WO2001016219A1 - Microporous film - Google Patents
Microporous film Download PDFInfo
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- WO2001016219A1 WO2001016219A1 PCT/JP2000/005779 JP0005779W WO0116219A1 WO 2001016219 A1 WO2001016219 A1 WO 2001016219A1 JP 0005779 W JP0005779 W JP 0005779W WO 0116219 A1 WO0116219 A1 WO 0116219A1
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- microporous film
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- 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
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- 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
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- 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
- C08J9/0066—Use of inorganic compounding ingredients
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- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- 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
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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 microporous film. More specifically, the present invention relates to a microporous film used for a battery separator.
- Conventional technology relates to a microporous film used for a battery separator.
- Non-aqueous electrolyte batteries that use light metals such as lithium as their electrodes have a high energy density and low self-discharge, and their use has been greatly expanded in the background of higher performance and smaller electronic devices.
- a spiral wound body having a wide effective electrode area secured by laminating and winding a strip-shaped positive electrode, a negative electrode, and a separator is used.
- Separation is basically to prevent short-circuiting of both electrodes, and to allow ions to pass through its microporous structure to enable battery reaction.However, an abnormal current was generated due to incorrect connection outside the battery, etc.
- a resin with a so-called shirt down function (SD function) is used from the viewpoint of improving safety, in which the resin is thermally deformed as the battery internal temperature rises to prevent microporosity and stop the battery reaction. .
- a separator having such an SD function for example, a microporous film made of polyethylene (a multi-layered microporous film made of polyethylene and polypropylene) is known.
- a battery separator which has a large difference between a shirt down temperature (SD temperature) and a rupture temperature, and has a higher temperature characteristic and a higher safety as the rupture temperature is higher.
- SD temperature shirt down temperature
- Japanese Patent Application Laid-Open No. 63-308866 discloses a microporous material having high strength and excellent high-temperature properties by laminating a single film composed of low-melting polyethylene and high-melting polypropylene. Although a porous film is disclosed, the internal resistance of the separator increases due to the lamination, and is not suitable as a separator for high-performance batteries such as high-output applications. Also, Japanese Patent Application Laid-Open No.
- H10-2983825 discloses a microporous membrane composed of a high-molecular-weight polyethylene composition containing low-molecular-weight polyethylene and polypropylene, but is exposed to a sharp temperature rise.
- the polyethylene material which occupies most of the microporous membrane, is easily melted, so that the material is easily broken and the danger is increased.
- high-performance batteries such as those for high-power applications, are expected to have heat resistance exceeding that of polypropylene-containing separators, which were conventionally considered to be high heat-resistant. Disclosure of the invention
- An object of the present invention is to provide a microporous film having excellent permeation performance and mechanical strength, as well as an SD function at a low temperature and a film rupture resistance at a high temperature.
- Another object of the present invention is to provide a battery separator comprising the microporous film of the present invention.
- Still another object of the present invention is to provide a battery using the battery separator of the present invention.
- the present inventors have conducted intensive studies to achieve the above object, and found that at least a ring-opened polymer of an unsaturated condensed alicyclic compound, a polyolefin having a weight average molecular weight of 500,000 or less, a thermoplastic elastomer or a graft.
- a microporous film consisting of a copolymer The present inventors have found that excellent functions having a low SD temperature and a high rupture temperature can be obtained, and have reached the present invention.
- the gist of the present invention is:
- a microporous film comprising a resin composition containing 1 to 50% by weight of at least one resin component,
- a battery separator comprising the microporous film according to (1), and
- the ring-opened polymer of the unsaturated condensed alicyclic compound used in the present invention (hereinafter also referred to as a first resin component) has an aliphatic ring derived from its monomer unit and a double bond in the main chain. .
- a part of the double bond may be hydrogenated.
- the unsaturated condensed alicyclic compounds are roughly classified into the following three series.
