US20010038942A1 - "polypropylene microporous membrane for battery separator" - Google Patents
"polypropylene microporous membrane for battery separator" Download PDFInfo
- Publication number
- US20010038942A1 US20010038942A1 US09/105,516 US10551698A US2001038942A1 US 20010038942 A1 US20010038942 A1 US 20010038942A1 US 10551698 A US10551698 A US 10551698A US 2001038942 A1 US2001038942 A1 US 2001038942A1
- Authority
- US
- United States
- Prior art keywords
- beta
- battery separator
- per mil
- polypropylene
- less
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- 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
- H01M50/489—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
- H01M50/489—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
- 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/918—Physical aftertreatment of a cellular product
Definitions
- This invention is directed to a polypropylene microporous membrane, made from a beta-nucleated precursor, for use as a battery separator.
- ER electrical resistance
- PS puncture strength
- Electrical resistance is a measure of the resistance to electrical flow between the anode and cathode and across the separator, and is generally preferred to be as low as possible.
- the micropores of the battery separator form channels through which electrolyte is in contact with the anode and cathode. Puncture strength is for withstanding the rigors of battery manufacture, among other things.
- Battery separators are usually extremely thin (approximately 1 mil or 25 micron), and are sandwiched between the anode and cathode which have sufficient surface roughness to cause puncture during the winding or folding of the sandwich. Puncture of the separator may lead to direct contact between the anode and cathode, which renders the battery unsuitable for use.
- a battery separator is a polypropylene microporous membrane, made from a beta-nucleated precursor, and having an electrical resistance of less than 30 ohms-inches per mil, and a puncture strength of greater than 400 grams-force per mil.
- a battery, or an electrochemical cell is a device generally comprising an anode, a cathode, an electrolyte, and a separator. Batteries may be used in portable devices, such as computers, cellular telephones, or the like, or in electric vehicles.
- Battery separator refers to a microporous membrane that is used to separate the anode and the cathode, thereby preventing their direct contact, and to contain, in the micropores, the electrolyte.
- the separator may be a monolayer or a multilayer structure (i.e., a sandwich in which the individual layers may be the same or different) in which the disclosed film may be one of those layers.
- Other layers may enhance safety (i.e., low-melting or shutdown function, e.g., U.S. Pat. No. 5,691,077) or enhance strength (i.e., cross-plied, e.g., U.S. Pat. No. 5,667,911).
- the battery separator has a thickness less than 3 mils and preferable less than 1.5 mils.
- the battery separator disclosed herein is a polypropylene microporous membrane made from a beta-nucleated precursor.
- Polypropylene refers to any polymer (e.g., homo -or co-polymer) of predominantly propylene monomers.
- the polypropylene is an isotactic, homopolymer with a melt flow index (MFI) of less than ( ⁇ ) 10. More preferably, the MFI is less than 5.
- MFI melt flow index
- Exemplary polypropylenes include: Huntsman Chemical Corp. of Woodbury, N.J. product 5550 (MFI-5.5); Exxon Chemical Co. of Houston, Tex. product Escorene PP 4352 FI (MFI-about 3) & PP 4292 (MFI-1.5); Aristech Chemical Corp. of Pittsburgh, Pa. product BEPOL (MFI-0.7).
- Beta-nucleated precursor refers to a pre-stretched polypropylene film having a beta-crystal structure. Beta- crystals are meta-stable and will revert to alpha-crystals when subjected to a combination of heat and stress. Beta- crystal may be formed in the polypropylene by any number of known techniques, but, the use of a beta-nucleating agent (or beta-nucleator) is preferred. See: U.S. Pat. Nos. 5,134,174; 5,231,126; 5,317,035; & 5,594,070; EPO Publication No. 632,095; Japanese Kokai Nos. 7-118429 & 9-176352; Chu, F.
- Beta-nucleating agents are commercially available, for example NJ-STAR NU-100 is available from New Japan Chemical Co., Ltd., Osaka, Japan.
- the amount of beta-crystals in the precursor should be on the order of 45 to 70% as measured by a differential scanning calorimeter (DSC) technique (sample size-10 milligrams, heating rate-10°/min, heating range-25° C. to 200° C., using Seiko Instrument Inc.'s model 220 C).
- DSC differential scanning calorimeter
- the amount of beta-crystal is reported as the ratio of beta-crystal (measured as the area under the beta-crystal peak of the DSC trace) to the sum of beta- and alpha-crystal (the sum of the areas under the beta-crystal and the alpha-crystal peaks).
- the beta-crystal content of the precursor is not preferably maximized.
- the porosity of the foregoing membranes should be in the range of 40-65%, preferably 45-60%, and more preferably 47-57%.
- Porosity (%) is: [1-(apparent density of membrane/resin density)] ⁇ 100.
- the average pore size should be on the order of 0.03 to 0.25 microns as measured from scanning electron microscope (SEM) photograph, magnification 20,000 ⁇ .
- a preferred average pore size is in the range of 0.04-0.10 with the distribution skewed toward the low end of the range.
- the electrical resistance of the separator should be less than 30 ohms-inches per mil of thickness. A more preferred range for electrical resistance is less than 20 ohm-inches per mil.
- the electrical resistance (or resistivity) is measured as follows: A R.A.I. AC Milliohm Resistance Meter, Model 2401 and R.A.I. test cell electrode (from RAI Research Corp. Hauppauge, N.Y.) are used. A 31% by wt KOH solution is used to wet the sample (samples should be methanol primed to ensure complete wetout then soaked in solution for 8 to 24 hours before testing). Samples should not be dry when tested. Three samples of material are tested and averaged. The results, reported in milliohm-inch 2 , are then divided by the material thickness and reported as ohm-inches per mil.
- a puncture strength of greater than 400 grams force per mil of thickness is preferred. There is no upper range on the puncture strength as in commercial operation, the greater the strength, the more preferred the separator is.
