JP2010176936A - Separator for nonaqueous secondary battery, and nonaqueous secondary battery - Google Patents
Separator for nonaqueous secondary battery, and nonaqueous secondary battery Download PDFInfo
- Publication number
- JP2010176936A JP2010176936A JP2009016291A JP2009016291A JP2010176936A JP 2010176936 A JP2010176936 A JP 2010176936A JP 2009016291 A JP2009016291 A JP 2009016291A JP 2009016291 A JP2009016291 A JP 2009016291A JP 2010176936 A JP2010176936 A JP 2010176936A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- secondary battery
- heat
- aqueous secondary
- porous layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002050 silicone resin Polymers 0.000 claims abstract description 39
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 21
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 8
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 16
- 239000004760 aramid Substances 0.000 claims description 10
- 229920003235 aromatic polyamide Polymers 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 6
- 238000007790 scraping Methods 0.000 abstract 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000000576 coating method Methods 0.000 description 17
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- 230000001112 coagulating effect Effects 0.000 description 7
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- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
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- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006255 coating slurry Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229940057995 liquid paraffin Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000005406 washing Methods 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- 239000007774 positive electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は非水系二次電池用セパレータに関し、特に、非水系二次電池用セパレータの構成要素である、耐熱性多孔質層の滑り性、耐削れ性の向上に関するものである。 The present invention relates to a separator for a non-aqueous secondary battery, and more particularly to improvement of slipperiness and abrasion resistance of a heat-resistant porous layer, which is a component of a separator for a non-aqueous secondary battery.
非水電解質電池、特に、リチウムイオン二次電池に代表される非水系二次電池は、高エネルギー密度であり、携帯電話・ノートパソコンといった携帯用電子機器の主電源として広範に普及している。このリチウムイオン二次電池は、更なる高エネルギー密度化が求められているが、安全性の確保が技術的な課題となっている。リチウムイオン二次電池の安全性確保においてセパレータの役割は重要であり、シャットダウン機能を有するという観点から、現状ではポリオレフィン、特にポリエチレン微多孔膜が用いられている。ここで、シャットダウン機能とは、電池の温度が上昇したときに、微多孔膜の孔が閉塞し電流を遮断する機能のことを言い、電池の熱暴走を食い止める働きがある。 Nonaqueous electrolyte batteries, particularly nonaqueous secondary batteries represented by lithium ion secondary batteries, have a high energy density and are widely used as main power sources for portable electronic devices such as mobile phones and laptop computers. This lithium ion secondary battery is required to have a higher energy density, but ensuring safety is a technical issue. The role of the separator is important in ensuring the safety of the lithium ion secondary battery, and from the viewpoint of having a shutdown function, polyolefins, particularly polyethylene microporous membranes are currently used. Here, the shutdown function refers to a function of blocking pores in the microporous membrane when the temperature of the battery rises, and blocking the current, and has a function of preventing thermal runaway of the battery.
一方、リチウムイオン二次電池は、年々高エネルギー密度化がなされており、安全性確保のためシャットダウン機能に加えて耐熱性も要求されてきている。しかしながら、シャットダウン機能は、ポリエチレンの溶融による孔の閉塞をその作動原理としているので耐熱性と相反するものである。このため、シャットダウン機能が作動した後、さらに電池がシャットダウン機能が作動する温度以上に曝され続けることで、セパレータの溶融（いわゆるメルトダウン）が進行してしまう場合がある。このメルトダウンの結果、電池内部で短絡が生じ、これに伴って大きな熱が発生してしまい、電池は発煙・発火・爆発といった危険に曝されることになる。このため、セパレータにはシャットダウン機能に加えて、シャットダウン機能が作動する温度近傍でメルトダウンが生じない程度の、十分な耐熱性が要求される。 On the other hand, lithium ion secondary batteries have been increased in energy density year by year, and heat resistance has been required in addition to a shutdown function to ensure safety. However, the shutdown function is contrary to heat resistance because the operating principle is to close the hole by melting polyethylene. For this reason, after the shutdown function is activated, the battery may continue to be exposed to a temperature higher than the temperature at which the shutdown function is activated, whereby the separator may be melted (so-called meltdown). As a result of this meltdown, a short circuit occurs inside the battery, and as a result, a large amount of heat is generated, and the battery is exposed to dangers such as smoke, ignition, and explosion. For this reason, in addition to the shutdown function, the separator is required to have sufficient heat resistance that does not cause meltdown in the vicinity of the temperature at which the shutdown function operates.
この点において、従来、耐熱性とシャットダウン機能を両立させるために、ポリオレフィン微多孔膜の片面又は両面（表面と裏面）を耐熱性多孔質層で被覆したり、耐熱性繊維からなる不織布を積層させるという技術が提案されている。例えば、ポリエチレン微多孔膜の片面又は両面に、湿式塗工法により芳香族アラミド等の耐熱性高分子からなる耐熱性多孔質層を積層した非水電解質電池セパレータが知られている（特許文献１〜４参照）。 In this regard, conventionally, in order to achieve both heat resistance and a shutdown function, one or both surfaces (front and back surfaces) of a polyolefin microporous film are covered with a heat resistant porous layer, or a nonwoven fabric made of heat resistant fibers is laminated. The technology is proposed. For example, a nonaqueous electrolyte battery separator is known in which a heat-resistant porous layer made of a heat-resistant polymer such as aromatic aramid is laminated on one side or both sides of a polyethylene microporous membrane by a wet coating method (Patent Documents 1 to 3). 4).
このような非水電解質電池セパレータは、ポリエチレンの融点近傍（１４０℃程度）でシャットダウン機能が作動すると共に、耐熱性多孔質層が十分な耐熱性を示すことにより２００℃以上においてもメルトダウンが発生しないため、優れた耐熱性及びシャットダウン機能を発揮する。しかしながら、かかる耐熱性多孔質層は、多孔構造を有するが故に積層膜が削れ易く、滑り性が不足するという問題点があり、多孔構造を保持しつつ耐削れ性及び滑り性の向上した耐熱性多孔質層の開発が望まれていた。 Such a non-aqueous electrolyte battery separator operates with a shutdown function near the melting point of polyethylene (about 140 ° C), and the heat-resistant porous layer exhibits sufficient heat resistance, so that meltdown occurs even at 200 ° C or higher. Therefore, it exhibits excellent heat resistance and shutdown function. However, such a heat-resistant porous layer has a problem that the laminated film is easy to scrape due to having a porous structure, and there is a problem that the slipperiness is insufficient. Development of a porous layer has been desired.
本発明は、耐削れ性及び滑り性の向上した耐熱性多孔質層を有し、耐熱性やシャットダウン機能等に優れたセパレータを提供することを目的とする。 An object of the present invention is to provide a separator having a heat-resistant porous layer with improved abrasion resistance and slipperiness, and having excellent heat resistance and shutdown function.
上記課題を解決するために、本発明は以下の構成を採用する。
１． 熱可塑性樹脂にて形成されシャットダウン機能を有する微多孔膜の少なくとも一方の表面に、耐熱性樹脂からなる耐熱性多孔質層が被覆されている非水系二次電池用セパレータにおいて、該耐熱性多孔質層に、平均粒子径が０．０１〜１．０μｍであり、かつ、粒子の８０重量％以上が下記式（１）で表される結合単位からなるシリコーン樹脂微粒子が、０．０１〜１０重量％含まれていることを特徴とする非水系二次電池用セパレータ。
２． 前記シリコーン樹脂微粒子がシランカップリング剤で処理されていることを特徴とする上記１記載の非水系二次電池用セパレータ。
３． 前記シリコーン樹脂微粒子が略真球状のポリメチルシルセスキオキサンからなる微粒子であることを特徴とする上記１または２記載の非水系二次電池用セパレータ。
４． 前記耐熱性多孔質層において、無機フィラーが重量分率で５０重量％以上９５重量％以下含まれていることを特徴とする上記１から３のいずれかに記載の非水系二次電池用セパレータ。
５． 前記耐熱性樹脂が芳香族ポリアミド、ポリイミド、ポリエーテルスルホン、ポリスルホン、ポリエーテルケトン、ポリエーテルイミドからなる群から選ばれる１種類以上であることを特徴とする上記１〜４のいずれかに記載の非水系二次電池用セパレータ。
６． 前記耐熱性樹脂が、メタ型全芳香族ポリアミドであることを特徴とする上記５記載の非水系二次電池用セパレータ。
７． 前記非水系二次電池用セパレータが、リチウムイオン二次電池用セパレータであることを特徴とする上記１〜６のいずれかに記載の非水系二次電池用セパレータ。
８． リチウムのドープ・脱ドープにより起電力を得る非水系二次電池において、上記１〜７のいずれかに記載の非水系二次電池用セパレータを用いることを特徴とする非水系二次電池。
In order to solve the above problems, the present invention employs the following configuration.
