JP5086132B2 - Nonaqueous electrolyte battery separator, manufacturing method thereof, and nonaqueous electrolyte secondary battery using the same - Google Patents
Nonaqueous electrolyte battery separator, manufacturing method thereof, and nonaqueous electrolyte secondary battery using the same Download PDFInfo
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- JP5086132B2 JP5086132B2 JP2008047749A JP2008047749A JP5086132B2 JP 5086132 B2 JP5086132 B2 JP 5086132B2 JP 2008047749 A JP2008047749 A JP 2008047749A JP 2008047749 A JP2008047749 A JP 2008047749A JP 5086132 B2 JP5086132 B2 JP 5086132B2
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- Prior art keywords
- electrolyte battery
- microporous membrane
- battery separator
- nonaqueous electrolyte
- aromatic polyamide
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000012982 microporous membrane Substances 0.000 claims description 53
- -1 polymetaphenylene isophthalamide Polymers 0.000 claims description 51
- 239000004760 aramid Substances 0.000 claims description 48
- 229920003235 aromatic polyamide Polymers 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 22
- 239000011256 inorganic filler Substances 0.000 claims description 21
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005345 coagulation Methods 0.000 claims description 14
- 230000015271 coagulation Effects 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical group 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Chemical group 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- 239000011260 aqueous acid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 25
- 239000004698 Polyethylene Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 229920000573 polyethylene Polymers 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 15
- 230000001112 coagulating effect Effects 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 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
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000010280 constant potential charging Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 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
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 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
- 238000012935 Averaging Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 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
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 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
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 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
Description
本発明は、劣化が少なく、且つ、安全性が向上した非水電解質電池セパレータとその製造方法、並びに、それを用いた非水電解質二次電池に関するものである。 The present invention relates to a non-aqueous electrolyte battery separator that is less deteriorated and improved in safety, a method for producing the same, and a non-aqueous electrolyte secondary battery using the same.
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電解質二次電池は、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 electrolyte secondary batteries represented by lithium ion secondary batteries, have high energy density and are widely used as the main power source 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）に耐熱性多孔質層を被覆させたり、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 surface or both surfaces (front and back surfaces) of the polyolefin microporous film are coated 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、優れた耐熱性およびシャットダウン機能を発揮する。 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.
ところで、非水電解質電池において、セパレータとして、芳香族ポリアミドからなる耐熱性多孔質層を有するものを用いた場合には、芳香族ポリアミドの末端ＣＯＯＸ基（Ｘは、水素、アルカリ金属又はアルカリ土類金属）の濃度を低くするほどセパレータの劣化が少なく、その結果、セパレータの強度が保持されるという特徴がある。本発明は、特許文献１〜４等では着目されたことのない、かかる知見を更に展開・発展させることによってなされたものである。 By the way, in the nonaqueous electrolyte battery, when a separator having a heat-resistant porous layer made of aromatic polyamide is used, the terminal COOX group of aromatic polyamide (X is hydrogen, alkali metal or alkaline earth). The lower the concentration of (metal), the less the deterioration of the separator. As a result, the strength of the separator is maintained. The present invention has been made by further developing and developing such knowledge that has not been noticed in Patent Documents 1 to 4 and the like.
従って本発明の課題は、ポリオレフィンに代表される熱可塑性樹脂からなる微多孔膜の片面又は両面に、湿式塗工法にて、芳香族ポリアミドからなる耐熱性多孔質層を形成して非水電解質電池セパレータを得るに際し、芳香族ポリアミドの末端基に着目し、それを規制することによって、長期間に亘ってセパレータの劣化が少なく強度が維持された非水電解質電池用のセパレータを提供することにある。 Accordingly, an object of the present invention is to form a heat-resistant porous layer made of an aromatic polyamide on one or both sides of a microporous film made of a thermoplastic resin typified by polyolefin by a wet coating method, thereby producing a nonaqueous electrolyte battery. In obtaining a separator, it is to provide a separator for a nonaqueous electrolyte battery in which the strength is maintained with little deterioration of the separator over a long period of time by focusing on the end group of the aromatic polyamide and regulating it. .
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） 主として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と、主として芳香族ポリアミドにて形成され前記微多孔膜の片面又は両面に積層された耐熱性多孔質層とを備えた非水電解質電池セパレータであって、前記芳香族ポリアミドの末端基濃度比が、［ＣＯＯＸ］／［ＮＨ２］＜１（Ｘは、水素、アルカリ金属又はアルカリ土類金属を表す）であることを特徴とする非水電解質電池セパレータ。
（２） 前記Ｘが、ナトリウムであることを特徴とする上記（１）記載の非水電解質電池セパレータ。
（３） 前記芳香族ポリアミドが、ポリメタフェニレンイソフタルアミドであることを特徴とする上記（１）又は（２）記載の非水電解質電池セパレータ。
（４） 前記ポリメタフェニレンイソフタルアミドが、イソフタル酸クロライドとメタフェニレンジアミンを、生成ポリアミドに対し良溶媒でない有機溶媒中で反応せしめて溶液若しくは分散液を作り、これを酸受容剤の水溶液と接触させ反応を完結せしめて製造されたものである
ことを特徴とする上記（３）に記載の非水電解質電池セパレータ。
（５） 前記耐熱性多孔質層が、重量分率で５０重量％以上９５重量％以下の無機フィラーを含むことを特徴とする上記（１）〜（４）のいずれかに記載の非水電解質電池セパレータ。
（６） 前記無機フィラーが、主として金属水酸化物からなることを特徴とする上記（５）記載の非水電解質電池セパレータ。
（７） 前記熱可塑性樹脂が、ポリオレフィンを主体とする熱可塑性樹脂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電解質電池セパレータ。
（８） 前記非水電解質電池セパレータが、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）〜（７）のいずれかに記載の非水電解質電池セパレータ。
（９） 主として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と、主としてメタ型芳香族ポリアミドにて形成され前記微多孔膜の片面又は両面に積層された耐熱性多孔質層とを備えた上記（１）に記載の非水電解質電池セパレータの製造方法であって、（i）メタ型芳香族ジカルボン酸ハライドとメタ型芳香族ジアミンを、生成するポリアミドに対し良溶媒でない有機溶媒中で反応せしめて溶液若しくは分散液を作り、これを酸受容剤の水溶液と接触させ反応を完結せしめて、末端基濃度比が［ＣＯＯＸ］／［ＮＨ２］＜１（Ｘは、水素、アルカリ金属又はアルカリ土類金属を表す）であるメタ型芳香族ポリアミドを製造する工程と、（ii）得られたメタ型芳香族ポリアミドの水溶性有機溶剤溶液を、前記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、メタ型芳香族ポリアミド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、を実施することを特徴とする非水電解質電池セパレータの製造方法。
（１０） 主として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と、主として芳香族ポリアミドにて形成され前記微多孔膜の片面又は両面に積層された耐熱性多孔質層とを備えた上記（１）に記載の非水電解質電池セパレータの製造方法であって、（i）芳香族ジカルボン酸ハライドと芳香族ジアミンを、生成するポリアミドに対し良溶媒である有機溶媒中で反応せしめて、末端基濃度比が［ＣＯＯＸ］／［ＮＨ２］＜１（Ｘは、水素、アルカリ金属又はアルカリ土類金属を表す）である芳香族ポリアミドを製造する工程と、（ii）得られた芳香族ポリアミドの水溶性有機溶剤溶液を、前記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芳香族ポリアミド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、を実施することを特徴とする非水電解質電池セパレータの製造方法。
（１１） リチウムのドープ・脱ドープにより起電力を得る非水電解質二次電池であって、上記（１）〜（８）のいずれかに記載の非水電解質電池セパレータを用いたことを特徴とする非水電解質二次電池。
In order to solve the above problems, the present invention employs the following configuration.
