WO2007069560A1 - ポリオレフィン製微多孔膜 - Google Patents
ポリオレフィン製微多孔膜 Download PDFInfo
- Publication number
- WO2007069560A1 WO2007069560A1 PCT/JP2006/324655 JP2006324655W WO2007069560A1 WO 2007069560 A1 WO2007069560 A1 WO 2007069560A1 JP 2006324655 W JP2006324655 W JP 2006324655W WO 2007069560 A1 WO2007069560 A1 WO 2007069560A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microporous membrane
- battery
- polyolefin
- less
- polyolefin microporous
- Prior art date
Links
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 59
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- 238000009998 heat setting Methods 0.000 claims description 18
- 238000004898 kneading Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 5
- 229920005672 polyolefin resin Polymers 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 73
- 239000010408 film Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 30
- -1 polyethylene Polymers 0.000 description 23
- 238000012360 testing method Methods 0.000 description 23
- 239000004698 Polyethylene Substances 0.000 description 22
- 229920000573 polyethylene Polymers 0.000 description 18
- 229940057995 liquid paraffin Drugs 0.000 description 17
- 229920001519 homopolymer Polymers 0.000 description 16
- 239000012528 membrane Substances 0.000 description 16
- 229920002959 polymer blend Polymers 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000000605 extraction Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000035699 permeability Effects 0.000 description 11
- 238000004804 winding Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 230000008602 contraction Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009863 impact test Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000036619 pore blockages Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- MLJRLEGXZUNRLY-UHFFFAOYSA-N 2,4-ditert-butylphenol;phosphorous acid Chemical compound OP(O)O.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 MLJRLEGXZUNRLY-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IZJSTXINDUKPRP-UHFFFAOYSA-N aluminum lead Chemical compound [Al].[Pb] IZJSTXINDUKPRP-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 238000009658 destructive testing Methods 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000001471 micro-filtration Methods 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
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
- B01D71/261—Polyethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/20—Plasticizers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/268—Monolayer with structurally defined element
Definitions
- the present invention relates to a separation membrane used for separation of substances, selective permeation, and the like, and a microporous membrane widely used as a separator for electrochemical reaction devices such as alkali, lithium secondary batteries, fuel cells, capacitors, etc. About.
- the present invention relates to a polyolefin microporous membrane suitably used as a lithium ion battery separator.
- Microporous membranes made of polyolefin are widely used as separation membranes and separators used for the separation and selective permeation of various substances.
- polyolefin microporous membranes are used as microfiltration membranes, fuel cell separators, capacitor separators, functional membrane base materials for filling functional materials into pores and new functions, battery separators, etc. It is used.
- polyolefin microporous membranes are particularly preferably used as separators for lithium-ion batteries that are widely used in notebook personal computers, mobile phones, digital cameras, and the like. The reason is that the microporous membrane made of polyolefin has excellent mechanical strength and pore blocking properties.
- Porosity is the performance that ensures the safety of the battery by blocking the battery reaction by melting the separator when the battery is overheated in an overcharged state. .
- the separator must have a certain level of strength in order to withstand the tension of the separator when the battery is wound, to prevent short circuits caused by foreign matter in the battery, and to prevent film breakage due to impact. There is.
- separators are required to have a high porosity in order to increase the battery output and capacity.
- the separator has excellent thermal shrinkage properties at high temperatures, such as a battery that shows excellent results in high-temperature storage tests, high-temperature cycle tests, oven tests, etc. It is necessary to In general, the heat shrinkage rate of separators at high temperatures, in particular the width direction (in the direction perpendicular to the machine, hereinafter referred to as “TD”), is preferably low. However, in general, there is a contradictory relationship between the increase in strength, pore blockage and porosity, and the size of TD heat shrinkage. It was difficult.
- the separator is required to have good winder storage property in a square battery or the like and adhesion to the electrode.
- Patent Documents 1 and 2 propose microporous membranes that have improved pore closing properties by using low-melting-point polyethylene such as copolymer polyethylene and low-density polyethylene.
- low-melting-point polyethylene such as copolymer polyethylene and low-density polyethylene.
- Patent Document 3 proposes a microporous film of a heterogeneous laminated film.
- the method proposed in Reference 3 does not stretch in the TD direction, so it can be said that there is no contraction in the TD direction.
- the film obtained in Document 3 is based on the uniaxial opening method only in the length direction (machine direction, hereinafter referred to as “MD”), and is extremely anisotropic with insufficient TD strength. It becomes a microporous membrane with For this reason, for example, in battery crushing tests and crash tests, there is a concern that V may easily tear in one direction! /.
- Patent Document 4 proposes a microporous membrane having a high strength and a low TD shrinkage rate by providing a step of reducing the shrinkage force in the TD direction.
- Patent Documents 5 to 9 it is proposed to obtain a microporous film having high porosity, high strength, and low shrinkage by providing heat relaxation treatment and heat fixation treatment in the film forming process.
- Patent Document 1 Japanese Patent No. 3113287
- Patent Document 2 Japanese Patent No. 3681720
- Patent Document 3 Japanese Patent Laid-Open No. 2005-56851
- Patent Document 4 Japanese Patent Laid-Open No. 2001-81221
- Patent Document 5 Japanese Unexamined Patent Publication No. 2003-103624
- Patent Document 6 Japanese Patent Laid-Open No. 2003-103625
- Patent Document 7 Japanese Patent Laid-Open No. 2003-103626
- Patent Document 8 Japanese Unexamined Patent Publication No. 2003-105121
- Patent Document 9 Japanese Unexamined Patent Publication No. 2003-105122
- An object of the present invention is to provide a polyolefin microporous membrane that can be used as a cell router having excellent battery characteristics and battery safety at high temperatures when used as a battery. Means for solving the problem
- the present inventors have found that the heat shrinkage characteristic force at 65 ° C close to the drying temperature of the battery is high temperature such as a high temperature storage test, a high temperature cycle test, and an oven test. It has been found that it affects the safety performance of the battery below, the storage capacity of the wound body and the adhesion to the electrode in a rectangular battery or the like.
- the inventors have found a method capable of providing a polyolefin microporous film having high porosity, high strength, low heat shrinkage, and excellent heat shrinkage balance.