1. In a nonaqueous secondary battery separator in which at least one surface of a microporous membrane formed of a thermoplastic resin and having a shutdown function is coated with a heat resistant porous layer made of a heat resistant resin, the heat resistant porous Silicone resin fine particles having an average particle diameter of 0.01 to 1.0 μm and comprising 80% by weight or more of a bond unit represented by the following formula (1) in the layer are 0.01 to 10% by weight. % Separator for non-aqueous secondary battery, characterized in that it is contained.
2. 2. The separator for a non-aqueous secondary battery according to 1, wherein the silicone resin fine particles are treated with a silane coupling agent.
3. 3. The separator for a non-aqueous secondary battery according to 1 or 2 above, wherein the silicone resin fine particles are fine particles made of substantially spherical polymethylsilsesquioxane.
4). 4. The separator for a non-aqueous secondary battery according to any one of 1 to 3 above, wherein the heat-resistant porous layer contains an inorganic filler in a weight fraction of 50% by weight to 95% by weight.
5). The heat-resistant resin is at least one selected from the group consisting of aromatic polyamide, polyimide, polyethersulfone, polysulfone, polyetherketone, and polyetherimide. Separator for non-aqueous secondary battery.
6). 6. The separator for a non-aqueous secondary battery according to 5 above, wherein the heat resistant resin is a meta-type wholly aromatic polyamide.
7). The separator for a non-aqueous secondary battery according to any one of the above 1 to 6, wherein the separator for a non-aqueous secondary battery is a separator for a lithium ion secondary battery.
8). A non-aqueous secondary battery using the non-aqueous secondary battery separator according to any one of the above 1 to 7 in a non-aqueous secondary battery that obtains an electromotive force by doping or dedoping lithium.
本発明の非水系二次電池用セパレータは、シャットダウン機能を有する微多孔膜を被覆している耐熱性多孔質層に、シリコーン樹脂の微粒子を含むことにより、耐熱性、シャットダウン機能に加えて、優れた耐摩耗性と滑り性を有する。かかるセパレータは、例えば、リチウムイオン二次電池等の非水系二次電池の性能を向上させるのに有効である。 The separator for non-aqueous secondary batteries of the present invention is excellent in addition to heat resistance and shutdown function by including fine particles of silicone resin in the heat resistant porous layer covering the microporous membrane having shutdown function. High wear resistance and slipperiness. Such a separator is effective, for example, for improving the performance of a non-aqueous secondary battery such as a lithium ion secondary battery.
［非水系二次電池用セパレータ］
本発明は、熱可塑性樹脂にて形成されシャットダウン機能を有する微多孔膜の少なくとも一方の表面に、耐熱性樹脂からなる耐熱性多孔質層が被覆されている非水系二次電池用セパレータにおいて、該耐熱性多孔質層に、平均粒子径が０．０１〜１．０μｍであり、かつ、粒子の８０重量％以上が下記式（１）で表される結合単位からなるシリコーン樹脂微粒子が、０．０１〜１０重量％含まれていることを特徴とする非水系二次電池用セパレータである。
[Separator for non-aqueous secondary battery]
The present invention provides a separator for a non-aqueous secondary battery in which at least one surface of a microporous membrane formed of a thermoplastic resin and having a shutdown function is coated with a heat-resistant porous layer made of a heat-resistant resin. Silicone resin fine particles having an average particle diameter of 0.01 to 1.0 μm and 80% by weight or more of the particles composed of a bond unit represented by the following formula (1) in the heat-resistant porous layer are: A separator for a non-aqueous secondary battery characterized by being contained in an amount of 01 to 10% by weight.
ここで、上記結合単位が８０重量％未満であると、耐削れ性、滑り性が十分ではなく好ましくない。前記シリコーン樹脂微粒子の製造方法は公知であり、例えばオルガノトリアルコキシシランを加水分解、縮合する方法（例えば特公昭４０―１４９１７号あるいは特公平２―２２７６７号等）やメチルトリクロロシランを出発原料とするポリメチルシルセスキオキサン微粒子の製造方法（例えばベルギ国特許５７２４１２号）などが挙げられる。前記式（１）におけるＲは炭素数１〜６のアルキル基およびフェニル基から選ばれる少なくとも１種であり、該アルキル基としては例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等を挙げることができる。これらは１種以上であることができる。Ｒが複数の基である場合、例えばメチル基とエチル基であるとき、メチルトリメトキシシランとエチルトリメトキシシランの混合物を出発原料として製造することで得ることができる。もっとも、製造コストや合成方法の容易さなどを考慮すると、Ｒがメチル基のシリコーン樹脂（ポリメチルシルセスキオキサン）微粒子が好ましい。 前記シリコーン樹脂微粒子はその形状が略球状、特に真球状であるものが好ましく、この場合滑り性付与に効果的である。 Here, if the bond unit is less than 80% by weight, the abrasion resistance and the slipperiness are not sufficient, which is not preferable. A method for producing the silicone resin fine particles is known, for example, a method of hydrolyzing and condensing organotrialkoxysilane (for example, Japanese Patent Publication No. 40-14917 or Japanese Patent Publication No. 22-22767), and methyltrichlorosilane as a starting material. Examples include a method for producing polymethylsilsesquioxane fine particles (for example, Belgian Patent No. 572412). R in the formula (1) is at least one selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Groups and the like. These can be one or more. When R is a plurality of groups, for example, when it is a methyl group and an ethyl group, it can be obtained by producing a mixture of methyltrimethoxysilane and ethyltrimethoxysilane as a starting material. However, in consideration of the manufacturing cost and the ease of the synthesis method, silicone resin (polymethylsilsesquioxane) fine particles having R as a methyl group are preferable. The silicone resin fine particles preferably have a substantially spherical shape, particularly a true spherical shape, and in this case, it is effective for imparting slipperiness.
本発明においては、かかるシリコーン樹脂微粒子をシランカップリング剤で表面処理して用いることもできる。この表面処理を施すことによって耐削れ性がさらに向上する。シランカップリング剤としては、不飽和結合を有するビニルトリエトキシシラン、ビニルトリクロルシラン、ビニルトリス（β―メトキシエトキシ）シランなど、アミノ系シランのＮ―β（アミノエチル）γ―アミノプロピルメチルジメトキシシラン、Ｎ―β（アミノエチル）γ―アミノプロピルトリメトキシシラン、γ―アミノプロピルトリメトキシシラン、γ―アミノプロピルトリエトキシシラン、Ｎ―フェニル―γ―アミノプロピルトリメトキシシランなど、エポキシ系シランのβ（３，４―エポキシシクロヘキシル）エチルトリメトキシシラン、γ―グリシドキシプロピルトリメトキシシラン、γ―グリシドキシプロピルメチルジエトキシシラン、γ―グリシドキシプロピルトリエトキシシランなど、メタクリレート系シランのγ―メタクリロキシプロピルメチルジメトキシシラン、γ―メタクリロキシプロピルトリメトキシシラン、γ―メタクリロキシプロピルメチルジエトキシシラン、γ―メタクリロキシプロピルトリエトキシシランなど、更にはγ―メルカプトプロピルトリメトキシシラン、γ―クロロプロピルトリメトキシシランなどが例示される。これらの中、エポキシ系シランカップリング剤が取り扱い易さ、添加したときの色の付き難さや耐削れ性の効果が大きいことなどから好ましい。 In the present invention, such silicone resin fine particles can be used after surface treatment with a silane coupling agent. By applying this surface treatment, the abrasion resistance is further improved. Examples of silane coupling agents include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane of amino silanes such as vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane having an unsaturated bond, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, etc. Metacri Xylpropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane, γ-chloropropyltri Examples include methoxysilane. Among these, an epoxy-based silane coupling agent is preferable because it is easy to handle, difficult to be colored when added, and has a large effect of abrasion resistance.
また、シランカップリング剤による表面処理は特に限定されるものではないが、例えば次のような方法を採用することができる。すなわち、合成直後のシリコーン樹脂微粒子スラリー（水スラリー又は有機溶媒スラリー）を濾過又は遠心分離機などで処理してシリコーン樹脂微粒子を分離した後、シランカップリング剤を分散させた水又は有機溶媒で再度スラリー化し、加熱処理後に再度微粒子を分離し、次いで分離微粒子を乾燥する方法である。この場合、シランカップリング剤の種類によっては更に熱処理を施してもよい。また、一旦乾燥されたシリコーン樹脂微粒子を同様の方法で再度スラリー化処理しても良い。 Further, the surface treatment with the silane coupling agent is not particularly limited, but for example, the following method can be employed. That is, the silicone resin fine particle slurry (water slurry or organic solvent slurry) immediately after synthesis is treated with a filter or a centrifugal separator to separate the silicone resin fine particles, and then again with water or an organic solvent in which a silane coupling agent is dispersed. This is a method of forming a slurry, separating the fine particles again after the heat treatment, and then drying the separated fine particles. In this case, heat treatment may be further performed depending on the type of the silane coupling agent. Further, once dried silicone resin fine particles may be slurried again by the same method.