(1) A non-porous membrane comprising a microporous membrane mainly made of thermoplastic resin and having a shutdown function, and a heat-resistant porous layer mainly made of aromatic polyamide and laminated on one or both sides of the microporous membrane. A water electrolyte battery separator, wherein the aromatic polyamide has a terminal group concentration ratio of [COOX] / [NH 2 ] <1 (X represents hydrogen, alkali metal or alkaline earth metal). Non-aqueous electrolyte battery separator.
(2) The nonaqueous electrolyte battery separator according to (1), wherein X is sodium.
(3) The non-aqueous electrolyte battery separator according to (1) or (2), wherein the aromatic polyamide is polymetaphenylene isophthalamide.
(4) The polymetaphenylene isophthalamide is reacted with isophthalic acid chloride and metaphenylenediamine in an organic solvent that is not a good solvent for the resulting polyamide to form a solution or dispersion, which is contacted with an acid acceptor aqueous solution. The nonaqueous electrolyte battery separator according to (3) above, wherein the separator is manufactured by completing the reaction.
(5) The nonaqueous electrolyte according to any one of (1) to (4), wherein the heat-resistant porous layer contains an inorganic filler in a weight fraction of 50% by weight to 95% by weight. Battery separator.
(6) The non-aqueous electrolyte battery separator according to (5), wherein the inorganic filler is mainly composed of a metal hydroxide.
(7) The nonaqueous electrolyte battery separator according to any one of (1) to (6), wherein the thermoplastic resin is a thermoplastic resin mainly composed of polyolefin.
(8) The nonaqueous electrolyte battery separator according to any one of (1) to (7), wherein the nonaqueous electrolyte battery separator is a separator for a lithium ion secondary battery.
(9) A microporous membrane formed mainly of a thermoplastic resin and having a shutdown function, and a heat-resistant porous layer mainly formed of a meta-type aromatic polyamide and laminated on one or both sides of the microporous membrane. A method for producing a non-aqueous electrolyte battery separator as described in (1) above, wherein (i) a meta-type aromatic dicarboxylic acid halide and a meta-type aromatic diamine are produced in an organic solvent that is not a good solvent for the resulting polyamide. Reaction is performed to form a solution or dispersion, which is contacted with an aqueous solution of an acid acceptor to complete the reaction, and the terminal group concentration ratio is [COOX] / [NH 2 ] <1 (where X is hydrogen, alkali metal or (Ii) a water-soluble organic solvent solution of the obtained meta-type aromatic polyamide is added to one side or the other of the microporous membrane. A step of coating on both sides; and (iii) a step of coagulating the meta-type aromatic polyamide by immersing the coated microporous membrane in a coagulating liquid comprising water or a mixture of water and the organic solvent. And (iv) a step of washing and drying the microporous membrane after the coagulation step, and a method for producing a non-aqueous electrolyte battery separator.
(10) The above-described microporous membrane formed mainly of a thermoplastic resin and having a shutdown function, and the heat-resistant porous layer formed mainly of an aromatic polyamide and laminated on one or both sides of the microporous membrane. (1) A method for producing a non-aqueous electrolyte battery separator according to (1), wherein (i) an aromatic dicarboxylic acid halide and an aromatic diamine are reacted in an organic solvent which is a good solvent with respect to the produced polyamide, A step of producing an aromatic polyamide having a group concentration ratio of [COOX] / [NH 2 ] <1 (X represents hydrogen, an alkali metal or an alkaline earth metal), and (ii) the obtained aromatic polyamide A step of coating the water-soluble organic solvent solution on one side or both sides of the microporous membrane, and (iii) in the coagulating liquid comprising water or a mixture of water and the organic solvent. Soak in And a step of solidifying the aromatic polyamide, (iv) the production method of the nonaqueous electrolyte battery separator which comprises carrying out the steps of the above after the solidifying step is washed with water microporous membrane drying, the.
(11) A nonaqueous electrolyte secondary battery that obtains an electromotive force by doping or dedoping of lithium, wherein the nonaqueous electrolyte battery separator according to any one of (1) to (8) is used. Non-aqueous electrolyte secondary battery.
本発明の非水電解質電池セパレータにおいては、ポリオレフィン等の熱可塑性樹脂にて形成された微多孔膜の、片面又は両面に積層される耐熱性多孔質層を形成するための、芳香族ポリアミドとして、末端カルボキシル基濃度が末端アミノ基濃度よりも低いもの用いることを特徴とする。末端カルボキシル基（その塩を含む）を低くすることによって、セパレータの劣化を抑えることができ、特に、末端アミノ基濃度よりも低くすることによってその効果が顕著となる。例えば、充放電を１００サイクル繰り返した後でも、セパレータはなお良好な強度を維持している。 In the nonaqueous electrolyte battery separator of the present invention, as an aromatic polyamide for forming a heat-resistant porous layer laminated on one side or both sides of a microporous membrane formed of a thermoplastic resin such as polyolefin, The terminal carboxyl group concentration is lower than the terminal amino group concentration. By lowering the terminal carboxyl group (including the salt thereof), deterioration of the separator can be suppressed, and in particular, by lowering the terminal amino group concentration, the effect becomes remarkable. For example, even after 100 cycles of charging / discharging, the separator still maintains good strength.
