WO2013141306A1 - 多孔性フィルムおよび蓄電デバイス - Google Patents
多孔性フィルムおよび蓄電デバイス Download PDFInfo
- Publication number
- WO2013141306A1 WO2013141306A1 PCT/JP2013/058105 JP2013058105W WO2013141306A1 WO 2013141306 A1 WO2013141306 A1 WO 2013141306A1 JP 2013058105 W JP2013058105 W JP 2013058105W WO 2013141306 A1 WO2013141306 A1 WO 2013141306A1
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- WO
- WIPO (PCT)
- Prior art keywords
- porous film
- temperature
- film
- stretching
- porosity
- Prior art date
Links
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- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
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- 229910001369 Brass Inorganic materials 0.000 description 1
- VFHFYNVERRHRMI-UHFFFAOYSA-N C(=C)C1=CCCCC1.C=CCCCCCCCCCCCCCCCCCC Chemical compound C(=C)C1=CCCCC1.C=CCCCCCCCCCCCCCCCCCC VFHFYNVERRHRMI-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JOKYEDJSHIKSBI-UHFFFAOYSA-N n-cyclohexyl-4-[3-[4-(cyclohexylcarbamoyl)phenyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]benzamide Chemical compound C=1C=C(C2OCC3(CO2)COC(OC3)C=2C=CC(=CC=2)C(=O)NC2CCCCC2)C=CC=1C(=O)NC1CCCCC1 JOKYEDJSHIKSBI-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 1
- 208000019585 progressive encephalomyelitis with rigidity and myoclonus Diseases 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- OKUCEQDKBKYEJY-UHFFFAOYSA-N tert-butyl 3-(methylamino)pyrrolidine-1-carboxylate Chemical class CNC1CCN(C(=O)OC(C)(C)C)C1 OKUCEQDKBKYEJY-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a porous film and an electricity storage device. More specifically, the present invention relates to a porous film that can be suitably used for a separator used in an electricity storage device such as a non-aqueous solvent battery or a capacitor and has high output, process suitability, and excellent long-term storage.
- Porous films are used in various applications such as separators for batteries and electrolytic capacitors, various separation membranes, clothing, and moisture-permeable waterproof membranes for medical applications. Particularly recently, it is widely used for separators of lithium ion secondary batteries.
- One of the properties that should be provided as a separator for a lithium ion secondary battery is voltage resistance and high output power of the battery. Withstand voltage is an index indicating whether or not a separator can withstand a short-circuit when a constant voltage is applied to the separator. When the voltage resistance of the separator is low, when used in a battery, it tends to be difficult to effectively prevent self-discharge, and the battery may have poor long-term storage stability. In addition, since the short-circuit rate of the battery increases, the yield increases, and the process suitability may deteriorate.
- a dry-stretched porous film (known as the CELGARD process) is disclosed.
- the dry-stretching method uses a low temperature extrusion and a high draft ratio at the time of melt extrusion of the film material, thereby controlling the lamella structure in the film before stretching, which is uniaxially stretched in the longitudinal direction.
- This is a method of generating a void at the interface (see Patent Documents 1 and 2).
- This method is excellent in air permeability due to a specific linear through-hole structure, but has a problem that the voltage is small and electrons easily pass when voltage is applied, resulting in poor voltage resistance.
- a biaxially stretched porous film in which a withstand voltage is improved by containing a crosslinked product obtained by crosslinking a polyolefin polymer and a polymer having a double bond (Patent Document 3). reference).
- Patent Document 3 a crosslinked product obtained by crosslinking a polyolefin polymer and a polymer having a double bond
- the main component is a polypropylene resin containing a ⁇ crystal nucleating agent, an ethylene / ⁇ -olefin copolymer is included, and the longitudinal and lateral stretching temperatures are adjusted to a predetermined range, thereby providing high permeability and an average pore diameter.
- a method for producing a microporous membrane having a large thickness is disclosed (see Patent Document 4). However, in this case, although the porosity is high and the output characteristics are excellent, there are cases where coarse pores of a certain level or more exist in the film surface and the voltage resistance is inferior.
- an object of the present invention is to solve the above-mentioned problems. That is, an object of the present invention is to provide a porous film and an electricity storage device that are excellent in output characteristics, process suitability, and long-term storage stability when used as a separator.
- the dielectric breakdown strength Ea value defined by the following formula (A) is 160 kV / mm or more, It can be achieved by a porous film with a rate of 45-85%.
- Ea V / T (A)
- the present invention can be suitably used as a porous film excellent in output characteristics, process suitability and long-term storage stability when used as a separator.
- the dielectric breakdown voltage is applied to the porous film while increasing the voltage stepwise, the number of breakdowns at each applied voltage is measured, and the voltage when the total exceeds 10 Say.
- the dielectric breakdown strength is a numerical value obtained by dividing the dielectric breakdown voltage by the film thickness of the porous film. Since the film thickness of the porous film corresponds to the distance between the electrodes and greatly affects the dielectric breakdown voltage, the dielectric breakdown voltage is normalized by the film thickness. When the value of the dielectric breakdown strength is increased, a porous film having a thinner film and excellent voltage resistance can be obtained.
- the Ea of the porous film of the present invention is preferably 170 kV / mm or more, and more preferably 180 kV / mm or more. From the viewpoint of process suitability and long-term storage stability, a higher value is preferable, but if it is too high, air permeability may be lowered, so 400 kV / mm is the upper limit.
- the stretching conditions during transverse stretching such as preheating temperature, initial stretching temperature, late stretching temperature, stretching speed, heat treatment temperature, heat treatment time, and relaxation rate should be controlled within the ranges described below. Can be achieved.
- the porous film of the present invention has a porosity of 45 to 85%.
- the porosity is less than 45%, battery resistance increases when used as a separator, and output characteristics may be inferior.
- the porosity exceeds 85% the puncture strength of the film, which is an index of dendrite resistance, becomes too low, and may be inferior in safety when used as a battery separator.
- the porosity of the porous film of the present invention is preferably 50 to 85%, more preferably 57 to 85%, and more preferably 60 to 85%. If so, it is more preferable.
- preheating temperature, initial stretching temperature, late stretching temperature, and stretching speed during transverse stretching, heat treatment temperature, heat treatment time, relaxation rate, and stretching temperature and magnification during longitudinal stretching Can be achieved by controlling to a range described later.