- conventional separators with high strength and high porosity even after the heat setting process, the shrinkage remains in the slit product without being released, and the battery The separator that was released from the shrinkage force during rotation could cause width shrinkage in the TD direction during battery drying processes and high-temperature storage tests. Therefore, high porosity, high strength, and low heat shrinkability are satisfied at the same time. It was considered difficult.
- the present inventors have been able to obtain a high porosity and high strength polyolefin microporous membrane by providing a specific heat treatment step in the separator manufacturing method and optimizing the stretching balance.
- a separator having a low heat shrinkage and an excellent balance of heat shrinkage ratio can be obtained. That is, the present invention is as follows.
- Thickness of 1 ⁇ m or more and 50 ⁇ m or less, porosity of 30% or more and 70% or less, puncture strength converted to film thickness of 1 ⁇ m is 0.15 NZ wm or more
- tensile strength in the length direction MD tensile strength
- width direction tensile strength TD tensile strength
- heat shrinkage rate in the width direction at 65 ° C TD heat shrinkage rate
- MD heat shrinkage ratio is greater than 2.
- Tensile elongation in the length direction (MD tensile elongation) and tensile elongation in the width direction (TD tensile elongation) are 10% or more and 200% or less, respectively, and the sum of MD tensile elongation and TD tensile elongation
- the polyolefin microporous membrane of the present invention has improved porosity, strength, and thermal shrinkage compared to the conventional polyolefin microporous membrane. Therefore, when the microporous membrane of the present invention is used as a battery separator, it is possible to provide a battery having excellent battery characteristics and battery safety.
- the thickness of the polyolefin microporous membrane of the present invention is 1 m or more, more preferably 5 m or more, from the viewpoint of membrane strength.
- the thickness of the microporous membrane is 50 m or less, more preferably 30 m or less from the viewpoint of permeability.
- the porosity of the polyolefin microporous membrane of the present invention is 30% or more from the viewpoint of permeability. From the viewpoint of dramatically improving battery characteristics such as cycle characteristics, it is particularly preferable that 40% or more is preferably 43% or more, more preferably 44% or more.
- the porosity of the microporous membrane is 70% or less, preferably 60% or less from the viewpoint of membrane strength and withstand voltage.
- the air permeability of the polyolefin microporous membrane of the present invention is preferably as low as possible, but from the balance between thickness and porosity, lsec or more is preferred, and 50sec or more is more preferred. From the viewpoint of permeability, lOOOsec or less is preferable, and 500 sec or less is more preferable.
- the puncture strength of the polyolefin microporous film converted to a film thickness of 1 ⁇ m is 0.15 N / ⁇ m or more, and more preferably 0.2 NZwm or more.
- the puncture strength is preferably high.
- the absolute strength is 3N or more. 3. It is more preferable that the absolute strength is 2N or more! /.
- the tensile strength is 30 MPa or more in both the MD and TD directions, preferably 40 MPa or more, and more preferably 50 MPa or more. If the tensile strength is weak, the battery winding property is deteriorated, or a short circuit is likely to occur due to a battery impact test from the outside or a foreign substance in the battery. Especially TD It is advantageous for destructive testing that the absolute strength of the direction is greater than lONZcm.
- the MD and TD tensile elongations are each preferably 10 to 200%, more preferably 10 to 150%, and even more preferably 10 to 120%. Further, the total of MD tensile elongation and TD tensile elongation is preferably 20 to 250%, more preferably 20 to 230% force, and particularly preferably 20 to 210%.
- a microporous membrane having an MD and TD tensile elongation in the above-mentioned range is preferable because it is less susceptible to deformation in a battery impact test or the like when the battery winding property is good.
- the heat shrinkage rate of the microporous membrane made of polyolefin at 65 ° C is 1% or less in the TD direction, preferably 0.8% or less. If the thermal shrinkage rate in the TD direction is greater than 1%, the microporous membrane tends to shrink in the width direction in the battery drying process, battery high-temperature cycle test, battery high-temperature storage test, etc., which is not preferable.
- the ratio of MD thermal contraction rate and MD thermal contraction rate at 65 ° C is larger than 2 and preferably larger than 2.5, more preferably larger than 3. . If the MDZTD heat shrinkage ratio is 2 or less, the force to wind the battery in the MD direction will be insufficient. As a result, especially when molded into a prismatic battery, there is a problem that the entire wound body is too thick, and the adhesion between the electrode and the separator deteriorates, so the separator shrinks in the TD direction during oven tests and the like. It becomes easy and is not preferable.
- Some degree of isotropic viewpoint power M DZTD heat shrinkage ratio at 65 ° C is preferred to be 40 or less.
- the thermal contraction rate of MD at 105 ° C is preferably large to some extent. Specifically, it is preferably greater than 5% and less than 20%. 6% or more is more preferable 7% or more is particularly preferable 8% or more is most preferable. A separator having a thermal contraction rate in such a range is preferable because the effect of tightening the battery described above is more manifested.
- the MDZTD thermal shrinkage ratio at 105 ° C is also preferably larger than 2. This is because the above-described battery thickness is also effective in the heat press process at 80 ° C. and 90 ° C., which is a temperature higher than 65 ° C., and in the battery drying process. From a certain degree of isotropic viewpoint, the MDZTD thermal shrinkage ratio at 105 ° C is preferably 40 or less.
- the porous membrane has the characteristics satisfying the present invention
- the polymer species, the solvent species, the extrusion method, the stretching method, the extraction method, the pore opening method, the heat setting method and the heat treatment method are not limited at all.
- the microporous membrane of the present invention includes a step of melt-kneading and extruding a resin composition containing at least polyolefin and a plasticizer to obtain a sheet-like material, and a step of drawing a sheet-like material to obtain a film. It can be suitably obtained by a production method including a step of extracting a plasticizer from a form or film and a step of heat setting.
- microporous membrane of the present invention can be suitably obtained by a method having the following process powers (a) to (e).
- Polyolefin and a plasticizer such as a single polyolefin or a polyolefin mixture, or a polyolefin, a plasticizer, and an inorganic agent are melt-kneaded.
- the polyolefin used in the present invention is a homopolymer of ethylene or propylene, or a mixture of the above polymers such as ethylene, propylene, 1-butene, 4-methyl-1 pentene, 1-hexene and 1-octene, norbornene. Include. Of these, polyethylene and copolymers thereof are preferred from the viewpoint of the performance of the porous membrane. Examples of such a polyolefin polymerization catalyst include a Ziegler-Natta catalyst, a Philips catalyst, and a metallocene catalyst. Polyolefin may be obtained by a one-stage polymerization method or may be obtained by a multi-stage polymerization method.