［非水電解質電池セパレータ］
本発明は、主として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と、主として芳香族ポリアミドにて形成され前記微多孔膜の片面又は両面に積層された耐熱性多孔質層とを備えた非水電解質電池セパレータであって、前記芳香族ポリアミドの末端基濃度比が、［ＣＯＯＸ］／［ＮＨ２］＜１であることを特徴とするものである。Ｘは、水素、アルカリ金属又はアルカリ土類金属を表し、アルカリ金属、中でもナトリウムの場合が好ましい。前記比の値が１に等しいかより大きい場合には、セパレータの劣化が起こり易くなるので不適当である。
[Nonaqueous electrolyte battery separator]
The present invention includes a microporous membrane formed mainly of a thermoplastic resin and having a shutdown function, and a heat-resistant porous layer formed mainly of an aromatic polyamide and laminated on one or both sides of the microporous membrane. A non-aqueous electrolyte battery separator is characterized in that a terminal group concentration ratio of the aromatic polyamide is [COOX] / [NH 2 ] <1. X represents hydrogen, an alkali metal or an alkaline earth metal, and is preferably an alkali metal, particularly sodium. When the value of the ratio is equal to or greater than 1, it is not appropriate because the separator is likely to deteriorate.
芳香族ポリアミドの末端基濃度の比である［ＣＯＯＸ］／［ＮＨ２］は、ポリマー末端カルボキシル基の単位重量当たりのモル濃度（ｍｏｌ／ｇ）と、アミノ基の単位重量当たりのモル濃度（ｍｏｌ／ｇ）との比として表される。測定法については後述する。 [COOX] / [NH 2 ], which is the ratio of the end group concentration of the aromatic polyamide, is the molar concentration per unit weight of the polymer terminal carboxyl group (mol / g) and the molar concentration per unit weight of the amino group (mol / G) as a ratio. The measurement method will be described later.
本発明の非水電解質電池セパレータの膜厚は３０μｍ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３０μｍ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。非水電解質電池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 nonaqueous electrolyte battery separator of the present invention is preferably 30 μm or less, more preferably 20 μm or less. When the thickness of the separator exceeds 30 μm, the energy density and output characteristics of a battery to which the separator is applied are lowered, which is not preferable. As the physical properties of the nonaqueous electrolyte battery separator, 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 shutdown function is remarkably lowered, which is not practical. 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.
本発明において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。ポリエチレンとポリメタフェニレンイソフタルアミドは、なじみが良く良好な接着性を示すので、本発明においては、特に好ましい組合せである。本発明の微多孔膜に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。 As the thermoplastic resin used in the present invention, a thermoplastic resin having a melting point of less than 200 ° C. is suitable, preferably polyolefin, and particularly preferably polyethylene. Polyethylene and polymetaphenylene isophthalamide are a particularly preferred combination in the present invention because they are well known and exhibit good adhesiveness. The polyethylene used for the microporous membrane of 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.
ポリエチレン等の微多孔膜の膜厚は５μｍ以上１８μｍ以下であることが好ましい。該微多孔膜の膜厚が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、該微多孔膜の膜厚が１８μｍより厚いと適切なセパレータ厚みを実現することが困難となるため好ましくない。該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。該微多孔膜のガーレ値（ＪＩＳ・Ｐ８１１７）は、１０ｓｅｃ／１００ｃｃ以上、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。該微多孔膜の突刺強度は、１０ｇ以上が好適である。 The film thickness of the microporous film such as polyethylene is preferably 5 μm or more and 18 μm or less. If the thickness of the microporous film is less than 5 μm, mechanical properties such as tensile strength and puncture strength are insufficient, and if the thickness of the microporous film is greater than 18 μm, it is difficult to achieve an appropriate separator thickness. It is not preferable. 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 lowered, which is not preferable. On the other hand, if it exceeds 60%, the shutdown characteristic is remarkably deteriorated. The Gurley value (JIS P8117) of the microporous membrane is preferably 10 sec / 100 cc or more and 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 deteriorated. The puncture strength of the microporous membrane is preferably 10 g or more.
本発明で用いられる芳香族ポリアミドとは、芳香族ジアミンと芳香族ジカルボン酸から得られるポリアミドを意味し、例えば、ポリメタフェニレンイソフタルアミド、ポリパラフェニレンイソフタルアミドが挙げられる。好ましいのはポリメタフェニレンイソフタルアミドであり、その製法は問わないが、界面重合法で得られたものが好ましい。界面重合法によると、芳香族ポリアミドの末端基をコントロールし易いので、前記末端基濃度の比のものが容易に得られる。 The aromatic polyamide used in the present invention means a polyamide obtained from an aromatic diamine and an aromatic dicarboxylic acid, and examples thereof include polymetaphenylene isophthalamide and polyparaphenylene isophthalamide. Preference is given to polymetaphenylene isophthalamide, and its production method is not limited, but those obtained by interfacial polymerization are preferred. According to the interfacial polymerization method, it is easy to control the end groups of the aromatic polyamide, so that the end group concentration ratio can be easily obtained.
芳香族ポリアミド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。なお、耐熱性多孔質層は、主として、即ち、約９０重量％以上が耐熱性高分子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。 A heat-resistant porous layer formed of an aromatic polyamide 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 liquid can pass. The heat-resistant porous layer should be mainly composed of heat-resistant polymer in an amount of about 90% by weight or more, and contains about 10% by weight or less of other components that do not affect the battery characteristics. You can leave.
本発明において該耐熱性多孔質層は、該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、耐久性およ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。そして、耐熱性多孔質層が該微多孔膜の両面に形成されている場合は該耐熱性多孔質層の厚みの合計が３μｍ以上１２μｍ以下であるか、または、該耐熱性多孔質層が該微多孔膜の片面にのみ形成されている場合は該耐熱性多孔質層の厚みが３μｍ以上１２μｍ以下であることが好ましい。いずれの場合においても、該耐熱性多孔質層の厚みの合計が３μｍ未満となると、十分な耐熱性、特に熱収縮抑制効果が得られなくなる。一方、該耐熱性多孔質層の厚みの合計が１２μｍを超えると、適切なセパレータ厚みを実現することが困難となる。該耐熱性多孔質層の空孔率は６０〜９０％の範囲が好適である。該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、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。 In the present invention, the heat-resistant porous layer may be formed on at least one surface of the microporous membrane. 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. When the heat resistant porous layer is formed on both surfaces of the microporous membrane, the total thickness of the heat resistant porous layer is 3 μm or more and 12 μm or less, or the heat resistant porous layer is When formed only on one side of the microporous membrane, the thickness of the heat-resistant porous layer is preferably 3 μm or more and 12 μm or less. In any case, when the total thickness of the heat-resistant porous layer is less than 3 μm, sufficient heat resistance, particularly a heat shrinkage suppressing effect cannot be obtained. On the other hand, when the total thickness of the heat-resistant porous layer exceeds 12 μm, it is difficult to realize an appropriate separator thickness. The porosity of the heat resistant porous layer is preferably in the range of 60 to 90%. If the porosity of the heat-resistant porous layer exceeds 90%, the heat resistance tends to be insufficient, and if it is lower than 60%, the cycle characteristics, storage characteristics, and discharge characteristics tend to decrease, such being undesirable.