- the test procedure is as follows: A Mitech Stevens LFRA Texture Analyzer with a needle (1.65 mm in diameter, 0.5 mm radius tip) is used. The rate of descent is 2 mm/sec and the maximum amount of deflection is 6 mm. The film is held taut in a clamping device with a central opening of 11.3 mm in diameter. Ten measurements are taken, averaged and normalized to one mil of thickness.
- the separator is preferably manufactured by the following ‘dry-stretch’ or OPP (oriented polypropylene) technique: the polypropylene resin is doped with the nucleator; the resin is extruded; a precursor is formed; and the precursor is stretched (drawn) into the battery separator.
- the precursor preferably has a beta- crystal content of 45-70%, more preferably 46-60%, and preferably undergoes a total stretch (TS) ranging from at least 16 ⁇ 7 to 36 ⁇ 7, preferably at least 16 ⁇ 4 to 36 ⁇ 7, and most preferably 16 ⁇ 4 to 20 ⁇ 4.
- TS total stretch
- the beta-nucleator may be added to the resin during resin polymerization, by compounding, or at the extruder. Sufficient nucleator should be added to insure that the precursor's required content of beta-crystal is obtained prior to stretching.
- the beta-crystals After extrusion of the precursor, the beta-crystals must be given sufficient time to form within the precursor. The amount of time depends upon numerous factors including, but not limited to, amount and type of nucleator, type of polypropylene, residence time/temperature; and type of equipment. Beta-crystal growth begins at a higher temperature than the alpha-crystal growth. Ideally, one should maximize the time of the polymer at a temperature above the initiation temperature of alpha-crystal growth but below the initiation temperature of beta-crystal growth.
- the precursor may be annealed before stretching.
- Stretching may be uniaxial or biaxial, but biaxial is preferred.
- Biaxial stretching includes a machine direction (MD) stretch, a transverse direction (TD) stretch, and optionally a relax (or stress relief) step.
- the MD stretch conditions include: temperature preferably ranging from 70-110° C., most preferred at 90° C.; and stretch ratio preferably ranging from 1.5-6.0, preferably 4.
- the TD stretch conditions include: temperature preferably ranging from 110-140° C., most preferred at 120° C.; and stretch ratio ranging from 1.5-6.0, most preferred at 4-5. During stretching, it is assumed that the polymer is at or near the stated temperatures.
- BOPP biaxially oriented polypropylene
- an extruder i.e., a variable speed roll with temperature control
- a drawframe i.e., temperature controlled with variable machine direction (MD) stretch, transverse direction (TD) stretch, and relax (or stress relief).
- Residence time in the crystal formation section i.e., time on the roll
- the polypropylene resin was Exxon's Escorene PP 4352FI (MFI-about 3)
- the beta nucleator was NJ Star NU-100 and 0.2% by weight resin was used.
- Other conditions and properties are set forth in TABLE 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
- This invention is directed to a polypropylene microporous membrane, made from a beta-nucleated precursor, for use as a battery separator.
- Polypropylene microporous membranes, made from beta-nucleated precursors, are known. U.S. Pat. Nos. 5,134,174; 5,231,126; 5,317,035; & 5,594,070; EPO Publication No. 632,095; Japanese Kokai No. 7-118429; Chu, F. et al., “Microvoid formation process during the plastic deformation of Beta-form polypropylene”,POLYMER v34 n16, 1994; Chu, F. et al., “Crystal transformation and micropore formation during uniaxial drawing of Beta-form polypropylene film”, POLYMER v36 n13, 1995; Ikeda, N. et al., “NJ-Star NU-100: A Novel Beta-Nucleator for Polypropylene”, Polypropylene & World Congress, Sep. 18-20, 1996; Zhu, W. et al., “A New Polypropylene Microporous Film”, Polymers for Advanced Technologies, v7, 1996. Such membranes have been suggested for use as battery separators. U.S. Pat. No. 5,134,174; EPO Publication No. 632,095; Japanese Kokai No. 7-118429. Beta-nucleating agents for polypropylene are also known. U.S. Pat. Nos. 5,134,174; 5,231,126; 5,317,035; & 5,594,070; EPO Publication Nos. 557,721 & 632,095; Japanese Kokai Nos. 7-118429 & 9-176352; Chu, F. et al., “Microvoid formation process during the plastic deformation of Beta-form polypropylene”, POLYMER v34 n16, 1994; Chu, F. et al., “Crystal transformation and micropore formation during uniaxial drawing of Beta-form polypropylene film”, POLYMER v36 n13, 1995; Ikeda, N. et al., “NJ-Star NU-100: A Novel Beta-Nucleator for Polypropylene”, Polypropylene & World Congress, Sep. 18-20, 1996; Zhu, W. et al., “A New Polypropylene Microporous Film”, Polymers for Advanced Technologies, v7, 1996.
- Commercially viable battery separators need to have a balance of properties. Two of these properties are electrical resistance (ER) and strength, typically measured as puncture strength (PS). Electrical resistance is a measure of the resistance to electrical flow between the anode and cathode and across the separator, and is generally preferred to be as low as possible. The micropores of the battery separator form channels through which electrolyte is in contact with the anode and cathode. Puncture strength is for withstanding the rigors of battery manufacture, among other things. Battery separators are usually extremely thin (approximately 1 mil or 25 micron), and are sandwiched between the anode and cathode which have sufficient surface roughness to cause puncture during the winding or folding of the sandwich. Puncture of the separator may lead to direct contact between the anode and cathode, which renders the battery unsuitable for use.
- In U.S. Pat. No. 5,134,174, EPO Publication No. 632,095, and Japanese Kokai No. 7-118429, polypropylene microporous films, made from beta-nucleated precusors, for use as battery separator are disclosed. These films, while theoretically functional as separators, are limited. For example, the limitation of the films disclosed in the U.S. and the Japanese references arises from poor puncture strength. The puncture strength is apparent from the stretching (or drawing) conditions, as well as, the pore size, and the porosity.