本発明におけるシランカップリング剤で表面処理されたシリコーン樹脂微粒子は、白粉などの発生を防止し、耐削れ性を向上させる。このメカニズムの一つとしては次のことが考えられる。まず、シリコーン樹脂微粒子中の特定成分（例えば、出発原料成分や、原料の一つであるオルガノトリアルコキシシランの加水分解物などの未反応物、あるいはシリコーン樹脂中の末端シラノール基など）が、シランカップリング剤と化学的に結合することにより安定化する。これにより、シリコーン樹脂微粒子のフイルム表面への偏析あるいは逃散などが抑制され、微粒子の脱落や、微粒子周辺の耐熱性樹脂の削れが抑制され、結果として白粉の発生が押さえられるためではないかと思われる。 The silicone resin fine particles surface-treated with the silane coupling agent in the present invention prevent the generation of white powder and the like, and improve the abrasion resistance. The following can be considered as one of the mechanisms. First, specific components in the silicone resin fine particles (for example, unreacted materials such as starting raw material components, hydrolyzate of organotrialkoxysilane, which is one of the raw materials, or terminal silanol groups in the silicone resin) are silane. Stabilizes by chemically binding to the coupling agent. As a result, segregation or escape of silicone resin fine particles to the film surface is suppressed, and fine particles are prevented from falling off and the heat-resistant resin around the fine particles is suppressed. As a result, generation of white powder is suppressed. .
本発明において、かかるシリコーン樹脂微粒子は、界面活性剤の存在下で重合することができ、このような方法は不定形の粗大粒子数が減少することから好ましい。シリコーン樹脂微粒子の平均粒径は、０．０１〜１．０μｍであり、好ましくは０．０５〜１．０μｍである。この平均粒径が０．０１μｍ未満では滑り性や耐削れ性の向上効果が得られ難く、一方１μｍを超えると表面平坦性が得られ難く、耐削れ性が低下するため好ましくない。シリコーン樹脂微粒子の添加量は、耐熱性多孔質層の重量に対して、０．０１〜１０重量％、好ましくは０．０５〜５重量％である。この添加量が少なすぎると滑り性が悪くなり、一方添加量が多すぎると耐熱性多孔質層中の分散性が十分でなくなる等の問題が生じる。 In the present invention, such silicone resin fine particles can be polymerized in the presence of a surfactant, and such a method is preferred because the number of irregularly shaped coarse particles is reduced. The average particle diameter of the silicone resin fine particles is 0.01 to 1.0 μm, preferably 0.05 to 1.0 μm. When the average particle size is less than 0.01 μm, it is difficult to obtain the effect of improving the slipperiness and abrasion resistance. On the other hand, when the average particle diameter exceeds 1 μm, it is difficult to obtain surface flatness and the abrasion resistance is lowered. The addition amount of the silicone resin fine particles is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the weight of the heat-resistant porous layer. If the amount added is too small, the slipping property is deteriorated. On the other hand, if the amount added is too large, problems such as insufficient dispersibility in the heat-resistant porous layer occur.
本発明においては、非水系二次電池用セパレータの耐熱性多孔質層に、無機フィラーが含まれているのが好ましい。無機フィラーの耐熱性多孔質層中の重量分率は、特に限定されるものではないが、５０〜９５重量％であることが好ましく、更に５０〜８５重量％であることが好ましい。無機フィラーの重量分率が５０％より低いと、高温における寸法安定性といった耐熱性にかかわる特性や耐酸化性が不十分となる。また、９５重量％より高いと、耐熱性多孔質層の強度が不足し粉落ちの問題からハンドリング性が不良となったり、成形性が困難となったりという不具合が生じ好ましくない。 In this invention, it is preferable that the inorganic filler is contained in the heat resistant porous layer of the separator for non-aqueous secondary batteries. The weight fraction of the inorganic filler in the heat resistant porous layer is not particularly limited, but is preferably 50 to 95% by weight, and more preferably 50 to 85% by weight. When the weight fraction of the inorganic filler is lower than 50%, characteristics related to heat resistance such as dimensional stability at high temperature and oxidation resistance become insufficient. On the other hand, if it is higher than 95% by weight, the strength of the heat-resistant porous layer is insufficient, resulting in problems such as poor handling properties and difficulty in moldability due to the problem of powder falling.
無機フィラーとしては、例えば金属水酸化物、金属酸化物、金属窒化物、炭酸塩、硫酸塩、粘土鉱物等が挙げられる。金属水酸化物としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化クロム、水酸化ジルコニウム、水酸化ニッケル、水酸化ホウ素、ベーマイト等、金属酸化物としては、酸化アルミニウム、酸化チタン、酸化亜鉛、酸化珪素、 酸化イットリウム、酸化セリウム、酸化錫、酸化鉄等、金属窒化物としては、窒化アルミニウム、窒化ホウ素、窒化チタニウム等、炭酸塩としては、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等、硫酸塩としては、硫酸バリウム、硫酸カルシウム等、粘土鉱物としては、ケイ酸カルシウム、タルク、マイカ、モンモリロナイト、ハイドロタルサイト、ベントナイト、ゼオライト、セピオライト、カオリン、ヘクトライト、サポナイト、スチブンサイト、バイデライト等が挙げられ、もしくはこれらの２種以上の組合せが挙げられる。 Examples of the inorganic filler include metal hydroxide, metal oxide, metal nitride, carbonate, sulfate, clay mineral and the like. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, boron hydroxide, and boehmite. Examples of the metal oxide include aluminum oxide, oxidized Titanium, zinc oxide, silicon oxide, yttrium oxide, cerium oxide, tin oxide, iron oxide, etc., as metal nitride, aluminum nitride, boron nitride, titanium nitride, etc., as carbonate, calcium carbonate, magnesium carbonate, barium carbonate Etc., sulfate as barium sulfate, calcium sulfate, etc., clay mineral as calcium silicate, talc, mica, montmorillonite, hydrotalcite, bentonite, zeolite, sepiolite, kaolin, hectorite, saponite, stevensite, beidellite, etc. But Or a combination of two or more of these.
本発明のセパレータ構成において、耐熱性多孔質層はセパレータに耐熱性を付与する機能があるが、この層に前記のような無機フィラーを添加することで、高温時の短絡防止や寸法安定性といった観点から耐熱性多孔質層の耐熱性をより向上させることができる。また、一般的に耐熱性多孔質層で被覆したセパレータは、この耐熱層が強く静電気を帯びる傾向にあり、このような観点からハンドリング性が好ましくないことが多い。ここにおいて、耐熱性多孔質層に金属水酸化物等の無機フィラーを添加した場合は、帯電した電荷の減衰が速くなるため、帯電を低いレベルに保つことが可能となり、ハンドリング性が改善される。このような理由から、耐熱性多孔質層中へこのような無機フィラーを添加することは好適である。 In the separator configuration of the present invention, the heat-resistant porous layer has a function of imparting heat resistance to the separator. By adding an inorganic filler as described above to this layer, such as prevention of short circuit at high temperatures and dimensional stability, etc. From the viewpoint, the heat resistance of the heat resistant porous layer can be further improved. In general, a separator coated with a heat-resistant porous layer tends to be strongly charged with static electricity, and handling properties are often not preferable from such a viewpoint. Here, when an inorganic filler such as a metal hydroxide is added to the heat-resistant porous layer, since the charged charge decays quickly, the charge can be kept at a low level and the handling property is improved. . For these reasons, it is preferable to add such an inorganic filler into the heat-resistant porous layer.
一方で、耐熱性多孔質層は多孔構造を有するが故に削れ易く、滑り性が不足するという問題点を有していた。また、耐熱性多孔質層に無機フィラーを添加することにより、滑り性が多少向上するものの、耐削れ性については不十分であった。ところが、本発明者は、耐熱性多孔質層にさらにシリコーン樹脂微粒子を添加することにより、滑り性及び耐削れ性も向上できることを見出した。 On the other hand, since the heat-resistant porous layer has a porous structure, it has a problem that it is easy to scrape and lacks slipperiness. Moreover, although the slipperiness is somewhat improved by adding an inorganic filler to the heat resistant porous layer, the abrasion resistance is insufficient. However, the present inventor has found that slipping properties and abrasion resistance can be improved by further adding silicone resin fine particles to the heat resistant porous layer.
無機フィラーの平均粒子径は特に限定されるものではないが、０．１〜１μｍの範囲が好ましい。無機フィラーの平均粒子径が１μｍを超えると、耐熱性多孔質層の高温時の耐短絡性が低下し好ましくない。更に、耐熱性多孔質層を適切な厚みで成形する上で支障をきたすといった不具合もある。また、無機フィラーの平均粒子径が０．１μｍより小さくなると、塗膜強度が低下し粉落ちの課題が生じるだけでなく、このように小さいものを用いることは、コスト上の観点から実質的に困難である。 The average particle diameter of the inorganic filler is not particularly limited, but is preferably in the range of 0.1 to 1 μm. When the average particle diameter of the inorganic filler exceeds 1 μm, the short circuit resistance at high temperature of the heat resistant porous layer is lowered, which is not preferable. Further, there is a problem that it hinders the formation of the heat-resistant porous layer with an appropriate thickness. Moreover, when the average particle diameter of the inorganic filler is smaller than 0.1 μm, not only the coating strength is reduced and the problem of powder falling occurs, but using such a small one is substantially from the viewpoint of cost. Have difficulty.