本発明においては、前記耐熱性多孔質層に、重量分率５０〜９５重量％の範囲で、無機フィラーが含まれているのが好ましい。無機フィラーとは、無機微粒子であり、その種類は特に限定されるものではないが、好ましいのは、アルミナ、チタニア、シリカ、ジルコニアなどの酸化物、炭酸塩、リン酸塩、水酸化物などである。特に、金属水酸化物が好ましい。金属水酸化物としては、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、若しくはこれらの２種以上の組合せが好適である。無機フィラーの平均粒子径は、０．１〜１μｍの範囲にあるものが好ましい。 In the present invention, it is preferable that the heat resistant porous layer contains an inorganic filler in a range of 50 to 95% by weight. The inorganic filler is an inorganic fine particle, and the kind thereof is not particularly limited, but is preferably an oxide such as alumina, titania, silica, zirconia, carbonate, phosphate, hydroxide, etc. is there. In particular, a metal hydroxide is preferable. As the metal hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, boron hydroxide, or combinations of two or more thereof are suitable. The average particle diameter of the inorganic filler is preferably in the range of 0.1 to 1 μm.
無機フィラーの量が５０〜９５重量％の範囲であると、無機フィラーは耐熱性高分子と十分になじみ、分散性も良い。また、無機フィラーの作用で、耐熱性多孔質層を水中凝固により形成させる際に、耐熱性高分子の低分子量ポリマーが凝固液中に流出しにくくなるので、好適な孔形成が可能になる。そして、後述のガーレ値や膜抵抗が更に低くなるという効果も得られる。 When the amount of the inorganic filler is in the range of 50 to 95% by weight, the inorganic filler is sufficiently compatible with the heat-resistant polymer and has good dispersibility. In addition, when the heat-resistant porous layer is formed by solidification in water due to the action of the inorganic filler, it is difficult for the low-molecular weight polymer of the heat-resistant polymer to flow out into the coagulation liquid, so that suitable pore formation is possible. And the effect that the below-mentioned Gurley value and film resistance become still lower is also acquired.
また、無機フィラーは、本発明の非水電解質電池セパレータを難燃化する上で有効に機能する。例えば、無機フィラーとして金属水酸化物を用いた場合には、金属水酸化物を加熱すると脱水反応が起こり酸化物となり、水が放出される。更に、この脱水反応は大きな吸熱を伴う反応である。この脱水反応時に水を放出することと、この反応の吸熱により、難燃効果が得られる。また、水を放出するため可燃性である電解液を水で希釈し、セパレータだけでなく電解液にも効果があり、電池そのものを難燃化する上で有効である。 The inorganic filler functions effectively in making the nonaqueous electrolyte battery separator of the present invention flame retardant. For example, when a metal hydroxide is used as the inorganic filler, when the metal hydroxide is heated, a dehydration reaction occurs to become an oxide, and water is released. Furthermore, this dehydration reaction is a reaction with a large endotherm. The release of water during this dehydration reaction and the endothermic effect of this reaction provide a flame retardant effect. In addition, an electrolyte that is flammable to release water is diluted with water and is effective not only for the separator but also for the electrolyte, and is effective in making the battery itself flame-retardant.
無機フィラーとしての金属水酸化物は、ハンドリング性の観点からも好ましい。また、金属水酸化物は、アルミナのような金属酸化物と比較して軟らかいため、従来のセパレータにあるような問題、即ち、セパレータに含まれる無機フィラーによって、製造時の各工程にて使用する部品が磨耗してしまうといった、ハンドリング性に関する問題が発生しにくいという点でも好ましい。 The metal hydroxide as the inorganic filler is also preferable from the viewpoint of handling properties. In addition, since metal hydroxide is softer than metal oxide such as alumina, it is used in each process at the time of manufacture depending on the problem with conventional separators, that is, the inorganic filler contained in the separator. It is also preferable in that a problem relating to handling properties such as wear of parts is unlikely to occur.
［非水電解質電池セパレータの製造方法］
本発明の非水電解質電池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）末端基濃度が［ＣＯＯＸ］／［ＮＨ２］＜１である芳香族ポリアミドを製造し、この耐熱性高分子を水溶性有機溶剤に溶かし塗工液を製造する工程と、（ii）得られた塗工液を、ポリオレフィン等の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高分子を凝固させる工程と、その後、（iv）水洗し乾燥する工程、を実施することからなる製造方法である。
[Method for producing non-aqueous electrolyte battery separator]
Although the manufacturing method of the nonaqueous electrolyte battery separator of this invention is not specifically limited, For example, it is possible to manufacture through the following processes (i)-(iv). That is, (i) a process for producing an aromatic polyamide having a terminal group concentration of [COOX] / [NH 2 ] <1, and dissolving the heat-resistant polymer in a water-soluble organic solvent to produce a coating liquid; ii) coating the obtained coating liquid on one or both sides of a microporous membrane made of a thermoplastic resin such as polyolefin; and (iii) coating the microporous membrane with water or water and the above It is a production method comprising performing a step of solidifying a heat-resistant polymer by immersing it in a coagulation solution comprising a mixed solution of an organic solvent, and then a step of (iv) washing and drying.
芳香族ジカルボン酸と芳香族ジアミンを、生成するポリアミドに対し良溶媒である有機溶媒中で反応せしめて芳香族ポリアミドを製造（溶液重合）した場合には、直接、前記工程（i）の塗工液を製造することができる。末端基濃度比は、香族ジカルボン酸と芳香族ジアミンの反応モル比等を変更したり、あるいは、末端封止剤を用いる方法等によって調整することができる。末端封止剤としては、アニリンなどの１級又は２級モノアミンや、無水酢酸、無水フタル酸などの有機酸の無水物、塩化アセチル、塩化ベンゾイルなどの酸クロライド、又はこれらを２種以上組み合わせたものを用いることができる。芳香族ジアミンのモル量を芳香族ジカルボン酸のそれより多くして反応させれば、一般的に、アミノ末端が多いポリマーが得られる。 When the aromatic polyamide is produced (solution polymerization) by reacting the aromatic dicarboxylic acid and the aromatic diamine in an organic solvent which is a good solvent for the polyamide to be produced, the coating in the step (i) is directly performed. A liquid can be produced. The terminal group concentration ratio can be adjusted by changing the reaction molar ratio of the aromatic dicarboxylic acid and the aromatic diamine, or by a method using a terminal blocking agent. As end-capping agents, primary or secondary monoamines such as aniline, organic acid anhydrides such as acetic anhydride and phthalic anhydride, acid chlorides such as acetyl chloride and benzoyl chloride, or a combination of two or more of these Things can be used. If the reaction is carried out with the molar amount of the aromatic diamine being larger than that of the aromatic dicarboxylic acid, a polymer having a large number of amino ends is generally obtained.
