JP5040058B2 - Porous membrane, method for producing the same, and lithium ion secondary battery using the same - Google Patents
Porous membrane, method for producing the same, and lithium ion secondary battery using the same Download PDFInfo
- Publication number
- JP5040058B2 JP5040058B2 JP2004279617A JP2004279617A JP5040058B2 JP 5040058 B2 JP5040058 B2 JP 5040058B2 JP 2004279617 A JP2004279617 A JP 2004279617A JP 2004279617 A JP2004279617 A JP 2004279617A JP 5040058 B2 JP5040058 B2 JP 5040058B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamideimide resin
- lithium ion
- ion secondary
- porous membrane
- separator
- 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.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000004962 Polyamide-imide Substances 0.000 claims description 77
- 229920002312 polyamide-imide Polymers 0.000 claims description 77
- 239000011347 resin Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 63
- 229920000098 polyolefin Polymers 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- 230000009477 glass transition Effects 0.000 claims description 15
- 230000035699 permeability Effects 0.000 claims description 13
- 239000000539 dimer Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920001281 polyalkylene Polymers 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 22
- 239000002131 composite material Substances 0.000 description 19
- -1 Aliphatic dicarboxylic acids Chemical class 0.000 description 13
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000005442 diisocyanate group Chemical group 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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
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Description
本発明は、安全性の改善が要求されているリチウムイオン二次電池のセパレーターとして、優れたシャットダウン温度特性及び高いメルトダウン温度特性を示すポリアミドイミド多孔質膜、その製造方法及びこれを用いたリチウムイオン二次電池に関する。 The present invention relates to a polyamide-imide porous membrane that exhibits excellent shutdown temperature characteristics and high meltdown temperature characteristics as a separator for lithium ion secondary batteries that are required to improve safety, a method for producing the same, and lithium using the same The present invention relates to an ion secondary battery.
近年、電子携帯機器の発達により、高エネルギー密度、高起電力の電池が開発されている。それらの中でも高起電力の点から非水電解液電池、特にリチウムイオン二次電池が精力的に開発されている。このような非水電解液電池の問題点の1つに可燃性有機溶媒を用いるがための危険性が指摘されている。電池の両極が短絡、電池内容物の分解反応を起こした場合、電池内部の急激な温度上昇により、内容物が噴出したりする。この様な問題に対して現在、安全弁の取り付け、溶融性成分含有のセパレーターによるシャットダウン機能付与などが挙げられる。 In recent years, with the development of electronic portable devices, batteries with high energy density and high electromotive force have been developed. Among them, nonaqueous electrolyte batteries, particularly lithium ion secondary batteries, have been vigorously developed from the viewpoint of high electromotive force. One of the problems with such non-aqueous electrolyte batteries is the danger of using flammable organic solvents. When both electrodes of the battery are short-circuited and a decomposition reaction of the battery contents occurs, the contents are ejected due to a rapid temperature rise inside the battery. In order to solve such problems, there are currently attachment of a safety valve and provision of a shutdown function by a separator containing a meltable component.
しかしながら安全弁は短絡に対する本質的な防護策ではなく、電池内部の急激な圧力上昇を緩和するだけのものである。 However, the safety valve is not an essential protective measure against a short circuit, but only relieves a sudden pressure increase inside the battery.
一方、セパレーターのシャットダウン機能は熱溶融性材料を用いた多孔質膜を用いることにより、短絡などにより電池内部の温度がある一定の温度に達したときに、材料の熱溶融により多孔質膜の穴が塞がることにより、イオン導電性が妨げられ発熱の原因となる電池反応を抑えるというものである。このようなセパレーターは、特許文献1〜3等に示されているオレフィン系高分子材料の多孔質膜が開示されている。しかしながら、このような熱溶融性材料を用いた場合、熱上昇でシャットダウン機能が働いても更なる温度上昇がある場合、膜自体が溶融して本来の機能である電極間の隔離が損なわれてしまう。これはメルトダウンと呼ばれる現象であり電池としては好ましくない。このような問題点の改善策としてシャットダウン温度の範囲を広げることが提案されている。例えば特許文献4〜7等に示されるように多孔質膜、不織布基材に熱溶融性材料を積層、コーテイングするなどの技術である。しかしながらこれらの作成手法は煩雑になる場合があることと必ずしもシャットダウン時の絶縁性が十分なものが得られてはいない。 On the other hand, the shutdown function of the separator uses a porous film made of a heat-meltable material. When the temperature inside the battery reaches a certain temperature due to a short circuit or the like, By blocking, the ionic conductivity is hindered and the battery reaction that causes heat generation is suppressed. As such a separator, a porous membrane of an olefin polymer material disclosed in Patent Documents 1 to 3 is disclosed. However, when such a heat-meltable material is used, even if the shutdown function works due to heat rise, if there is a further temperature rise, the film itself melts and the isolation between the electrodes, which is the original function, is impaired. End up. This is a phenomenon called meltdown, which is not preferable for a battery. It has been proposed to widen the range of the shutdown temperature as a remedy for such problems. For example, as disclosed in Patent Documents 4 to 7 and the like, it is a technique of laminating and coating a heat-meltable material on a porous film or a nonwoven fabric substrate. However, these preparation methods may be complicated and an insulation property at the time of shutdown is not necessarily obtained.
本発明はかかる事情に鑑みてなされたものであって、従来使用されている多孔膜セパレーターに代わるシャットダウン特性及びメルトダウン特性が良好で絶縁性に優れた安価なセパレーターを提供することを目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide an inexpensive separator that has excellent shutdown characteristics and melt-down characteristics, which are superior to conventional porous membrane separators, and is excellent in insulation. .
本発明は上記目的を達成するために、鋭意検討を重ねた結果、多孔質のポリアミドイミド樹脂製膜を単独又は他の材料と組み合わせてセパレーターとして使用することにより、安全性、サイクル耐久性に優れたリチウムイオン二次電池が得られることを見出した。即ち本発明は以下の多孔質膜とその製造法及びこれを用いたリチウムイオン二次電池である。 As a result of intensive studies to achieve the above object, the present invention is excellent in safety and cycle durability by using a porous polyamideimide resin film alone or in combination with other materials as a separator. It was found that a lithium ion secondary battery was obtained. That is, this invention is the following porous membrane, its manufacturing method, and a lithium ion secondary battery using the same.