- the composition to be supplied includes an ultra-high molecular weight polyolefin having a viscosity average molecular weight (Mv) of 700,000 or more and a polyolefin having a viscosity of 300,000 or less. It has both low fuse characteristics and high short characteristics. This is preferable. Particularly preferred are polyolefins including ultrahigh molecular weight polyolefins with ⁇ ⁇ , ⁇ , 000 or more and polyolefins with Mv of 200,000 or less.
- Mv viscosity average molecular weight
- a resin composition containing polyolefin and a plasticizer includes metal stalagmites such as calcium stearate and zinc stearate, ultraviolet absorbers, light stabilizers, antistatic agents, antifogging agents, and coloring pigments. Also known additives such as can be mixed and used.
- An inorganic agent typified by alumina, titer and the like can be added to the resin composition containing polyolefin and a plasticizer. This inorganic agent can be extracted in whole or in part during the entire process! / Or it can remain in the product!
- the plasticizer used in the present invention is an organic compound that can form a uniform solution with polyolefin at a temperature below the boiling point.
- specific examples include decalin, xylene, dioctyl phthalate, dibutyl phthalate, stearyl alcohol, oleyl alcohol, decyl alcohol, noral alcohol, diphenyl ether, n -decane, n -dodecane, and paraffin oil. Of these, paraffin oil and dioctyl phthalate are preferable.
- the proportion of the plasticizer is not particularly limited! However, it is preferably 90% by weight or less from the viewpoint of viscosity, which is preferably 20% by weight or more from the viewpoint of the porosity of the obtained film. More preferably, it is 50% by weight and 70% by weight.
- the extraction solvent used in the present invention is preferably a poor solvent for polyolefin, a good solvent for plasticizer, and a boiling point lower than the melting point of polyolefin.
- extraction solvents include hydrocarbons such as n-xane and cyclohexane, halogenated hydrocarbons such as methylene chloride, 1,1,1 trichloroethane, fluorocarbon, ethanol, isopropanol, and the like.
- Examples include alcohols and ketones such as acetone and 2-butanone. It selects from these and uses it individually or in mixture.
- These extraction solvents may be regenerated by distillation after extraction of the plasticizer and used again.
- the total weight ratio of the plasticizer and the inorganic agent in the entire mixture to be melt-kneaded is preferably 2095 wt%, more preferably 3080 wt%, from the viewpoints of film permeability and film forming properties.
- an antioxidant From the viewpoint of preventing thermal deterioration during melt-kneading and resulting quality deterioration, it is preferable to add an antioxidant.
- the concentration of the antioxidation agent is preferably 0.3 wt% or more, more preferably 0.5 wt% or more, based on the total polyolefin weight. Further, 5 wt% or less is preferable, and 3 wt% or less is more preferable.
- phenol is the primary antioxidant.
- 2,6-di-tert-butyl-4-methylphenol pentaerythrityl-tetrakis [3— (3,5-di-tert-butyl-4-hydroxyphenol) propionate], Octadecyl 3— (3, 5 —Di-tert-butyl-4-hydroxyphenol) propionate.
- Secondary anti-oxidation agents can also be used in combination with tris (2,4 di-t-butylphenol) phosphite, tetrakis (2,4 di-tert-butylphenol) -4, Examples thereof include phosphorus-based antioxidants such as 4-biphenol-lendiphosphonite, and io-acid antioxidants such as dilauryl thiodipropionate.
- a method of melt kneading and extruding first, a part or all of raw materials are premixed by a Henschel mixer, a ribbon blender, a tumbler blender or the like as necessary. If the amount is small, it may be stirred by hand. Next, all the raw materials are melt-kneaded with a screw extruder such as a single screw extruder or a twin screw extruder, an adder, a mixer or the like, and extruded from a T-type die or the like.
- a screw extruder such as a single screw extruder or a twin screw extruder, an adder, a mixer or the like, and extruded from a T-type die or the like.
- the polyolefin microporous membrane of the present invention is preferably obtained by mixing the raw acid polymer with an anti-oxidation agent at a predetermined concentration, then substituting it with a nitrogen atmosphere and performing melt kneading while maintaining the nitrogen atmosphere. Is obtained.
- the temperature at the time of melt kneading is preferably 160 ° C or higher, more preferably 180 ° C or higher. Further, less than 300 ° C is preferable, and less than 240 ° C is more preferable, and less than 230 ° C is more preferable.
- the melt in the present invention may contain an unmelted inorganic agent that can be extracted in the inorganic agent extraction step. Further, the melt that has been homogenized by melt kneading may be passed through a screen to improve the film quality.
- a melted and kneaded and extruded melt is solidified by compression cooling.
- the cooling method include a method of directly contacting a cooling medium such as cold air or cooling water, a method of contacting a roll cooled by a refrigerant or a press, and a method of contacting a roll cooled by a refrigerant or a press. This is preferable in terms of excellent thickness control.
- rolling by bank forming is preferred because it makes it easier to achieve the MDZTD heat shrinkage ratio of the present invention.
- stretching, extraction of plasticizer, etc. are performed, but the order, method, and number of times of stretching and plasticizer extraction, or stretching, plasticizer extraction, and inorganic agent extraction are particularly limited. There is no. The inorganic agent extraction may not be performed as necessary.
- the stretching method used is MD-axial stretching by a roll stretching machine, TD-axial stretching by a tenter, sequential biaxial stretching by a roll stretching machine and a tenter, or a combination of a tenter and a tenter, or a simultaneous biaxial tenter. And simultaneous biaxial stretching by inflation molding.
- the draw ratio is the total surface magnification, and from the viewpoint of film thickness uniformity, it is preferably 8 times or more, more preferably 15 times or more, and most preferably 40 times or more.
- the MDZTD stretching ratio is 1.1 or more, particularly 1.2 or more because the MDZTD heat shrinkage ratio of the present invention is easily achieved.
- sequential biaxial stretching it is preferable to first stretch in the MD direction and then in the TD direction because the MDZTD heat shrinkage ratio of the present invention can be easily achieved.
- the plasticizer is extracted by dipping or showering in an extraction solvent. Then, it is sufficiently dried.