- the first series includes, among those classified as condensed alicyclic compounds in a narrow sense, unsaturated compounds having a double bond incorporated into a main chain in one of the rings after ring-opening polymerization. Further, it can be used as unsaturated condensed alicyclic compounds, including derivatives in which some of the hydrogen atoms of those unsaturated compounds are replaced by other substituents. An example of this is bicyclo
- the second series includes unsaturated compounds having a double bond incorporated into the main chain of one of the rings after ring-opening polymerization, among those classified as acyclic compounds.
- the unsaturated condensed alicyclic compound can be used, including derivatives in which some of the hydrogen atoms of the unsaturated compounds are replaced by other substituents.
- bicyclo [2.2.1] heptose 5-ene in the present specification, norbornene and
- Norbornene derivatives such as bicyclo [2.2.1] hept-5-ene-12,3-dicarboxymethyl ester, bicyclo [2.2.2] oct-2-ene and derivatives thereof, etc. Is mentioned.
- the third series includes compounds having a bridged ring and a condensed alicyclic ring, and having an aliphatic ring and a double bond in the main chain after ring-opening polymerization.
- Torishi black [5 2 1 0 2 '6...] Dec one 3, 8 - Gen (Jishikuropen evening Zhen), tetracyclododecene and derivatives thereof.
- norbornene and norbornene derivatives are preferable from the viewpoint of raw material supply and the like.
- these unsaturated condensed alicyclic compounds can be subjected to ring-opening polymerization alone or in combination of two or more, or sequentially.
- polynorbornene or the like As the ring-opening polymer of the unsaturated condensed alicyclic compound, polynorbornene or the like is preferably used, and among them, polynorbornene rubber having a high average molecular weight is more preferably used from the viewpoint of dispersibility.
- the microporous film of the present invention includes one or more resin components selected from the group consisting of polyolefins having a weight average molecular weight of 500,000 or less, a thermoplastic elastomer, and a graft cobolimer (hereinafter referred to as a second resin). (Also referred to as a resin component).
- Polyolefins having a weight-average molecular weight of 500,000 or less are preferably polyolefins having a weight-average molecular weight of less than 500,000, more preferably 300,000 or less from the viewpoint of lowering the SD temperature.
- modified polyolefin resins such as ethylene-acryl monomer copolymer and ethylene-vinyl acetate copolymer.
- Particularly preferred is a polyethylene resin having a weight average molecular weight of less than 500,000, and particularly preferably a weight average molecular weight of 300,000 or less.
- thermoplastic elastomer examples include thermoplastic elastomers such as polystyrene, polyolefin, polygene, polyvinyl chloride, and polyester.
- graft copolymer examples include a graft copolymer obtained by grafting a polyolefin having a main chain having a polyolefin and a vinyl polymer having an incompatible group in a side chain.
- vinyl polymer include polyacryls, polymethacryls, polystyrene, and the like. Polyacrylonitrile and polyoxyalkylenes are preferred.
- the incompatible group means a group that is incompatible with polyolefin, and includes, for example, a group derived from a vinyl polymer.
- polyolefin resins having a weight-average molecular weight of 500,000 or less especially low-melting polyethylene having a weight-average molecular weight of less than 500,000, crystalline polyolefin-based elastomers, and polymethacrylates having a low melting temperature are used as side chains.
- Graft copolymers having a low SD temperature Specifically, polyolefins having a weight-average molecular weight of less than 500,000 and Z or Z correspond to a portion where the low-temperature side observed by a differential scanning calorimeter (DSC) has a peak at 100 to 140 ° C. Thermoplastic elastomers are preferred.
- an ultrahigh molecular weight polyolefin resin such as ultrahigh molecular weight polyethylene having a weight average molecular weight of more than 500,000.
- the microporous film of the present invention comprises a resin composition containing the first resin component, the second resin component, and, if desired, an ultrahigh molecular weight polyolefin resin having a weight average molecular weight of more than 500,000.
- the amount of the first resin component is in the range of 1 to 50% by weight, preferably 1 to 40% by weight, more preferably 1 to 35% by weight in the resin composition.