- the present applicant can set the film withstand voltage and high porosity.
- the preheating temperature and the initial stretching temperature by increasing the preheating temperature and the initial stretching temperature by 3 ° C. or more, the stress at the time of fibril cleavage can be relaxed and controlled by making the holes more uniform.
- the temperature in the initial stretching section during transverse stretching was defined as the initial stretching temperature
- the temperature in the section until the end of subsequent stretching (before heat treatment) was defined as the late stretching temperature.
- through holes are formed by cleaving fibrils uniaxially oriented in the machine direction during longitudinal stretching and transversely stretching the fibrils. Therefore, relieving the stress at the time of fibril cleavage is very important for uniform pore generation.
- the horizontal stretching temperature is generally carried out at the same temperature from preheating to the end of stretching, but in this case, the temperature is high from preheating to the initial stage of stretching, and then the temperature from the end to the end of stretching is low. A specific method will be described later.
- the preheating temperature is set higher than the stretching temperature in the stretching process in the transverse direction, hot air with temperature spots in the width direction generated in the preheating zone flows into the stretching zone, and stretching spots easily occur in the width direction during stretching. In some cases, the spots and physical properties were worsened.
- the pore formation may become uneven and the withstand voltage may be reduced. If the temperature is high, the stress at the time of fibril cleavage is relieved, but In some cases, the output characteristics deteriorate due to a decrease in porosity.
- the preheating temperature and the initial stretching temperature by 3 ° C. or more with respect to the latter stretching temperature at the time of transverse stretching, it is excellent in thickness unevenness and physical property unevenness, and further has both voltage resistance and output characteristics. It came to.
- the porous film of the present invention preferably has a curvature of 2.0 to 3.0.
- the curvature is less than 2.0, the continuous pore structure is substantially close to a linear structure, electrons are easy to pass when voltage is applied, the withstand voltage is low, battery process suitability, and long-term storage. May be inferior.
- the curvature exceeds 3.0, the air permeability is insufficient.
- the curvature of the porous film of the present invention is more preferably from 2.0 to 2.6, and even more preferably from 2.2 to 2.6.
- Controlling the curvature in such a range can be achieved by controlling the preheating temperature, initial stretching temperature, late stretching temperature, stretching speed, heat treatment temperature, heat treatment time, and relaxation rate during transverse stretching.
- calculation of the curvature ⁇ in the present invention can be obtained from the following relational expression.
- the relationship between the fluid permeation rate and the porosity, the pore diameter, or the fluid viscosity is expressed by the equation (1).
- u (d 2 ⁇ ⁇ / 100) ⁇ P / (2 ⁇ T 1 ⁇ 2 ) (1)
- u (m / sec) is the fluid permeation rate
- d (m) is the pore diameter
- ⁇ (%) is the porosity
- ⁇ P (Pa) is the pressure difference
- ⁇ (Pa ⁇ sec) is the fluid viscosity
- T 1 (m) is the film thickness
- ⁇ (dimensionless) is the curvature.
- the porous film of the present invention preferably has a product of a curvature and a porosity of 120% or more. If it is less than 120%, it is difficult to satisfy a high curvature and a high porosity at the same time. Therefore, the withstand voltage is low due to the low curvature, and there are cases where the process suitability and long-term storage stability are degraded, and the output characteristics are degraded due to the low porosity.
- the product of the curvature and porosity is preferably 130% or more, and more preferably 150% or more. Higher values are preferable from the viewpoint of process suitability, long-term storage properties, and output characteristics, but if it is too high, the upper limit is 300% because safety may be insufficient due to a decrease in air permeability or insufficient strength.
- the preheating temperature, the initial stretching temperature, the later stretching temperature, and the stretching speed during transverse stretching, the heat treatment temperature, the heat treatment time, the relaxation rate, and This can be achieved by controlling the stretching temperature and magnification during longitudinal stretching to the ranges described below.
- the porous film of the present invention is per resin thickness defined by the following formula (B).
- the dielectric breakdown strength Er is preferably 400 (kV / mm) or more. If Er is less than 400 (kV / mm), it indicates that the high voltage resistance and the high porosity are not satisfied at the same time, the process suitability due to the low voltage resistance, the deterioration of long-term storage stability, the porosity In some cases, there is a problem in that the output characteristics are lowered due to the low film thickness and the safety is lowered due to the thin film thickness.
- the porous film of the present invention preferably has a heat shrinkage rate of 0 to 5% at 120 ° C. for 60 minutes in both the longitudinal direction and the width direction. If the thermal shrinkage rate exceeds 5%, the separator may shrink and lead to a short circuit when the environmental temperature rises during use of the battery or when the temperature inside the battery rises due to a slight short circuit. From the viewpoint of improving safety as a battery separator, the thermal shrinkage rate in the longitudinal direction and the width direction at 120 ° C. for 60 minutes is preferably 4% or less, more preferably 3% or less.
- Controlling the heat shrinkage to such a range is achieved by controlling the preheating temperature, initial stretching temperature, late stretching temperature, stretching speed, heat treatment temperature, heat treatment time, and relaxation rate during transverse stretching to the ranges described below. Is possible.
- the porous film of the present invention preferably has an air resistance of 50 to 1,000 seconds / 100 ml. More preferred is 100 to 600 seconds / 100 ml, and even more preferred is 150 to 400 seconds / 100 ml. If the air permeation resistance is less than 50 seconds / 100 ml, the puncture strength of the film, which is an index of dendrite resistance, becomes too low, which may be inferior in safety. When the air resistance exceeds 1,000 seconds / 100 ml, the output characteristics may be deteriorated particularly when used as a separator for a high-power battery.
- the preheating temperature, the initial stretching temperature, the latter stretching temperature, and the stretching speed during transverse stretching, the heat treatment temperature, the heat treatment time, the relaxation rate, and the longitudinal stretching temperature and magnification will be described later. This can be achieved by controlling the range.
- the porous film of the present invention is preferably made of a thermoplastic resin.
- the thermoplastic resin include polyolefin resins, polycarbonate resins, polyamide resins, polyimide resins, polyamideimides, aromatic polyamide resins, and fluorine resins.
- polyolefin resins are preferred from the viewpoints of heat resistance, moldability, reduction in production cost, chemical resistance, oxidation resistance, and reduction resistance.