芳香族ポリアミドの中でもポリメタフェニレンイソフタルアミドを用いる方法は特に好ましく、この場合には、前記工程（i）で、イソフタル酸クロライドとメタフェニレンジアミンを、生成するポリアミドに対し良溶媒でない有機溶媒、例えば、テトラハイドロフラン中で反応せしめて溶液若しくは分散液を作り、これを、炭酸ソーダ等の酸受容剤の水溶液と接触させ反応を完結せしめる、いわゆる界面重合法でポリメタフェニレンイソフタルアミドを製造するのが便利である。そして、得られたポリメタフェニレンイソフタルアミドの水溶性有機溶剤溶液を、前記微多孔膜の片面又は両面に塗工すれば良い。界面重合法によればポリメタフェニレンイソフタルアミドの末端基濃度比の調整が容易であるので好適である。 Among aromatic polyamides, a method using polymetaphenylene isophthalamide is particularly preferred. In this case, in the step (i), an organic solvent which is not a good solvent for the polyamide to be produced, such as isophthalic acid chloride and metaphenylenediamine, for example, The polymetaphenylene isophthalamide is produced by a so-called interfacial polymerization method in which a reaction or a dispersion is made by reacting in tetrahydrofuran and this is brought into contact with an aqueous solution of an acid acceptor such as sodium carbonate to complete the reaction. Is convenient. Then, the obtained water-soluble organic solvent solution of polymetaphenylene isophthalamide may be applied to one side or both sides of the microporous membrane. The interfacial polymerization method is preferable because it is easy to adjust the terminal group concentration ratio of polymetaphenylene isophthalamide.
前記工程（i）において、芳香族ポリアミドに対し良溶媒である有機溶媒又は水溶性有機溶媒としては、特に限定されないが、具体的には極性溶媒（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全芳香族ポリアミド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。 In the step (i), the organic solvent or the water-soluble organic solvent which is a good solvent for the aromatic polyamide is not particularly limited, but specifically, a polar solvent (solvent) is preferable, for example, N-methylpyrrolidone, dimethyl Examples include acetamide, dimethylformamide, dimethyl sulfoxide and the like. Moreover, a solvent which becomes a poor solvent for the wholly aromatic polyamide may be partially 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.
耐熱性多孔質層として、重量分率で５０〜９５重量％の無機フィラーを含むものを作製する場合には、工程（i）において、全芳香族ポリアミドの溶液に無機フィラーを分散させ、塗工用スラリー（塗工液）を作製すれば良い。本発明においては、かかる塗工用スラリーも、工程（i）の塗工液の概念に含まれるものである。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し、分散性を改善する手法も適用可能である。 When producing a heat-resistant porous layer containing 50 to 95% by weight of an inorganic filler by weight fraction, in step (i), the inorganic filler is dispersed in a wholly aromatic polyamide solution, and coating is performed. A slurry for coating (coating solution) may be prepared. In the present invention, such a coating slurry is also included in the concept of the coating liquid in the step (i). When the dispersibility of the inorganic filler is not good, a method of improving the dispersibility by surface-treating the inorganic filler with a silane coupling agent or the like is also applicable.
工程（ii）では、微多孔膜の少なくとも一方の表面に芳香族ポリアミド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。塗工液の濃度は４〜９重量％、微多孔膜への塗工量は２〜３ｇ／ｍ２程度が好ましい。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芳香族ポリアミド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), an aromatic polyamide 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. The concentration of the coating solution is preferably 4 to 9% by weight, and the coating amount on the microporous membrane is preferably about 2 to 3 g / m 2 . 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, when an aromatic polyamide coating solution is applied to both sides of a polyethylene microporous membrane, the coating solution is excessively applied to both sides of the polyethylene microporous membrane 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、芳香族ポリアミドを凝固させることが可能な凝固液中に浸漬することで、芳香族ポリアミドを凝固させ、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、芳香族ポリアミド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媒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％より少ないと芳香族ポリアミド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 step (iii), the coated microporous membrane is immersed in a coagulating liquid capable of coagulating the aromatic polyamide, thereby coagulating the aromatic polyamide and 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 the aromatic polyamide can be coagulated, but water or an organic solvent used for the coating liquid is preferably mixed with an appropriate amount. 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 coagulating the aromatic polyamide becomes long or coagulation becomes insufficient. On the other hand, if 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 too rapidly solidified to make the surface 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 a drying temperature of 50 to 80 ° C. is appropriate. When a high drying temperature is applied, a method of contacting with a roll in order to prevent a dimensional change due to heat shrinkage occurs. It is preferable to apply.
［非水電解質電池］
非水電解質電池セパレータが、前記のような熱可塑性樹脂を主として形成された微多孔膜と、その片面又は両面に積層された前記のような芳香族ポリアミドを主として形成された耐熱性多孔質層とからなるものである限り、本発明の非水電解質電池セパレータは、公知のいかなる構成の非水電解質電池にも適用することができ、安全性に優れた電池が得られる。適用される非水電解質電池は一次電池であっても二次電池であっても良く、その種類や構成は、何ら限定されるものではないが、本発明の非水電解質電池セパレータは、リチウムのドープ・脱ドープにより起電力を得る非水電解質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。
[Nonaqueous electrolyte battery]
The nonaqueous electrolyte battery separator is a microporous membrane mainly formed of the thermoplastic resin as described above, and a heat resistant porous layer mainly formed of the aromatic polyamide as described above laminated on one or both sides thereof. The nonaqueous electrolyte battery separator of the present invention can be applied to any known nonaqueous electrolyte battery of any configuration, and a battery having excellent safety can be obtained. The applied nonaqueous electrolyte battery may be a primary battery or a secondary battery, and the type and configuration of the nonaqueous electrolyte battery are not limited in any way. It can be suitably applied to a non-aqueous electrolyte secondary battery that obtains an electromotive force by doping and dedoping. Among these, application to a lithium ion secondary battery is preferable.
一般に非水電解質二次電池とは、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、スズかが用いられる。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。外装材は金属缶また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 nonaqueous electrolyte secondary battery refers to a battery element in which a battery element in which a negative electrode and a positive electrode face each other with a separator interposed therebetween is impregnated with an electrolytic solution and sealed 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。なお、本発明における各種の測定方法は、以下の通りである。 Hereinafter, the present invention will be described in detail by way of examples. Various measurement methods in the present invention are as follows.