- a relaxation operation is performed at a predetermined relaxation rate in a predetermined temperature atmosphere.
- the heat setting can be performed using a tenter or a roll drawing machine.
- the relaxation operation is an operation to reduce the film to MD, Z, or TD.
- the relaxation rate is the value obtained by dividing the MD dimension of the film after the relaxation operation by the MD dimension of the film before the operation, or the value obtained by dividing the TD dimension after the relaxation operation by the TD dimension of the film before the operation, or MD When both TDs are relaxed, the value is the product of the MD relaxation rate and the TD relaxation rate.
- the predetermined temperature is preferably less than 135 ° C from the viewpoint of porosity and permeability, which is preferably 100 ° C or higher from the viewpoint of heat shrinkage.
- the predetermined relaxation rate is preferably 0.9 or less, more preferably 0.8 or less, from the viewpoint of the heat shrinkage rate. Further, it is preferably 0.6 or more from the viewpoint of preventing wrinkle generation, porosity and permeability.
- the relaxation operation may be performed in both MD and TD directions. It is possible to reduce the heat shrinkage rate in both the MD and TD relaxation operations and in the vertical direction and the operation only in the operation direction.
- the heat-fixed master roll is treated at a predetermined temperature, and then the master roll is rewound. Through this process, the polyolefin in the master roll In addition to releasing the residual stress of the indium, it becomes easy to adjust to the MDZTD heat shrinkage ratio of the present invention.
- the heat treatment temperature of the master roll is preferably 35 ° C or higher, more preferably 45 ° C or higher, and particularly preferably 60 ° C or higher. From the viewpoint of maintaining permeability, 120 ° C or less is preferred.
- the temperature of the heating roll is preferably 60 ° C or higher, particularly preferably 80 ° C or higher. From the viewpoint of maintaining permeability, 150 ° C or less is preferred.
- Mv was calculated according to the following formula.
- the measurement was performed at room temperature of 23 people at 2 ° C using a KBM (trademark) micro thickness gauge manufactured by Toyo Seiki.
- Porosity (volume mass Z film density) Z volume X 100
- the film density was calculated from the density of the material used.
- Gurley type air permeability meter (G-B2 (trademark), manufactured by Toyo Seiki Co., Ltd.) was used.
- the inner cylinder weight was 567 g, and the time required for 100 ml of air to pass through an area of 28.6 mm and 645 mm 2 in diameter was measured.
- the piercing strength (N) is calculated as the maximum piercing load by conducting a piercing test in a 25 ° C atmosphere with a radius of curvature of the needle tip of 0.5 mm and a piercing speed of 2 mmZsec at the center of the fixed microporous membrane. Obtained. By multiplying this by 1Z film thickness m), the puncture strength (NZ ⁇ m) converted to a film thickness of 1 ⁇ m was calculated.
- the tensile elongation (%) was obtained by dividing the amount of elongation (mm) up to fracture by the distance between chucks (50 mm) and multiplying by 100.
- Tensile strength (MPa) was determined by dividing the strength at break by the cross-sectional area of the sample before the test.
- the sum (%) of MD tensile elongation and TD tensile elongation was obtained by summing the values of MD and TD. Measurement is performed at a temperature of 23 ⁇ 2 ° C, a chuck pressure of 0.3 MPa, a tensile speed of 200 mmZ (a distance between chucks of 50 mm cannot be secured! /, For a sample, a strain rate of 400% Z) It was.
- TD thermal shrinkage (%) (200—TD length after heating) Z200 X 100
- the MDZTD heat shrinkage ratio was calculated according to the following formula.
- MDZTD heat shrinkage ratio absolute value of MD heat shrinkage rate Absolute value of ZTD heat shrinkage rate (8) 105 ° C heat shrinkage
- TD thermal shrinkage (%) (100—TD length after heating) Z100 X 100
- the MDZTD heat shrinkage ratio was calculated according to the following formula. (For samples for which the sample length could not be secured, the longest possible sample was used within the range of 100mm x 100mm.)
- MDZTD heat shrinkage ratio absolute value of MD heat shrinkage rate Absolute value of ZTD heat shrinkage rate
- PVDF polyvinylidene as a binder one mold - isopropylidene
- NMP N-methylpyrrolidone
- This slurry was applied to one side of a 20 m thick aluminum foil serving as a positive electrode current collector with a die coater, dried at 130 ° C. for 3 minutes, and then compression molded with a roll press.
- the active material coating amount of the positive electrode is 250 gZm 2 and the bulk density of the active material is 3. OOgZcm 3 . This was cut to a width of about 40 mm to form a strip.
- the above microporous membrane separator, strip-shaped positive electrode and strip-shaped negative electrode are stacked in the order of strip-shaped negative electrode, separator, strip-shaped positive electrode and separator in a spiral shape, and wound several times until the desired thickness is obtained.
- An electrode plate laminate was produced. This electrode plate laminate was pressed into a flat plate at 65 ° C and then housed in an aluminum container. The aluminum lead derived from the positive electrode current collector force was placed on the container wall and the nickel current derived from the negative electrode current collector force. The manufactured lead was connected to the container lid terminal.
- the lithium-ion battery produced in this way is 6.3 mm in length (thickness), 30 mm in width, and 48 mm in height.
- This battery is charged to a battery voltage of 4.2 V at a current value of (0.5 C) in an atmosphere of 25 ° C, and then the current value is started to be reduced to maintain 4.2 V for a total of 6 hours.
- the first charge after the battery was made was performed.
- a tumbler blender 95 wt% of a homopolymer polyethylene having an Mv force of 250,000 and 5 wt% of a homopolymer polypropylene having an Mv400,000 were dry blended. 99% by weight of the obtained pure polymer mixture was added with pentaerythritylte as an antioxidant. 1 wt% of trakis [3- (3,5 di-tert-butyl-4-hydroxyphenol) propionate] was added and dry blended again using a tumbler blender to obtain a homogeneous polymer mixture. The obtained polymer mixture was substituted with nitrogen, and then fed to the twin screw extruder through a feeder in a nitrogen atmosphere. Liquid paraffin (37.78 ° C kinematic viscosity 7.59 X 10 _5 m 2 Zs) was injected into the extruder cylinder by a plunger pump.
- the feeder and the pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 55 wt%.