- Accordingly, there is a need for a polypropylene microporous membrane, made from a beta-nucleated precursor, that is commercially viable as a battery separator.
- A battery separator is a polypropylene microporous membrane, made from a beta-nucleated precursor, and having an electrical resistance of less than 30 ohms-inches per mil, and a puncture strength of greater than 400 grams-force per mil.
- A battery, or an electrochemical cell, is a device generally comprising an anode, a cathode, an electrolyte, and a separator. Batteries may be used in portable devices, such as computers, cellular telephones, or the like, or in electric vehicles.
- Battery separator, as used herein, refers to a microporous membrane that is used to separate the anode and the cathode, thereby preventing their direct contact, and to contain, in the micropores, the electrolyte. The separator may be a monolayer or a multilayer structure (i.e., a sandwich in which the individual layers may be the same or different) in which the disclosed film may be one of those layers. Other layers may enhance safety (i.e., low-melting or shutdown function, e.g., U.S. Pat. No. 5,691,077) or enhance strength (i.e., cross-plied, e.g., U.S. Pat. No. 5,667,911). The battery separator has a thickness less than 3 mils and preferable less than 1.5 mils.
- The battery separator disclosed herein is a polypropylene microporous membrane made from a beta-nucleated precursor. Polypropylene refers to any polymer (e.g., homo -or co-polymer) of predominantly propylene monomers. Preferably, the polypropylene is an isotactic, homopolymer with a melt flow index (MFI) of less than (<) 10. More preferably, the MFI is less than 5. Exemplary polypropylenes include: Huntsman Chemical Corp. of Woodbury, N.J. product 5550 (MFI-5.5); Exxon Chemical Co. of Houston, Tex. product Escorene PP 4352 FI (MFI-about 3) & PP 4292 (MFI-1.5); Aristech Chemical Corp. of Pittsburgh, Pa. product BEPOL (MFI-0.7).
- Beta-nucleated precursor refers to a pre-stretched polypropylene film having a beta-crystal structure. Beta- crystals are meta-stable and will revert to alpha-crystals when subjected to a combination of heat and stress. Beta- crystal may be formed in the polypropylene by any number of known techniques, but, the use of a beta-nucleating agent (or beta-nucleator) is preferred. See: U.S. Pat. Nos. 5,134,174; 5,231,126; 5,317,035; & 5,594,070; EPO Publication No. 632,095; Japanese Kokai Nos. 7-118429 & 9-176352; Chu, F. et al., “Microvoid formation process during the plastic deformation of Beta-form polypropylene”,POLYMER v34 n16, 1994; Chu, F. et al., “Crystal transformation and micropore formation during uniaxial drawing of Beta-form polypropylene film”, POLYMER v36 n13, 1995; Ikeda, N. et al., “NJ-Star NU-100: A Novel Beta-Nucleator for Polypropylene”, Polypropylene & World Congress, Sep. 18-20, 1996; Zhu, W. et al., “A New Polypropylene Microporous Film”, Polymers for Advanced Technologies, v7, 1996, each of which is incorporated herein by reference. Beta-nucleating agents are commercially available, for example NJ-STAR NU-100 is available from New Japan Chemical Co., Ltd., Osaka, Japan. The amount of beta-crystals in the precursor should be on the order of 45 to 70% as measured by a differential scanning calorimeter (DSC) technique (sample size-10 milligrams, heating rate-10°/min, heating range-25° C. to 200° C., using Seiko Instrument Inc.'s model 220 C). By this technique, the amount of beta-crystal is reported as the ratio of beta-crystal (measured as the area under the beta-crystal peak of the DSC trace) to the sum of beta- and alpha-crystal (the sum of the areas under the beta-crystal and the alpha-crystal peaks). The beta-crystal content of the precursor is not preferably maximized.
- The porosity of the foregoing membranes should be in the range of 40-65%, preferably 45-60%, and more preferably 47-57%. Porosity (%) is: [1-(apparent density of membrane/resin density)]×100.
- The average pore size should be on the order of 0.03 to 0.25 microns as measured from scanning electron microscope (SEM) photograph, magnification 20,000×. A preferred average pore size is in the range of 0.04-0.10 with the distribution skewed toward the low end of the range.
- The electrical resistance of the separator should be less than 30 ohms-inches per mil of thickness. A more preferred range for electrical resistance is less than 20 ohm-inches per mil. The electrical resistance (or resistivity) is measured as follows: A R.A.I. AC Milliohm Resistance Meter, Model 2401 and R.A.I. test cell electrode (from RAI Research Corp. Hauppauge, N.Y.) are used. A 31% by wt KOH solution is used to wet the sample (samples should be methanol primed to ensure complete wetout then soaked in solution for 8 to 24 hours before testing). Samples should not be dry when tested. Three samples of material are tested and averaged. The results, reported in milliohm-inch2, are then divided by the material thickness and reported as ohm-inches per mil.
- A puncture strength of greater than 400 grams force per mil of thickness is preferred. There is no upper range on the puncture strength as in commercial operation, the greater the strength, the more preferred the separator is. The test procedure is as follows: A Mitech Stevens LFRA Texture Analyzer with a needle (1.65 mm in diameter, 0.5 mm radius tip) is used. The rate of descent is 2 mm/sec and the maximum amount of deflection is 6 mm. The film is held taut in a clamping device with a central opening of 11.3 mm in diameter. Ten measurements are taken, averaged and normalized to one mil of thickness.
- The separator is preferably manufactured by the following ‘dry-stretch’ or OPP (oriented polypropylene) technique: the polypropylene resin is doped with the nucleator; the resin is extruded; a precursor is formed; and the precursor is stretched (drawn) into the battery separator. To obtain the balance of physical properties (e.g., porosity, average pore size, electrical resistance, and puncture strength), the precursor preferably has a beta- crystal content of 45-70%, more preferably 46-60%, and preferably undergoes a total stretch (TS) ranging from at least 16±7 to 36±7, preferably at least 16±4 to 36±7, and most preferably 16±4 to 20±4.