- Examples of the monomer component constituting the polyolefin resin here include ethylene, propylene, 1-butene, 1-pentene, 3-methylpentene-1, 3-methyl-1-butene, 1-hexene, 4 -Methyl-1-pentene, 5-ethyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene Vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene, 5-methyl-2-norbornene and the like.
- copolymers chosen from these homopolymers and the said monomer component, the blend of these homopolymers and a copolymer, etc. can be used.
- vinyl alcohol, maleic anhydride, acrylic acid compounds and the like may be copolymerized and graft polymerized with the above monomer components, but are not limited thereto. is not.
- polypropylene resin is preferably used because of excellent properties such as permeability and low specific gravity.
- the polypropylene resin used is isotactic with a melt flow rate (hereinafter referred to as MFR) of 2 to 30 g / 10 min.
- MFR melt flow rate
- a polypropylene resin is preferable from the viewpoint of extrusion moldability and uniform formation of pores.
- MFR is an index indicating the melt viscosity of a resin defined in JIS K 7210 (1995), and is a physical property value indicating the characteristics of a polyolefin resin. In the present invention, it refers to a value measured at 230 ° C. and 2.16 kg.
- the polypropylene resin used in the present invention preferably has an isotactic index in the range of 90 to 99.9%.
- the isotactic index is less than 90%, the crystallinity of the resin is lowered, and the film-forming property may be lowered, or the strength of the film may be insufficient.
- the porous film in the present invention has a plurality of through holes penetrating both surfaces of the film and having air permeability.
- a method for forming the through-hole in the film either a wet method or a dry method may be used, but a dry method is desirable because the process can be simplified.
- the through holes of the porous film of the present invention are preferably formed in the film by at least uniaxial or biaxial stretching.
- the porous film is obtained by stretching in the uniaxial direction, the obtained porous film is bent.
- the road ratio becomes too small, and the voltage resistance may be inferior.
- the ⁇ resin forming ability of the polypropylene resin to be used is 60% or more. If the ⁇ -crystal forming ability is less than 60%, the amount of ⁇ -crystal is small at the time of film production, so the number of voids formed in the film is reduced by utilizing the transition to ⁇ -crystal. It may not be obtained.
- the upper limit of ⁇ -crystal forming ability is not particularly limited, but it exceeds 99.9% by adding a large amount of the ⁇ -crystal nucleating agent described later or the stereoregulation of the polypropylene resin to be used. The industrial practical value is low, for example, the film forming stability is lowered. Industrially, the ⁇ -crystal forming ability is preferably 65 to 99.9%, particularly preferably 70 to 95%.
- a polypropylene resin with a high isotactic index is used, or a ⁇ crystal is selectively formed by adding it to a polypropylene resin called a ⁇ crystal nucleating agent.
- the crystallization nucleating agent to be used is preferably used as an additive.
- Examples of ⁇ crystal nucleating agents include alkali or alkaline earth metal salts of carboxylic acids such as calcium 1,2-hydroxystearate and magnesium succinate, and N, N′-dicyclohexyl-2,6-naphthalenedicarboxyamide.
- Amide compounds such as 3,9-bis [4- (N-cyclohexylcarbamoyl) phenyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, benzenesulfonic acid
- aromatic sulfonic acid compounds such as sodium and sodium naphthalene sulfonate, imide carboxylic acid derivatives, phthalocyanine pigments, and quinacridone pigments.
- amides disclosed in JP-A-5-310665 are preferred.
- the addition amount (content) of the ⁇ crystal nucleating agent is preferably 0.05 to 0.5% by mass, and preferably 0.1 to 0.3% by mass, based on the whole polypropylene resin. More preferable. If it is less than 0.05% by mass, formation of ⁇ crystals becomes insufficient, and the air permeability of the porous polyolefin film may be lowered. When it exceeds 0.5 mass%, when a coarse hole is formed and it uses for the separator for electrical storage devices, safety
- security may fall.
- polypropylene resin used in the present invention it is possible to use a homopolypropylene resin, as well as from the viewpoint of stability in the film-forming process, film-forming properties, and uniformity of physical properties, polypropylene with an ethylene component or butene, A resin obtained by copolymerizing an ⁇ -olefin component such as hexene or octene in an amount of 5% by mass or less, more preferably 2.5% by mass or less can also be used.
- the form of introduction of the comonomer (copolymerization component) into polypropylene may be either random copolymerization or block copolymerization.
- the above-mentioned polypropylene resin it is preferable for the above-mentioned polypropylene resin to contain a high-molecular-weight polypropylene resin, a low-melting-point polypropylene resin, a high-melting-strength polypropylene resin, or the like as long as the effects of the present invention are not hindered from the viewpoint of improving safety and improving film-forming properties.
- the high molecular weight polypropylene resin is a polypropylene resin having an MFR of 0.1 to 2 g / 10 min
- the low melting point polypropylene resin is a polypropylene resin having a melting point lower than 153 ° C.
- polypropylene resins for example, ethylene component, butene, Polypropylene resins copolymerized with ⁇ -olefin components such as hexene and octene
- high melt tension polypropylene resins are mixed with high molecular weight components or components having a branched structure in polypropylene, or long-chain branched components are combined with polypropylene. It is a polypropylene resin in which the tension in the molten state is increased by polymerization.
- the polypropylene resin used in the present invention is composed of 80 to 99 parts by mass of homopolypropylene resin and ethylene from the viewpoint of improving the void formation efficiency during biaxial stretching, and improving the air permeability due to the uniform opening of the holes and the expansion of the hole diameter.
- ⁇ -olefin copolymer is preferably a mixture having a mass ratio of 20 to 1 part by mass.
- examples of the ethylene / ⁇ -olefin copolymer include linear low-density polyethylene and ultra-low-density polyethylene. Among them, ethylene / ⁇ is copolymerized with octene-1 and has a melting point of 60 to 90 ° C.
- An olefin copolymer (copolymerized PE resin) can be preferably used.
- Examples of the ethylene / ⁇ -olefin copolymer include commercially available resins such as “Engage (registered trademark)” (type names: 8411, 8452, 8100, etc.) manufactured by Dow Chemical.
- the ethylene / ⁇ -olefin copolymer is preferably contained in an amount of 1 to 10% by mass when the total resin constituting the porous film of the present invention is 100% by mass from the viewpoint of improving the mechanical properties. More preferably, it is 1 to 7% by mass, and further preferably 1 to 5% by mass.