本発明で用いられる耐熱性樹脂は、融点２００℃以上のポリマーあるいは融点を有しないが分解温度が２００℃以上のポリマーが適当であり、好ましくは、芳香族ポリアミド、ポリイミド、ポリエーテルスルホン、ポリスルホン、ポリエーテルケトン、ポリエーテルイミドからなる群から選ばれる１種又は２種以上のものである。特に、耐高温酸化性及び耐久性の観点から芳香族ポリアミドが好適であり、多孔質層を形成し易いという観点から、ポリメタフェニレンイソフタルアミド等のメタ型全芳香族ポリアミドが更に好適である。 The heat-resistant resin used in the present invention is suitably a polymer having a melting point of 200 ° C. or higher, or a polymer having a melting point of 200 ° C. or higher, preferably aromatic polyamide, polyimide, polyethersulfone, polysulfone, One type or two or more types selected from the group consisting of polyetherketone and polyetherimide. In particular, aromatic polyamides are preferable from the viewpoint of high-temperature oxidation resistance and durability, and meta-type wholly aromatic polyamides such as polymetaphenylene isophthalamide are more preferable from the viewpoint of easily forming a porous layer.
本発明において、耐熱性樹脂にて形成される耐熱性多孔質層とは、内部に多数の微細孔を有し、これら微細孔が連結された構造となっており、一方の面から他方の面へと気体あるいは液体が通過可能となった層を意味する。この耐熱性多孔質層の空孔率は、６０〜９０％の範囲が好適である。耐熱性多孔質層の空孔率が９０％を超えると、耐熱性が不十分となる傾向にあり好ましくない。また、６０％より低いとサイクル特性や保存特性、放電性が低下する傾向となり好ましくない。なお、耐熱性多孔質層は、主として、即ち、約９０重量％以上が前記のような耐熱性樹脂からなるものであれば良く、約１０重量％以下の、電池特性に影響を与えない他の成分を含んでいても良い。耐熱性多孔質層の厚みは２μｍ以上が好適である。耐熱性多孔質層の厚みが２μｍより薄くなると十分な耐熱性を得ることが困難となる。 In the present invention, the heat-resistant porous layer formed of a heat-resistant resin has a structure in which a large number of micropores are connected to each other, and these micropores are connected to each other. It means a layer through which gas or liquid can pass. The porosity of the heat resistant porous layer is preferably in the range of 60 to 90%. When the porosity of the heat resistant porous layer exceeds 90%, the heat resistance tends to be insufficient, which is not preferable. On the other hand, if it is lower than 60%, the cycle characteristics, storage characteristics and discharge properties tend to decrease, which is not preferable. The heat-resistant porous layer may be mainly composed of the above-mentioned heat-resistant resin, ie, about 90% by weight or more, and about 10% by weight or less, which does not affect the battery characteristics. Ingredients may be included. The thickness of the heat resistant porous layer is preferably 2 μm or more. When the thickness of the heat-resistant porous layer is less than 2 μm, it becomes difficult to obtain sufficient heat resistance.
本発明において微多孔膜に用いられる熱可塑性樹脂としては、融点２００℃未満の熱可塑性樹脂が適当であり、好ましくはポリオレフィンであり、特に好ましいのは、ポリエチレンである。本発明で用いられるポリエチレンは、特に限定されるものではないが、高密度ポリエチレンや、高密度ポリエチレンと超高分子量ポリエチレンの混合物が好適である。また、例えば、ポリエチレン以外に、ポリプロピレン、ポリメチルペンテン等の他のポリオレフィンを混合して用いても良い。微多孔膜とは、内部に多数の微細孔を有し、これら微細孔が連結された構造となっており、一方の面から他方の面へと気体あるいは液体が通過可能となった膜を意味する。なお、微多孔膜は、主として、即ち、約９０重量％以上が熱可塑性樹脂からなるものであれば良く、約１０重量％以下の、電池特性に影響を与えない他の成分を含んでいても良い。微多孔膜の膜厚は、５μｍ以上であることが好ましい。この微多孔膜の膜厚が５μｍより薄いと、引張強度や突刺強度といった機械物性が不十分となり好ましくない。 As the thermoplastic resin used for the microporous membrane in the present invention, a thermoplastic resin having a melting point of less than 200 ° C. is suitable, preferably a polyolefin, and particularly preferably polyethylene. The polyethylene used in the present invention is not particularly limited, but high-density polyethylene or a mixture of high-density polyethylene and ultrahigh molecular weight polyethylene is suitable. For example, in addition to polyethylene, other polyolefins such as polypropylene and polymethylpentene may be mixed and used. A microporous membrane means a membrane that has a large number of micropores inside and has a structure in which these micropores are connected, allowing gas or liquid to pass from one surface to the other. To do. The microporous membrane may be mainly composed of a thermoplastic resin in an amount of about 90% by weight or more, and may contain about 10% by weight or less of other components that do not affect the battery characteristics. good. The thickness of the microporous membrane is preferably 5 μm or more. If the thickness of the microporous film is less than 5 μm, mechanical properties such as tensile strength and puncture strength are insufficient, which is not preferable.
微多孔膜の空孔率は２０〜６０％のものが好ましい。微多孔膜の空孔率が２０％未満となると、セパレータの膜抵抗が高くなり過ぎ、電池の出力を顕著に低下させるため好ましくない。また、６０％を超えると、シャットダウン特性の低下が顕著となり好ましくない。この微多孔膜のガーレ値（ＪＩＳ・Ｐ８１１７）は、１０〜５００ｓｅｃ／１００ｃｃ以下が好ましい。微多孔膜のガーレ値が５００ｓｅｃ／１００ｃｃより高いと、イオン透過性が不十分となりセパレータの抵抗が高くなるという不具合が生じる。微多孔膜のガーレ値が１０ｓｅｃ／１００ｃｃより低いと、シャットダウン機能の低下が著しく実用的でない。 The porosity of the microporous membrane is preferably 20 to 60%. When the porosity of the microporous membrane is less than 20%, the membrane resistance of the separator becomes too high, and the output of the battery is remarkably reduced. On the other hand, if it exceeds 60%, the shutdown characteristic is remarkably deteriorated. The Gurley value (JIS P8117) of this microporous membrane is preferably 10 to 500 sec / 100 cc or less. If the Gurley value of the microporous membrane is higher than 500 sec / 100 cc, the ion permeability is insufficient and the resistance of the separator increases. When the Gurley value of the microporous film is lower than 10 sec / 100 cc, the shutdown function is remarkably not practical.
本発明において前記耐熱性多孔質層は、前記微多孔膜の少なくとも一方の面に形成すればよいが、ハンドリング性、耐久性及び熱収縮の抑制効果の観点から、表裏両面に形成した方がより好ましい。 In the present invention, the heat-resistant porous layer may be formed on at least one surface of the microporous membrane, but from the viewpoint of handling properties, durability, and the effect of suppressing heat shrinkage, it is more preferable to form the heat-resistant porous layer on both front and back surfaces. preferable.
本発明の非水系二次電池用セパレータの膜厚は２５μｍ以下が好ましく、さらに２０μｍ以下が好ましい。セパレータの膜厚が２５μｍを超えると、これを適用した電池のエネルギー密度や出力特性が低下し好ましくない。非水系二次電池用セパレータの物性としては、ガーレ値（ＪＩＳ・Ｐ８１１７）が１０〜１０００ｓｅｃ／１００ｃｃ、好ましくは１００〜４００ｓｅｃ／１００ｃｃである。ガーレ値が１０ｓｅｃ／１００ｃｃ未満である場合は、微多孔膜のガーレ値が低過ぎ、シャットダウン機能の低下が著しく実用的でない。ガーレ値が１０００ｓｅｃ／１００ｃｃを超えると、イオン透過性が不十分となり、セパレータの膜抵抗が増加して電池の出力低下を招くという不具合が生じる。膜抵抗は０．５〜１０ｏｈｍ・ｃｍ２、好ましくは１〜５ｏｈｍ・ｃｍ２である。突き刺し強度は１０〜１０００ｇ、好ましくは２００〜６００ｇの範囲のものである。 The film thickness of the separator for non-aqueous secondary batteries of the present invention is preferably 25 μm or less, more preferably 20 μm or less. When the thickness of the separator exceeds 25 μm, the energy density and output characteristics of a battery to which the separator is applied are undesirably lowered. As a physical property of the separator for non-aqueous secondary batteries, the Gurley value (JIS P8117) is 10 to 1000 sec / 100 cc, preferably 100 to 400 sec / 100 cc. When the Gurley value is less than 10 sec / 100 cc, the Gurley value of the microporous membrane is too low, and the deterioration of the shutdown function is remarkably impractical. When the Gurley value exceeds 1000 sec / 100 cc, the ion permeability becomes insufficient, resulting in a problem that the membrane resistance of the separator is increased and the output of the battery is lowered. The membrane resistance is 0.5 to 10 ohm · cm 2 , preferably 1 to 5 ohm · cm 2 . The puncture strength is in the range of 10 to 1000 g, preferably 200 to 600 g.
