plotted against the number of porous films placed in the cell, and the slope is obtained by linear approximation of this plot. It was.
  • Those porous membrane resistance value of the film ( ⁇ ⁇ cm 2) was the 1.4 ⁇ cm 2 / 10 ⁇ m or less ⁇ (good), it was ⁇ (poor) to in excess of 1.4 ⁇ cm 2 / 10 ⁇ m.
  • the film resistance is 1.4 ⁇ cm 2 / 10 ⁇ m or less, when used as a battery separator in a secondary battery, it is expected that the output characteristics of the battery is improved.
  • a wound body was prepared using a tab attached to a positive electrode (manufactured by Yayama Co., Ltd.) and a negative electrode (manufactured by Yayama Co., Ltd.) and each microporous membrane.
  • ⁇ Cycle performance test> A cycle performance test was performed under the following charge / discharge conditions using the above test battery. Charging: 1C, 4.35V constant current constant voltage charging, cut-off current 0.05C Discharge: 1C, 3V constant current discharge Measurement temperature: 25 ° C The test was carried out using three test batteries, and the ratio of the 200th charge capacity based on the 1C charge capacity of the first time, that is, the average value of the capacity retention rate, was derived and used as an index of cycle performance. A sample having an average capacity retention rate of 85% or more was evaluated as “good” and a sample having a capacity retention rate of less than 85% was evaluated as “poor”.
  • the capacity maintenance rate is 85% or more, it can be determined that the charge capacity can be sufficiently retained even after repeated charge and discharge for a long period of time, and a good battery can be expected.
  • Example 5 As the polyolefin resin, ultra high molecular weight polyethylene (UHMwPE) with Mw of 2.5 ⁇ 10 6 and high density polyethylene (HDPE) with Mw of 2.8 ⁇ 10 5 are included in the blending ratio (mass%) shown in Table 1, respectively.
  • UHMwPE ultra high molecular weight polyethylene
  • HDPE high density polyethylene
  • Table 1 shows the polyolefin resin concentration with respect to 100 parts by mass in total of the polyolefin resin and the film-forming solvent in the polyolefin solution.
  • the polyolefin solution was fed from a twin screw extruder to a T die and extruded.
  • the extruded product was cooled while being taken up by a cooling roll to form a gel-like sheet.
  • the gel sheet was wet-stretched in the MD direction and the TD direction under the conditions shown in Table 1.
  • the polyolefin microporous membrane of this embodiment is extremely excellent in impact resistance when incorporated into a secondary battery as a separator. Moreover, since the polyolefin microporous film of this embodiment can achieve both impact resistance and battery characteristics, it can be suitably used as a separator for non-aqueous electrolyte secondary batteries.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Cell Separators (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une membrane microporeuse en polyoléfine qui, lorsqu'elle est incorporée dans une batterie en tant que séparateur, présente une excellente résistance aux chocs et contribue à conférer à la batterie d'excellentes caractéristiques. Cette membrane microporeuse en polyoléfine présente les caractéristiques (1) à (5) suivantes. (1) La résistance à la traction (MPa) et l'allongement à la traction (%) dans le sens machine et le sens travers sont conformes à la relation (I) suivante : [(résistance à la traction dans le sens machine × allongement à la traction dans le sens machine/100)2 + (résistance à la traction dans le sens travers × allongement à la traction dans le sens travers/100)2]1/2 ≥ 300. (2) La résistance à la traction dans le sens machine et le sens travers est égale ou supérieure à 196 MPa. (3) La taille maximale des pores déterminée à l'aide d'un poromètre Perm est inférieure ou égale à 60 nm. (4) La taille moyenne des pores d'écoulement déterminée à l'aide d'un poromètre Perm est inférieure ou égale à 40 nm. (5) La porosité est égale ou supérieure à 40 %.
PCT/JP2018/010834 2017-03-31 2018-03-19 Membrane microporeuse en polyoléfine, séparateur pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux WO2018180714A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2019509353A JP6665966B2 (ja) 2017-03-31 2018-03-19 ポリオレフィン微多孔膜、非水電解液系二次電池用セパレータ、及び非水電解液系二次電池
KR1020197019996A KR102126212B1 (ko) 2017-03-31 2018-03-19 폴리올레핀 미다공막, 비수전해액계 2차전지용 세퍼레이터, 및 비수전해액계 2차전지
CN201880020119.1A CN110431176B (zh) 2017-03-31 2018-03-19 聚烯烃微多孔膜、非水电解液系二次电池用隔膜及非水电解液系二次电池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-071066 2017-03-31
JP2017071066 2017-03-31

Publications (1)

Publication Number Publication Date
WO2018180714A1 true WO2018180714A1 (fr) 2018-10-04