- the resin forming the porous film of the present invention includes an antioxidant, a heat stabilizer, a neutralizing agent, an antistatic agent, and further an anti-blocking agent and a filler, as long as the effects of the present invention are not impaired.
- Various additives such as a soluble polymer may be contained.
- an antioxidant for the purpose of suppressing the oxidative deterioration due to the thermal history of the polypropylene resin to be used, but the amount of the antioxidant added is 100 parts by mass or less with respect to 100 parts by mass of the polypropylene resin. Is more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass or less.
- the manufacturing method of the porous film in this invention is demonstrated, the manufacturing method of the film of this invention is not limited to this.
- the polypropylene resin constituting the base film is supplied to an extruder and melted at a temperature of 200 to 320 ° C., passed through a filtration filter, extruded from a slit-shaped base, cast into a cooling metal drum, and formed into a sheet. Cool and solidify to make an unstretched sheet.
- the melt extrusion temperature is preferably low, but if it is less than 200 ° C., an unmelted material is generated in the molten polymer discharged from the die. , It may cause a process failure such as tearing in the subsequent stretching process. Moreover, when it exceeds 320 degreeC, the thermal decomposition of a polypropylene resin will become intense, and it may be inferior to the film characteristics, for example, Young's modulus, breaking strength, etc. of the obtained porous film.
- the temperature of the cooling metal drum is 105 to 130 ° C., and ⁇ crystals are produced uniformly in large quantities, and a highly permeable porous film is obtained after stretching. If the temperature of the cooling metal drum is lower than 105 ° C, the ⁇ -crystal fraction of the first run of the unstretched sheet obtained may decrease. If the temperature exceeds 130 ° C, the solidification of the sheet on the drum is insufficient. Thus, it may be difficult to uniformly separate the sheet from the cooling metal drum.
- the amount of ⁇ crystals in the unstretched sheet corresponds to the ⁇ crystal fraction obtained from the first run caloric curve obtained by using the unstretched sheet as a sample and using a differential scanning calorimeter.
- the end portion is sprayed with spot air to be in close contact with the drum. Further, air may be blown over the entire surface using an air knife as necessary based on the state of close contact of the entire sheet on the drum. Moreover, you may laminate
- the obtained unstretched sheet is biaxially stretched to form pores (through holes) in the film.
- a biaxial stretching method it is preferable to stretch in the width direction after stretching in the longitudinal direction.
- an unstretched sheet is controlled to a temperature at which it can be stretched in the longitudinal direction.
- a temperature control method a method using a temperature-controlled rotating roll, a method using a hot air oven, or the like can be adopted.
- the stretching temperature in the longitudinal direction it is preferable to employ a temperature of 110 to 140 ° C., more preferably 120 to 135 ° C., from the viewpoint of film characteristics and uniformity.
- the draw ratio is preferably 1.1 to 8 times, more preferably 1.5 to 6 times, still more preferably 2 to 5 times. If the draw ratio is less than 1.1 times, the air permeability may be lowered, and the productivity may be lowered. As the draw ratio is increased, the air permeability is improved. However, if the draw ratio is more than 8 times, the film may be easily broken in the next transverse drawing step.
- the end of the film uniaxially stretched in the longitudinal direction is introduced by being held by a tenter type stretching machine, and stretched in the width direction to obtain a biaxially stretched film.
- the preheating temperature and the initial stretching temperature during transverse stretching are increased by 3 ° C. or more with respect to the latter stretching temperature. It is preferable to increase the temperature by 5 ° C. or more.
- the temperature difference is less than 3 ° C., it cannot be said that the stress relaxation at the time of fibril cleavage is sufficient, uneven pore formation occurs, and the voltage resistance may be inferior. In addition, the film may be broken. If the preheating temperature or the initial stretching temperature is too high with respect to the later stretching temperature, the uneven thickness or physical properties of the porous film cannot be suppressed, so the upper limit of the temperature difference is about 10 ° C.
- the preheating temperature during transverse stretching and the initial stretching temperature are preferably 133 to 158 ° C, more preferably 143 to 158 ° C.
- the late stretching temperature is preferably 130 to 155 ° C, more preferably 140 to 155 ° C.
- the preheating time during transverse stretching is preferably 10 to 70 seconds, more preferably 15 to 50 seconds. If the preheating time is less than 10 seconds, the film may not be sufficiently warmed and may cause film breakage. Moreover, when preheating time exceeds 70 second, productivity may be inferior.
- the initial draw ratio is preferably 1.02 to 2.0 times, more preferably 1.05 to 1.5 times.
- the initial draw ratio is less than 1.02, the stress relaxation at the time of fibril cleavage cannot be said to be sufficient, and uneven hole formation may occur, resulting in poor voltage resistance.
- an initial stretch ratio exceeds 2.0 times, the physical property spot and thickness spot of a porous film may become large.
- the latter draw ratio is preferably 1.05 to 10 times, more preferably 3 to 7 times.
- the latter draw ratio is less than 1.05, pore formation due to fibril cleavage is insufficient, the porosity may be lowered, and output characteristics may be inferior.
- the latter draw ratio exceeds 10 times, the film may be easily broken.
- the initial stretching speed is preferably 500 to 3,000% / min, more preferably 700 to 2,500% / min. It is particularly preferable that the initial stretching speed is as low as 2,000% / min or less. When the initial stretching speed is less than 500% / min, productivity may be inferior. Further, when the initial stretching speed exceeds 3,000% / min, the hole formation becomes non-uniform and the voltage resistance may be inferior.
- the late stretching speed is preferably 500 to 6,000% / min, more preferably 1,000 to 5,000% / min. If the late stretching speed is less than 500% / min, the productivity may be inferior. Further, when the late stretching speed exceeds 6,000% / min, the porosity is lowered and the output characteristics may be inferior.
- the hot air blowing nozzle in the preheating zone during transverse stretching as close as possible to the porous film, or to use a nozzle that is wide in the width direction.
- the draw ratio in the transverse draw width direction is preferably 1.1 to 10 times, more preferably 1.5 to 8 times.
- the transverse stretching speed at this time is preferably 500 to 6,000% / min, more preferably 1,000 to 5,000% / min. It is particularly preferable that the stretching speed is as low as 2,000% / min or less.
- the heat treatment step includes a first heat treatment, a relaxation treatment, and a second heat treatment (heat setting treatment). Further, in the heat treatment step of the present invention, the relaxation treatment and the second heat treatment (heat setting treatment) may be performed without performing the first heat treatment.