［非水系二次電池用セパレータの製造方法］
本発明の非水系二次電池用セパレータの製造方法は特に限定されないが、例えば、以下の（i）〜（iv）の工程を経て製造することが可能である。即ち、（i）主として耐熱性樹脂の水溶性有機溶剤溶液に、シリコーン樹脂微粒子と無機フィラーを分散させ、塗工用スラリーを作製する工程と、（ii）得られた塗工用スラリーを、主として熱可塑性樹脂からなる微多孔膜の片面又は両面に塗工する工程と、（iii）塗工された前記微多孔膜を、水又は水と前記有機溶剤の混合液からなる凝固液中に浸漬して耐熱性樹脂を凝固させる工程と、（iv）この凝固工程後の前記微多孔膜を、水洗し乾燥する工程と、を実施することからなる製造方法である。
[Method for producing separator for non-aqueous secondary battery]
Although the manufacturing method of the separator for non-aqueous secondary batteries of this invention is not specifically limited, For example, it is possible to manufacture through the following processes (i)-(iv). That is, (i) a step of dispersing a silicone resin fine particle and an inorganic filler in a water-soluble organic solvent solution mainly of a heat-resistant resin to prepare a slurry for coating; and (ii) a coating slurry obtained mainly. A step of coating on one or both sides of a microporous membrane made of a thermoplastic resin, and (iii) immersing the coated microporous membrane in a coagulating liquid consisting of water or a mixture of water and the organic solvent. And a step of coagulating the heat-resistant resin, and (iv) a step of washing and drying the microporous membrane after the coagulation step.
前記工程（i）において、水溶性有機溶剤としては、特に限定されないが、具体的には極性溶剤が好ましく、例えばＮ−メチルピロリドン、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシドなどが挙げられる。また、これらの極性溶剤に耐熱性樹脂に対して貧溶剤となる溶剤も、一部混合して用いることもできる。このような溶剤を適用することで、ミクロ相分離構造が誘発され、耐熱性多孔質層を形成する上で多孔化が容易となる。貧溶剤としては、アルコールの類が好適であり、特にグリコールのような多価アルコールが好適である。なお、無機フィラーの分散性が良好でない場合は、無機フィラーをシランカップリング剤等で表面処理する手法も適用可能である。 In the step (i), the water-soluble organic solvent is not particularly limited, but specifically, a polar solvent is preferable, and examples thereof include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like. In addition, a solvent that becomes a poor solvent for the heat-resistant resin may be mixed with these polar solvents. By applying such a solvent, a microphase separation structure is induced, and the formation of a heat-resistant porous layer is facilitated. As the poor solvent, alcohols are preferable, and polyhydric alcohols such as glycol are particularly preferable. In addition, when the dispersibility of an inorganic filler is not favorable, the method of surface-treating an inorganic filler with a silane coupling agent etc. is applicable.
工程（ii）では、微多孔膜の少なくとも一方の表面に、耐熱性樹脂の塗工液を塗工する。本発明においては、微多孔膜の両面に塗工するのが好ましい。塗工する方法は、ナイフコーター法、グラビアコーター法、スクリーン印刷法、マイヤーバー法、ダイコーター法、リバースロールコーター法、インクジェット法、スプレー法、ロールコーター法などが挙げられる。塗膜を均一に塗布するという観点において、特にリバースロールコーター法が好適である。より具体的には、例えば、ポリエチレン微多孔膜の両面に耐熱性樹脂の塗工液を塗工する場合は、一対のマイヤーバーの間を通してポリエチレン微多孔膜の両面に過剰に塗工液を塗布し、これを一対のリバースロールコーターの間を通し、過剰な塗工液を掻き落すことで精密計量するという方法が挙げられる。 In step (ii), a heat-resistant resin coating solution is applied to at least one surface of the microporous membrane. In the present invention, it is preferable to apply on both surfaces of the microporous membrane. Examples of the coating method include knife coater method, gravure coater method, screen printing method, Mayer bar method, die coater method, reverse roll coater method, ink jet method, spray method, roll coater method and the like. From the viewpoint of uniformly applying the coating film, the reverse roll coater method is particularly suitable. More specifically, for example, in the case of applying a heat-resistant resin coating liquid on both sides of a polyethylene microporous film, the coating liquid is applied excessively on both sides of the polyethylene microporous film through a pair of Meyer bars. In addition, there is a method in which this is passed between a pair of reverse roll coaters and the excess coating solution is scraped off to precisely measure.
工程（iii）では、塗工された微多孔膜を、耐熱性樹脂を凝固させることが可能な凝固液中に浸漬することで、耐熱性樹脂を凝固させ、多孔質層を成形する。凝固の方法としては、凝固液をスプレーで吹き付ける方法や、凝固液の入った浴（凝固浴）中に浸漬する方法などが挙げられる。凝固液は、耐熱性樹脂を凝固できるものであれば特に限定されないが、水又は塗工液に用いた有機溶剤に、水を適当量混合させたものが好ましい。ここで、水の混合量は凝固液に対して４０〜８０重量％が好適である。水の量が４０重量％より少ないと、耐熱性樹脂を凝固するのに必要な時間が長くなったり、凝固が不十分になるという問題が生じる。また、８０重量％より多いと溶剤回収においてコスト高となったり、凝固液と接触する表面の凝固が速すぎ、表面が十分に多孔化されないという問題が生じる。 In the step (iii), the heat-resistant resin is solidified by immersing the coated microporous film in a coagulating liquid capable of coagulating the heat-resistant resin, thereby forming a porous layer. Examples of the coagulation method include a method of spraying a coagulation liquid with a spray and a method of immersing in a bath (coagulation bath) containing the coagulation liquid. The coagulation liquid is not particularly limited as long as it can coagulate the heat-resistant resin, but is preferably a mixture of water or an appropriate amount of water in the organic solvent used for the coating liquid. Here, the mixing amount of water is preferably 40 to 80% by weight with respect to the coagulation liquid. When the amount of water is less than 40% by weight, there arises a problem that the time required for solidifying the heat-resistant resin becomes long or the solidification becomes insufficient. On the other hand, when the amount is more than 80% by weight, there arises a problem that the cost for solvent recovery becomes high, or the surface that comes into contact with the coagulating liquid is solidified too quickly and the surface is not sufficiently porous.
工程（iv）は、工程（iii）に引き続き、得られたセパレータから水洗で凝固液を除去し、次いで乾燥する工程である。乾燥方法は特に限定されないが、乾燥温度は５０〜８０℃が適当であり、高い乾燥温度を適用する場合は、熱収縮による寸法変化が起こらないようにするために、ロールに接触させるような方法を適用することが好ましい。 Step (iv) is a step of removing the coagulating liquid from the obtained separator by washing with water, and then drying, following step (iii). The drying method is not particularly limited, but the drying temperature is suitably 50 to 80 ° C. When a high drying temperature is applied, a method of contacting the roll in order to prevent dimensional change due to heat shrinkage. Is preferably applied.
［非水系二次電池］
本発明の非水系二次電池用セパレータは、公知のいかなる構成の非水系二次電池にも適用することができ、安全性と耐熱性多孔質層の耐削れ性に優れた電池が得られる。
適用される非水系二次電池の種類や構成は、何ら限定されるものではないが、本発明の非水系二次電池用セパレータは、リチウムのドープ・脱ドープにより起電力を得る非水系二次電池に好適に応用することができる。中でも、リチウムイオン二次電池への適用が好ましい。
[Non-aqueous secondary battery]
The separator for nonaqueous secondary batteries of the present invention can be applied to any known nonaqueous secondary battery, and a battery excellent in safety and wear resistance of the heat-resistant porous layer can be obtained.
The type and configuration of the applied non-aqueous secondary battery is not limited in any way, but the non-aqueous secondary battery separator of the present invention is a non-aqueous secondary battery that obtains an electromotive force by doping or dedoping lithium. It can be suitably applied to a battery. Among these, application to a lithium ion secondary battery is preferable.