- the melt-kneading conditions were a set temperature of 200 ° C, a screw rotation speed of 240 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a 2000 m thick gel sheet.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 6.4 times, and set temperature 118 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the heat setting temperature was 125 ° C and the TD relaxation rate was 0.80.
- the master roll taken up to 1000m was left in a constant temperature room at 50 ° C for 6 hours, and then rolled up with a winding tension of 10kg / m.
- the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 65 wt%.
- the melt-kneading conditions were a set temperature of 200 ° C, a screw rotation speed of 240 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a gel sheet having a thickness of 1300 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 6.4 times, and set temperature 120 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the heat setting temperature was 125 ° C and the TD relaxation rate was 0.80.
- the master roll taken up to 1000m was left in a constant temperature room at 50 ° C for 6 hours, and then rolled up with a winding tension of 10kg / m.
- a microporous membrane was obtained in the same manner as Example 2 except for the above.
- Mv force 2500,000 homopolymer polyethylene 20wt%, Mv force 700,000 homopolymer polyethylene 15wt%, Mv force ⁇ 250,000 homopolymer polyethylene 30wt%, Mv force 20 , 000 ethylene propylene copolymer (comonomer: propylene, content ratio of 0.6 mol%) was 30% by weight and drive-blended using a tumbler blender. 99% by weight of the pure polymer mixture obtained was pentaerythrityl as an antioxidant. Add tetrawt-one [3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate] with lwt% and dry-blend again using a tumbler blender to obtain a polymer or other mixture. Obtained.
- the obtained polymer mixture was substituted with nitrogen and then fed to the twin-screw extruder with a feeder under a nitrogen atmosphere.
- Liquid paraffin (kinematic viscosity at 37.78 ° C 7.59 X 10 _5 m 2 Zs) was injected into the extruder cylinder by a plunger pump.
- the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 65 wt%.
- the melt-kneading conditions were a set temperature of 200 ° C, a screw rotation speed of 240 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded material was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a gel sheet having a thickness of 1800 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 6.4 times, and set temperature 120 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the heat setting temperature was 120 ° C and the TD relaxation rate was 0.75.
- the master roll taken up to 1000 m was left in a constant temperature room at 60 ° C. for 10 hours, and then rolled up with a winding tension of 10 kg / m.
- Mv force 2,500,000 homopolymer polyethylene 20wt%, Mv force 700,000 homopolymer polyethylene 15wt%, Mv force ⁇ 250,000 homopolymer polyethylene 30wt%, Mv force 20 , 000 ethylene propylene copolymer (comonomer: propylene, content ratio of 0.6 mol%) was 30% by weight and drive-blended using a tumbler blender. 99 wt% of the resulting pure polymer mixture was charged with lwt% of pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate] as an antioxidant. Again by dry blending using a tumbler blender. A mixture such as limer was obtained.
- the obtained polymer mixture was substituted with nitrogen and then fed to the twin-screw extruder with a feeder under a nitrogen atmosphere.
- Liquid paraffin (kinematic viscosity at 37.78 ° C 7.59 X 10 _5 m 2 Zs) was injected into the extruder cylinder by a plunger pump.
- the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 65 wt%.
- the melt-kneading conditions were a set temperature of 200 ° C, a screw rotation speed of 240 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T die to obtain a gel sheet having a thickness of 800 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 6.4 times, and set temperature 118 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the heat setting temperature was 120 ° C
- the TD relaxation rate was 0.80.
- the master roll taken up to 1000 m was left in a constant temperature room at 60 ° C. for 10 hours, and then rolled up with a winding tension of 8 kg / m.
- Mv force 2500,000 homopolymer polyethylene 20wt%, Mv force 700,000 homopolymer polyethylene 15wt%, Mv force ⁇ 250,000 homopolymer polyethylene 30wt%, Mv 30 wt% of an ethylene propylene copolymer (comonomer: propylene, content ratio 0.6 mol%) having a strength of 20,000 was driven using a tumbler blender. 99 wt% of the resulting pure polymer mixture was charged with lwt% of pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate] as an antioxidant.
- the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 65 wt%.
- the melt-kneading conditions were a set temperature of 200 ° C, a screw rotation speed of 240 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a gel sheet having a thickness of 1200 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 6.4 times, and set temperature 118 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the heat setting temperature was 115 ° C and the TD relaxation rate was 0.80. After that, it was wound up by being brought into contact with a heating drum adjusted to 100 ° C. for 5 seconds.
- a microporous membrane was obtained in the same manner as in Example 6 except that the cast sheet thickness was 950 m, the biaxial stretching ratio was 7 ⁇ 4 times, and the biaxial stretching temperature was 117 ° C.
- Example 2 except that the cast sheet thickness was 800 m, the biaxial stretching ratio was 5 x 5 times, the biaxial stretching temperature was 118 ° C, and the TD relaxation rate during heat setting was 0.90. A microporous membrane was obtained. As a result of battery evaluation, good results were not obtained for items other than short circuit.
- a microporous membrane was obtained in the same manner as in Example 2 except that the biaxial stretching temperature was 125 ° C. As a result of battery evaluation, good results were obtained in terms of battery roll storage and short circuit.
- Example 3 A microporous membrane was obtained in the same manner as in Example 2 except that the heat setting temperature was 120 ° C. and the heat treatment and rewinding of the master roll were not performed. As a result of battery evaluation, good results were not obtained in the oven test.
- the obtained polymer mixture was substituted with nitrogen and then fed to the twin-screw extruder with a feeder under a nitrogen atmosphere.
- Liquid paraffin 37.78 8 ° C kinematic viscosity 7.59 X 10 _5 m 2 Zs
- the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 68 wt%.
- the melt-kneading conditions were a set temperature of 240 ° C, a screw rotation speed of 120 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a gel sheet having a thickness of 1400 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 6.8 times, and set temperature 123 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
- it was guided to a TD tenter and heat fixed.
- the thermosetting temperature was 125 ° C and the TD relaxation rate was 0.80.
- Mv force 300 000, 50 wt from homo a Mw / Mn force 7 0/0, Mv force of 1,000, a PE homopolymer is 000, MwZMn 7 to 50 wt%, pentaerythrityl over as antioxidants Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate] was added in an amount of lwt% and dry blended using a tumbler blender to obtain a mixture of polymers and the like. The obtained polymer mixture was substituted with nitrogen and then fed to the twin-screw extruder with a feeder under a nitrogen atmosphere. Liquid paraffin (kinematic viscosity at 37.78 ° C 7.59 X 10 _5 m 2 Zs) was poured into the extruder cylinder by a plunger pump.