［末端基濃度の測定］
１重量の％ポリマーと０．０５％重量の塩化リチウムを含むＤＭＦ溶液を測定サンプルとして用い、島津クロマトパックＣ−Ｒ４ＡおよびＯＤＳ（OctaDecylSilyl）カラムを使用して、検出波長２８０ｎｍで測定した。評価するポリマーは、ポリマー製造後のポリマー、あるいは、セパレータに組み込まれた耐熱層から採取した。セパレータに組み込まれた耐熱層からｍ−アラミドの分子量分布を測定する方法としては、先ずセパレータ１ｇをサンプリングし、ＬｉＣｌを０．０１モル／Ｌ溶解させたＤＭＦ２０ｇを加えて、８０℃でｍ−アラミドだけを溶解させ測定サンプルとした。
[Measurement of end group concentration]
Using a DMF solution containing 1% by weight of polymer and 0.05% by weight of lithium chloride as a measurement sample, measurement was performed at a detection wavelength of 280 nm using Shimadzu Chromatopack C-R4A and an ODS (OctaDecylSilyl) column. The polymer to be evaluated was collected from the polymer after polymer production or from the heat-resistant layer incorporated in the separator. As a method for measuring the molecular weight distribution of m-aramid from the heat-resistant layer incorporated in the separator, first, 1 g of the separator was sampled, 20 g of DMF in which 0.01 mol / L of LiCl was dissolved was added, and m-aramid was added at 80 ° C. Only a sample was dissolved and used as a measurement sample.
［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.
［突刺強度］
カトーテック社製ＫＥＳ−Ｇ５ハンディー圧縮試験器を用いて、針先端の曲率半径０．５ｍｍ、突刺速度２ｍｍ／ｓｅｃの条件で突刺試験を行い、最大突刺荷重を突刺強度とした。ここでサンプルはΦ１１．３ｍｍの穴があいた金枠（試料ホルダー）にシリコンゴム製のパッキンも一緒に挟み固定した。
[Puncture strength]
Using a KES-G5 handy compression tester manufactured by Kato Tech Co., Ltd., a piercing test was conducted under the conditions of a radius of curvature of the needle tip of 0.5 mm and a piercing speed of 2 mm / sec, and the maximum piercing load was defined as the piercing strength. Here, the sample was fixed by sandwiching a silicon rubber packing in a metal frame (sample holder) having a hole of Φ11.3 mm.
［無機フィラーの平均粒子径］
レーザー回折式粒度分布測定装置（シスメックス社製、マスターサイザー２０００）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 inorganic filler]
Measurement was performed using a laser diffraction particle size distribution analyzer (manufactured by Sysmex Corporation, Mastersizer 2000). Water was used as a dispersion medium, and a small amount of a 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.
［実施例１］
１）ポリメタフェニレンイソフタルアミドの製造
イソフタル酸クロライド１６０．５ｇをテトラヒドロフラン１１２０ｍｌに溶解し、撹拌しながら、メタフェニレンジアミン８６．４ｇをテトラヒドロフラン１１２０ｍｌに溶解した溶液を、細流として徐々に加えていくと白濁した乳白色の溶液が得られた。撹拌を約５分間継続した後、更に撹拌しながら炭酸ソーダ１６７．６ｇ、食塩３１７ｇを３４００ｍｌの水に溶かした水溶液を速やかに加え、５分間撹拌した。反応系は数秒後に粘度が増大後、再び低下し、白色の懸濁液が得られた。これを静置し、分離した透明な水溶液層を取り除き、ろ過によってポリメタフェニレンイソフタルアミドの白色重合体１８５．０ｇが得られた。ポリアミドの末端基濃度比は、［ＣＯＯＸ］／［ＮＨ２］＝０．８であった。
[Example 1]
1) Production of polymetaphenylene isophthalamide When 160.5 g of isophthalic acid chloride is dissolved in 1120 ml of tetrahydrofuran and stirred, a solution of 86.4 g of metaphenylenediamine in 1120 ml of tetrahydrofuran is gradually added as a trickle and becomes cloudy. A milky white solution was obtained. Stirring was continued for about 5 minutes, and then an aqueous solution in which 167.6 g of sodium carbonate and 317 g of sodium chloride were dissolved in 3400 ml of water was rapidly added while stirring for 5 minutes. The reaction system increased in viscosity after a few seconds and then decreased again to obtain a white suspension. This was left still, the separated transparent aqueous solution layer was removed, and 185.0 g of a white polymer of polymetaphenylene isophthalamide was obtained by filtration. The terminal group concentration ratio of the polyamide was [COOX] / [NH 2 ] = 0.8.
２）ポリエチレン多孔膜の製造
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（松村石油研究所社製；スモイルP−３５０P；沸点４８０℃）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。この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）であった。
2) Manufacture of a polyethylene porous membrane As polyethylene powder, 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) by a Ticona company were used. GUR2126 and GURX143 are made to be 1: 9 (weight ratio), and liquid paraffin (manufactured by Matsumura Oil Research Co., Ltd .; Smoyl P-350P; boiling point 480 ° C.) and decalin so that the polyethylene concentration becomes 30% by weight A polyethylene solution was prepared by dissolving in a mixed solvent. The composition of this polyethylene solution was polyethylene: liquid paraffin: decalin = 30: 45: 25 (weight ratio).
このポリエチレン溶液を１４８℃でダイから押し出し、水浴中で冷却してゲル状テープ（ベーステープ）を作製した。このベーステープを６０℃で８分、９５℃で１５分乾燥し、次いで、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℃でアニール処理しポリエチレン微多孔膜を得た。膜厚は１２μｍ、空孔率３７％、ガーレ値３０１ｓｅｃ／１００ｃｃ、膜抵抗２．６ｏｈｍ・ｃｍ２、突刺し強度３７５ｇであった。 This polyethylene solution was extruded from a die at 148 ° C. and cooled in a water bath to prepare a gel tape (base tape). The base tape was dried at 60 ° C. for 8 minutes and at 95 ° C. for 15 minutes, and then the base tape was stretched by biaxial stretching that was performed in the order of 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 annealed at 120 degreeC, and obtained the polyethylene microporous film. The film thickness was 12 μm, the porosity was 37%, the Gurley value was 301 sec / 100 cc, the film resistance was 2.6 ohm · cm 2 , and the puncture strength was 375 g.
３）非水電解質電池セパレータの製造
前記で得られたポリメタフェニレンイソフタルアミドとポリエチレン多孔膜を用い、そして、これに無機フィラーを併用して、本発明の非水電解質電池セパレータを製造した。
具体的には、ポリメタフェニレンイソフタルアミドと平均粒子径０．８μｍの水酸化アルミニウム（昭和電工社製；Ｈ−４３Ｍ）からなる無機フィラーが、重量比で２５：７５となるように調整し、これらをポリメタフェニレンイソフタルアミド濃度が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。
3) Production of Nonaqueous Electrolyte Battery Separator The polymetaphenylene isophthalamide obtained above and a polyethylene porous membrane were used, and an inorganic filler was used in combination with this to produce the nonaqueous electrolyte battery separator of the present invention.