- the heat treatment temperature is preferably 140 to 165 ° C. If the temperature is lower than 140 ° C., the heat setting may not be sufficient, and the tensile strength in the width direction may decrease. If the temperature exceeds 165 ° C., the polymer around the pores melts due to the high temperature, the air resistance increases, and the output characteristics may deteriorate. 140 to 150 ° C.
- the heat treatment time is preferably 0.1 second or longer and 10 seconds or shorter, more preferably 3 seconds or longer and 8 seconds or shorter, from the viewpoint of achieving both the Young's modulus in the width direction and productivity.
- the relaxation rate is preferably 8 to 35%. If the relaxation rate is less than 8%, the thermal contraction rate in the width direction may increase. If it exceeds 35%, the air permeability may be reduced to deteriorate the output characteristics, or the thickness unevenness or flatness in the width direction may be deteriorated. From the viewpoint of achieving both output characteristics and safety, it is more preferably 10 to 25%.
- the relaxation temperature is preferably 155 to 170 ° C. When the relaxation temperature is less than 155 ° C., the shrinkage stress for relaxation is lowered, and the above-described high relaxation rate may not be achieved, or the thermal shrinkage rate in the width direction may be increased. If the temperature exceeds 170 ° C., the polymer around the pores may melt at a high temperature and the air permeability may be lowered. From the viewpoint of output characteristics and safety, 160 to 165 ° C. is more preferable.
- the film after heat treatment is removed by slitting the ears gripped by the tenter clip and wound around the core with a winder.
- the porous film of the present invention has a high porosity and excellent voltage resistance, it is used for packaging products, sanitary products, agricultural products, building products, medical products, separation membranes, light diffusion plates, and reflective sheet applications. However, since it is particularly excellent in output characteristics, process suitability and long-term storage stability, it can be preferably used as a separator for an electricity storage device.
- the electricity storage device include a non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery, and an electric double layer capacitor such as a lithium ion capacitor. Since such an electricity storage device can be repeatedly used by charging and discharging, it can be used as a power supply device for industrial devices, household equipment, electric vehicles, hybrid electric vehicles, and the like.
- Dielectric breakdown strength Ea (kV / mm)
- the dielectric breakdown strength Ea (kV / mm) is obtained by the following formula (A) where the dielectric breakdown voltage is V (kV) and the film thickness is T (mm).
- Ea V / T (A)
- the method for obtaining the dielectric breakdown voltage V is as follows. A porous film for measurement cut into 60 cm ⁇ 70 cm is placed on a copper plate of 60 cm ⁇ 70 cm, and a biaxially stretched polypropylene film deposited with aluminum of 50 cm ⁇ 60 cm is placed on it. SDH-1020P DC type pressure resistance made by Kasuga Electric A tester was connected.
- the starting voltage is 0.5 kV
- the voltage is stepped up by 0.1 kV at a step-up rate of 0.01 kV / second
- the number of dielectric breakdowns is held for 30 seconds at each applied voltage. I counted.
- the applied voltage when the number of breakdowns exceeded 10 was defined as the breakdown voltage.
- the measurement was performed 5 times and the average value was evaluated.
- this measurement method is not a generally well-known measurement method, it is a very important measurement method because it can evaluate the voltage resistance in an area of 50 cm ⁇ 60 cm by a single measurement.
- a generally well-known method for evaluating withstand voltage is a method shown in (8) described later. However, since the electrode area is small in this method, it is difficult to evaluate the withstand voltage over a wide range. Therefore, the dielectric breakdown voltage was measured and evaluated by the above method.
- Dielectric breakdown strength per resin thickness Er (kV / mm)
- the dielectric breakdown strength Er (kV / mm) per resin thickness is obtained by the following formula (B), where the porosity is ⁇ (%), the film thickness is T (mm), and the dielectric breakdown voltage is V (kV).
- Er V / [ ⁇ (100 ⁇ ) / 100 ⁇ ⁇ T] (B) The measurement was performed 5 times and the average value was evaluated.
- d C ⁇ / P ⁇ 10 ⁇ 6 [However, d: pore diameter (m), C: constant, ⁇ : surface tension of fluorinate (16 mN / m), P: pressure (Pa). ]
- the average pore diameter was calculated from the 1/2 half-wetting curve using the data analysis software attached to the apparatus.
- the measurement limit was set to 37 nm due to the problem of the upper limit of pressure during measurement. The same measurement was performed for the same sample five times at different locations, and the average value of the average pore diameters obtained was taken as the pore diameter of the through holes in the sample.
- ⁇ crystal fraction, ⁇ crystal forming ability 5 mg of a resin or film to be measured is sampled and loaded into an aluminum pan as a sample, and a differential scanning calorimeter (DSC, RDC220 manufactured by Seiko Denshi Kogyo Co., Ltd.) is used. Measured. First, the temperature is raised from room temperature to 240 ° C. at 40 ° C./min (first run) in a nitrogen atmosphere, held for 10 minutes, and then cooled to 30 ° C. at 40 ° C./min. The melting peak observed when the temperature is raised (second run) again at 40 ° C./min after holding for 5 minutes is the melting peak of the ⁇ crystal at the melting temperature of 145 to 157 ° C., 158 ° C.
- DSC differential scanning calorimeter
- the melting at which the peak is observed is defined as the melting peak of the ⁇ crystal, and the amount of heat of fusion is determined from the base line drawn on the high temperature side flat portion of the DSC curve and the area of the region surrounded by the peak.
- the value calculated by the following formula is the ⁇ crystal forming ability.
- calibration of the heat of fusion was performed using indium. The measurement was carried out with 5 samples and evaluated with an average value.
- Air permeability resistance A square having a size of 100 mm ⁇ 100 mm was cut out from the porous film and used as a sample. Using a JIS P 8117 (1998) B-type Gurley tester, the permeation time of 100 ml of air was measured at 23 ° C. and a relative humidity of 65%. The measurement was performed 5 times and the average value was evaluated.
- Electrode breakdown strength A porous film cut to a diameter of 30 mm is placed on a 150 mm square aluminum plate, and a brass cylindrical electrode having a diameter of 25 mm is placed on it. SDH-1020P DC type manufactured by Kasuga Electric A pressure tester was connected. A voltage was applied at a boosting rate of 0.2 kV / sec, and the value when dielectric breakdown occurred was read. The value converted per cross-sectional film thickness of 1 mm was defined as the electrode dielectric breakdown strength (kV / mm). The measurement was carried out 20 times and the average value was evaluated. The porous films of Example 1 and Comparative Example 1 described later were evaluated.