- The beta-nucleator may be added to the resin during resin polymerization, by compounding, or at the extruder. Sufficient nucleator should be added to insure that the precursor's required content of beta-crystal is obtained prior to stretching.
- After extrusion of the precursor, the beta-crystals must be given sufficient time to form within the precursor. The amount of time depends upon numerous factors including, but not limited to, amount and type of nucleator, type of polypropylene, residence time/temperature; and type of equipment. Beta-crystal growth begins at a higher temperature than the alpha-crystal growth. Ideally, one should maximize the time of the polymer at a temperature above the initiation temperature of alpha-crystal growth but below the initiation temperature of beta-crystal growth. Optionally, the precursor may be annealed before stretching.
- Stretching may be uniaxial or biaxial, but biaxial is preferred. Biaxial stretching includes a machine direction (MD) stretch, a transverse direction (TD) stretch, and optionally a relax (or stress relief) step. The MD stretch conditions include: temperature preferably ranging from 70-110° C., most preferred at 90° C.; and stretch ratio preferably ranging from 1.5-6.0, preferably 4. The TD stretch conditions include: temperature preferably ranging from 110-140° C., most preferred at 120° C.; and stretch ratio ranging from 1.5-6.0, most preferred at 4-5. During stretching, it is assumed that the polymer is at or near the stated temperatures.
- Further details of the process are set forth in the examples below.
- The following examples were made on pilot equipment representing a conventional BOPP (biaxially oriented polypropylene) line that includes as major components: an extruder, an crystal formation section (i.e., a variable speed roll with temperature control), and a drawframe (i.e., temperature controlled with variable machine direction (MD) stretch, transverse direction (TD) stretch, and relax (or stress relief). Residence time in the crystal formation section (i.e., time on the roll) was about 30 seconds for all samples. The polypropylene resin was Exxon's Escorene PP 4352FI (MFI-about 3), the beta nucleator was NJ Star NU-100 and 0.2% by weight resin was used. Other conditions and properties are set forth in TABLE 1.
- Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be obvious that certain changes and modifications may be practiced within the scope of the appended claims.
TABLE 1 Quench Ave Roll MD MD TD TD Pore Temp. Temp. Stretch Temp. Stretch Total Thickness Size Porosity PS/mil ER/mil PS/ Sample ° C. ° C. Ratio ° C. Ratio Stretch mil μm % g/mil Ohm-in ER 1 120 95 4.0 140 3.0 12.0 1.2 0.05 50.4 522 11.2 47 2 120 90 3.0 135 3.2 9.6 2.1 — 45.1 381 16.6 23 3 120 90 4.0 135 3.2 12.8 1.5 0.05 44.6 499 10.2 49 4 120 90 3.5 120 3.0 11.2 1.6 — 47.6 402 14.6 28 5 125 90 3.0 120 3.0 9.0 2.2 — 48.5 350 12.4 28 6 125 90 4.0(?) 120 4.0 16.0 1.7 0.03 51.6 418 11.9 35 7 125 90 3.0(?) 120 3.8-4.0 11.7 1.6 0.03 48.5 425 7.8 55 8 120 90 4.0 120 4.5 18.0 1.6 0.03 49.4 527 11.7 45 9 120 90 4.0 120 3.8-4.0 15.2 1.1 0.03 47.8 569 12.7 45 10 120 90 4.0 120 3.8-4.0 15.2 1.3 0.04 46.5 490 12.5 39
Claims (12)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/105,516 US6368742B2 (en) | 1998-06-26 | 1998-06-26 | Polypropylene microporous membrane for battery separator |
CA002273127A CA2273127A1 (en) | 1998-06-26 | 1999-05-27 | Polypropylene microporous membrane for battery separator |
TW088108744A TW447161B (en) | 1998-06-26 | 1999-05-27 | Polypropylene microporous membrane for battery separator |
EP99111843A EP0967671A3 (en) | 1998-06-26 | 1999-06-19 | Polypropylene microporous membrane for battery separator and process for making |
JP17814499A JP4535527B2 (en) | 1998-06-26 | 1999-06-24 | Polypropylene microporous membrane for battery separator |
KR1019990024275A KR100628610B1 (en) | 1998-06-26 | 1999-06-25 | Process for making a battery separator and a microporous film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/105,516 US6368742B2 (en) | 1998-06-26 | 1998-06-26 | Polypropylene microporous membrane for battery separator |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010038942A1 true US20010038942A1 (en) | 2001-11-08 |
US6368742B2 US6368742B2 (en) | 2002-04-09 |
Family
ID=22306285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/105,516 Expired - Lifetime US6368742B2 (en) | 1998-06-26 | 1998-06-26 | Polypropylene microporous membrane for battery separator |
Country Status (6)
Country | Link |
---|---|
US (1) | US6368742B2 (en) |
EP (1) | EP0967671A3 (en) |
JP (1) | JP4535527B2 (en) |
KR (1) | KR100628610B1 (en) |
CA (1) | CA2273127A1 (en) |
TW (1) | TW447161B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020034684A1 (en) * | 2000-09-15 | 2002-03-21 | Vb Autobatterie Gmbh | Separator for lead storage batteries |
US20070196638A1 (en) * | 2006-02-21 | 2007-08-23 | Xiangyun Wei | Biaxially oriented microporous membrane |
US20070269719A1 (en) * | 2001-02-21 | 2007-11-22 | New Japan Chemical Co., Ltd. | Successively biaxial-oriented porous polypropylene film and process for production thereof |