(1)ガラス転移温度が70℃以上、対数粘度が0.5dl/g以上で、下記構造式(I)及び(II)を必須成分としたポリアミドイミド樹脂層を含む、全体の膜厚が5〜100μmの多孔質膜。
(2)ポリアミドイミド樹脂の酸成分の一部が、ダイマー酸、ポリアルキレンエーテル、ポリエステル並びに末端にカルボキシル基、水酸基及びアミノ基のいずれかを含有するブタジエン系ゴムからなる群のうち少なくとも1種で置き換えられた共重合ポリアミドイミド樹脂である請求項1に記載の多孔質膜。 (2) A part of the acid component of the polyamide-imide resin is at least one selected from the group consisting of dimer acid, polyalkylene ether, polyester, and butadiene rubber containing any one of carboxyl group, hydroxyl group and amino group at the terminal. The porous membrane according to claim 1, which is a substituted copolymerized polyamideimide resin.
(3)(1)または(2)に記載の多孔質膜において、ポリアミドイミド樹脂層とポリオレフィン系多孔質膜とを組み合わせたことを特徴とする複合多孔質膜。 (3) A composite porous membrane according to (1) or (2), wherein a polyamideimide resin layer and a polyolefin-based porous membrane are combined.
(4)透気度が1〜2000sec/100ccAirである請求項1〜3のいずれかに記載の多孔質膜。 (4) The porous film according to any one of claims 1 to 3, which has an air permeability of 1 to 2000 sec / 100 cc Air.
(5)請求項1〜4のいずれかに記載の多孔質膜を、リチウムイオンを吸蔵、放出可能な正極および負極の間にセパレーターとして介装してなるリチウムイオン二次電池。 (5) A lithium ion secondary battery comprising the porous film according to any one of claims 1 to 4 interposed as a separator between a positive electrode and a negative electrode capable of inserting and extracting lithium ions.
(6)請求項1または2に記載のポリアミドイミド樹脂溶液を基材に塗布又は浸漬した後、ポリアミドイミド樹脂を溶解した溶剤とは混和するが、ポリアミドイミド樹脂に対しては貧溶剤である溶液中に投入して凝固させる多孔質膜の製造方法。 (6) After applying or immersing the polyamideimide resin solution according to claim 1 or 2 on a substrate, the solution is miscible with the solvent in which the polyamideimide resin is dissolved, but is a poor solvent for the polyamideimide resin. A method for producing a porous membrane that is solidified by being introduced into the inside.
(7)ポリオレフィン系多孔質膜の片面又は両面に請求項1又は2に記載のポリアミドイミド樹脂溶液を塗布又は浸漬した後、ポリアミドイミド樹脂を溶解した溶剤と混和するが、ポリアミドイミド樹脂に対しては貧溶剤である溶液中に投入して凝固させる複合多孔質膜の製造方法。 (7) After applying or immersing the polyamideimide resin solution according to claim 1 or 2 on one or both surfaces of the polyolefin-based porous membrane, it is mixed with a solvent in which the polyamideimide resin is dissolved. Is a method for producing a composite porous membrane that is poured into a poor solvent and solidified.
本発明は、特定構造を有するポリアミドイミド樹脂の多孔質膜又はポリアミドイミド樹脂の多孔質膜とポリオレフィン膜を積層した複合多孔質膜を用いることによりシャットダウン特性とメルトダウン特性のバランスに優れたリチウムイオン二次電池用セパレーターを提供できる。 The present invention provides lithium ion excellent in balance between shutdown characteristics and meltdown characteristics by using a polyamideimide resin porous film having a specific structure or a composite porous film in which a polyamideimide resin porous film and a polyolefin film are laminated. A separator for a secondary battery can be provided.
以下本発明を詳細に説明する。本発明に用いられるポリアミドイミド樹脂は下記構造式(I)と(II)を必須成分とするものである。式(I)と式(II)の合計量は全成分の合計を100モル%としたとき、20モル%以上が好ましく、より好ましくは40モル%以上、さらに好ましくは50モル%以上、最も好ましくは60モル%以上である。 The present invention will be described in detail below. The polyamideimide resin used in the present invention contains the following structural formulas (I) and (II) as essential components. The total amount of the formula (I) and the formula (II) is preferably 20 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, most preferably, when the total of all components is 100 mol%. Is 60 mol% or more.
ここで式(I)と式(II)のモル比率は90/10〜10/90の範囲、好ましくは85/15〜30/70、更に好ましくは80/20〜50/50の範囲である。式(I)の比率が90以上では溶剤溶解性が低下して安定な溶液が得られないことがあり、また、10以下では多孔質膜にしたときの強度が不足することがあるからである。 Here, the molar ratio of the formula (I) and the formula (II) is in the range of 90/10 to 10/90, preferably in the range of 85/15 to 30/70, and more preferably in the range of 80/20 to 50/50. This is because when the ratio of formula (I) is 90 or more, the solvent solubility is lowered and a stable solution may not be obtained, and when it is 10 or less, the strength when formed into a porous film may be insufficient. .
一般に、ポリアミドイミド樹脂の合成はトリメリット酸クロリドとジアミンを用いる酸クロリド法やトリメリット酸無水物とジイソシアネートを用いるジイソシアネート法等の通常の方法で合成されるが製造コストの点からジイソシアネート法が好ましい。 In general, the polyamideimide resin is synthesized by a conventional method such as an acid chloride method using trimellitic acid chloride and diamine or a diisocyanate method using trimellitic anhydride and diisocyanate, but the diisocyanate method is preferable from the viewpoint of production cost. .
本発明におけるポリアミドイミド樹脂の合成に用いられる酸成分はトリメリット酸無水物(クロリド)であるが、その一部を他の多塩基酸またはその無水物に置き換えることができる。例えば、ピロメリット酸、ビフェニルテトラカルボン酸、ビフェニルスルホンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ビフェニルエーテルテトラカルボン酸、エチレングリコールビストリメリテート、プロピレングリコールビストリメリテート等のテトラカルボン酸及びこれらの無水物、シュウ酸、アジピン酸、マロン酸、セバチン酸、アゼライン酸、ドデカンジカルボン酸、ジカルボキシポリブタジエン、ジカルボキシポリ(アクリロニトリル−ブタジエン)、ジカルボキシポリ(スチレン−ブタジエン)等の脂肪族ジカルボン酸、1,4−シクロヘキサンジカルボン酸、1,3−シクロヘキサンジカルボン酸、4,4’−ジシクロヘキシルメタンジカルボン酸、ダイマー酸等の脂環族ジカルボン酸、テレフタル酸、イソフタル酸、ジフェニルスルホンジカルボン酸、ジフェニルエーテルジカルボン酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸が挙げられる。これらの中で耐電解液性の点からは1,3−シクロヘキサンジカルボン酸、1,4−シクロヘキサンジカルボン酸が好ましく、シャットダウン特性からダイマー酸、分子量が1000以上のジカルボキシポリブタジエン、ジカルボキシポリ(アクリロニトリルブタジエン)、ジカルボキシポリ(スチレンーブタジエン)が好ましい。 Although the acid component used for the synthesis | combination of the polyamideimide resin in this invention is trimellitic anhydride (chloride), the one part can be substituted by another polybasic acid or its anhydride. For example, tetracarboxylic acids such as pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, ethylene glycol bistrimellitate, propylene glycol bistrimellitate and their anhydrides, Aliphatic dicarboxylic acids such as oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene), 1,4 -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethanedicarboxylic acid, alicyclic dicarboxylic acids such as dimer acid, terephthalic acid, Le acid, diphenyl sulfone dicarboxylic acid, diphenylether dicarboxylic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid. Among these, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid are preferable from the viewpoint of the resistance to electrolytic solution, and dimer acid, dicarboxypolybutadiene having a molecular weight of 1000 or more and dicarboxypoly (acrylonitrile) from the shutdown characteristics. Butadiene) and dicarboxypoly (styrene-butadiene) are preferred.