Family

ID=63675766

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/010834 WO2018180714A1 (fr) 2017-03-31 2018-03-19 Membrane microporeuse en polyoléfine, séparateur pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux

Country Status (5)

Country Link
JP (1) JP6665966B2 (fr)
KR (1) KR102126212B1 (fr)
CN (3) CN110431176B (fr)
TW (1) TWI700851B (fr)
WO (1) WO2018180714A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021065585A1 (fr) * 2019-09-30 2021-04-08 東レ株式会社 Film de polyoléfine microporeux, séparateur pour batterie et batterie secondaire
CN113631644A (zh) * 2019-03-29 2021-11-09 东丽株式会社 聚烯烃微多孔膜、电池用隔板、二次电池和聚烯烃微多孔膜的制造方法
WO2022052469A1 (fr) 2020-09-09 2022-03-17 上海恩捷新材料科技有限公司 Membrane microporeuse de polyoléfine et son procédé de préparation
WO2024019069A1 (fr) * 2022-07-20 2024-01-25 東レ株式会社 Membrane microporeuse en polyoléfine, séparateur pour batteries et batterie
US12247110B2 (en) 2019-06-21 2025-03-11 Asahi Kasei Battery Separator Corporation Polyolefin microporous membrane

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110815763B (zh) * 2019-11-19 2021-06-08 青岛蓝科途膜材料有限公司 制备高强度高模量的聚烯烃薄膜的设备及方法和高强度高模量的聚烯烃薄膜
CN112864528B (zh) * 2021-04-26 2021-07-13 江苏厚生新能源科技有限公司 一种锂离子电池用双向拉伸涂覆微孔隔膜及其制备方法
US20230299417A1 (en) * 2021-09-02 2023-09-21 Lg Energy Solution, Ltd. Method for manufacturing electrode assembly for electrochemical device, electrode assembly obtained by same method, and method for manufacturing electrochemical device
EP4376202A4 (fr) * 2022-10-12 2025-04-16 Sinoma Lithium Battery Separator (Nanjing) Co., Ltd. Membrane poreuse en polyoléfine et son procédé de préparation, séparateur de batterie et dispositif électrochimique
CN115312973B (zh) * 2022-10-12 2023-01-31 中材锂膜有限公司 一种聚烯烃多孔膜及其制备方法、电池隔膜、电化学装置
CN115798613B (zh) * 2022-11-30 2023-07-28 四川倍佳新材料有限公司 一种聚合物微孔膜在溶液中力学性能的评价方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124652A (ja) * 2004-09-30 2006-05-18 Asahi Kasei Chemicals Corp ポリオレフィン製微多孔膜
WO2007069560A1 (fr) * 2005-12-15 2007-06-21 Asahi Kasei Chemicals Corporation Membrane microporeuse de polyolefine
WO2009136648A1 (fr) * 2008-05-09 2009-11-12 旭化成イーマテリアルズ株式会社 Séparateur pour pile secondaire au lithium-ion à densité de puissance élevée
JP2011527710A (ja) * 2008-07-11 2011-11-04 東レ東燃機能膜合同会社 微多孔性膜、微多孔膜の製造方法および使用方法
WO2015194504A1 (fr) * 2014-06-20 2015-12-23 東レバッテリーセパレータフィルム株式会社 Membrane microporeuse polyoléfinique, séparateur pour cellule et cellule

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100676080B1 (ko) * 1999-02-19 2007-01-31 토넨 케미칼 코퍼레이션 폴리올레핀 미세다공성 막과 그의 제조방법
DE112008001272B4 (de) 2007-05-14 2018-04-26 Smc Corp. Hydraulischer Stoßdämpfer
KR101101157B1 (ko) 2008-12-18 2012-01-05 제일모직주식회사 난연성 불포화 폴리에스테르 수지 조성물
CN102942706A (zh) * 2008-12-19 2013-02-27 旭化成电子材料株式会社 聚烯烃制微多孔膜及锂离子二次电池用分隔件
CN102248713B (zh) * 2011-04-22 2014-12-31 佛山市东航光电科技有限公司 一种聚烯微多孔多层隔膜及其制造方法
JP5942145B2 (ja) 2012-05-09 2016-06-29 旭化成株式会社 ポリオレフィン製微多孔膜及びその製造方法
US20150372276A1 (en) * 2013-02-13 2015-12-24 Toray Battery Separator Film Co., Ltd. Separator for batteries and method of producing separator for batteries
KR101601787B1 (ko) * 2013-02-28 2016-03-09 제일모직주식회사 인장 강도가 높은 분리막 및 그 제조 방법
MY175572A (en) * 2013-12-06 2020-07-01 Toray Industries Polyolefin microporous film, separator for non-aqueous electrolyte secondary battery, wound product of polyolefin microporous film, non-aqueous electrolyte secondary battery, and method for producing polyolefin microporous film
JP6295641B2 (ja) * 2013-12-20 2018-03-20 東レ株式会社 微多孔膜およびそれを用いてなるセパレータ
CN107250234B (zh) * 2014-12-26 2020-09-18 东丽株式会社 聚烯烃微多孔膜、其制造方法以及电池用隔膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006124652A (ja) * 2004-09-30 2006-05-18 Asahi Kasei Chemicals Corp ポリオレフィン製微多孔膜
WO2007069560A1 (fr) * 2005-12-15 2007-06-21 Asahi Kasei Chemicals Corporation Membrane microporeuse de polyolefine
WO2009136648A1 (fr) * 2008-05-09 2009-11-12 旭化成イーマテリアルズ株式会社 Séparateur pour pile secondaire au lithium-ion à densité de puissance élevée
JP2011527710A (ja) * 2008-07-11 2011-11-04 東レ東燃機能膜合同会社 微多孔性膜、微多孔膜の製造方法および使用方法
WO2015194504A1 (fr) * 2014-06-20 2015-12-23 東レバッテリーセパレータフィルム株式会社 Membrane microporeuse polyoléfinique, séparateur pour cellule et cellule