- Liquid paraffin kinematic viscosity at 37.78 ° C 7.59 X 10 _5 m 2 Zs
- the feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 65 wt%.
- the melt-kneading conditions were a set temperature of 250 ° C, a screw rotation speed of 200 rpm, and a discharge amount of 15 kgZh.
- melt-kneaded material was extruded and cast on a cooling roll controlled at a surface temperature of 30 ° C. through a T-die to obtain a gel sheet having a thickness of 1600 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 7.0 times, and set temperature 119 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the heat setting temperature was 125-130 ° C, and the TD relaxation rate was 0.83.
- Mv force 2 000, 000 of the ⁇ 30wt 0/0, the density of PE Mv force 300, 000 to 70 wt 0/0, pentaerythrityl over tetrakis one [3- (3 as Sani ⁇ inhibitor, 5 [Di-tert-butyl 4-hydroxyphenol) propionate] was added in an amount of lwt% and dry blended using a tumbler blender to obtain a mixture of polymers.
- the obtained polymer mixture was substituted with nitrogen and then fed to the twin-screw extruder with a feeder in a nitrogen atmosphere.
- Liquid paraffin (kinematic viscosity at 37.78 ° C 7.59 X 10 _5 m 2 Zs) was injected into the extruder cylinder by a plunger pump.
- the ratio of liquid paraffin in the total mixture that is melt-kneaded and extruded is 80 wt%.
- the feeder and pump were adjusted as follows.
- the melt-kneading conditions were a set temperature of 200 ° C., a screw speed of 200 rpm, and a discharge amount of 12 kgZh.
- melt-kneaded material was extruded and cast on a cooling roll controlled at a surface temperature of 30 ° C. through a T-die to obtain a gel sheet having a thickness of 1800 m.
- the set stretching conditions are MD magnification 7.0 times, TD magnification 7.0 times, and set temperature 105 ° C.
- the solution was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove the fluid paraffin, and then the methyl ethyl ketone was removed by drying.
- the obtained film was stretched 1.4 times in the MD direction at 115 ° C. using a roll stretching machine.
- it was led to a TD tenter and increased to 2.0 times at 115 ° C in the TD direction.
- relaxed at 110 ° C for 10 seconds with a tenter so that the MD is 95% and the TD is 95%, and then heat-fixed at 120 ° C for 15 minutes with the tenter. went.
- a microporous membrane was obtained in the same manner using a commercially available microporous membrane that was a laminate of polyethylene and polypropylene, and was obtained by the stretch opening method.
- the present invention relates to a microporous membrane used for a separation membrane used for separation or selective permeation of substances, a separator, and the like, and is particularly suitably used as a separator for lithium ion batteries and the like.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007550162A JP5216327B2 (ja) | 2005-12-15 | 2006-12-11 | ポリオレフィン製微多孔膜 |
CN2006800469978A CN101331178B (zh) | 2005-12-15 | 2006-12-11 | 聚烯烃制微多孔膜 |
US12/097,231 US8003261B2 (en) | 2005-12-15 | 2006-12-11 | Polyolefin microporous membrane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-362151 | 2005-12-15 | ||
JP2005362151 | 2005-12-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007069560A1 true WO2007069560A1 (ja) | 2007-06-21 |
Family
ID=38162868
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/324655 WO2007069560A1 (ja) | 2005-12-15 | 2006-12-11 | ポリオレフィン製微多孔膜 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8003261B2 (ja) |
JP (1) | JP5216327B2 (ja) |
KR (1) | KR100977345B1 (ja) |
CN (1) | CN101331178B (ja) |
TW (1) | TW200738799A (ja) |
WO (1) | WO2007069560A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2065953A1 (en) * | 2007-11-28 | 2009-06-03 | SK Energy Co., Ltd. | Microporous polyolefin film possessing good mechanical properties and thermal stability |
WO2009136648A1 (ja) * | 2008-05-09 | 2009-11-12 | 旭化成イーマテリアルズ株式会社 | 高出力密度リチウムイオン二次電池用セパレータ |
JP2010100845A (ja) * | 2008-09-29 | 2010-05-06 | Toray Ind Inc | 多孔性ポリオレフィンフィルムの製造方法 |
WO2015190487A1 (ja) * | 2014-06-13 | 2015-12-17 | 東レバッテリーセパレータフィルム株式会社 | ポリオレフィン微多孔フィルム、その製造方法及び電池用セパレータ |
WO2016006453A1 (ja) * | 2014-07-11 | 2016-01-14 | 帝人株式会社 | セパレータロール及び非水系二次電池 |
WO2016051656A1 (ja) * | 2014-09-30 | 2016-04-07 | 三洋電機株式会社 | 非水電解質二次電池 |
JP2017103046A (ja) * | 2015-11-30 | 2017-06-08 | 住友化学株式会社 | 非水電解液二次電池用セパレータ |