また、トリメリット酸化合物の一部をグリコールに置き換えてウレタン基を分子内に導入することもできる。グリコールとしてはエチレングリコール、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール、ヘキサンジオール等のアルキレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリアルキレングリコールや上記ジカルボン酸の1種又は2種以上と上記グリコールの1種又は2種以上とから合成される末端水酸基のポリエステル等が挙げられ、これらの中ではシャットダウン効果からポリエチレングリコール、末端水酸基のポリエステルが好ましい。また、これらの数平均分子量は500以上が好ましく、1000以上がより好ましい。上限は特に限定されないが8000未満が好ましい。 In addition, a urethane group can be introduced into the molecule by replacing part of the trimellitic acid compound with glycol. Examples of glycols include alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, and hexanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and one or more of the above dicarboxylic acids. And polyesters having terminal hydroxyl groups synthesized from one or two or more of the above-mentioned glycols. Among these, polyethylene glycol and polyesters having terminal hydroxyl groups are preferred because of the shutdown effect. Moreover, these number average molecular weights are preferably 500 or more, and more preferably 1000 or more. The upper limit is not particularly limited, but is preferably less than 8000.
酸成分の一部をダイマー酸、ポリアルキレンエーテル、ポリエステル並びに末端にカルボキシル基、水酸基及びアミノ基のいずれかを含有するブタジエン系ゴムからなる群のうち少なくとも1種で置き換える場合は、酸成分のうち、1〜60モル%を置き換えることが好ましい。 When replacing a part of the acid component with at least one of the group consisting of dimer acid, polyalkylene ether, polyester and butadiene rubber containing any of carboxyl group, hydroxyl group and amino group at the end, 1 to 60 mol% is preferably replaced.
本発明のポリアミドイミド樹脂の合成に用いられるジアミン(ジイソシアネート)成分としては、前記式(I)及び式(II)に記載されたo−トリジンとトリレンジアミンを必須成分とするが、その一部を置き換える成分としてエチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン及びこれらのジイソシアネート、1,4−シクロヘキサンジアミン、1,3−シクロヘキサンジアミン、ジシクロヘキシルメタンジアミン等の脂環族ジアミン及びこれらのジイソシアネート、m−フェニレンジアミン、p−フェニレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルスルホン、ベンジジン、キシリレンジアミン、ナフタレンジアミン等の芳香族ジアミン及びこれらのジイソシアネート等が挙げられ、これらの中では反応性、コスト、耐電解液性の点からジシクロヘキシルメタンジアミン及びこれのジイソシアネートが最も好ましく、4,4’−ジアミノジフェニルメタン、ナフタレンジアミン及びこれらのジイソシアネートも好ましい。 The diamine (diisocyanate) component used in the synthesis of the polyamideimide resin of the present invention includes o-tolidine and tolylenediamine described in the above formulas (I) and (II) as essential components, part of which. Aliphatic diamines such as ethylenediamine, propylenediamine, and hexamethylenediamine and their diisocyanates, alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and dicyclohexylmethanediamine, and their diisocyanates, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, benzidine, xylylenediamine, naphthalenediamine Aromatic diamines and diisocyanates thereof, and the like. Among them, dicyclohexylmethanediamine and diisocyanates thereof are most preferable from the viewpoint of reactivity, cost, and electrolyte resistance, and 4,4′-diaminodiphenylmethane, naphthalenediamine. And these diisocyanates are also preferred.
本発明に用いるポリアミドイミド樹脂はN,N’−ジメチルホルムアミド、N,N’−ジメチルアセトアミド、N−メチル−2−ピロリドン、γ−ブチロラクトン等の極性溶剤中、60〜200℃に加熱しながら攪拌することで容易に製造することができる。この場合、必要に応じてトリエチルアミン、ジエチレントリアミン等のアミン類、フッ化ナトリウム、フッ化カリウム、フッ化セシウム、ナトリウムメトキシド等のアルカリ金属塩等を触媒として用いることもできる。 The polyamideimide resin used in the present invention is stirred while heating at 60 to 200 ° C. in a polar solvent such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. By doing so, it can be easily manufactured. In this case, amines such as triethylamine and diethylenetriamine, alkali metal salts such as sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, and the like can be used as a catalyst as necessary.
本発明に用いるポリアミドイミド樹脂はガラス転移温度が70℃以上で対数粘度は0.5dl/g以上が好ましい。ガラス転移温度が70℃未満では、シャットダウン効果はあるが、メルトダウン温度が低くなり、セパレーターに用いた場合、正極と負極が短絡を起こすおそれがある。一方上限は加工性や溶剤溶解性を考慮すると400℃未満が好ましい。また、対数粘度が0.5dl/g未満でも溶融温度の低下により同様の危険性が増すことと分子量が低いため多孔質膜が脆くなるからである。一方上限は加工性や溶剤溶解性を考慮すると2.0dl/g未満が好ましい。 The polyamideimide resin used in the present invention preferably has a glass transition temperature of 70 ° C. or higher and a logarithmic viscosity of 0.5 dl / g or higher. If the glass transition temperature is less than 70 ° C., there is a shutdown effect, but the meltdown temperature becomes low, and when used for a separator, the positive electrode and the negative electrode may be short-circuited. On the other hand, the upper limit is preferably less than 400 ° C. in consideration of workability and solvent solubility. Further, even when the logarithmic viscosity is less than 0.5 dl / g, the porous film becomes brittle because the similar danger increases due to the decrease in melting temperature and the molecular weight is low. On the other hand, the upper limit is preferably less than 2.0 dl / g in consideration of processability and solvent solubility.