- the lower limit of the amount is 1% by weight or more from the viewpoint of obtaining a microporous film having sufficient heat resistance, and the upper limit thereof is from the viewpoint of maintaining the characteristics of the microporous film as a battery separator. From 50% by weight or less.
- the amount of the second resin component is in the range of 1 to 50% by weight in the resin composition. It is preferably from 5 to 45% by weight, more preferably from 5 to 40% by weight.
- the lower limit of the compounding amount is 1% by weight or more from the viewpoint of obtaining a sufficient SD temperature, and the upper limit thereof has a sufficient porosity and characteristics of the microporous film as a battery separator. From the viewpoint of maintaining the content, the content is 50% by weight or less.
- the amount of the ultrahigh molecular weight polyolefin resin having a weight average molecular weight exceeding 500,000 is preferably 5 to 98% by weight, more preferably 10 to 90% by weight in the resin composition.
- a dry film forming method and a wet film forming method can be used.
- it can be manufactured by mixing the resin composition with a solvent, kneading, forming into a sheet while heating and melting, rolling, stretching in one or more axial directions, and extracting and removing the solvent.
- the solvent examples include aliphatic or cyclic hydrocarbons such as nonane, decane, pendecane, dodecane, decalin, and liquid paraffin, and mineral oil fractions having a boiling point corresponding to these solvents. Non-volatile solvents rich in formula hydrocarbons are preferred.
- the amount of the solvent used is preferably 60 to 95% by weight of the mixture of the resin composition and the solvent.
- the step of kneading the mixture of the resin composition and the solvent and shaping the mixture into a sheet can be performed by a known method, and kneading is performed in a batch manner using a Banbury mixer, kneader, or the like, and then cooled.
- a sheet-shaped molded product may be obtained using an extruder equipped with a T-die or the like.
- the kneading may be performed under appropriate temperature conditions, and is not particularly limited, but is preferably 100 to 200 ° C.
- the thickness of the sheet-like molded product thus obtained is not particularly limited, but is preferably 3 to 20 mm, and may be 0.5 to 2 mm by a rolling process such as a heat press.
- the temperature of the rolling treatment is preferably from 100 to 140 ° C. 1/16219 P
- the method of stretching the sheet-like molded product is not particularly limited, and may be a normal ten-in-one method, a roll method, an inflation method, or a combination of these methods. Any method such as biaxial stretching and biaxial stretching can be applied. In the case of biaxial stretching, either vertical or horizontal simultaneous stretching or sequential stretching may be used.
- the temperature of the stretching treatment is preferably from 100 to 140 ° C.
- Desolvation treatment is a process in which a solvent is removed from a sheet-like molded product to form a microporous structure.For example, it can be performed by washing the sheet-like molded product with a solvent to remove the residual solvent. it can.
- the solvent examples include hydrocarbons such as pentane, hexane, heptane, and decane; chlorinated hydrocarbons such as methylene chloride and carbon tetrachloride; fluorinated hydrocarbons such as ethane trifluoride; and ethers such as getyl ether and dioxane. And the like. These can be used alone or as a mixture of two or more.
- the washing method using such a solvent is not particularly limited, and examples thereof include a method of immersing a sheet-like molded product in a solvent to extract the solvent, a method of showering the solvent to a sheet-like molded product, and the like.
- the resin composition constituting the microporous film is crosslinked.
- One or more members selected from the group consisting of heat, ultraviolet rays and electron beams can be used for cross-linking, and this cross-linking eliminates all or part of the double bonds of the ring-opened polymer of the unsaturated condensed alicyclic compound. .
- a cross-linking treatment using heat and ultraviolet rays is desirable from the viewpoint of the structural stability of the microporous film. By performing these crosslinking treatments, the heat resistance (high-temperature film rupture resistance) of the microporous film is greatly improved.