一般に非水系二次電池とは、負極と正極がセパレータを介して対向している電池要素に電解液が含浸され、これが外装に封入された構造となっているものをいう。負極は、負極活物質、導電助剤、バインダーからなる負極合剤が集電体（銅箔、ステンレス箔、ニッケル箔等）上に成形された構造となっている。負極活物質としては、リチウムを電気化学的にドープすることが可能な材料、例えば、炭素材料、シリコン、アルミニウム、スズが用いられる。正極は、正極活物質、導電助剤、バインダーからなる正極合剤が集電体上に成形された構造となっている。正極活物質としては、リチウム含有遷移金属酸化物、例えば、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ０．５Ｎｉ０．５Ｏ２、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＭｎ２Ｏ４、ＬｉＦｅＰＯ４が用いられる。電解液は、リチウム塩、例えば、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４を非水系溶媒に溶解した構成である。非水系溶媒としては、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ−ブチロラクトン、ビニレンカーボネートなどが挙げられる。外装材としては、金属缶又はアルミラミネートパック等が挙げられる。電池の形状は角型、円筒型、コイン型などがあるが、本発明のセパレータはいずれの形状においても好適に適用することが可能である。 In general, a non-aqueous secondary battery means a battery element in which a negative electrode and a positive electrode are opposed to each other with a separator interposed therebetween and an electrolytic solution is impregnated, and this is enclosed in an exterior. The negative electrode has a structure in which a negative electrode mixture composed of a negative electrode active material, a conductive additive, and a binder is formed on a current collector (copper foil, stainless steel foil, nickel foil, etc.). As the negative electrode active material, a material capable of electrochemically doping lithium, for example, a carbon material, silicon, aluminum, or tin is used. The positive electrode has a structure in which a positive electrode mixture composed of a positive electrode active material, a conductive additive, and a binder is formed on a current collector. Examples of the positive electrode active material include lithium-containing transition metal oxides such as LiCoO 2 , LiNiO 2 , LiMn 0.5 Ni 0.5 O 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiMn 2 O. 4 and LiFePO 4 are used. The electrolytic solution has a configuration in which a lithium salt, for example, LiPF 6 , LiBF 4 , or LiClO 4 is dissolved in a non-aqueous solvent. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, and vinylene carbonate. Examples of the exterior material include a metal can or an aluminum laminate pack. The shape of the battery includes a square shape, a cylindrical shape, a coin shape, and the like, but the separator of the present invention can be suitably applied to any shape.
以下、実施例により本発明を詳述する。各種の物性値及び性能の測定方法は以下のとおりである。 Hereinafter, the present invention will be described in detail by way of examples. Various physical property values and methods for measuring performance are as follows.
［シリコーン樹脂微粒子の平均粒径］
レーザー回折式粒度分布測定装置を用いて測定を行った。分散媒としては水を用い、分散剤として非イオン性界面活性剤「Ｔｒｉｔｏｎ Ｘ−１００」を微量用いた。体積粒度分布における中心粒子径（Ｄ５０）を平均粒子径とした。
[Average particle size of silicone resin fine particles]
Measurement was performed using a laser diffraction particle size distribution measuring apparatus. Water was used as a dispersion medium, and a small amount of nonionic surfactant “Triton X-100” was used as a dispersant. The central particle size (D50) in the volume particle size distribution was taken as the average particle size.
［膜厚］
接触式の膜厚計（ミツトヨ社製）にて２０点測定し、これを平均することで求めた。ここで接触端子は底面が直径０．５ｃｍの円柱状のものを用い、接触端子に１．２ｋｇ／ｃｍ２の荷重が印加されるような条件で測定した。
[Film thickness]
It was determined by measuring 20 points with a contact-type film thickness meter (manufactured by Mitutoyo Co., Ltd.) and averaging them. Here, the contact terminal used was a cylindrical one having a bottom surface of 0.5 cm in diameter, and measurement was performed under a condition that a load of 1.2 kg / cm 2 was applied to the contact terminal.
［透気度］
透気度（秒／１００ｃｃ）はＪＩＳ・Ｐ８１１７に従い測定した。
[Air permeability]
The air permeability (second / 100 cc) was measured according to JIS P8117.
［空孔率］
構成材料がa、ｂ、ｃ…、ｎからなり、構成材料の重量がＷａ、Ｗｂ、Ｗｃ…、Ｗｎ（ｇ・ｃｍ２）であり、それぞれの真密度がｄａ、ｄｂ、ｄｃ…、ｄｎ（ｇ／ｃｍ３）で、着目する層の膜厚をｔ（ｃｍ）としたとき、空孔率ε（％）は
ε＝｛１−（Ｗａ／ｄａ＋Ｗｂ／ｄｂ＋Ｗｃ／ｄｃ＋…＋Ｗｎ／ｄｎ）／ｔ｝×１００
より求めた。
[Porosity]
The constituent materials are a, b, c..., N, and the weights of the constituent materials are Wa, Wb, Wc..., Wn (g · cm 2 ), and their true densities are da, db, dc. g / cm 3 ), where the thickness of the layer of interest is t (cm), the porosity ε (%) is ε = {1− (Wa / da + Wb / db + Wc / dc +... + Wn / dn) / t } × 100
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［シャットダウン（ＳＤ）特性］
まず、セパレータをΦ１９ｍｍに打ち抜き、非イオン性界面活性剤（花王社製；エマルゲン２１０Ｐ）の３重量％メタノール溶液中に浸漬して風乾する。そしてセパレータに電解液を含浸させＳＵＳ板（Φ１５．５ｍｍ）に挟んだ。ここで電解液は１Ｍ ＬｉＢＦ４ プロピレンカーボネート／エチレンカーボネート（１／１重量比）を用いた。これを２０３２型コインセルに封入した。コインセルからリード線をとり、熱電対を付けてオーブンの中に入れた。昇温速度１．６℃／分で昇温させ、同時に振幅１０ｍＶ、１ｋＨｚの周波数の交流を印加することでセルの抵抗を測定した。その結果、昇温時に抵抗値が１．０×１０３ｏｈｍ・ｃｍ２以上まで上昇した場合にシャットダウン機能を有しているとみなし、シャットダウン機能の有無を○×で評価した。
[Shutdown (SD) characteristics]
First, the separator is punched to Φ19 mm, dipped in a 3% by weight methanol solution of a nonionic surfactant (manufactured by Kao Corporation; Emulgen 210P), and air-dried. Then, the separator was impregnated with the electrolytic solution and sandwiched between SUS plates (Φ15.5 mm). Here, 1 M LiBF 4 propylene carbonate / ethylene carbonate (1/1 weight ratio) was used as the electrolytic solution. This was enclosed in a 2032 type coin cell. I took the lead from the coin cell, put a thermocouple, and put it in the oven. The cell resistance was measured by raising the temperature at a rate of temperature increase of 1.6 ° C./min and simultaneously applying alternating current with an amplitude of 10 mV and a frequency of 1 kHz. As a result, when the resistance value increased to 1.0 × 10 3 ohm · cm 2 or more at the time of temperature rise, it was regarded as having a shutdown function, and the presence / absence of the shutdown function was evaluated by ○ ×.
［耐熱性］
上記のＳＤ特性の評価において、シャットダウン機能が発現した後、１５０〜１９０℃の温度下においても抵抗値が１．０×１０３ｏｈｍ・ｃｍ２以上のレベルを維持し続けた場合は、メルトダウンが生じておらず耐熱性に優れているため、○と判断した。一方、１５０〜１９０℃における抵抗値が１．０×１０３ｏｈｍ・ｃｍ２を下回った場合は、×と判断した。
[Heat-resistant]
In the evaluation of the above SD characteristics, if the resistance value continues to maintain a level of 1.0 × 10 3 ohm · cm 2 or higher even at a temperature of 150 to 190 ° C. after the shutdown function is exhibited, Since it was excellent in heat resistance without generating, it was judged as “good”. On the other hand, if the resistance value at 150 to 190 ° C. is below 1.0 × 10 3 ohm · cm 2 , was determined to ×.
［滑り性］
ＳＵＳ板上にセパレータをのせて引張ったとき容易に滑ったものを○、滑ったものを△、滑り難かったものを×とした。
[Sliding]
When the separator was placed on a SUS plate and pulled, the one that slipped easily was marked with ◯, the slipped one was marked with Δ, and the one that was difficult to slip was marked with ×.
［耐削れ性］
乾燥ガーゼをセットした学研式摩耗試験機（テスター産業社製）を使用し、サンプルフィルムの塗膜面上を、１００ｇの荷重を与えながら５往復ラビング処理し、塗膜表面の損傷状態を目視にて判定する。処理前後においてその表面がほとんど変化のないものを○、塗膜にやや損傷が認められるものを△、明らかに塗膜が脱落しているものを×と評価した。
[Scratch resistance]
Using a Gakken abrasion tester (made by Tester Sangyo Co., Ltd.) with dry gauze, the coating surface of the sample film was rubbed 5 times while giving a load of 100 g, and the damaged state of the coating surface was visually observed. Judgment. The case where the surface hardly changed before and after the treatment was evaluated as ◯, the case where the coating film was slightly damaged was evaluated as Δ, and the case where the coating film was clearly dropped was evaluated as X.