次にポリアミドイミド多孔質膜の製造方法について説明する。本発明の多孔質膜の製造は特に制限はないが、上記のポリアミドイミド重合溶液をポリエステルフィルム等の基材に所定の厚みにコーテイングした後、あるいは重合溶液をスリットダイからフィルム状に押し出して、該ポリアミドイミド樹脂を溶解している溶剤と混和するが、該ポリアミドイミド樹脂に対しては貧溶剤である溶液中に投入して凝固させるのが好ましい。なお、ここで言う貧溶剤とは該ポリアミドイミド樹脂を25℃で5重量%濃度で溶解できないものとする。 Next, a method for producing a polyamideimide porous membrane will be described. The production of the porous membrane of the present invention is not particularly limited, but after coating the polyamideimide polymerization solution on a substrate such as a polyester film to a predetermined thickness, or extruding the polymerization solution from a slit die into a film, The polyamidoimide resin is mixed with a dissolving solvent, but it is preferable that the polyamidoimide resin is put into a poor solvent and solidified. In addition, the poor solvent said here shall not be able to melt | dissolve this polyamidoimide resin in 25weight% at a 5 weight% density | concentration.
ポリアミドイミド樹脂を溶解する溶剤は上記のようにN−メチル−2−ピロリドンやジメチルアセトアミド、N,N’−ジメチルホルムアミドなどのアミド系溶剤が主体になるが、多孔質膜形成時の凝固速度を調節して、孔径や孔径分布を調節するためにメタノール、エタノール、プロピルアルコール、エチレングリコール、ジエチレングリコールやポリエチレングリコール、ポリプロピレングリコールなどのアルコール類、アセトン、メチルエチルケトンなどのケトン類などを添加することが出きる。これらの添加剤はポリアミドイミド樹脂溶液100部に対して5〜300部、好ましくは10〜200部、更に好ましくは20〜100部である。 As described above, amide solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, and N, N′-dimethylformamide are mainly used as the solvent for dissolving the polyamideimide resin. It is possible to add alcohols such as methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol and polypropylene glycol, and ketones such as acetone and methyl ethyl ketone to adjust the pore size and pore size distribution. . These additives are 5 to 300 parts, preferably 10 to 200 parts, more preferably 20 to 100 parts with respect to 100 parts of the polyamideimide resin solution.
本発明多孔質を製造する際に用いる凝固浴は水を主体とした溶液が好ましい。この凝固浴には凝固速度や多孔質膜の孔径及びその分布を調節するために水と混和する他の溶剤を混合することができる。このような溶剤としてはメタノール、エタノール、プロピルアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ポリエチレングリコール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、N,N’−ジメチルホルムアミド、N,N’−ジメチルアセトアミド、N−メチル−2−ピロリドン等のアミド系溶剤等が挙げられこれらの中では孔径の多孔質膜中の均一さの点からエチレングリコール、ポリエチレングリコールなどのグリコール類やN−メチル−2−ピロリドン、N,N’−ジメチルアセトアミド、N,N’−ジメチルホルムアミドなどのアミド系溶剤が好ましい。これらの溶剤の添加量は水100部に対して5〜500部、好ましくは10〜400部、更に好ましくは20〜300部である。これら凝固浴への添加剤の量は特に制限はないが、水100部に対して5〜500部、好ましくは10〜400部、更に好ましくは20〜300部である The coagulation bath used when producing the porous material of the present invention is preferably a solution mainly composed of water. This coagulation bath can be mixed with other solvents miscible with water in order to adjust the coagulation rate, the pore size of the porous membrane and its distribution. Such solvents include alcohols such as methanol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, diethylene glycol and polyethylene glycol, ketones such as acetone and methyl ethyl ketone, N, N′-dimethylformamide, N, N′-dimethyl. Examples include amide solvents such as acetamide and N-methyl-2-pyrrolidone. Among these, glycols such as ethylene glycol and polyethylene glycol and N-methyl-2- Amide solvents such as pyrrolidone, N, N′-dimethylacetamide, and N, N′-dimethylformamide are preferred. The amount of these solvents added is 5 to 500 parts, preferably 10 to 400 parts, and more preferably 20 to 300 parts with respect to 100 parts of water. The amount of the additive to the coagulation bath is not particularly limited, but is 5 to 500 parts, preferably 10 to 400 parts, more preferably 20 to 300 parts with respect to 100 parts of water.
ポリアミドイミド多孔質膜は単層でも積層でも良いが全体の膜厚は5〜100μm、好ましくは10〜70μm、更に好ましくは15〜50μmである。膜厚が5μm以下では膜が弱くなり破断するおそれがある。逆に膜厚が100μmを越えるとサイクル特性が低下することがある。ポリアミドイミド多孔質膜の空孔率は30〜90%が好ましい。更に好ましくは40〜70%であり、空孔率が30%以下では膜の電気抵抗が高くなり、大電流を流しにくくなる。一方、90%以上では膜強度が弱くなる。また孔径の尺度である透気度はJIS−P8117に準拠した方法により測定した値が1〜2000sec/100ccAirであることが好ましい。より好ましくは50〜1500sec/100ccAir、さらに好ましくは100〜1000sec/100ccAirである。透気度が1sec/100ccAir未満では膜強度が弱くなり、2000sec/100ccAirを越えるとサイクル特性が悪くなることがある。 The polyamideimide porous membrane may be a single layer or a laminate, but the total film thickness is 5 to 100 μm, preferably 10 to 70 μm, and more preferably 15 to 50 μm. If the film thickness is 5 μm or less, the film becomes weak and may break. Conversely, when the film thickness exceeds 100 μm, the cycle characteristics may deteriorate. The porosity of the polyamideimide porous membrane is preferably 30 to 90%. More preferably, it is 40 to 70%. When the porosity is 30% or less, the electric resistance of the film becomes high and it becomes difficult to flow a large current. On the other hand, if it is 90% or more, the film strength becomes weak. The air permeability, which is a measure of the pore diameter, is preferably 1 to 2000 sec / 100 cc Air measured by a method based on JIS-P8117. More preferably, it is 50-1500 sec / 100 cc Air, More preferably, it is 100-1000 sec / 100 cc Air. When the air permeability is less than 1 sec / 100 cc Air, the film strength becomes weak, and when it exceeds 2000 sec / 100 cc Air, the cycle characteristics may be deteriorated.
このようにして製造されるポリアミドイミド多孔質膜はセパレーターとして単独で用いられた場合でも優れたシャットダウン特性とメルトダウン特性を示す。特に数平均分子量1000以上のブタジエン系ゴムやポリアルキレングリコール、ポリエステル等がブロック状に共重合されたポリアミドイミド樹脂からなる多孔質フィルムの場合その効果が顕著である。数平均分子量の上限はポリアミドイミド樹脂のガラス転移温度を考慮すると8000未満が好ましい。 The polyamideimide porous membrane thus produced exhibits excellent shutdown characteristics and meltdown characteristics even when used alone as a separator. In particular, the effect is remarkable in the case of a porous film made of a polyamideimide resin in which a butadiene rubber having a number average molecular weight of 1000 or more, polyalkylene glycol, polyester, or the like is copolymerized in a block shape. The upper limit of the number average molecular weight is preferably less than 8000 considering the glass transition temperature of the polyamideimide resin.