- the polymer radical generated in each treatment is added to the double bond, and at that time, the ring-opened polymer of the unsaturated condensed alicyclic compound, A cross-linking reaction occurs between the ring polymer and other resin components, and the glass transition temperature of the polymer chain itself due to disappearance of the double bond in the main chain. Is likely to rise significantly.
- the ratio at which the double bond is eliminated is appropriately selected in consideration of the desired heat resistance, but is preferably 80 to 100% (calculated based on the size of the IR peak). It is considered that these greatly improve heat resistance.
- a single-step heat treatment method in which heat treatment is performed in a single step a multi-step heat treatment method in which heat treatment is performed first at a low temperature and then a heat treatment at a higher temperature may be performed, or
- a temperature-raising heat treatment method in which a heat treatment is performed while raising the temperature may be used, it is desirable to carry out the treatment without impairing the original characteristics of the microporous film such as the air permeability.
- the temperature is preferably from 40 ° C to 140 ° C, though it depends on the composition of the microporous film.
- heat treatment is started at a low temperature, and then the treatment temperature is raised.
- the heat resistance gradually increases with the hardening of the microporous film. Exposure to high temperatures is possible without loss. Therefore, in order to complete the heat treatment in a short time without deteriorating various characteristics, a multi-stage or elevated temperature heat treatment is preferable.
- the initial heat treatment temperature of the multistage heat treatment method depends on the composition of the microporous film, preferably 40 to 90 ° C, and the second heat treatment temperature also depends on the composition of the microporous film. Force, preferably 90-140 ° C. If necessary, heat treatment at a higher temperature and for a shorter time in the third and subsequent stages may be performed.
- the treatment time is preferably a force depending on the composition of the microporous film, about 3 to 48 hours for the first heat treatment, and about 0.5 to 6 hours for the second heat treatment at a higher temperature.
- the heat treatment may be performed under the same conditions as those of the above-described multi-stage heat treatment.
- the atmosphere during the heat treatment may be air, or may be an atmosphere of an inert gas such as nitrogen gas or argon gas in order to control the state of crosslinking.
- the microporous film after film formation is directly impregnated in the air or in a methanol solution containing a polymerization initiator, and after drying the solvent, the microporous film is irradiated with a mercury lamp to crosslink. Processing can be performed. In addition, ultraviolet irradiation may be performed in water for heat control during irradiation. When an electron beam is used, the irradiation is performed, for example, by irradiating a microporous film after film formation with a radiation dose of 0.1 to 10 Mrad.
- the atmosphere at the time of irradiation may be air as in the case of the heat treatment method, or may be an atmosphere of an inert gas such as nitrogen gas or argon gas in order to control the state of crosslinking.
- the microporous film may be generally heat-set (heat-set) to prevent thermal shrinkage.
- heat-set heat-set
- the present invention by performing the cross-linking treatment using heat as described above, heat setting can be substantially performed depending on the processing conditions. However, when the heat setting is insufficient, heat shrinkage is prevented.
- heat setting may be performed by further heating after the crosslinking treatment. Temperature for the heat setting, for example, 1 1 0-1 4 0 0.5 to 2 hours about irxJ Yore, 0
- the thickness of the microporous film obtained as described above is preferably 1 to 60 cm, more preferably 5 to 45 m.
- the porosity is preferably from 20 to 80%, more preferably from 25 to 75%.
- the permeability for example, the air permeability according to JISP 8117 is preferably 100 to 100 seconds / ⁇ 0.0 cc, and 200 to 900 seconds is more preferable.
- the mechanical strength for example, the piercing strength is preferably at least 200 gm / 25 m, more preferably at least 300 gfZ25 m. In addition, as a method of measuring the piercing strength, a method described in Examples described later can be used.
- the SD temperature of the microporous film is preferably from 120 to 150 ° C, more preferably from 120 to 140 ° C.
- the thermal rupture temperature is preferably 150 ° C. or higher, more preferably 200 ° C. or higher.
- the microporous film of the present invention has excellent permeability and mechanical strength, and also has excellent low-temperature SD effect and high resistance to film rupture at high temperatures. Improve safety for various sizes and applications Can be expected.