［実施例１］
１）ポリエチレン微多孔膜の製造
ポリエチレンパウダーとしてＴｉｃｏｎａ社製のＧＵＲ２１２６（重量平均分子量４１５万、融点１４１℃）とＧＵＲＸ１４３（重量平均分子量５６万、融点１３５℃）を用いた。ＧＵＲ２１２６とＧＵＲＸ１４３を１：９（重量比）となるようにして、ポリエチレン濃度が３０重量％となるように流動パラフィンとデカリンの混合溶媒中に溶解させ、ポリエチレン溶液を作製した。該ポリエチレン溶液の組成はポリエチレン：流動パラフィン：デカリン＝３０：４５：２５（重量比）である。このポリエチレン溶液を１４８℃でダイから押し出し、水浴中で冷却して、６０℃で８分、９５℃で１５分乾燥し、ゲル状テープ（ベーステープ）を作製した。該ベーステープを縦延伸、横延伸と逐次行う２軸延伸にて延伸した。ここで、縦延伸は５．５倍、延伸温度は９０℃、横延伸は延伸倍率１１．０倍、延伸温度は１０５℃とした。横延伸の後に１２５℃で熱固定を行った。次にこれを塩化メチレン浴に浸漬し、流動パラフィンとデカリンを抽出した。その後、５０℃で乾燥し、１２０℃でアニール処理することでポリエチレン微多孔膜を得た。このポリエチレン微多孔膜の物性は、膜厚１２．０μｍ、空孔率３６％、透気度３０１秒／１００ｃｃであった。
[Example 1]
1) Manufacture of a polyethylene microporous film Ticona GUR2126 (weight average molecular weight 4150,000, melting | fusing point 141 degreeC) and GURX143 (weight average molecular weight 560,000, melting | fusing point 135 degreeC) were used as polyethylene powder. A polyethylene solution was prepared by dissolving GUR2126 and GURX143 in a mixed solvent of liquid paraffin and decalin such that the polyethylene concentration was 30% by weight so that the ratio was 1: 9 (weight ratio). The composition of the polyethylene solution is polyethylene: liquid paraffin: decalin = 30: 45: 25 (weight ratio). This polyethylene solution was extruded from a die at 148 ° C., cooled in a water bath, and dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes to produce a gel tape (base tape). The base tape was stretched by biaxial stretching, which was sequentially performed with longitudinal stretching and lateral stretching. Here, the longitudinal stretching was 5.5 times, the stretching temperature was 90 ° C., the transverse stretching was 11.0 times the stretching ratio, and the stretching temperature was 105 ° C. After transverse stretching, heat setting was performed at 125 ° C. Next, this was immersed in a methylene chloride bath to extract liquid paraffin and decalin. Then, it dried at 50 degreeC and obtained the polyethylene microporous film by annealing at 120 degreeC. The properties of this polyethylene microporous membrane were a film thickness of 12.0 μm, a porosity of 36%, and an air permeability of 301 seconds / 100 cc.
２）シリコーン樹脂微粒子の製造
撹拌翼付きの１０リットルのガラス容器に０．２重量％の水酸化ナトリウムを含む水溶液７０００ｇを張り込み、上層へ１０００ｇのメチルトリメトキシシランを静かに注入し、２層を形成したのち１０〜１５℃で２０ｒｐｍの回転数で３時間界面反応させ、これにより粒子を生成させた。その後温度を７０℃として４時間熟成し、冷却後、減圧濾過機で濾過し、続いて３０００ｇの水で洗浄を行い、水分約５０％のシリコーン樹脂微粒子のケーク状物を得た。得られたケークを９０℃で１５Ｔｏｒｒにて２時間減圧乾燥し、更に１５０℃で５時間常圧乾燥を行い、シリコーン樹脂微粒子粉末約４００ｇを得た。得られた該微粒子の平均粒子径は０．６μｍであった。
2) Manufacture of silicone resin fine particles 7000 g of an aqueous solution containing 0.2% by weight of sodium hydroxide was put in a 10 liter glass container equipped with a stirring blade, and 1000 g of methyltrimethoxysilane was gently injected into the upper layer, and the two layers were After the formation, an interfacial reaction was performed at 10 to 15 ° C. and a rotation speed of 20 rpm for 3 hours, thereby generating particles. Thereafter, the temperature was aged at 70 ° C. for 4 hours, and after cooling, the mixture was filtered with a vacuum filter, and then washed with 3000 g of water to obtain a cake of silicone resin fine particles having a water content of about 50%. The obtained cake was dried under reduced pressure at 90 ° C. and 15 Torr for 2 hours, and further dried at 150 ° C. for 5 hours at atmospheric pressure to obtain about 400 g of silicone resin fine particle powder. The obtained fine particles had an average particle size of 0.6 μm.
３）非水系二次電池用セパレータの製造
メタ型全芳香族ポリアミドであるコーネックス（登録商標；帝人テクノプロダクツ社製）、シリコーン樹脂及び水酸化アルミニウム（昭和電工社製；Ｈ−４３Ｍ）が重量比で２５：２：７３となるように調整し、これらをメタ型全芳香族ポリアミド濃度が５．５重量％となるようにジメチルアセトアミド（ＤＭＡｃ）とトリプロピレングリコール（ＴＰＧ）が重量比５０：５０となっている混合溶媒に混合し塗工用スラリーを得た。
一対のマイヤーバー（番手＃６）を２０μｍのクリアランスで対峙させた。マイヤーバーに上記塗工用スラリーを適量のせ、一対のマイヤーバー間にポリエチレン微多孔膜を通すことでポリエチレン微多孔膜の両面に塗工用スラリーを塗工した。これを重量比で水：ＤＭＡｃ：ＴＰＧ＝５０：２５：２５で４０℃となっている凝固液中に浸漬した。次いで水洗・乾燥を行い、該ポリエチレン微多孔膜の表裏に耐熱性多孔質層を形成し、本発明の非水系二次電池用セパレータを得た。
得られたセパレータの膜厚は２０.３μｍで、耐熱性多孔質層の空孔率は７０％、セパレータの透気度３１０秒/１００ｃｃであった。セパレータは、シャットダウン特性は○、耐熱性は○、滑り性は○、削れ性は△であった。
3) Manufacture of separator for non-aqueous secondary battery Conex (registered trademark; manufactured by Teijin Techno Products), silicone resin and aluminum hydroxide (manufactured by Showa Denko; H-43M), which is a meta-type wholly aromatic polyamide, is weight The ratio of dimethylacetamide (DMAc) and tripropylene glycol (TPG) was adjusted to a weight ratio of 50: 2: 73. A slurry for coating was obtained by mixing with 50 mixed solvent.
A pair of Meyer bars (count # 6) was confronted with a clearance of 20 μm. An appropriate amount of the above slurry for coating was placed on a Mayer bar, and the coating slurry was applied to both sides of the polyethylene microporous membrane by passing the polyethylene microporous membrane between a pair of Meyer bars. This was immersed in a coagulating liquid having a weight ratio of water: DMAc: TPG = 50: 25: 25 and 40 ° C. Next, washing with water and drying were performed to form heat-resistant porous layers on the front and back of the polyethylene microporous membrane, thereby obtaining a separator for a non-aqueous secondary battery of the present invention.
The film thickness of the obtained separator was 20.3 μm, the porosity of the heat-resistant porous layer was 70%, and the air permeability of the separator was 310 seconds / 100 cc. The separator had a shutdown characteristic of ◯, a heat resistance of ◯, a slipperiness of ◯, and a shaving property of △.
［実施例２］
１）シリコーン樹脂微粒子の製造
撹拌翼付きの１０リットルのガラス容器に０．２重量％の水酸化ナトリウムを含む水溶液７０００ｇを張り込み、上層へ１０００ｇのメチルトリメトキシシランを静かに注入し、２層を形成したのち１０〜１５℃で２０ｒｐｍの回転数で３時間界面反応させ、これにより粒子を生成させた。その後温度を７０℃として１時間熟成し、冷却後、減圧濾過機で濾過し、水分約３０％のシリコーン樹脂微粒子のケーク状物を得た。次に反応に用いた先のガラス容器にシランカップリング剤としてγ―グリシドキシプロピルトリメトキシシランを２重量％分散させた水溶液４０００ｇに、先の反応で得られたケーク状物を全量加えスラリー化し、内温７０℃、６０ｒｐｍの回転数にて３時間かけて表面処理を行い、冷却後減圧濾過機で濾過を行った。続いて今度はシランカップリング剤を含まない水６０００ｇに表面処理されたケーク状物を全量加え再度スラリー化し、常温、６０ｒｐｍにて１時間撹拌し、その後減圧濾過機にて濾過を行うことにより、余分のシランカップリング剤が除去された水分約４０％のケーク状物を得た。最後にこのケーク状物を１２０℃で１５Ｔｏｒｒにて１０時間減圧乾燥を行うことにより、シランカップリング剤で表面処理されたシリコーン樹脂微粒子粉末約４００ｇを得た。得られた該微粒子の平均粒子径は０．６μｍの微粒子であった。
[Example 2]
1) Manufacture of silicone resin fine particles 7000 g of an aqueous solution containing 0.2% by weight of sodium hydroxide was put into a 10 liter glass container with a stirring blade, and 1000 g of methyltrimethoxysilane was gently injected into the upper layer, and two layers were formed. After the formation, an interfacial reaction was performed at 10 to 15 ° C. and a rotation speed of 20 rpm for 3 hours, thereby generating particles. Thereafter, the temperature was aged at 70 ° C. for 1 hour, and after cooling, the mixture was filtered with a vacuum filter to obtain a cake of silicone resin fine particles having a water content of about 30%. Next, a total amount of the cake-like material obtained in the previous reaction was added to 4000 g of an aqueous solution in which 2% by weight of γ-glycidoxypropyltrimethoxysilane was dispersed as a silane coupling agent in the previous glass container used for the reaction. The surface treatment was performed for 3 hours at an internal temperature of 70 ° C. and a rotation speed of 60 rpm, and after cooling, filtration was performed with a vacuum filter. Subsequently, by adding the whole amount of the cake-like material surface-treated in 6000 g of water not containing a silane coupling agent, the slurry is again slurried, stirred at room temperature and 60 rpm for 1 hour, and then filtered with a vacuum filter. A cake having a water content of about 40% from which excess silane coupling agent was removed was obtained. Finally, the cake-like material was dried under reduced pressure at 120 ° C. and 15 Torr for 10 hours to obtain about 400 g of a silicone resin fine particle powder surface-treated with a silane coupling agent. The average particle size of the obtained fine particles was 0.6 μm.