US20090068554A1 (en) * | 2006-03-28 | 2009-03-12 | Vb Autobatterie & Co. Kgaa | Separator for lead-acid rechargeable battery |
US20100003401A1 (en) * | 2004-10-21 | 2010-01-07 | Evonik Degussa Gmbh | Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries |
CN102015251A (en) * | 2008-05-02 | 2011-04-13 | 特里奥凡德国有限公司及两合公司 | Single-layer membrane film for batteries, having a shut-off function |
WO2016085970A1 (en) * | 2014-11-26 | 2016-06-02 | Celgard, Llc | Improved multilayer microporous separators for lithium ion secondary batteries and related methods |
US9419266B2 (en) | 2011-01-27 | 2016-08-16 | Mitsubishi Plastics, Inc. | Polyolefin resin porous film, and non-aqueous electrolyte cell separator using same |
US9620754B2 (en) | 2008-12-19 | 2017-04-11 | Asahi Kasei E-Materials Corporation | Polyolefin microporous membrane and separator for lithium ion secondary battery |
TWI588185B (en) * | 2012-12-25 | 2017-06-21 | Toyo Boseki | Biaxially oriented polypropylene film |
EP2544841B1 (en) | 2010-03-12 | 2018-01-17 | Celgard LLC | Biaxially oriented porous membranes, composites, and methods of manufacture and use |
Families Citing this family (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6602593B1 (en) * | 1999-08-30 | 2003-08-05 | Celgard Inc. | Battery separators with reduced splitting propensity |
US6432586B1 (en) | 2000-04-10 | 2002-08-13 | Celgard Inc. | Separator for a high energy rechargeable lithium battery |
KR100433951B1 (en) * | 2000-05-03 | 2004-06-04 | 주식회사 엘지화학 | Multi-component polymer membrane and method for preparing the same |
US6921608B2 (en) * | 2000-07-11 | 2005-07-26 | Celgard, Inc. | Battery separator |
US6632850B2 (en) | 2001-04-04 | 2003-10-14 | 3M Innovative Properties Company | Microporous materials and methods of making the same |
US8007940B2 (en) * | 2001-12-11 | 2011-08-30 | Eveready Battery Company, Inc. | High discharge capacity lithium battery |
US20050112462A1 (en) * | 2003-11-21 | 2005-05-26 | Marple Jack W. | High discharge capacity lithium battery |
US7195818B2 (en) | 2002-05-01 | 2007-03-27 | Exxonmobil Oil Corporation | Sealable multi-layer opaque film |
EP1364986A1 (en) * | 2002-05-21 | 2003-11-26 | Borealis Technology Oy | Polypropylene compositions especially for pipes |
US20040105994A1 (en) * | 2002-12-03 | 2004-06-03 | Pang-Chia Lu | Thermoplastic film structures with a low melting point outer layer |
MXPA05011892A (en) * | 2003-05-08 | 2006-05-25 | Applied Extrusion Technologies | Methods of making thick, highly oriented, opaque, low-density, microporous polyolefin films and the films made thereby. |
US8124274B2 (en) * | 2003-11-21 | 2012-02-28 | Eveready Battery Company, Inc. | High discharge capacity lithium battery |
US8283071B2 (en) | 2003-11-21 | 2012-10-09 | Eveready Battery Company, Inc. | High discharge capacity lithium battery |
US20050233214A1 (en) * | 2003-11-21 | 2005-10-20 | Marple Jack W | High discharge capacity lithium battery |
WO2005118260A1 (en) * | 2004-06-04 | 2005-12-15 | The Tensar Corporation | Lightweight polypropylene nets manufactured with a beta nucleation additive, the method of manufacture and uses thereof |
EP1623996A1 (en) * | 2004-08-06 | 2006-02-08 | Deutsches Krebsforschungszentrum Stiftung des öffentlichen Rechts | Improved method of selecting a desired protein from a library |
CN100368065C (en) * | 2004-09-08 | 2008-02-13 | 比亚迪股份有限公司 | Production of polyolefin microporous membrane |
JP5145712B2 (en) | 2005-10-18 | 2013-02-20 | 東レ株式会社 | Microporous film for power storage device separator and power storage device separator using the same |
CA2700185C (en) * | 2007-09-28 | 2016-07-12 | Eveready Battery Company, Inc. | Processes for producing synthetic pyrite |
CN101255236B (en) * | 2008-03-19 | 2010-11-10 | 中国科学院化学研究所 | Use of asymmetric polypropylene porous membrane |
DK2274168T3 (en) * | 2008-05-02 | 2013-08-26 | Treofan Germany Gmbh & Co Kg | Polypropylene base microporous multilayer membrane foil for decoupling batteries |
DK2321126T3 (en) | 2008-05-02 | 2016-08-29 | Treofan Germany Gmbh & Co Kg | Membrane film for batteries with switch function |
CN103311484A (en) | 2008-09-03 | 2013-09-18 | 三菱树脂株式会社 | Laminated porous film for separator |
JP5500424B2 (en) * | 2008-12-24 | 2014-05-21 | 三菱樹脂株式会社 | Battery separator and non-aqueous lithium secondary battery |
JP5422374B2 (en) * | 2008-12-24 | 2014-02-19 | 三菱樹脂株式会社 | Battery separator and non-aqueous lithium secondary battery |
JP5422372B2 (en) * | 2008-12-24 | 2014-02-19 | 三菱樹脂株式会社 | Battery separator and non-aqueous lithium secondary battery |
JP5422373B2 (en) * | 2008-12-24 | 2014-02-19 | 三菱樹脂株式会社 | Battery separator and non-aqueous lithium secondary battery |
EP2381510A4 (en) * | 2008-12-24 | 2016-04-20 | Mitsubishi Plastics Inc | Separator for battery, and non-aqueous lithium battery |
KR101249180B1 (en) * | 2009-06-19 | 2013-04-03 | 미쓰비시 쥬시 가부시끼가이샤 | Porous polypropylene film |
KR101741854B1 (en) * | 2009-06-20 | 2017-05-30 | 트레오판 저머니 게엠베하 앤 코. 카게 | Microporous foil for batteries having shutdown function |