Specifically, an inorganic filler composed of polymetaphenylene isophthalamide and aluminum hydroxide having an average particle size of 0.8 μm (Showa Denko KK; H-43M) is adjusted so that the weight ratio is 25:75. These were mixed in a mixed solvent in which dimethylacetamide (DMAc) and tripropylene glycol (TPG) had a weight ratio of 50:50 so that the polymetaphenylene isophthalamide concentration was 5.5% by weight. A slurry was obtained.
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して、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。そして、塗工されたものを、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、ポリエチレン微多孔膜の両面（表裏面）にポリメタフェニレンイソフタルアミドからなる耐熱性多孔質層を形成し、本発明の非水電解質電池セパレータを得た。得られた非水電解質電池セパレータの平均膜厚は２０μｍであった。 A pair of Meyer bars (count # 6) was opposed to each other with a clearance of 20 μm. An appropriate amount of the above slurry for coating was placed on a Mayer bar, a polyethylene microporous membrane was passed between a pair of Mayer bars, and the coating slurry was coated on both sides of the polyethylene microporous membrane. And what was coated was immersed in the coagulating liquid which is 40 degreeC by water: DMAc: TPG = 50: 25: 25 by weight ratio. Next, washing with water and drying were performed to form a heat-resistant porous layer made of polymetaphenylene isophthalamide on both surfaces (front and back surfaces) of the polyethylene microporous membrane, thereby obtaining the nonaqueous electrolyte battery separator of the present invention. The average film thickness of the obtained nonaqueous electrolyte battery separator was 20 μm.
［実施例２］
１）正極
コバルト酸リチウム（ＬｉＣｏＯ2、日本化学工業社製）粉末８９．５重量部と、アセチレンブラック４．５重量部及びＰＶｄＦの乾燥重量が６重量部となるように、６重量％のＰＶｄＦのＮＭＰ溶液を用い、正極剤ペーストを作製した。得られたペーストを、厚さ２０μｍのアルミ箔上に塗布乾燥後プレスして、厚さ９７μｍの正極を得た。
[Example 2]
1) Positive electrode 6 wt% PVdF so that the lithium cobalt oxide (LiCoO 2 , Nippon Chemical Industry Co., Ltd.) powder 89.5 parts by weight, acetylene black 4.5 parts by weight and PVdF dry weight 6 parts by weight. A positive electrode paste was prepared using the NMP solution. The obtained paste was applied onto an aluminum foil having a thickness of 20 μm, dried and pressed to obtain a positive electrode having a thickness of 97 μm.
２）負極
負極活物質としてメソフェーズカーボンマイクロビーズ（ＭＣＭＢ、大阪瓦斯化学社製）粉末８７重量部と、アセチレンブラック３重量部及びＰＶｄＦの乾燥重量が１０重量部となるように、６重量％のＰＶｄＦのＮＭＰ溶液を用い、負極剤ペーストを作製した。得られたペーストを、厚さ１８μｍの銅箔上に塗布乾燥後プレスして、厚さ９０μｍの負極を作製した。
2) Negative electrode 6 wt% PVdF so that the dry weight of mesophase carbon microbeads (MCMB, manufactured by Osaka Gas Chemical Co., Inc.) powder 87 parts by weight, acetylene black 3 parts by weight and PVdF 10 parts by weight as the negative electrode active material. An NMP solution was used to prepare a negative electrode agent paste. The obtained paste was applied onto a copper foil having a thickness of 18 μm, dried and pressed to prepare a negative electrode having a thickness of 90 μm.
３）ボタン電池の作製
実施例１で作製した複合多孔膜をセパレータとし、上記の正極及び負極を用いて容量が４．５ｍＡｈ程度のボタン電池（ＣＲ２０３２）を作製した。電解液には１Ｍ ＬｉＰＦ6 ＥＣ／ＤＥＣ／ＭＥＣ（１／２／１重量比）を用いた。作製したボタン電池は問題なく充放電可能であった。このボタン電池の４．２Ｖ定電流・定電圧充電、２．７５Ｖ定電流放電を１００サイクル繰り返した後に、分解してセパレータの突刺し強度を測定したところ、４３０ｇであった。
3) Production of Button Battery A button battery (CR2032) having a capacity of about 4.5 mAh was produced using the composite porous membrane produced in Example 1 as a separator and the above positive electrode and negative electrode. As the electrolytic solution, 1M LiPF 6 EC / DEC / MEC (1/2/1 weight ratio) was used. The manufactured button battery could be charged and discharged without any problem. The button battery was subjected to 4.2 V constant current / constant voltage charging and 2.75 V constant current discharging for 100 cycles, and then decomposed and measured for the puncture strength of the separator.
［実施例３］
温度計、撹拌装置及び原料投入口を備えた反応容器に、水分率が１００ｐｐｍ以下のＮＭＰ７５３ｇを入れ、このＮＭＰ中にメタフェニレンジアミン８６．４ｇを溶解し、０℃に冷却した。この冷却したジアミン溶液にイソフタル酸クロライド１６０．５ｇを撹拌しながら徐々に添加し反応させた。この反応で溶液の温度は７０℃に上昇した。粘度変化が止まった後、水酸化カルシウム粉末を５８．４ｇ添加し、さらに４０分間撹拌して反応を終了させて重合溶液を取り出し、水中で再沈殿させポリメタフェニレンイソフタルアミドを１８４．０ｇ得た。ポリアミドの末端基濃度比は、［ＣＯＯＸ］／［ＮＨ２］＝０．８であった。
[Example 3]
In a reaction vessel equipped with a thermometer, a stirrer, and a raw material inlet, 753 g of NMP having a moisture content of 100 ppm or less was placed, 86.4 g of metaphenylenediamine was dissolved in this NMP, and cooled to 0 ° C. To this cooled diamine solution, 160.5 g of isophthalic acid chloride was gradually added with stirring to react. This reaction increased the temperature of the solution to 70 ° C. After the change in viscosity stopped, 58.4 g of calcium hydroxide powder was added and stirred for another 40 minutes to complete the reaction, and the polymerization solution was taken out and reprecipitated in water to obtain 184.0 g of polymetaphenylene isophthalamide. . The terminal group concentration ratio of the polyamide was [COOX] / [NH 2 ] = 0.8.
これを用いて実施例１の場合と同様にして、平均膜厚２０μｍの非水電解質電池セパレータを得た。そして、得られたセパレータを用いて実施例２の場合と同様にしてボタン電池を作製し、４．２Ｖ定電流・定電圧充電、２．７５Ｖ定電流放電を１００サイクル繰り返した後に、分解してセパレータの突刺し強度を測定したところ、４３０ｇであった。 Using this, in the same manner as in Example 1, a nonaqueous electrolyte battery separator having an average film thickness of 20 μm was obtained. Then, using the obtained separator, a button battery was produced in the same manner as in Example 2, and 4.2V constant current / constant voltage charging and 2.75V constant current discharging were repeated 100 cycles, then disassembled. The puncture strength of the separator was measured and found to be 430 g.