また、本発明のもう一つの特徴はポリアミドイミド多孔質膜をポリオレフィン系の多孔質膜と積層、組み合わせて用いることができることにある。ポリオレフィン系多孔質膜とはポリエチレンやポリプロピレンフィルムを例えば第7回ポリマー材料フォーラム(1998)要旨集1BIL09等に記載される延伸開孔法や相分離法等によって製造されるものである。ポリアミドイミド多孔質膜とポリオレフィン多孔質膜を積層する場合の構成はポリアミドイミド多孔質膜をA、ポリオレフィン系多孔質膜をBとすると、A/B、A/B/A又はB/A/Bの構成となる。 Another feature of the present invention is that a polyamide-imide porous membrane can be used in combination with a polyolefin-based porous membrane. The polyolefin-based porous membrane is a polyethylene or polypropylene film produced by, for example, the stretch opening method or the phase separation method described in 7th Polymer Material Forum (1998) Abstract 1 BIL09. When the polyamide-imide porous membrane and the polyolefin porous membrane are laminated, the polyamide-imide porous membrane is A, and the polyolefin-based porous membrane is B. A / B, A / B / A or B / A / B It becomes the composition of.
これらの複合多孔質膜の製造も特に制限はないが、以下の方法が好ましい。
(1)ポリアミドイミド多孔質膜とポリオレフィン多孔質膜を単純に重ねる。
(2)ポリオレフィン多孔質膜を支持体にしてその片面又は両面にポリアミドイミド樹脂溶液を含浸又は塗布し、前記と同様な方法で凝固浴に投入して凝固させる。
(3)上記(1)と(2)を組み合わせる。
The production of these composite porous membranes is not particularly limited, but the following method is preferred.
(1) A polyamide-imide porous membrane and a polyolefin porous membrane are simply stacked.
(2) Using a polyolefin porous membrane as a support, impregnating or coating one or both sides with a polyamideimide resin solution, and putting it in a coagulation bath by the same method as described above, to solidify.
(3) Combine (1) and (2) above.
これら複合多孔質膜の場合、全体の膜厚は10〜100μm、好ましくは15〜70μmである。空孔率は30〜80%、透気度は1〜2000sec/100ccAirが好ましい。 In the case of these composite porous membranes, the total film thickness is 10 to 100 μm, preferably 15 to 70 μm. The porosity is preferably 30 to 80% and the air permeability is preferably 1 to 2000 sec / 100 cc Air.
このように構成された本発明のポリアミドイミド多孔質膜をセパレーターとして使用したリチウムイオン二次電池は従来と同様の電池性能を発揮し、シャットダウン特性、メルトダウン特性に優れた安全な電池を得ることができる。本発明に関わるリチウムイオン二次電池は本発明の多孔質膜をセパレーターとして用いること以外は、常法に従って製造することができる。 The lithium ion secondary battery using the polyamideimide porous membrane of the present invention configured as described above as a separator exhibits the same battery performance as before, and obtains a safe battery excellent in shutdown characteristics and meltdown characteristics. Can do. The lithium ion secondary battery according to the present invention can be produced according to a conventional method except that the porous membrane of the present invention is used as a separator.
即ち、正極活物質としてはリチウムを含んだ材料、負極としてはリチウムをイオンとして吸蔵、放出可能な材料、電解液としてはリチウムとフッ素を含む化合物からなる電解質の有機溶剤溶液を用いることができる。 That is, a material containing lithium can be used as the positive electrode active material, a material that can store and release lithium as ions can be used as the negative electrode, and an organic solvent solution of an electrolyte composed of a compound containing lithium and fluorine can be used as the electrolytic solution.
具体的には、正極活物質としてはリチウムイオンを挿入、離脱できるコバルト酸リチウムやマンガン酸リチウム等のリチウム金属酸化物を使用することができる。正極活物質には導電剤として公知の活性炭、各種コークス、カーボンブラック、結着剤及び溶剤等を配合し、この分散液をアルミニウム等の集電体に塗布、乾燥したものを正極材とすることができる。 Specifically, lithium metal oxides such as lithium cobaltate and lithium manganate that can insert and remove lithium ions can be used as the positive electrode active material. A known active carbon, various cokes, carbon black, a binder, a solvent, and the like are blended into the positive electrode active material as a conductive agent, and this dispersion is applied to a current collector such as aluminum and dried to form a positive electrode material. Can do.
負極活物質としてはコークス、グラファイト、非晶質カーボン等が用いられ、これらを結着剤と有機溶剤からなる分散液を銅箔等の集電体に塗布、乾燥して負極材とすることができる。 Coke, graphite, amorphous carbon, etc. are used as the negative electrode active material, and these are applied to a current collector such as a copper foil with a dispersion composed of a binder and an organic solvent, and dried to form a negative electrode material. it can.
電解液に使用される電解質としては、LiClO4,LiAsF6,LiPF4,LiBF4,LiBr,LiCF3SO3,等が挙げられ、有機溶剤としてはプロピレンカービネート、エチレンカーボネート、γ−ブチロラクトン、ジメチルカーボネート、エチルメチルカーボネート、1,2−ジメトキシエタン、1,2−ジエトキシエタン、テトラヒドロフラン等の1種又は2種以上が用いられる。 Examples of the electrolyte used for the electrolytic solution include LiClO 4 , LiAsF 6 , LiPF 4 , LiBF 4 , LiBr, LiCF 3 SO 3 , and the like. Examples of the organic solvent include propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl One or more of carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran and the like are used.
以下、実施例で本発明を更に詳細に説明するが、本発明はこれらの実施例で制限されるものではない。
尚、実施例中の測定値は以下の方法で測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples.
In addition, the measured value in an Example was measured with the following method.
対数粘度:ポリアミドイミド樹脂0.5gを100mlのN−メチル−2−ピロリドンに溶解した溶液を30℃に保ちウベローデ粘度管を用いて測定した。 Logarithmic viscosity: A solution obtained by dissolving 0.5 g of polyamideimide resin in 100 ml of N-methyl-2-pyrrolidone was kept at 30 ° C. and measured using an Ubbelohde viscosity tube.