- the container and the lid are insulated, the container is in contact with the negative electrode copper foil, and the lid is in contact with the positive electrode aluminum foil.
- a battery was produced for each example and comparative example.
- Each of the fabricated secondary batteries was subjected to a charge / discharge operation in a 25 ° C. atmosphere at a charge of 3 mA to 4.2 V for 1.5 hours and a discharge of 3 mA to 2.7 V, and the discharge capacity was examined.
- a charging / discharging operation was performed in which charging was performed at 3 mA up to 4.2 V for 1.5 hours, and discharging was performed at 30 mA up to 2.7 V, and the discharge capacity was examined.
- the value obtained by the formula of [(30 mA discharge capacity) / (3 mA discharge capacity)] ⁇ 100 was evaluated according to the following criteria. In addition, 20 test pieces were measured, and the average value was evaluated. ⁇ : 90% or more ⁇ : 85% or more and less than 90% ⁇ : 80% or more and less than 85% ⁇ : less than 80%
- Example 1 95 parts by mass of homopolypropylene resin FLX80E4 manufactured by Sumitomo Chemical Co., Ltd. as a raw material resin for a porous film, “Enage (registered trademark)” 8411 (MFR: 18 g, manufactured by Dow Chemical Co., which is an ethylene / ⁇ -olefin copolymer) / 10 minutes, melting point: 163 ° C.) is added to 3 parts by mass, and N, N′-dicyclohexyl-2,6-naphthalenedicarboxyamide (Nippon Rika Co., Ltd., Nu-100) is a ⁇ crystal nucleating agent ), 0.2 parts by weight, and the antioxidants “IRGANOX (registered trademark)” 1010 and “IRGAFOS (registered trademark)” 168 manufactured by Ciba Specialty Chemicals, respectively.
- Enage registered trademark
- MFR 18 g, manufactured by Dow Chemical Co., which is an ethylene / ⁇ -ole
- the raw material is supplied from the weighing hopper to the twin screw extruder so as to be mixed in the melt, kneaded at 300 ° C., discharged from the die in a strand shape, and 2 At °C water bath was cooled and solidified to obtain a chip raw material and cut into chips.
- This chip is supplied to a single screw extruder and melt extruded at 220 ° C. After removing foreign matter with a 30 ⁇ m cut sintered filter, it is discharged from a T-die to a cast drum whose surface temperature is controlled at 120 ° C. An unstretched sheet was obtained by casting for 15 seconds. Next, preheating was performed using a ceramic roll heated to 120 ° C., and the film was stretched 5 times in the longitudinal direction of the film at 120 ° C. Next, the end portion is gripped with a clip and preheated at a preheating temperature of 155 ° C. for 25 seconds. The initial drawing temperature is 155 ° C., and the initial drawing speed is 1000% / min.
- the film was stretched in the width direction so that the final stretching speed was 1500% / min.
- heat treatment was performed at 160 ° C. for 5 seconds while maintaining the distance between the clips after stretching, and further relaxation was performed at a relaxation rate of 17% at 163 ° C., and finally at 163 ° C. while maintaining the distance between the clips after relaxation.
- the film was heat-treated for 5 seconds, and then the ear portion of the film held by the clip was cut and removed to obtain a porous film having a thickness of 17 ⁇ m.
- the film forming conditions and film characteristics are shown in Table 1.
- Example 2 In Example 1, except that the preheating temperature in the transverse stretching and the initial stretching temperature were set to 153 ° C., the same operation as in Example 1 was performed to obtain a porous film, and each physical property value is shown in Table 1.
- Example 3 In Example 1, except that the preheating temperature in the transverse stretching and the initial stretching temperature were set to 157 ° C., the same operation as in Example 1 was performed to obtain a porous film, and each physical property value is shown in Table 1.
- Example 4 In Example 1, except that the preheating temperature in transverse stretching, the initial stretching temperature was 160 ° C., and the late stretching temperature was 155 ° C., the same operation as in Example 1 was performed to obtain a porous film. Is shown in Table 1.
- Example 1 (Comparative Example 1) In Example 1, except that the preheating temperature in transverse stretching and the initial stretching temperature were 150 ° C., the same operation as in Example 1 was performed to obtain a porous film, and each physical property value is shown in Table 1.
- Example 2 (Comparative Example 2) In Example 1, except that the preheating temperature in transverse stretching, the initial stretching temperature was 157 ° C., and the late stretching temperature was 157 ° C., the same operation as in Example 1 was performed to obtain a porous film. Is shown in Table 1.
- the porous film of the present invention has high voltage resistance while maintaining a high porosity, when used as a separator, it can be provided as a porous film excellent in output characteristics, process suitability, and long-term storage stability. .