２）非水系二次電池用セパレータの製造
シリコーン樹脂微粒子を上記のものに変更した以外は実施例１と同様にして、非水系二次電池用セパレータを作製した。
得られたセパレータの膜厚は２０．１μｍで、耐熱性多孔質層の空孔率は６９％、セパレータの透気度３４０秒/１００ｃｃであった。セパレータは、シャットダウン特性は○、耐熱性は○、滑り性は○、耐削れ性は○であった。
2) Production of non-aqueous secondary battery separator A non-aqueous secondary battery separator was produced in the same manner as in Example 1 except that the silicone resin fine particles were changed to the above.
The film thickness of the obtained separator was 20.1 μm, the porosity of the heat-resistant porous layer was 69%, and the air permeability of the separator was 340 seconds / 100 cc. The separator had a shutdown characteristic of ◯, heat resistance of ◯, slipperiness of ◯, and wear resistance of ◯.
［実施例３］
１）シリコーン樹脂微粒子の製造
撹拌翼付きの１０リットルのガラス容器に０．０６重量％の水酸化ナトリウムを含む水溶液７０００ｇを張込み、上層へノニルフェノールのエチレンオキシド付加物０．０１％を含む１０００ｇのメチルトリメトキシシランを静かに注入し、２層を形成したのち、１０〜１５℃でわずかに撹拌しながら２時間界面反応させ、球状粒子を生成させた。その後、系内の温度を７０℃として約１時間熟成させ、冷却後、減圧濾過機で濾過し、水分率約４０％のシリコーン樹脂微粒子のケーク状物を得た。次に別のガラス容器に、シランカップリング剤として、γ―グリシドキシプロピルトリメトキシシランを２重量％分散させた水溶液４０００ｇを仕込み、そこへ先の反応で得られたケーク状物を全量加えてスラリー化し、温度７０℃で撹拌しながら３時間かけて表面処理を行い、冷却後、減圧濾過機で濾過処理し、ケーク状物を得た。続いて、このケーク状物を純水６０００ｇに全量加えて再度スラリー化し、常温にて１時間撹拌し、その後再度減圧濾過機にて濾過処理することにより、余分の乳化剤およびシランカップリング剤が除去された水分率約４０％のケーク状物を得ることができた。最後に、このケーク状物を、１００℃で高減圧下１０時間処理し、凝集粒子の少ないシリコーン樹脂微粒子粉末約４００ｇを得た。得られた微粒子の平均粒子径は０．６μｍの微粒子であった。
[Example 3]
1) Production of silicone resin fine particles 7000 g of an aqueous solution containing 0.06 wt% sodium hydroxide was placed in a 10 liter glass container equipped with a stirring blade, and 1000 g of methyl containing 0.01% of nonylphenol ethylene oxide adduct was added to the upper layer. Trimethoxysilane was gently injected to form two layers, and then subjected to an interfacial reaction for 2 hours with slight stirring at 10 to 15 ° C. to produce spherical particles. Thereafter, the temperature inside the system was aged for about 1 hour at 70 ° C., and after cooling, it was filtered with a vacuum filter to obtain a cake-like product of silicone resin fine particles having a moisture content of about 40%. Next, in another glass container, 4000 g of an aqueous solution in which 2% by weight of γ-glycidoxypropyltrimethoxysilane was dispersed as a silane coupling agent was charged, and the total amount of cake-like material obtained in the previous reaction was added thereto. The slurry was made into a slurry, surface-treated for 3 hours with stirring at a temperature of 70 ° C., cooled, and filtered with a vacuum filter to obtain a cake. Subsequently, the entire amount of this cake-like material was added to 6000 g of pure water to make a slurry again, stirred at room temperature for 1 hour, and then filtered again with a vacuum filter to remove excess emulsifier and silane coupling agent. A cake having a moisture content of about 40% could be obtained. Finally, the cake was treated at 100 ° C. under high vacuum for 10 hours to obtain about 400 g of a silicone resin fine particle powder with few aggregated particles. The average particle diameter of the obtained fine particles was 0.6 μm.
２）非水系二次電池用セパレータの製造
シリコーン樹脂微粒子を上記のものに変更した以外は実施例１と同様にして、非水系二次電池用セパレータを作製した。
得られたセパレータの膜厚は１９．８μｍで、耐熱性多孔質層の空孔率は７２％、セパレータの透気度は３６０秒/１００ｃｃであった。セパレータは、シャットダウン特性は○、耐熱性は○、滑り性は○、耐削れ性は○であった。
2) Production of non-aqueous secondary battery separator A non-aqueous secondary battery separator was produced in the same manner as in Example 1 except that the silicone resin fine particles were changed to the above.
The film thickness of the obtained separator was 19.8 μm, the porosity of the heat-resistant porous layer was 72%, and the air permeability of the separator was 360 seconds / 100 cc. The separator had a shutdown characteristic of ◯, heat resistance of ◯, slipperiness of ◯, and wear resistance of ◯.
［比較例１］
塗工用スラリーの組成をメタ型全芳香族ポリアミドであるコーネックス（登録商標；帝人テクノプロダクツ社製）と水酸化アルミニウム（昭和電工社製；Ｈ−４３Ｍ）が重量比で２５：７５となるように変更した以外は実施例１と同様にして、非水系二次電池用セパレータを作製した。
得られたセパレータの膜厚は２０μｍで、耐熱性多孔質層の空孔率は７０％、セパレータの透気度は３１０秒/１００ｃｃであった。セパレータは、シャットダウン特性は○、耐熱性は○、滑り性は△、耐削れ性は×であった。
[Comparative Example 1]
The composition of the coating slurry is a meta-type wholly aromatic polyamide Conex (registered trademark; manufactured by Teijin Techno Products) and aluminum hydroxide (Showa Denko; H-43M) in a weight ratio of 25:75. A separator for a nonaqueous secondary battery was produced in the same manner as in Example 1 except that the above was changed.
The film thickness of the obtained separator was 20 μm, the porosity of the heat resistant porous layer was 70%, and the air permeability of the separator was 310 seconds / 100 cc. The separator had a shutdown characteristic of ◯, a heat resistance of ◯, a slipping property of △, and an abrasion resistance of x.
［比較例２］
シリコーン樹脂微粒子を東芝シリコーン(株)製の平均粒子径１．３μｍであるポリメチルシルセスキオキサン（商品名：トスパール１２０）に変更した以外は実施例１と同様にして、非水系二次電池用セパレータを作製した。
得られたセパレータの膜厚は２０μｍで、耐熱性多孔質層の空孔率は７１％、セパレータの透気度３３０秒/１００ｃｃであった。セパレータは、シャットダウン特性は○、耐熱性は○、滑り性は△、耐削れ性は×であった。
[Comparative Example 2]
Nonaqueous secondary battery in the same manner as in Example 1, except that the silicone resin fine particles were changed to polymethylsilsesquioxane (trade name: Tospearl 120) manufactured by Toshiba Silicone Co., Ltd. and having an average particle diameter of 1.3 μm. A separator was prepared.
The film thickness of the obtained separator was 20 μm, the porosity of the heat-resistant porous layer was 71%, and the air permeability of the separator was 330 seconds / 100 cc. The separator had a shutdown characteristic of ◯, a heat resistance of ◯, a slipping property of △, and an abrasion resistance of x.
Claims (8)
該耐熱性多孔質層に、平均粒子径が０．０１〜１．０μｍであり、かつ、粒子の８０重量％以上が下記式（１）で表される結合単位からなるシリコーン樹脂微粒子が、０．０１〜１０重量％含まれていることを特徴とする非水系二次電池用セパレータ。
Silicone resin fine particles having an average particle diameter of 0.01 to 1.0 μm and 80% by weight or more of the particles composed of a bond unit represented by the following formula (1) are added to the heat resistant porous layer. A separator for a non-aqueous secondary battery, characterized by containing 0.01 to 10% by weight.
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