US9453805B2 (en) | 2010-01-19 | 2016-09-27 | Celgard, Llc | X-ray sensitive battery separators and related methods |
US8592071B2 (en) | 2010-02-26 | 2013-11-26 | Mitsubishi Plastics, Inc. | Laminated porous film and separator for battery |
CN102782027B (en) | 2010-03-02 | 2016-05-25 | 三菱树脂株式会社 | Polypropylene-based resin perforated membrane, battery separator and battery |
KR20120116468A (en) | 2010-03-18 | 2012-10-22 | 미쓰비시 쥬시 가부시끼가이샤 | Porous polypropylene resin film, separator for use in a battery, and battery |
US8889572B2 (en) | 2010-09-29 | 2014-11-18 | Milliken & Company | Gradient nanofiber non-woven |
US8795561B2 (en) | 2010-09-29 | 2014-08-05 | Milliken & Company | Process of forming a nanofiber non-woven containing particles |
EP2720291A4 (en) | 2011-06-13 | 2015-03-18 | Nitto Denko Corp | Separator for nonaqueous electrolytic electricity storage device and nonaqueous electrolytic electricity storage device |
JP4940367B1 (en) | 2011-06-13 | 2012-05-30 | 日東電工株式会社 | Separator for nonaqueous electrolyte electricity storage device, nonaqueous electrolyte electricity storage device, and production method thereof |
JP2013020948A (en) | 2011-06-13 | 2013-01-31 | Nitto Denko Corp | Separator for nonaqueous electrolyte power storage device, nonaqueous electrolyte power storage device, and manufacturing methods thereof |
US20140137399A1 (en) | 2011-06-13 | 2014-05-22 | Nitto Denko Corporation | Method for producing separator for nonaqueous electrolyte electricity storage devices and method for producing nonaqueous electrolyte electricity storage device |
JP5934580B2 (en) | 2011-06-13 | 2016-06-15 | 日東電工株式会社 | Epoxy resin porous membrane, separator for nonaqueous electrolyte electricity storage device, nonaqueous electrolyte electricity storage device, composite semipermeable membrane, and production method thereof |
JP2013020947A (en) | 2011-06-13 | 2013-01-31 | Nitto Denko Corp | Separator for nonaqueous electrolyte power storage device, nonaqueous electrolyte power storage device, and manufacturing methods thereof |
JP2013020946A (en) | 2011-06-13 | 2013-01-31 | Nitto Denko Corp | Method for manufacturing separator for nonaqueous electrolytic electricity storage device and method for manufacturing nonaqueous electrolytic electricity storage device |
JP2013020960A (en) | 2011-06-13 | 2013-01-31 | Nitto Denko Corp | Manufacturing method of separator for nonaqueous electrolyte power storage device and manufacturing method of nonaqueous electrolyte power storage device |
KR20140051240A (en) | 2011-06-13 | 2014-04-30 | 닛토덴코 가부시키가이샤 | Nonaqueous electrolytic electricity storage device and production method therefor |
US9278471B2 (en) | 2011-12-13 | 2016-03-08 | 3M Innovative Properties Company | Method of detecting a component of an article and method of preparing a component for detection |
US9358714B2 (en) | 2011-12-13 | 2016-06-07 | 3M Innovative Properties Company | Structured film containing beta-nucleating agent and method of making the same |
US8911540B2 (en) | 2012-05-01 | 2014-12-16 | Case Western Reserve University | Gas separation membrane |
CN104335391A (en) | 2012-05-22 | 2015-02-04 | 日东电工株式会社 | Method for producing a separator for a nonaqueous electrolyte power storage device and method for producing epoxy resin porous membrane |
TW201351758A (en) | 2012-06-11 | 2013-12-16 | Enerage Inc | Isolation film of electrochemical device and manufacturing method thereof |
CA2887356A1 (en) * | 2012-10-08 | 2014-04-17 | Treofan Germany Gmbh & Co. Kg | Microporous separator film having homogeneous porosity and greater resistance to puncturing |
JP5833999B2 (en) * | 2012-12-03 | 2015-12-16 | 三菱樹脂株式会社 | Method for producing laminated porous film |
US10376420B2 (en) | 2013-06-13 | 2019-08-13 | 3M Innovative Properties Company | Personal hygiene article and container for the same |
US20160128876A1 (en) | 2013-06-13 | 2016-05-12 | 3M Innovative Properties Company | Tape including microporous film |
JP6782638B2 (en) * | 2014-03-19 | 2020-11-11 | セルガード エルエルシー | Embossed Microporous Membrane Battery Separator Materials and Methods of Their Manufacture and Use |
US9777237B2 (en) | 2014-11-12 | 2017-10-03 | Element 1 Corp. | Refining assemblies and refining methods for rich natural gas |
US9605224B2 (en) | 2014-11-12 | 2017-03-28 | Element 1 Corp. | Refining assemblies and refining methods for rich natural gas |
US9828561B2 (en) | 2014-11-12 | 2017-11-28 | Element 1 Corp. | Refining assemblies and refining methods for rich natural gas |
US10256447B2 (en) * | 2015-06-03 | 2019-04-09 | Celgard, Llc | Low electrical resistance microporous battery separator membranes, separators, cells, batteries, and related methods |
US11027040B2 (en) | 2016-12-29 | 2021-06-08 | Industrial Technology Research Institute | Method for manufacturing a porous film, porous film and method for tissue adhesion |
US10870810B2 (en) | 2017-07-20 | 2020-12-22 | Proteum Energy, Llc | Method and system for converting associated gas |
WO2020240366A1 (en) | 2019-05-31 | 2020-12-03 | 3M Innovative Properties Company | Composite cooling film and article including the same |