［比較例１］
メタフェニレンジアミン８４．９ｇをテトラヒドロフラン１１２０ｍｌに溶解した溶液を用いた以外は、実施例１と同様にして、ポリメタフェニレンイソフタルアミドの白色重合体１８５．３ｇを得た。ポリアミドの末端基濃度比は、［ＣＯＯＸ］／［ＮＨ２］＝２．２であった。
[Comparative Example 1]
185.3 g of a white polymer of polymetaphenylene isophthalamide was obtained in the same manner as in Example 1 except that a solution obtained by dissolving 84.9 g of metaphenylenediamine in 1120 ml of tetrahydrofuran was used. The terminal group concentration ratio of the polyamide was [COOX] / [NH 2 ] = 2.2.
これを用いて実施例1の場合と同様にして、平均膜厚は２０μｍの非水電解質電池セパレータを得た。そして、得られたセパレータを用いて実施例２の場合と同様にしてボタン電池を作製し、４．２Ｖ定電流・定電圧充電、２．７５Ｖ定電流放電を１００サイクル繰り返した後に、分解してセパレータの突刺し強度を測定したところ、３８０ｇであった。 Using this, a nonaqueous electrolyte battery separator having an average film thickness of 20 μm was obtained in the same manner as in Example 1. Then, using the obtained separator, a button battery was produced in the same manner as in Example 2, and 4.2V constant current / constant voltage charging and 2.75V constant current discharging were repeated 100 cycles, then disassembled. The puncture strength of the separator was measured and found to be 380 g.
Claims (10)
前記芳香族ポリアミドの末端基濃度比が、［ＣＯＯＸ］／［ＮＨ２］＜１（Ｘは、水素、アルカリ金属又はアルカリ土類金属を表す）である
ことを特徴とする非水電解質電池セパレータ。 A non-aqueous electrolyte battery comprising a microporous membrane formed mainly of a thermoplastic resin and having a shutdown function, and a heat-resistant porous layer formed mainly of an aromatic polyamide and laminated on one or both surfaces of the microporous membrane A separator,
The non-aqueous electrolyte battery separator, wherein the aromatic polyamide has a terminal group concentration ratio of [COOX] / [NH 2 ] <1 (X represents hydrogen, alkali metal or alkaline earth metal).
ことを特徴とする請求項１記載の非水電解質電池セパレータ。 The non-aqueous electrolyte battery separator according to claim 1.
ことを特徴とする請求項２に記載の非水電解質電池セパレータ。 The nonaqueous electrolyte battery separator according to claim 2.
ことを特徴とする請求項１〜３のいずれか１項記載の非水電解質電池セパレータ。 The nonaqueous electrolyte battery separator according to any one of claims 1 to 3.
ことを特徴とする請求項４記載の非水電解質電池セパレータ。 The nonaqueous electrolyte battery separator according to claim 4.
ことを特徴とする請求項１〜５のいずれか１項記載の非水電解質電池セパレータ。 The nonaqueous electrolyte battery separator according to any one of claims 1 to 5, wherein
ことを特徴とする請求項１〜６のいずれか１項記載の非水電解質電池セパレータ。 The nonaqueous electrolyte battery separator according to claim 1, wherein the nonaqueous electrolyte battery separator is a nonaqueous electrolyte battery separator.
（i）メタ型芳香族ジカルボン酸ハライドとメタ型芳香族ジアミンを、生成するポリアミドに対し良溶媒でない有機溶媒中で反応せしめて溶液若しくは分散液を作り、これを酸受容剤の水溶液と接触させ反応を完結せしめて、末端基濃度比が［ＣＯＯＸ］／［ＮＨ (I) A meta-type aromatic dicarboxylic acid halide and a meta-type aromatic diamine are reacted in an organic solvent that is not a good solvent for the resulting polyamide to form a solution or dispersion, which is brought into contact with an acid acceptor aqueous solution. When the reaction is completed, the terminal group concentration ratio is [COOX] / [NH ２2 ］＜１（Ｘは、水素、アルカリ金属又はアルカリ土類金属を表す）であるメタ型芳香族ポリアミドを製造する工程と、] Producing a meta-type aromatic polyamide in which <1 (X represents hydrogen, an alkali metal or an alkaline earth metal);
（ii）得られたメタ型芳香族ポリアミドの水溶性有機溶剤溶液を、前記微多孔膜の片面又は両面に塗工する工程と、 (Ii) applying a water-soluble organic solvent solution of the obtained meta-type aromatic polyamide to one or both surfaces of the microporous membrane;
（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、メタ型芳香族ポリアミドを凝固させる工程と、 (Iii) immersing the coated microporous membrane in a coagulation liquid comprising water or a mixture of water and the organic solvent to coagulate the meta-type aromatic polyamide;
（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 (Iv) performing the step of washing and drying the microporous membrane after the coagulation step.
ことを特徴とする非水電解質電池セパレータの製造方法。 A method for producing a non-aqueous electrolyte battery separator.
（i）芳香族ジカルボン酸ハライドと芳香族ジアミンを、生成するポリアミドに対し良溶媒である有機溶媒中で反応せしめて、末端基濃度比が［ＣＯＯＸ］／［ＮＨ (I) The aromatic dicarboxylic acid halide and the aromatic diamine are reacted with the produced polyamide in an organic solvent which is a good solvent, and the terminal group concentration ratio is [COOX] / [NH ２2 ］＜１（Ｘは、水素、アルカリ金属又はアルカリ土類金属を表す）である芳香族ポリアミドを製造する工程と、] Producing an aromatic polyamide wherein <1 (X represents hydrogen, alkali metal or alkaline earth metal);
（ii）得られた芳香族ポリアミドの水溶性有機溶剤溶液を、前記微多孔膜の片面又は両面に塗工する工程と、 (Ii) applying a water-soluble organic solvent solution of the obtained aromatic polyamide to one or both surfaces of the microporous membrane;
（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芳香族ポリアミドを凝固させる工程と、 (Iii) a step of solidifying the aromatic polyamide by immersing the coated microporous membrane in a coagulation liquid comprising water or a mixture of water and the organic solvent;
（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 (Iv) performing the step of washing and drying the microporous membrane after the coagulation step.
ことを特徴とする非水電解質電池セパレータの製造方法。 A method for producing a non-aqueous electrolyte battery separator.
請求項１〜７のいずれか１項記載の非水電解質電池セパレータを用いた The nonaqueous electrolyte battery separator according to any one of claims 1 to 7 was used.
ことを特徴とする非水電解質二次電池。 A non-aqueous electrolyte secondary battery.
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