ガラス転移温度:測定幅4mm、長さ15mmのポリアミドイミドフィルムをレオロジー社製DVE−V4レオスペクトラーを用い、周波数110Hzの振動を与えて測定した動的粘弾性の損失弾性率の変曲点をガラス転移温度とした。 Glass transition temperature: The inflection point of the loss elastic modulus of dynamic viscoelasticity measured by applying a vibration of a frequency of 110 Hz to a polyamideimide film having a measurement width of 4 mm and a length of 15 mm, using a DVE-V4 rheospectr made by Rheology. The glass transition temperature was taken.
膜厚:ポリアミドイミド多孔質膜をSONY μ−メーターで測定した。 Film thickness: The polyamideimide porous film was measured with a SONY μ-meter.
空孔率:ポリアミドイミド樹脂溶液から流延乾燥して作成した約25μmフィルム(A)の平均膜厚(At)と10cm□の重量(Aw)を測定し、同じポリアミドイミド樹脂溶液から水中で凝固させて作成した多孔質膜(B)の平均膜厚(Bt)と10cm□の重量(Bw)とから下記式によって空孔率を算出した。
空孔率=[1−(Bw/Bt)/(Aw/At)]×100(%)
Porosity: The average film thickness (At) and weight (Aw) of about 25 μm film (A) prepared by casting and drying from a polyamideimide resin solution were measured and coagulated in water from the same polyamideimide resin solution. The porosity was calculated from the average film thickness (Bt) of the porous film (B) thus prepared and the weight (Bw) of 10 cm □ by the following formula.
Porosity = [1- (Bw / Bt) / (Aw / At)] × 100 (%)
シャットダウン温度特性:プロピレンカーボネートに4フッ化ホウ酸リチウムを1モル/l溶解した溶液を充填した多孔質膜を用い、交流周波数1kHz、交流振幅100mV、昇温速度2℃/分で測定した。温度上昇に伴うインピーダンス値の上昇が一旦100Ωcm2になったときの温度をシャットダウン開始温度とし、インピーダンスの値が1kΩcm2を越え、更に上昇した後低下し再び1kΩcm2になった温度をメルトダウン温度とした。 Shutdown temperature characteristics: A porous membrane filled with 1 mol / l of lithium tetrafluoroborate dissolved in propylene carbonate was used and measured at an AC frequency of 1 kHz, an AC amplitude of 100 mV, and a heating rate of 2 ° C./min. The temperature at which the rise in impedance value due to temperature rise once becomes 100 Ωcm 2 is the shutdown start temperature, and the temperature at which the impedance value exceeds 1 kΩcm 2 , then rises and decreases again to 1 kΩcm 2 is the meltdown temperature. It was.
[実施例1]
温度計、冷却管、窒素ガス導入管のついた4ツ口フラスコにトリメリット酸無水物(TMA)1モル、o−トリジンジイソシアネート(TODI)0.8モル、2,4−トリレンジイソシアネート(TDI)0.2モル、フッ化カリウム0.01モルを固形分濃度が20%となるようにN−メチル−2−ピロリドンと共に仕込み、100℃で5時間攪拌した後、固形分濃度が10%となるようにN−メチル−2−ピロリドンで希釈してポリアミドイミド樹脂を合成した。得られたポリアミドイミド樹脂の対数粘度は1.35dl/g、ガラス転移温度は310℃であった。
このポリアミドイミド樹脂溶液100部にポリエチレングリコール#400を20部配合したドープを市販のセパレーター(東燃化学製ポリオレフィン多孔質膜:25μm)に膜厚が1μmとなるように塗布し、25℃の水中に約3分間浸漬した後金属枠で固定して100℃で10分間乾燥した。得られた複合多孔質膜の透気度は340sec/100ccAirであった。この膜のシャットダウン温度は121℃、メルトダウン温度は200℃以上であった。この多孔質膜をセパレーターに用い、正極活物質としてコバルト酸リチウム、導電剤としてアセチレンブラック、バインダーとしてポリフッ化ビニリデンを用いた正極及び黒鉛と非晶質炭素を混合した負極活物質とポリフッ化ビニリデンをバインダーにした負極、電解液としてソルライト(三菱化学製)を用いてコイン型電池を作成して電池特性を評価した。市販のセパレーター(東燃化学製ポリオレフィン多孔質膜:25μ)単独膜に比べて放電容量、サイクル特性ともほぼ同等の性能を示した。
[Example 1]
In a four-necked flask equipped with a thermometer, a condenser tube, and a nitrogen gas inlet tube, 1 mole of trimellitic anhydride (TMA), 0.8 mole of o-tolidine diisocyanate (TODI), 2,4-tolylene diisocyanate (TDI) ) 0.2 mol and 0.01 mol of potassium fluoride were charged together with N-methyl-2-pyrrolidone so that the solid content concentration was 20%, stirred at 100 ° C. for 5 hours, and then the solid content concentration was 10%. In this way, a polyamide-imide resin was synthesized by diluting with N-methyl-2-pyrrolidone. The obtained polyamideimide resin had a logarithmic viscosity of 1.35 dl / g and a glass transition temperature of 310 ° C.
A dope in which 20 parts of polyethylene glycol # 400 is blended with 100 parts of this polyamideimide resin solution is applied to a commercial separator (polyolefin porous film manufactured by Tonen Chemical Co., Ltd .: 25 μm) so that the film thickness becomes 1 μm. After being immersed for about 3 minutes, it was fixed with a metal frame and dried at 100 ° C. for 10 minutes. The air permeability of the obtained composite porous membrane was 340 sec / 100 cc Air. The shutdown temperature of this film was 121 ° C., and the meltdown temperature was 200 ° C. or higher. Using this porous membrane as a separator, a positive electrode using lithium cobaltate as a positive electrode active material, acetylene black as a conductive agent, polyvinylidene fluoride as a binder, a negative electrode active material mixed with graphite and amorphous carbon, and polyvinylidene fluoride A coin-type battery was prepared using a negative electrode as a binder and Sollite (manufactured by Mitsubishi Chemical) as an electrolytic solution, and the battery characteristics were evaluated. Compared to a commercially available separator (polyolefin porous membrane manufactured by Tonen Chemical Co., Ltd .: 25 μm) alone, the discharge capacity and cycle characteristics were almost the same.