- the battery separator of the present invention is preferably used as a non-aqueous electrolyte battery separator, and the battery of the present invention is preferably used as a non-aqueous electrolyte battery.
- Any non-aqueous electrolyte battery may be used as long as the microporous film is used as a separator, and its structure, constituent materials, and manufacturing method are the same as those of a normal non-aqueous electrolyte battery and its manufacturing method. There is no particular limitation as long as it is used.
- the nonaqueous electrolyte battery of the present invention is excellent in safety because the microporous film of the present invention is used.
- the present invention will be described with reference to examples, but the present invention is not limited to these examples.
- the test method in an Example is as follows. (Film thickness)
- the cross section of a 1/10000 thickness gauge and microporous film was measured by a scanning electron microscope.
- a piercing test was performed using a compression tester “KES-G5” manufactured by Kato Tech Co., Ltd. The maximum load was read from the obtained load displacement curve, and the puncture strength was determined.
- the needle used had a diameter of 1 mm and a radius of curvature of 0.5 mm at the tip, and was moved at a speed of 2 cmZ seconds.
- shutdown temperature (Shutdown temperature (SD temperature) It has a 25 mm ⁇ cylindrical test chamber, and uses a stainless steel cell that can be sealed.
- the lower electrode is 2 Omm0
- the upper electrode is a 10 mm ⁇ platinum plate (1.0 mm thick). mm) was used.
- a measurement sample punched to 24 mm ⁇ was immersed in an electrolyte to impregnate the electrolyte, sandwiched between electrodes, and set in a cell.
- the electrodes were applied with a constant surface pressure by a spring provided in the cell.
- As the electrolytic solution a solution prepared by dissolving lithium borofluoride to a concentration of 1. Omo 1/1 in a solvent in which propylene carbonate and dimethoxetane were mixed at a volume ratio of 1: 1 was used.
- thermocouple thermometer and an ohmmeter were connected to this cell so that temperature and resistance could be measured.
- the cell was placed in a thermostat at 180 and the temperature and resistance were measured.
- the average rate of temperature rise from 100 to 150 ° C was 10 ° CZ minutes. Based on this measurement, the temperature at which the resistance reached 100 ⁇ ⁇ cm 2 was defined as the SD temperature.
- a strip-shaped sample having a width of 3 mm was mounted with a chuck interval of 1 Omm, set on a thermal stress / strain analyzer “TMAZSS 100” manufactured by Seiko Electronics, and heated at a rate of 2 ° C./min. Evaluation was made from the state at the time of this temperature rise, and the temperature at which the strip-shaped sample broke was defined as the thermal rupture temperature.
- the film cut to 60 mm ⁇ was read at 144 dpi with an image scanner, and the area was converted to the number of pixels to obtain a blank value.
- the film was kept in a thermostatic dryer at 105 ° C for XI hour, taken out, read at 144 dpi by an image scanner, and the area was converted into the number of pixels to obtain the value after heat treatment.
- the area shrinkage R (%) was obtained from the blank and the number of area pixels after heat treatment according to the following equation.
- these kneaded materials were sandwiched between metal plates cooled to 0 ° C and rapidly cooled in a sheet shape.
- These quenched sheet resins are heat pressed at a temperature of 115 ° C until the sheet thickness becomes 0.4 to 0.6 mm, and simultaneously at a temperature of 115 ° C 3.5 ⁇ 3.
- the film was biaxially stretched by a factor of 5 and desolvation treatment was performed using heptane.
- the obtained microporous film was subjected to a cross-linking treatment using heat at 85 ° C. for 6 hours in air, and then heat-treated at 110 ° C. for 2 hours to obtain a microporous film.
- a resin composition 25 and 5 parts by weight of liquid paraffin are uniformly mixed in a slurry form, and are heated at a temperature of 160 ° C using a small kneader for about 60 minutes. It was dissolved and kneaded. Thereafter, these kneaded materials were sandwiched between metal plates cooled to 0 ° C. and rapidly cooled in a sheet form. These quenched sheet resins are heated at a temperature of 110 ° C to reduce the sheet thickness.