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113631644A (zh) * 2019-03-29 2021-11-09 东丽株式会社 聚烯烃微多孔膜、电池用隔板、二次电池和聚烯烃微多孔膜的制造方法
US12247110B2 (en) 2019-06-21 2025-03-11 Asahi Kasei Battery Separator Corporation Polyolefin microporous membrane
WO2021065585A1 (fr) * 2019-09-30 2021-04-08 東レ株式会社 Film de polyoléfine microporeux, séparateur pour batterie et batterie secondaire
WO2022052469A1 (fr) 2020-09-09 2022-03-17 上海恩捷新材料科技有限公司 Membrane microporeuse de polyoléfine et son procédé de préparation
WO2024019069A1 (fr) * 2022-07-20 2024-01-25 東レ株式会社 Membrane microporeuse en polyoléfine, séparateur pour batteries et batterie

Also Published As

Publication number Publication date
CN110431176A (zh) 2019-11-08
TW201838224A (zh) 2018-10-16
CN113024881A (zh) 2021-06-25
CN113024882A (zh) 2021-06-25
TWI700851B (zh) 2020-08-01
KR102126212B1 (ko) 2020-06-24
KR20190127663A (ko) 2019-11-13
JPWO2018180714A1 (ja) 2019-12-26
JP6665966B2 (ja) 2020-03-13
CN110431176B (zh) 2021-03-19

Similar Documents

Publication Publication Date Title
JP6665966B2 (ja) ポリオレフィン微多孔膜、非水電解液系二次電池用セパレータ、及び非水電解液系二次電池
CN101796108B (zh) 微孔聚烯烃膜、其制备方法、电池隔板和电池
US12110382B2 (en) Polyolefin microporous membrane
JP7283080B2 (ja) ポリオレフィン製微多孔膜、電池用セパレータおよび二次電池
WO2018164056A1 (fr) Film microporeux polyoléfinique
JP7088162B2 (ja) ポリオレフィン微多孔膜
JP2021034260A (ja) 電池用セパレータ及びその製造方法
JP6988880B2 (ja) ポリオレフィン微多孔膜
JP7409301B2 (ja) ポリオレフィン微多孔膜及びポリオレフィン微多孔膜の製造方法
JP2019102126A (ja) 電池用セパレータ及び非水電解液二次電池
JP7386209B2 (ja) ポリオレフィン微多孔膜
KR20220069831A (ko) 폴리올레핀 미다공막, 전지용 세퍼레이터 및 이차 전지
JPWO2019151220A1 (ja) ポリオレフィン微多孔膜、コーティングフィルム及び電池、並びにポリオレフィン微多孔膜の製造方法
JP2021123614A (ja) ポリオレフィン微多孔膜
JP7483653B2 (ja) ポリオレフィン微多孔膜
JP2022048518A (ja) ポリオレフィン微多孔膜、それを用いたコーティングフィルム及び二次電池
WO2021065283A1 (fr) Film microporeux de polyoléfine, séparateur pour batterie rechargeable à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux
JP7567443B2 (ja) ポリオレフィン微多孔膜、及び二次電池
JP6741884B1 (ja) ポリオレフィン微多孔膜
JP2021021067A (ja) ポリオレフィン微多孔膜、及び非水電解液二次電池
JP2021021068A (ja) ポリオレフィン微多孔膜、及び非水電解液二次電池

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019509353

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18775980

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197019996

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18775980

Country of ref document: EP

Kind code of ref document: A1