WO2020240447A1 (en) | 2019-05-31 | 2020-12-03 | 3M Innovative Properties Company | Composite cooling film and article including the same |
US20220355567A1 (en) | 2019-12-19 | 2022-11-10 | 3M Innovative Properties Company | Composite cooling film comprising a reflective microporous layer and a uv-absorbing layer |
EP4078049A4 (en) | 2019-12-19 | 2024-01-24 | 3M Innovative Properties Company | Composite cooling film comprising an organic polymeric layer, a uv-absorbing layer, and a reflective metal layer |
EP4085174A1 (en) | 2019-12-31 | 2022-11-09 | 3M Innovative Properties Co. | Multi-surface passive cooling articles |
CN115461581A (en) | 2020-05-06 | 2022-12-09 | 3M创新有限公司 | Solar energy absorption and radiation cooling article and method |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5231126A (en) | 1985-04-01 | 1993-07-27 | Shi Guan Yi | Beta-crystalline form of isotactic polypropylene and method for forming the same |
JPH075780B2 (en) * | 1987-02-17 | 1995-01-25 | 東レ株式会社 | Method for producing polypropylene microporous film |
CN1017682B (en) | 1990-11-13 | 1992-08-05 | 中国科学院化学研究所 | High penetrability polypropylene microporous barrier and its production method |
US5176953A (en) | 1990-12-21 | 1993-01-05 | Amoco Corporation | Oriented polymeric microporous films |
US6235823B1 (en) | 1992-01-24 | 2001-05-22 | New Japan Chemical Co., Ltd. | Crystalline polypropylene resin composition and amide compounds |
US5491188A (en) | 1993-05-20 | 1996-02-13 | New Japan Chemical Co., Ltd. | Porous stretched article of polypropylene-based resin and process for its preparation |
JPH07118429A (en) | 1993-10-26 | 1995-05-09 | Tonen Chem Corp | Production of polypropylene porous film |
US5667911A (en) | 1994-11-17 | 1997-09-16 | Hoechst Celanese Corporation | Methods of making cross-ply microporous membrane battery separator, and the battery separators made thereby |
US5565281A (en) * | 1994-12-02 | 1996-10-15 | Hoechst Celanese Corporation | Shutdown, bilayer battery separator |
TW297171B (en) * | 1994-12-20 | 1997-02-01 | Hoechst Celanese Corp | |
JPH09176352A (en) | 1995-12-26 | 1997-07-08 | Tokuyama Corp | Production of microporous membrane |
JP3939778B2 (en) * | 1996-02-09 | 2007-07-04 | 日東電工株式会社 | Battery separator |
US5952120A (en) * | 1997-04-15 | 1999-09-14 | Celgard Llc | Method of making a trilayer battery separator |
-
1998
- 1998-06-26 US US09/105,516 patent/US6368742B2/en not_active Expired - Lifetime
-
1999
- 1999-05-27 CA CA002273127A patent/CA2273127A1/en not_active Abandoned
- 1999-05-27 TW TW088108744A patent/TW447161B/en not_active IP Right Cessation
- 1999-06-19 EP EP99111843A patent/EP0967671A3/en not_active Withdrawn
- 1999-06-24 JP JP17814499A patent/JP4535527B2/en not_active Expired - Lifetime
- 1999-06-25 KR KR1019990024275A patent/KR100628610B1/en not_active IP Right Cessation
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020034684A1 (en) * | 2000-09-15 | 2002-03-21 | Vb Autobatterie Gmbh | Separator for lead storage batteries |
US7682689B2 (en) | 2001-02-21 | 2010-03-23 | New Japan Chemical Co., Ltd. | Successively biaxial-oriented porous polypropylene film and process for production thereof |
US20070269719A1 (en) * | 2001-02-21 | 2007-11-22 | New Japan Chemical Co., Ltd. | Successively biaxial-oriented porous polypropylene film and process for production thereof |
US8105733B2 (en) | 2004-10-21 | 2012-01-31 | Evonik Degussa Gmbh | Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries |
US20100003401A1 (en) * | 2004-10-21 | 2010-01-07 | Evonik Degussa Gmbh | Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries |
US8163441B2 (en) | 2004-10-21 | 2012-04-24 | Evonik Degussa Gmbh | Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries |
EP1993811A2 (en) | 2006-02-21 | 2008-11-26 | Celgard LLC | Biaxially oriented microporous membrane |
WO2007098339A3 (en) * | 2006-02-21 | 2008-04-03 | Celgard Llc | Biaxially oriented microporous membrane |
US20070196638A1 (en) * | 2006-02-21 | 2007-08-23 | Xiangyun Wei | Biaxially oriented microporous membrane |
US11420416B2 (en) | 2006-02-21 | 2022-08-23 | Celgard, Llc | Biaxially oriented microporous membrane |
US10913237B2 (en) | 2006-02-21 | 2021-02-09 | Celgard, Llc | Biaxially oriented microporous membrane |
US8795565B2 (en) * | 2006-02-21 | 2014-08-05 | Celgard Llc | Biaxially oriented microporous membrane |
EP1993811B1 (en) | 2006-02-21 | 2016-04-06 | Celgard LLC | Biaxially oriented microporous membrane |
US20090068554A1 (en) * | 2006-03-28 | 2009-03-12 | Vb Autobatterie & Co. Kgaa | Separator for lead-acid rechargeable battery |
CN102015251A (en) * | 2008-05-02 | 2011-04-13 | 特里奥凡德国有限公司及两合公司 | Single-layer membrane film for batteries, having a shut-off function |
US9620754B2 (en) | 2008-12-19 | 2017-04-11 | Asahi Kasei E-Materials Corporation | Polyolefin microporous membrane and separator for lithium ion secondary battery |
EP2544841B1 (en) | 2010-03-12 | 2018-01-17 | Celgard LLC | Biaxially oriented porous membranes, composites, and methods of manufacture and use |