- microporous film was subjected to a crosslinking treatment using heat at 85 ° C. for 6 hours in air, and then heat-treated at 110 ° C. for 2 hours to obtain a microporous film.
- a ring-opening polymer of norpolene, graft copolymer (main chain: low-density polyethylene, side chain: methyl methacrylate resin, composition ratio: 700, softening temperature: 97 ° C, Nippon Yushi's MODIPER A 1 200 ”) 15% by weight, ultrahigh molecular weight polyethylene with a weight average molecular weight of 300,000 73% by weight resin composition composed of 33% by weight and 80% by weight of liquid paraffin in a slurry state Mix at a temperature of 160 ° C The mixture was dissolved and kneaded for about 60 minutes using a small kneader.
- Resin composition 2 consisting of 75% by weight of ultra-high molecular weight polyethylene having a weight average molecular weight of 300,000 and 25% by weight of low molecular weight polyethylene (molecular weight: 2000, "High Wax 200 P” manufactured by Mitsui Chemicals)
- a film was formed in the same manner as in Example 1 except that 0 parts by weight and 80 parts by weight of liquid paraffin were used, and the obtained microporous film was heat-treated in air at 115 ° C for 2 hours to give a fine powder. A porous film was obtained.
- a resin composition consisting of 67% by weight of polyethylene having a weight average molecular weight of 300,000% and 33% by weight of ultrahigh molecular weight polyethylene having a weight average molecular weight of 300,000 and 85 parts by weight of liquid paraffin were used. Except for the above, a film was formed in the same manner as in Example 1, and the obtained microporous film was heat-treated at 115 ° C for 2 hours in air to obtain a microporous film.
- a film was formed in the same manner as in Example 1 except that 17 parts by weight of ultrahigh molecular weight polyethylene having a weight average molecular weight of 200,000 (melting point: 144 ° C.) and 83 parts by weight of liquid paraffin were used. Heat treated porous film at 125 ° C for 2 hours in air to obtain microporous film was.
- a resin composition consisting of 2% by weight of a powder of a ring-opening polymer of norbornene, an ultra-high molecular weight polyethylene having a weight-average molecular weight of 300,000 98% by weight, and 15 parts by weight of liquid paraffin and 85 parts by weight of liquid paraffin in a slurry form
- the mixture was uniformly mixed and melt-kneaded at a temperature of 160 ° C. using a twin-screw kneader for 5 minutes to obtain a kneaded product.
- the kneaded product was formed into a gel-like sheet having a thickness of 5 mm while being rapidly cooled.
- This sheet is heat-pressed at a temperature of 120 ° C until the thickness becomes lmm, and simultaneously biaxially stretched at a temperature of 125 ° C to 4 ⁇ 4 times in length and width, and desolvation treatment is performed using heptane. went. Thereafter, the obtained microporous film was heat-treated in air at 85 ° C for 6 hours, and then heat-treated in air at 125 ° C for 1 hour to obtain a microporous film.
- Table 1 shows the properties of the microporous films obtained in Examples 1 to 6 and Comparative Examples 1 to 4.
- the microporous film of the present invention has excellent permeability and mechanical strength, as well as a low-temperature shirt-down function and a high-temperature heat-resistant film-breaking property. By using it as a separator, it is possible to obtain non-aqueous electrolyte batteries of various sizes and applications with excellent safety.