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Abstract
Description
Ea=V/T ・・・(A)
本発明の多孔性フィルムは、絶縁破壊電圧をV(kV)、膜厚をT(mm)としたときに、下記式(A)で定義される絶縁破壊強度Ea値が160kV/mm以上であることを特徴とする。
Ea=V/T ・・・(A)
多孔質体における細孔モデルにおいて、流体の透過速度と空孔率や孔径や流体の粘度との関係は、式(1)で表される。
ここで、u(m/sec)は流体の透過速度、d(m)は孔径、ε(%)は空孔率、ΔP(Pa)は圧力差、η(Pa・sec)は流体の粘度、T1(m)は膜厚、τ(無次元)は曲路率である。なお、本式を変形すると、曲路率は式(2)のように表され、上記各パラメータを代入することで求めることができる。
τ=d(εΔP/200ηT1u)0.5 ・・・(2)
Er=V/[{(100-ε)/100}×T] ・・・(B)
(株)尾崎製作所製ピーコックアプライトダイヤルゲージ(測定子:10mmφ、荷重50g)による測定値を用いた。
絶縁破壊電圧をV(kV)、膜厚をT(mm)として、絶縁破壊強度Ea(kV/mm)は下記式(A)によって求められる。
Ea=V/T ・・・(A)
絶縁破壊電圧Vの求め方は、以下の通りである。60cm×70cmの銅板上に60cm×70cmに切り出した測定用の多孔性フィルムを置き、その上に50cm×60cmのアルミ蒸着した2軸延伸ポリプロピレンフィルムを置いて、春日電機製SDH-1020P直流式耐圧試験器を接続した。0.5kVをスタート電圧とし、0.01kV/秒の昇圧速度で0.1kVずつ段階的に昇圧していき、各印加電圧において30秒間ホールドしている間の、絶縁破壊個数をそれぞれの印加電圧で数えていった。絶縁破壊個数が10個を超えたときの印加電圧を絶縁破壊電圧とした。測定は5回実施して平均値で評価を行った。
本測定方法は一般的にあまり知られた測定方法でないが、一回の測定で50cm×60cmの面積における耐電圧性を評価することができるので非常に重要な測定手法である。一般的に良く知られた耐電圧性評価方法は後述の(8)に示す方法である。しかし、該方法では電極面積が小さいために、広範囲において耐電圧性を評価することが困難であるため、上記の方法で絶縁破壊電圧を測定し、評価を行なった。
空孔率をε(%)、膜厚をT(mm)、絶縁破壊電圧をV(kV)として、樹脂厚み当たりの絶縁破壊強度Er(kV/mm)は下記式(B)によって求められる。
Er=V/[{(100-ε)/100}×T] ・・・(B)
測定は5回実施して平均値で評価を行った。
フィルムを30mm×40mmの大きさに切取り試料とした。電子比重計(ミラージュ貿易(株)製SD-120L)を用いて、室温23℃、相対湿度65%の雰囲気にて比重の測定を行った。測定を3回行い、平均値をそのフィルムの比重ρとした。
次に、測定したフィルムを280℃、5MPaで熱プレスを行い、その後、25℃の水で急冷して、空孔を除去したシートを作成した。このシートの比重を上記した方法で同様に測定し、平均値を樹脂の比重(d)とした。なお、後述する実施例においては、いずれの場合も樹脂の比重dは0.91であった。フィルムの比重と樹脂の比重から、以下の式により空孔率を算出した。測定は5回実施して平均値で評価を行った。
空孔率(%) = 〔( d - ρ ) / d 〕 × 100
多孔質体における細孔モデルにおいて、流体の透過速度と空孔率や孔径や流体の粘度との関係は、式(1)で表される。
u=(d2・ε/100)ΔP/(2ηT1τ2) ・・・(1)
ここで、u(m/sec)は流体の透過速度、d(m)は孔径、ε(%)は空孔率、ΔP(Pa)は圧力差、η(Pa・sec)は流体の粘度、T1(m)は膜厚、τ(無次元)は曲路率である。なお、本式を変形すると、曲路率は式(2)のように表される。
τ=d(εΔP/200ηT1u)0.5 ・・・(2)
ここで、各パラメータは以下に従って求め、それぞれ式(2)に代入し、曲路率を求めた。
POROUS MATERIALS,Inc.製自動細孔径分布測定器“PERM-POROMETER”を用いて多孔層面を上側として測定した。なお、測定条件は以下の通りである。
試験液:3M製“フロリナート”FC-40
試験温度:25℃
試験ガス:空気
解析ソフト:Capwin
測定条件:Capillary Flow Porometry-Wet up,Dry downのdefault条件による自動測定
なお、孔径(細孔直径)と試験圧力の間には以下の関係式が成立する。
d=Cγ/P×10-6
[ただし、d:細孔直径(m)、C:定数、γ:フロリナートの表面張力(16mN/m)、P:圧力(Pa)である。]
ここでは、上記に基づき、装置付属のデータ解析ソフトを用いて、1/2半濡れ曲線から平均孔径を算出した。但し、測定時の圧力上限の問題により、測定限界を37nmとした。同じサンプルについて同様の測定を、場所を変えて5回行い、得られた平均孔径の平均値を当該サンプルにおける貫通孔の孔径とした。
上記(4)に記載。
測定装置はティー・エイ・インスツルメント・ジャパン(株)社製レオメーターAR1000を使用し、測定用ジオメトリーには、直径40mm 角度2°のコーンアンドプレートを使用した。測定は25℃でステップ状にせん断速度を変化させた定常流測定を行った。本実験で用いた流体(ジメチルカーボネート:エチレンカーボネート=7:3(質量比))。測定条件の詳細はせん断速度100s-1で予備せん断(30秒間)後、せん断速度100s-1から0.01s-1まで対数間隔で計16点(1,000s-1、10s-1、0.1s-1、0.01s-1の計4点を含む16点)の測定を行った。結果、流体粘度は0.001Pa・sec(25℃)であった。
0.2MPa(=2×105Pa)にて測定。
上記(1)に記載の方法で得られた膜厚Tを1,000倍し用いた。
試料を円形に切り出し、アドバンテック東洋(株)社製タンク付きステンレスホルダーKST-47(濾過面積18.1cm2)に取り付けた。ここにジメチルカーボネート:エチレンカーボネート=7:3(質量比、密度1.115g/cm3)を入れ、圧力2×105Paで5g(=4.5cm3)透過するのにかかる時間t(sec)を計測し、下記式(3)より透過速度u(m/sec)を算出した。
u=0.01×4.5/(18.1×t) ・・・(3)
フィルムの長手方向および幅方向について、幅10mm、長さ200mmの大きさの試料を5本切り出し、両端から25mmの位置に印を付けて試長150mm(l0)とする。次に、荷重3gを付けて120℃に保温されたオーブン内に吊し、60分間加熱後に取り出して、室温で冷却後、寸法(l1)を測定して下記式にて求め、5本の平均値を熱収縮率とした。
熱収縮率={(l0-l1)/l0}×100(%)