WO2018180714A1 (ja) * | 2017-03-31 | 2018-10-04 | 東レ株式会社 | ポリオレフィン微多孔膜、非水電解液系二次電池用セパレータ、及び非水電解液系二次電池 |
KR20190070337A (ko) | 2016-10-24 | 2019-06-20 | 스미또모 가가꾸 가부시키가이샤 | 세퍼레이터 및 세퍼레이터를 포함하는 이차 전지 |
JP6741884B1 (ja) * | 2019-03-04 | 2020-08-19 | 旭化成株式会社 | ポリオレフィン微多孔膜 |
WO2020179101A1 (ja) * | 2019-03-04 | 2020-09-10 | 旭化成株式会社 | ポリオレフィン微多孔膜 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8795565B2 (en) * | 2006-02-21 | 2014-08-05 | Celgard Llc | Biaxially oriented microporous membrane |
CN105150655B (zh) * | 2009-03-09 | 2018-09-14 | 旭化成株式会社 | 层叠分隔件及其制造方法 |
US8460591B2 (en) * | 2010-03-23 | 2013-06-11 | GM Global Technology Operations LLC | Porous membranes and methods of making the same |
US9941498B2 (en) | 2010-12-28 | 2018-04-10 | Asahi Kasei E-Materials Corporation | Polyolefin-based porous film and method for producing the same |
KR101516225B1 (ko) | 2013-05-03 | 2015-05-04 | 주식회사 제낙스 | 부직포 집전체, 이를 이용한 전지의 제조 방법 및 이의 제조 시스템 |
CN106103045B (zh) * | 2014-03-28 | 2019-05-21 | 东丽株式会社 | 双轴取向聚丙烯膜 |
KR20160002447A (ko) | 2014-06-30 | 2016-01-08 | 제일모직주식회사 | 다공성 폴리올레핀계 분리막 및 이의 제조 방법 |
KR102264032B1 (ko) | 2017-03-27 | 2021-06-11 | 아사히 가세이 가부시키가이샤 | 폴리올레핀 미다공막 및 폴리올레핀 미다공막의 제조 방법 |
EP3719865A4 (en) * | 2017-11-28 | 2021-01-13 | Asahi Kasei Kabushiki Kaisha | SEPARATOR FOR ENERGY STORAGE DEVICE AND METHOD FOR MANUFACTURING THEREOF, AND ENERGY STORAGE DEVICE AND METHOD FOR MANUFACTURING THEREOF |
US20210115206A1 (en) * | 2018-02-23 | 2021-04-22 | Toray Industries, Inc. | Porous polyolefin film |
CN108832064A (zh) * | 2018-06-26 | 2018-11-16 | 河北金力新能源科技股份有限公司 | 一种复合陶瓷多孔锂电隔膜、制备方法及其应用 |
CN112886136A (zh) * | 2019-11-13 | 2021-06-01 | 上海恩捷新材料科技有限公司 | 一种聚烯烃微多孔隔离膜 |
CN112795066B (zh) * | 2019-11-13 | 2023-10-24 | 上海恩捷新材料科技有限公司 | 一种聚烯烃微多孔膜 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11106534A (ja) * | 1997-10-02 | 1999-04-20 | Nitto Denko Corp | ポリオレフィン多孔質膜の製造方法 |
JP2000248088A (ja) * | 1999-03-03 | 2000-09-12 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法 |
JP2001229907A (ja) * | 2000-02-15 | 2001-08-24 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法 |
JP2003003008A (ja) * | 2001-06-19 | 2003-01-08 | Tonen Chem Corp | 熱可塑性樹脂微多孔膜の製造方法 |
JP2003003007A (ja) * | 2001-06-19 | 2003-01-08 | Tonen Chem Corp | 熱可塑性樹脂微多孔膜の製造方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03113287A (ja) | 1989-09-28 | 1991-05-14 | Toshiba Ceramics Co Ltd | 高温処理用連続炉 |
JP2000017100A (ja) | 1998-07-03 | 2000-01-18 | Asahi Chem Ind Co Ltd | ポリエチレン微多孔膜の製造方法 |
JP4494638B2 (ja) * | 1998-10-01 | 2010-06-30 | 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 |
DE60035656T3 (de) * | 1999-02-19 | 2013-12-12 | Toray Battery Separator Film Co., Ltd. | Mikroporöse Polyolefinfolie und Verfahren zu deren Herstellung |
JP4606532B2 (ja) | 1999-09-17 | 2011-01-05 | 旭化成イーマテリアルズ株式会社 | ポリオレフィン製微多孔膜 |
JP2002284918A (ja) | 2001-03-23 | 2002-10-03 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法並びに用途 |
JP4794100B2 (ja) | 2001-09-28 | 2011-10-12 | 東レ東燃機能膜合同会社 | ポリオレフィン微多孔膜の製造方法 |
JP4794099B2 (ja) | 2001-09-28 | 2011-10-12 | 東レ東燃機能膜合同会社 | ポリオレフィン微多孔膜の製造方法 |
JP4794098B2 (ja) | 2001-09-28 | 2011-10-12 | 東レ東燃機能膜合同会社 | ポリオレフィン微多孔膜の製造方法 |
JP4817565B2 (ja) | 2001-09-28 | 2011-11-16 | 東レ東燃機能膜合同会社 | ポリオレフィン微多孔膜の製造方法 |
JP4817566B2 (ja) | 2001-09-28 | 2011-11-16 | 東レ東燃機能膜合同会社 | ポリオレフィン微多孔膜及びその製造方法 |
KR100599898B1 (ko) * | 2002-08-28 | 2006-07-19 | 아사히 가세이 케미칼즈 가부시키가이샤 | 폴리올레핀제 미다공막 및 그의 평가 방법 |
US20050031943A1 (en) | 2003-08-07 | 2005-02-10 | Call Ronald W. | Battery separator and method of making same |
KR100780523B1 (ko) * | 2003-10-27 | 2007-11-30 | 아사히 가세이 케미칼즈 가부시키가이샤 | 폴리올레핀 미다공막 및 그의 제조 방법 |
JP2005343958A (ja) | 2004-06-01 | 2005-12-15 | Tonen Chem Corp | ポリエチレン微多孔膜の製造方法並びにその微多孔膜及び用途 |
-
2006
- 2006-12-11 US US12/097,231 patent/US8003261B2/en active Active
- 2006-12-11 KR KR1020087014438A patent/KR100977345B1/ko active IP Right Review Request
- 2006-12-11 JP JP2007550162A patent/JP5216327B2/ja active Active
- 2006-12-11 CN CN2006800469978A patent/CN101331178B/zh active Active
- 2006-12-11 WO PCT/JP2006/324655 patent/WO2007069560A1/ja active Application Filing
- 2006-12-14 TW TW095146879A patent/TW200738799A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11106534A (ja) * | 1997-10-02 | 1999-04-20 | Nitto Denko Corp | ポリオレフィン多孔質膜の製造方法 |
JP2000248088A (ja) * | 1999-03-03 | 2000-09-12 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法 |