[実施例2]
実施例1の酸成分をTMA0.9モル、ジカルボキシポリ(アクリロニトリル−ブタジエン)ゴム(宇部興産製ハイカーCTBN1300×13:分子量3500)を0.1モルとした以外は実施例1と同じ条件で固形分濃度10%のポリアミドイミド樹脂を合成した。得られたポリアミドイミド樹脂の対数粘度は0.65dl/g、ガラス転移温度は213℃であった。このポリアミドイミド樹脂溶液100部にポリエチレングリコール#400を20部配合した溶液を用いて実施例1と同じ方法で複合多孔質膜を作成した。この複合多孔質膜の膜厚は27μ、透気度は460sec/100ccAirでシャットダウン温度は120℃、メルトダウン温度は200℃以上であった。
[Example 2]
Solid under the same conditions as in Example 1 except that the acid component of Example 1 was TMA 0.9 mol and dicarboxypoly (acrylonitrile-butadiene) rubber (Ube Industries Hiker CTBN 1300 × 13: molecular weight 3500) was 0.1 mol. A polyamideimide resin having a partial concentration of 10% was synthesized. The obtained polyamidoimide resin had a logarithmic viscosity of 0.65 dl / g and a glass transition temperature of 213 ° C. A composite porous membrane was prepared in the same manner as in Example 1 using a solution in which 20 parts of polyethylene glycol # 400 was blended with 100 parts of this polyamideimide resin solution. The composite porous membrane had a thickness of 27 μm, an air permeability of 460 sec / 100 cc Air, a shutdown temperature of 120 ° C., and a meltdown temperature of 200 ° C. or higher.
[実施例3]
実施例1と同じ装置を用い、TMA0.94モル、分子量2000のポリプロピレングリコール0.06モル、TODI0.5モル、TDI0.5モルを固形分濃度が30%となるようにN,N’−ジメチルアセトアミドと共に仕込み140℃で3時間反応させた後、固形分濃度が10%となるようにN,N’−ジメチルアセトアミドで希釈してポリアミドイミド樹脂を合成した。得られたポリアミドイミド樹脂の対数粘度は0.63dl/g、ガラス転移温度は198℃であった。このポリアミドイミド樹脂溶液100部にポリエチレングリコール#400を20部配合した溶液を用いて、実施例1と同じ方法で複合多孔質膜を作成した。この複合多孔質膜の厚みは27μm、透気度は410cc/100ccAirでシャットダウン温度は121℃、メルトダウン温度は200℃以上であった。
[Example 3]
Using the same apparatus as in Example 1, 0.94 mol of TMA, 0.06 mol of polypropylene glycol having a molecular weight of 2000, 0.5 mol of TODI, and 0.5 mol of TDI were added to N, N′-dimethyl so that the solid concentration would be 30%. After charging with acetamide and reacting at 140 ° C. for 3 hours, a polyamideimide resin was synthesized by diluting with N, N′-dimethylacetamide so that the solid content concentration would be 10%. The obtained polyamideimide resin had a logarithmic viscosity of 0.63 dl / g and a glass transition temperature of 198 ° C. A composite porous membrane was prepared in the same manner as in Example 1 using a solution in which 20 parts of polyethylene glycol # 400 was blended with 100 parts of this polyamideimide resin solution. This composite porous membrane had a thickness of 27 μm, an air permeability of 410 cc / 100 cc Air, a shutdown temperature of 121 ° C., and a meltdown temperature of 200 ° C. or higher.
[実施例4]
実施例1と同じ装置を用い、TMA0.93モル、ポリカプロラクトン(ダイセル化学製プラクセル220:分子量2000)0.07モル、TODI0.5モル、TDI0.3モル、ジフェニルメタン−4,4’−ジイソシアネート0.2モル、フッ化カリウム0.02モルを固形分濃度が30%となるようにN−メチル−2−ピロリドンと共に仕込み、150℃で約5時間反応させた後固形分濃度が20%となるようにN−メチル−2−ピロリドンで希釈した。得られたポリアミドイミド樹脂の対数粘度は0.71dl/g、ガラス転移温度は175℃であった。このポリアミドイミド樹脂溶液100部にエチレングリコール20部を配合した溶液を用いて、実施例1と同じ方法で複合多孔質膜を作成した。この複合多孔質膜の膜厚は27μm、透気度は670sec/100ccAirで、シャットダウン温度は121℃、メルトダウン温度は200℃以上であった。
[Example 4]
Using the same apparatus as in Example 1, 0.93 mol of TMA, 0.07 mol of polycaprolactone (Placcel 220: molecular weight 2000, manufactured by Daicel Chemical Industries), 0.5 mol of TODI, 0.3 mol of TDI, diphenylmethane-4,4′-diisocyanate 0 .2 mol and 0.02 mol of potassium fluoride were added together with N-methyl-2-pyrrolidone so that the solid content concentration would be 30%, and after reacting at 150 ° C. for about 5 hours, the solid content concentration would be 20%. Diluted with N-methyl-2-pyrrolidone. The obtained polyamideimide resin had a logarithmic viscosity of 0.71 dl / g and a glass transition temperature of 175 ° C. A composite porous membrane was prepared in the same manner as in Example 1 using a solution in which 20 parts of ethylene glycol was blended with 100 parts of this polyamideimide resin solution. The composite porous membrane had a thickness of 27 μm, an air permeability of 670 sec / 100 cc Air, a shutdown temperature of 121 ° C., and a meltdown temperature of 200 ° C. or higher.
[実施例5]
実施例1と同じ装置を用い、TMA0.5モル、ダイマー酸0.5モル、TODI0.5モル,TDI0.5モルを固形分濃度が30%となるようにN−メチル−2−ピロリドンと共に仕込み、120℃で1.5時間、180℃で3時間反応させた後、固形分濃度が20%となるようにN−メチル−2−ピロリドンで希釈した。得られたポリアミドイミド樹脂の対数粘度は0.70dl/g、ガラス転移温度は153℃であった。このポリアミドイミド樹脂溶液100部にエチレングリコール20部を配合した溶液を用いて、実施例1と同じ方法で複合多孔質膜を作成した。この多孔質膜の厚みは28μm、透気度は4.1sec/100ccAirでシャットダウン温度は121℃、メルトダウン温度は186℃であった。
[Example 5]
Using the same apparatus as in Example 1, 0.5 mol of TMA, 0.5 mol of dimer acid, 0.5 mol of TODI, and 0.5 mol of TDI were charged together with N-methyl-2-pyrrolidone so that the solid concentration was 30%. The mixture was reacted at 120 ° C. for 1.5 hours and at 180 ° C. for 3 hours, and then diluted with N-methyl-2-pyrrolidone so that the solid concentration was 20%. The obtained polyamideimide resin had a logarithmic viscosity of 0.70 dl / g and a glass transition temperature of 153 ° C. A composite porous membrane was prepared in the same manner as in Example 1 using a solution in which 20 parts of ethylene glycol was blended with 100 parts of this polyamideimide resin solution. The porous film had a thickness of 28 μm, an air permeability of 4.1 sec / 100 cc Air, a shutdown temperature of 121 ° C., and a meltdown temperature of 186 ° C.