測定する樹脂またはフィルムを5mg採取し、試料としてアルミニウム製のパンに装填し、示差走査熱量計(DSC、セイコー電子工業(株)製RDC220)を用いて測定した。まず、窒素雰囲気下で室温から240℃まで40℃/分で昇温(ファーストラン)し、10分間保持した後、30℃まで40℃/分で冷却する。5分保持後、再度40℃/分で昇温(セカンドラン)した際に観察される融解ピークについて、145~157℃の温度領域にピークが存在する融解をβ晶の融解ピーク、158℃以上にピークが観察される融解をα晶の融解ピークとして、DSC曲線の高温側平坦部を基準に引いたベースラインとピークに囲まれた領域の面積から、それぞれの融解熱量を求める。α晶の融解熱量をΔHα、β晶の融解熱量をΔHβとしたとき、以下の式で計算される値をβ晶形成能とした。なお、融解熱量の較正はインジウムを用いて行った。測定は5サンプル実施して平均値で評価を行った。
β晶形成能(%) = 〔 ΔHβ / ( ΔHα + ΔHβ )〕 × 100
なお、ファーストランで観察される融解ピークから同様にβ晶の存在比率を算出した値を、その試料のβ晶分率とした。
多孔性フィルムから100mm×100mmの大きさの正方形を切り取り試料とした。JIS P 8117(1998)のB形ガーレー試験器を用いて、23℃、相対湿度65%にて、100mlの空気の透過時間の測定を行った。測定は5回実施して平均値で評価を行った。
150mm四方のアルミニウム製の板状に、直径30mmに切り出した多孔性フィルムを置き、その上に真鍮製の直径25mm円柱電極を置いて、春日電機製SDH-1020P直流式耐圧試験器を接続した。0.2kV/秒の昇圧速度で電圧を加えていき、絶縁破壊したときの値を読みとった。断面膜厚1mm当たりに換算した値を電極絶縁破壊強度(kV/mm)とした。測定は20回実施して平均値で評価を行った。後述する実施例1および比較例1の多孔性フィルムについて評価を行なった。
宝泉(株)製のリチウムコバルト酸化物(LiCoO2)厚みが40μmの正極を使用し、直径15.9mmの円形に打ち抜き、また、宝泉(株)製の黒鉛厚みが50μmの負極を使用し、直径16.2mmの円形に打ち抜き、次に、各実施例・比較例の多孔性フィルムを直径24.0mmに打ち抜き、正極活物質と負極活物質面が対向するように、下から負極、多孔性フィルム、正極の順に重ね、蓋付ステンレス金属製小容器に収納した。容器と蓋とは絶縁され、容器は負極の銅箔と、蓋は正極のアルミ箔と接している。この容器内にエチレンカーボネート:ジメチルカーボネート=3:7(質量比)の混合溶媒に溶質としてLiPF6を濃度1M/Lとなるように溶解させた電解液を注入して密閉した。各実施例・比較例につき、電池を作製した。
作製した各二次電池について、25℃の雰囲気下、充電を3mAで4.2Vまで1.5時間、放電を3mAで2.7Vまでとする充放電操作を行い、放電容量を調べた。さらに、充電を3mAで4.2Vまで1.5時間、放電を30mAで2.7Vまでとする充放電操作を行い、放電容量を調べた。
[(30mAの放電容量)/(3mAの放電容量)]×100の計算式で得られる値を以下の基準で評価した。なお、試験個数は20個測定し、その平均値で評価した。
◎:90%以上
○:85%以上90%未満
△:80%以上85%未満
×:80%未満
多孔性フィルムの原料樹脂として、住友化学(株)製ホモポリプロピレン樹脂FLX80E4を95質量部、エチレン・α-オレフィン共重合体であるダウ・ケミカル社製 “Engage(登録商標)”8411(MFR:18g/10分、融点:163℃)を3質量部に加えて、β晶核剤であるN,N’-ジシクロヘキシル-2,6-ナフタレンジカルボキシアミド(新日本理化(株)製、Nu-100)を0.2質量部、さらに酸化防止剤であるチバ・スペシャリティ・ケミカルズ製“IRGANOX(登録商標)”1010、“IRGAFOS(登録商標)”168を各々0.15、0.1質量部の比率で混合されるように、計量ホッパーから二軸押出機に原料供給し、300℃で溶融混練を行い、ストランド状にダイから吐出して、25℃の水槽にて冷却固化し、チップ状にカットしてチップ原料とした。
実施例1において、横延伸での予熱温度、及び初期延伸温度を153℃とした以外は実施例1と同様の操作を行い、多孔性フィルムを得て、各物性値を表1に示した。
実施例1において、横延伸での予熱温度、及び初期延伸温度を157℃とした以外は実施例1と同様の操作を行い、多孔性フィルムを得て、各物性値を表1に示した。
実施例1において、横延伸での予熱温度、及び初期延伸温度を160℃、後期延伸温度を155℃とした以外は実施例1と同様の操作を行い、多孔性フィルムを得て、各物性値を表1に示した。
実施例1において、横延伸での予熱温度、及び初期延伸温度を150℃とした以外は実施例1と同様の操作を行い、多孔性フィルムを得て、各物性値を表1に示した。
実施例1において、横延伸での予熱温度、及び初期延伸温度を157℃、後期延伸温度を157℃とした以外は実施例1と同様の操作を行い、多孔性フィルムを得て、各物性値を表1に示した。
Claims (8)
- 絶縁破壊電圧をV(kV)、膜厚をT(mm)としたときに、下記式(A)で定義される絶縁破壊強度Ea値が160kV/mm以上であり、空孔率が45~85%であることを特徴とする多孔性フィルム。
Ea=V/T ・・・(A) - 前記空孔率をε(%)、膜厚をT(mm)、絶縁破壊電圧をV(kV)としたときに、下記式(B)で定義される樹脂厚み当たりの絶縁破壊強度Er値が400kV/mm以上であることを特徴とする、請求項1に記載の多孔性フィルム。
Er=V/[{(100-ε)/100}×T] ・・・(B) - 曲路率が2.0~3.0であり、前記曲路率と前記空孔率の積が120以上であることを特徴とする、請求項1または2に記載の多孔性フィルム。
- 長手方向および幅方向のいずれの方向についても、120℃、60分間の熱収縮率が0~5%であることを特徴とする、請求項1~3のいずれかに記載の多孔性フィルム。
- ポリオレフィン樹脂を含むことを特徴とする、請求項1~4のいずれかに記載の多孔性フィルム。
- 前記ポリオレフィン樹脂はポリプロピレン樹脂であることを特徴とする、請求項5に記載の多孔性フィルム。
- 蓄電デバイス用セパレータに使用されることを特徴とする、請求項1~6のいずれかに記載の多孔性フィルム。
- 請求項7に記載の多孔性フィルムをセパレータとして用いたことを特徴とする蓄電デバイス。
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KR20140148371A (ko) | 2014-12-31 |
JPWO2013141306A1 (ja) | 2015-08-03 |
JP6135665B2 (ja) | 2017-05-31 |
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