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- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00955052A EP1153967B1 (en) | 1999-08-31 | 2000-08-28 | Microporous film |
JP2001520770A JP4703076B2 (ja) | 1999-08-31 | 2000-08-28 | 微多孔フィルム |
DE60027274T DE60027274T2 (de) | 1999-08-31 | 2000-08-28 | Mikroporöser film |
US09/830,695 US6559195B1 (en) | 1999-08-31 | 2000-08-28 | Microporous film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/246235 | 1999-08-31 | ||
JP24623599 | 1999-08-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001016219A1 true WO2001016219A1 (en) | 2001-03-08 |
Family
ID=17145528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/005779 WO2001016219A1 (en) | 1999-08-31 | 2000-08-28 | Microporous film |
Country Status (6)
Country | Link |
---|---|
US (1) | US6559195B1 (ja) |
EP (1) | EP1153967B1 (ja) |
JP (1) | JP4703076B2 (ja) |
KR (1) | KR100696144B1 (ja) |
DE (1) | DE60027274T2 (ja) |
WO (1) | WO2001016219A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002141045A (ja) * | 2000-11-06 | 2002-05-17 | Nitto Denko Corp | 非水電解液電池用セパレータ及び非水電解液電池 |
JP2002321323A (ja) * | 2001-04-24 | 2002-11-05 | Asahi Kasei Corp | ポリオレフィン製微多孔膜 |
JP2003105114A (ja) * | 2001-09-28 | 2003-04-09 | Nitto Denko Corp | 多孔質フィルム |
JP2005158671A (ja) * | 2003-10-28 | 2005-06-16 | Nitto Denko Corp | 電池 |
JP2010244874A (ja) * | 2009-04-07 | 2010-10-28 | Panasonic Corp | リチウムイオン二次電池 |
JP2011063025A (ja) * | 2010-10-04 | 2011-03-31 | Asahi Kasei E-Materials Corp | ポリオレフィン製微多孔膜 |
JP2013126765A (ja) * | 2013-02-04 | 2013-06-27 | Asahi Kasei E-Materials Corp | ポリオレフィン製微多孔膜 |
JP2021093353A (ja) * | 2019-12-06 | 2021-06-17 | ダブリュー−スコープ コリア カンパニー,リミテッド | 架橋セパレータ及びその製造方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4641623B2 (ja) * | 1999-05-07 | 2011-03-02 | 日東電工株式会社 | 多孔質フィルム及びその製造方法 |
US7238744B2 (en) * | 2002-04-12 | 2007-07-03 | Daramic, Inc. | Ultrahigh molecular weight polyethylene articles and method of manufacture |
US20040043214A1 (en) * | 2002-08-30 | 2004-03-04 | Kimberly-Clark Worldwide, Inc. | Method of forming a 3-dimensional fiber and a web formed from such fibers |
JP3886124B2 (ja) * | 2002-10-28 | 2007-02-28 | 日東電工株式会社 | 多孔質フィルムの製造方法 |
JP4999292B2 (ja) * | 2004-07-21 | 2012-08-15 | 三洋電機株式会社 | 非水電解質電池 |
KR101310541B1 (ko) * | 2008-12-24 | 2013-09-23 | 미쓰비시 가가꾸 가부시키가이샤 | 전지용 세퍼레이터 및 비수계 리튬 전지 |
JP4846882B2 (ja) * | 2009-08-25 | 2011-12-28 | 旭化成イーマテリアルズ株式会社 | 微多孔膜捲回体及びその製造方法 |
US11021584B2 (en) | 2014-08-21 | 2021-06-01 | William Winchin Yen | Microporous sheet product and methods for making and using the same |
KR20170077221A (ko) | 2014-11-05 | 2017-07-05 | 윌리암 윈친 옌 | 미세다공성 시트 제품 및 그의 제조 및 사용 방법 |
US10829600B2 (en) | 2014-11-05 | 2020-11-10 | William Winchin Yen | Microporous sheet product and methods for making and using the same |