JP2001229907A (ja) * | 2000-02-15 | 2001-08-24 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法 |
JP2003003008A (ja) * | 2001-06-19 | 2003-01-08 | Tonen Chem Corp | 熱可塑性樹脂微多孔膜の製造方法 |
JP2003003007A (ja) * | 2001-06-19 | 2003-01-08 | Tonen Chem Corp | 熱可塑性樹脂微多孔膜の製造方法 |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8048936B2 (en) | 2007-11-28 | 2011-11-01 | Sk Innovation Co., Ltd. | Microporous polyolefin film possessing good mechanical properties and thermal stability |
EP2065953A1 (en) * | 2007-11-28 | 2009-06-03 | SK Energy Co., Ltd. | Microporous polyolefin film possessing good mechanical properties and thermal stability |
KR101263081B1 (ko) * | 2008-05-09 | 2013-05-09 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | 고출력 밀도 리튬 이온 이차 전지용 세퍼레이터 |
CN102017234A (zh) * | 2008-05-09 | 2011-04-13 | 旭化成电子材料株式会社 | 高功率密度锂离子二次电池用分隔件 |
JPWO2009136648A1 (ja) * | 2008-05-09 | 2011-09-08 | 旭化成イーマテリアルズ株式会社 | 高出力密度リチウムイオン二次電池用セパレータ |
WO2009136648A1 (ja) * | 2008-05-09 | 2009-11-12 | 旭化成イーマテリアルズ株式会社 | 高出力密度リチウムイオン二次電池用セパレータ |
JP2010100845A (ja) * | 2008-09-29 | 2010-05-06 | Toray Ind Inc | 多孔性ポリオレフィンフィルムの製造方法 |
WO2015190487A1 (ja) * | 2014-06-13 | 2015-12-17 | 東レバッテリーセパレータフィルム株式会社 | ポリオレフィン微多孔フィルム、その製造方法及び電池用セパレータ |
KR20170018329A (ko) | 2014-06-13 | 2017-02-17 | 도레이 배터리 세퍼레이터 필름 주식회사 | 폴리올레핀 미세 다공 필름, 이의 제조 방법 및 전지용 세퍼레이터 |
JPWO2015190487A1 (ja) * | 2014-06-13 | 2017-04-20 | 東レバッテリーセパレータフィルム株式会社 | ポリオレフィン微多孔フィルム、その製造方法及び電池用セパレータ |
WO2016006453A1 (ja) * | 2014-07-11 | 2016-01-14 | 帝人株式会社 | セパレータロール及び非水系二次電池 |
US10333175B2 (en) | 2014-09-30 | 2019-06-25 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
WO2016051656A1 (ja) * | 2014-09-30 | 2016-04-07 | 三洋電機株式会社 | 非水電解質二次電池 |
JPWO2016051656A1 (ja) * | 2014-09-30 | 2017-07-20 | 三洋電機株式会社 | 非水電解質二次電池 |
JP2017103046A (ja) * | 2015-11-30 | 2017-06-08 | 住友化学株式会社 | 非水電解液二次電池用セパレータ |
KR20190070337A (ko) | 2016-10-24 | 2019-06-20 | 스미또모 가가꾸 가부시키가이샤 | 세퍼레이터 및 세퍼레이터를 포함하는 이차 전지 |
US10840492B2 (en) | 2016-10-24 | 2020-11-17 | Sumitomo Chemical Company, Limited | Separator and secondary battery including the separator |
WO2018180714A1 (ja) * | 2017-03-31 | 2018-10-04 | 東レ株式会社 | ポリオレフィン微多孔膜、非水電解液系二次電池用セパレータ、及び非水電解液系二次電池 |
CN110431176A (zh) * | 2017-03-31 | 2019-11-08 | 东丽株式会社 | 聚烯烃微多孔膜、非水电解液系二次电池用隔膜及非水电解液系二次电池 |
JPWO2018180714A1 (ja) * | 2017-03-31 | 2019-12-26 | 東レ株式会社 | ポリオレフィン微多孔膜、非水電解液系二次電池用セパレータ、及び非水電解液系二次電池 |
CN110431176B (zh) * | 2017-03-31 | 2021-03-19 | 东丽株式会社 | 聚烯烃微多孔膜、非水电解液系二次电池用隔膜及非水电解液系二次电池 |
JP6741884B1 (ja) * | 2019-03-04 | 2020-08-19 | 旭化成株式会社 | ポリオレフィン微多孔膜 |
WO2020179101A1 (ja) * | 2019-03-04 | 2020-09-10 | 旭化成株式会社 | ポリオレフィン微多孔膜 |
CN111902470A (zh) * | 2019-03-04 | 2020-11-06 | 旭化成株式会社 | 聚烯烃微多孔膜 |
CN111902470B (zh) * | 2019-03-04 | 2021-09-21 | 旭化成株式会社 | 聚烯烃微多孔膜 |
Also Published As
Publication number | Publication date |
---|---|
TW200738799A (en) | 2007-10-16 |
KR100977345B1 (ko) | 2010-08-20 |
CN101331178A (zh) | 2008-12-24 |
KR20080077191A (ko) | 2008-08-21 |
KR100977345B9 (ko) | 2023-09-25 |
CN101331178B (zh) | 2011-07-06 |
TWI336718B (ja) | 2011-02-01 |
JP5216327B2 (ja) | 2013-06-19 |
US20090186280A1 (en) | 2009-07-23 |
JPWO2007069560A1 (ja) | 2009-05-21 |
US8003261B2 (en) | 2011-08-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2007069560A1 (ja) | ポリオレフィン製微多孔膜 | |
JP5586152B2 (ja) | ポリオレフィン製微多孔膜 | |
US9882190B2 (en) | Laminated polymicroporous membrane including propylene copolymer and method of producing the same | |
KR100899066B1 (ko) | 폴리올레핀 미다공막 | |
JP4931911B2 (ja) | ポリオレフィン微多孔膜 | |
JP5572334B2 (ja) | ポリオレフィン製微多孔膜 | |
WO2009136648A1 (ja) | 高出力密度リチウムイオン二次電池用セパレータ | |
JP6895570B2 (ja) | ポリオレフィン微多孔膜及びポリオレフィン微多孔膜の製造方法 | |
CN110621731B (zh) | 聚烯烃微多孔膜、蓄电装置用分隔件及蓄电装置 | |
JP4979252B2 (ja) | ポリオレフィン製微多孔膜 | |
JP6277225B2 (ja) | 蓄電デバイス用セパレータ | |
JP5909411B2 (ja) | ポリオレフィン微多孔膜及びその製造方法 | |
JP2017080977A (ja) | 多層微多孔膜及び蓄電デバイス用セパレータ | |
JP2009138159A (ja) | 微多孔膜 | |
JP2021036514A (ja) | シラン架橋ポリオレフィン混合樹脂を用いたセパレータ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200680046997.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2007550162 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12097231 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020087014438 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 06834410 Country of ref document: EP Kind code of ref document: A1 |