US9419266B2 (en) | 2011-01-27 | 2016-08-16 | Mitsubishi Plastics, Inc. | Polyolefin resin porous film, and non-aqueous electrolyte cell separator using same |
TWI588185B (en) * | 2012-12-25 | 2017-06-21 | Toyo Boseki | Biaxially oriented polypropylene film |
US10333125B2 (en) | 2014-11-26 | 2019-06-25 | Celgard, Llc | Multilayer microporous separators for lithium ion secondary batteries and related methods |
WO2016085970A1 (en) * | 2014-11-26 | 2016-06-02 | Celgard, Llc | Improved multilayer microporous separators for lithium ion secondary batteries and related methods |
US10938011B2 (en) | 2014-11-26 | 2021-03-02 | Celgard, Llc | Multilayer microporous separators for lithium ion secondary batteries and related methods |
US11799169B2 (en) | 2014-11-26 | 2023-10-24 | Celgard, Llc | Multilayer microporous separators for lithium ion secondary batteries and related methods |
Also Published As
Publication number | Publication date |
---|---|
JP4535527B2 (en) | 2010-09-01 |
CA2273127A1 (en) | 1999-12-26 |
JP2000030683A (en) | 2000-01-28 |
US6368742B2 (en) | 2002-04-09 |
EP0967671A2 (en) | 1999-12-29 |
TW447161B (en) | 2001-07-21 |
KR100628610B1 (en) | 2006-09-27 |
KR20000006475A (en) | 2000-01-25 |
EP0967671A3 (en) | 2003-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6368742B2 (en) | Polypropylene microporous membrane for battery separator | |
JP7046772B2 (en) | Co-extruded multi-layer battery separator | |
EP3159139B1 (en) | Method for producing polyolefin-based porous film | |
US8288033B2 (en) | Laminated porous film, separator for lithium cell, and cell | |
US9991494B2 (en) | Nano microporous diaphragm of post-crosslinked rubber and polyolefin composite, and manufacturing method thereof | |
EP0715364B1 (en) | Shutdown, bilayer battery separator | |
US8785032B2 (en) | Multilayer porous film, separator for batteries, and battery | |
KR100943236B1 (en) | Microporous polyolefin film with improved meltdown property and preparing method thereof | |
US8597775B2 (en) | Microporous polyolefin multi layer film | |
CN111902470B (en) | Polyolefin microporous membrane | |
US20200024419A1 (en) | Polyolefin Microporous Membrane and Production Method Thereof | |
US20210005860A1 (en) | Polyolefin microporous film | |
EP3594279A1 (en) | Polyolefin microporous membrane | |
JP5434661B2 (en) | Porous film and power storage device | |
EP2671909A1 (en) | Porous film, separator for electricity-storing device, and electricity-storing device | |
JPH11297297A (en) | Manufacture of porous film and porous film | |
WO2023276468A1 (en) | Polyolefin microporous membrane and battery separator | |
JP2000063551A (en) | Porous film and separator for battery | |
WO2023002818A1 (en) | Polyolefin multilayer microporous membrane, laminated polyolefin multilayer microporous membrane, and battery separator | |
WO2024024710A1 (en) | Polyolefin microporous membrane, separator for secondary batteries, and secondary battery | |
JP2022146342A (en) | Separator for power storage device and power storage device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CELGARD LLC, NORTH CAROLINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FISHER, H. M.;WENSLEY, C. G.;REEL/FRAME:009287/0239 Effective date: 19980626 |
|
AS | Assignment |
Owner name: CELGARD, INC., A CORP. OF DELAWARE, MASSACHUSETTS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CELGARD LLC;REEL/FRAME:010506/0869 Effective date: 19991214 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
AS | Assignment |
Owner name: CHASE MANHATTAN BANK, AS ADMINISTRATIVE AGENT, THE Free format text: SECURITY AGREEMENT;ASSIGNOR:CELGARD, INC.;REEL/FRAME:013964/0538 Effective date: 19991215 |
|
AS | Assignment |
Owner name: CELGARD, LLC, SOUTH CAROLINA Free format text: CHANGE OF NAME;ASSIGNOR:CELGARD, INC.;REEL/FRAME:014822/0710 Effective date: 20040630 |
|
AS | Assignment |
Owner name: JPMORGAN CHASE BANK, AS ADMINISTRATIVE AGENT, TEXA Free format text: SECURITY AGREEMENT;ASSIGNOR:CELGARD, LLC;REEL/FRAME:015348/0137 Effective date: 20041109 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT, NORTH CAROLINA Free format text: PATENT SECURITY AGREEMENT;ASSIGNOR:CELGARD, LLC (F/K/A CELGARD, INC.);REEL/FRAME:032631/0655 Effective date: 20140408 Owner name: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT, NO Free format text: PATENT SECURITY AGREEMENT;ASSIGNOR:CELGARD, LLC (F/K/A CELGARD, INC.);REEL/FRAME:032631/0655 Effective date: 20140408 |
|
AS | Assignment |
Owner name: CELGARD, LLC, NORTH CAROLINA Free format text: RELEASE OF SECURITY AGREEMENTS IN PATENT RIGHTS;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:033380/0608 Effective date: 20140408 |
|
AS | Assignment |
Owner name: CELGARD, LLC (F/K/A/ CELGARD, INC.), NORTH CAROLINA Free format text: TERMINATION AND RELEASE OF SECURITY INTEREST IN UNITED STATES PATENTS;ASSIGNOR:BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:036485/0267 Effective date: 20150826 Owner name: CELGARD, LLC (F/K/A/ CELGARD, INC.), NORTH CAROLIN Free format text: TERMINATION AND RELEASE OF SECURITY INTEREST IN UNITED STATES PATENTS;ASSIGNOR:BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:036485/0267 Effective date: 20150826 |