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JPH07133363A (ja) * | 1993-11-10 | 1995-05-23 | Toray Ind Inc | 白色フイルム |
JPH10204199A (ja) * | 1996-11-19 | 1998-08-04 | Mitsubishi Chem Corp | 多孔質成形体 |
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US4699857A (en) * | 1986-10-15 | 1987-10-13 | W. R. Grace & Co. | Battery separator |
JPH0750601B2 (ja) | 1987-06-10 | 1995-05-31 | 三洋電機株式会社 | 非水電解液電池 |
US5252385A (en) * | 1989-07-17 | 1993-10-12 | Tonen Sekiyukagaku Kabushiki Kaisha | Elastomer film and composite containing same |
JPH05230253A (ja) * | 1992-02-19 | 1993-09-07 | Unitika Ltd | 軽量化ポリエステルフィルム及びその製造方法 |
JP3699562B2 (ja) * | 1997-04-23 | 2005-09-28 | 東燃化学株式会社 | ポリオレフィン微多孔膜及びその製造方法 |
JP4641623B2 (ja) * | 1999-05-07 | 2011-03-02 | 日東電工株式会社 | 多孔質フィルム及びその製造方法 |
-
2000
- 2000-08-28 US US09/830,695 patent/US6559195B1/en not_active Expired - Lifetime
- 2000-08-28 WO PCT/JP2000/005779 patent/WO2001016219A1/ja active IP Right Grant
- 2000-08-28 DE DE60027274T patent/DE60027274T2/de not_active Expired - Lifetime
- 2000-08-28 JP JP2001520770A patent/JP4703076B2/ja not_active Expired - Fee Related
- 2000-08-28 EP EP00955052A patent/EP1153967B1/en not_active Expired - Lifetime
- 2000-08-28 KR KR1020017005440A patent/KR100696144B1/ko active IP Right Grant
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH07133363A (ja) * | 1993-11-10 | 1995-05-23 | Toray Ind Inc | 白色フイルム |
JPH10204199A (ja) * | 1996-11-19 | 1998-08-04 | Mitsubishi Chem Corp | 多孔質成形体 |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002141045A (ja) * | 2000-11-06 | 2002-05-17 | Nitto Denko Corp | 非水電解液電池用セパレータ及び非水電解液電池 |
JP4582675B2 (ja) * | 2000-11-06 | 2010-11-17 | 日東電工株式会社 | 非水電解液電池用セパレータ及び非水電解液電池 |
JP2002321323A (ja) * | 2001-04-24 | 2002-11-05 | Asahi Kasei Corp | ポリオレフィン製微多孔膜 |
JP2003105114A (ja) * | 2001-09-28 | 2003-04-09 | Nitto Denko Corp | 多孔質フィルム |
JP4659308B2 (ja) * | 2001-09-28 | 2011-03-30 | 日東電工株式会社 | 多孔質フィルム |
JP2005158671A (ja) * | 2003-10-28 | 2005-06-16 | Nitto Denko Corp | 電池 |
JP4537736B2 (ja) * | 2003-10-28 | 2010-09-08 | 日東電工株式会社 | 電池 |
JP2010244874A (ja) * | 2009-04-07 | 2010-10-28 | Panasonic Corp | リチウムイオン二次電池 |
JP2011063025A (ja) * | 2010-10-04 | 2011-03-31 | Asahi Kasei E-Materials Corp | ポリオレフィン製微多孔膜 |
JP2013126765A (ja) * | 2013-02-04 | 2013-06-27 | Asahi Kasei E-Materials Corp | ポリオレフィン製微多孔膜 |
JP2021093353A (ja) * | 2019-12-06 | 2021-06-17 | ダブリュー−スコープ コリア カンパニー,リミテッド | 架橋セパレータ及びその製造方法 |
JP7002779B2 (ja) | 2019-12-06 | 2022-01-20 | ダブリュー-スコープ コリア カンパニー,リミテッド | 架橋セパレータ及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60027274D1 (de) | 2006-05-24 |
US6559195B1 (en) | 2003-05-06 |
EP1153967A4 (en) | 2001-11-14 |
KR20010080363A (ko) | 2001-08-22 |
EP1153967A1 (en) | 2001-11-14 |
JP4703076B2 (ja) | 2011-06-15 |
DE60027274T2 (de) | 2007-01-11 |
KR100696144B1 (ko) | 2007-03-20 |
EP1153967B1 (en) | 2006-04-12 |
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