[実施例6]
実施例4のポリアミドイミド樹脂溶液100部にエチレングリコール20部を配合した溶液を100μmのポリエステルフィルムに塗布し、水中に浸漬して凝固させ、水洗、乾燥して厚さ32μmのポリアミドイミド多孔質膜を得た。この多孔質膜の空孔率は67%、透気度は6.3sec/100ccAirでシャットダウン温度は178℃、メルトダウン温度は200℃以上であった。このポリアミドイミド多孔質膜を実施例1と同じ様な構成でセパレーターに用いたコイン電池の放電容量、サイクル耐久性等の電池性能はポリオレフィン多孔質膜単独セパレーターと同様な特性を示した。
[Example 6]
A solution obtained by blending 20 parts of ethylene glycol with 100 parts of the polyamideimide resin solution of Example 4 was applied to a 100 μm polyester film, immersed in water to solidify, washed with water, and dried to form a polyamideimide porous film having a thickness of 32 μm. Got. This porous membrane had a porosity of 67%, an air permeability of 6.3 sec / 100 cc Air, a shutdown temperature of 178 ° C., and a meltdown temperature of 200 ° C. or higher. Battery performance such as discharge capacity and cycle durability of a coin battery using this polyamideimide porous membrane as a separator in the same configuration as in Example 1 showed the same characteristics as the polyolefin porous membrane single separator.
[実施例7]
実施例5のポリアミドイミド樹脂溶液100部にポリエチレングリコール#400を20部配合した溶液を用いて実施例6と同じ方法で厚さ35μm多孔質ポリアミドイミド膜を得た。この多孔質膜の空孔率は71%、透気度は6.8sec/100ccAirでシャットダウン温度は151℃、メルトダウン温度は200℃以上であった。
[Example 7]
Using a solution obtained by blending 20 parts of polyethylene glycol # 400 with 100 parts of the polyamideimide resin solution of Example 5, a 35 μm thick porous polyamideimide film was obtained in the same manner as in Example 6. This porous film had a porosity of 71%, an air permeability of 6.8 sec / 100 cc Air, a shutdown temperature of 151 ° C., and a meltdown temperature of 200 ° C. or higher.
[実施例8]
実施例1のポリアミドイミド樹脂溶液100部にポリエチレングリコール#400を20部配合した溶液に東燃化学製ポリオレフィン多孔質膜(25μm)を浸漬させた後、ポリオレフィン多孔質膜の両面に乾燥膜厚が各々1μmになるように絞りロールで掻き取り、水/N−メチル−2−ピロリドン比が70/30の凝固浴に投入して凝固させ、洗滌、乾燥して厚さ27μmの3層の複合多孔質膜を得た。この複合多孔質膜のシャットダウン温度は120℃、メルトダウン温度は200℃以上であった。この複合多孔質膜をセパレーターにして実施例1と同じ構成で作成したコイン電池の放電容量、サイクル耐久性などの電池性能はポリオレフィン多孔質膜単独セパレーターと同様な特性を示した。
[Example 8]
After immersing a polyolefin porous membrane (25 μm) manufactured by Tonen Chemical in a solution in which 20 parts of polyethylene glycol # 400 was blended with 100 parts of the polyamideimide resin solution of Example 1, the dry film thicknesses were measured on both sides of the polyolefin porous membrane. It is scraped with a squeeze roll so as to be 1 μm, put into a coagulation bath having a water / N-methyl-2-pyrrolidone ratio of 70/30, coagulated, washed and dried to form a composite porous layer having a thickness of 27 μm. A membrane was obtained. The composite porous membrane had a shutdown temperature of 120 ° C. and a meltdown temperature of 200 ° C. or higher. The battery performance such as the discharge capacity and cycle durability of the coin battery prepared by using the composite porous membrane as a separator and having the same structure as in Example 1 showed the same characteristics as the polyolefin porous membrane single separator.
[実施例9]
実施例1で作成したポリアミドイミド/ポリオレフィンの複合多孔質膜のポリアミドイミド多孔質膜側にポリオレフィン多孔質膜を重ねた複合膜を実施例1と同じ条件で作成したコイン電池の放電容量、サイクル耐久性等の電池性能はポリオレフィン多孔質膜単独セパレーターとほぼ同等の特性を示した。
[Example 9]
Discharge capacity and cycle endurance of a coin battery in which a composite membrane obtained by laminating a polyolefin porous membrane on the polyamideimide porous membrane side of the polyamideimide / polyolefin composite porous membrane prepared in Example 1 under the same conditions as in Example 1 The battery performance such as the property showed almost the same characteristics as the polyolefin porous membrane single separator.
[比較例1]
実施例1でTMAを1.07モルとした以外は実施例1と同じ条件でポリアミドイミド樹脂を合成した。得られたポリアミドイミド樹脂の対数粘度は0.35dl/g、ガラス転移温度は285℃であった。このポリアミドイミド樹脂を用いた多孔質膜は分子量が低いため脆く、セパレーターとしては不適であった。
[Comparative Example 1]
A polyamideimide resin was synthesized under the same conditions as in Example 1 except that TMA was changed to 1.07 mol in Example 1. The obtained polyamideimide resin had a logarithmic viscosity of 0.35 dl / g and a glass transition temperature of 285 ° C. A porous membrane using this polyamideimide resin is fragile because of its low molecular weight, and is not suitable as a separator.
[比較例2]
実施例1と同じ装置を用い、酸成分をTMA0.15モル、ダイマー酸0.85モルとした以外は実施例1同じ条件でポリアミドイミド樹脂を合成した。得られたポリアミドイミド樹脂の対数粘度は0.63dl/g、ガラス転移温度は55℃であった。このポリアミドイミド樹脂溶液を用い、実施例6と同じ方法で多孔質膜を作成した。この多孔質膜の膜厚は23μm、空孔率は67%、透気度は3.4sec/100ccAirと良好であったが、シャットダウン温度が62℃、メルトダウン温度が118℃と低くセパレーターとしての安全性が不十分であった。
[Comparative Example 2]
Using the same apparatus as in Example 1, a polyamideimide resin was synthesized under the same conditions as in Example 1 except that the acid component was 0.15 mol of TMA and 0.85 mol of dimer acid. The obtained polyamideimide resin had a logarithmic viscosity of 0.63 dl / g and a glass transition temperature of 55 ° C. Using this polyamideimide resin solution, a porous membrane was prepared in the same manner as in Example 6. The porous film had a thickness of 23 μm, a porosity of 67%, and an air permeability of 3.4 sec / 100 cc Air. The shutdown temperature was 62 ° C. and the meltdown temperature was 118 ° C. Safety was insufficient.
本発明は、特定構造を有するポリアミドイミド樹脂の多孔質膜又はポリアミドイミド樹脂の多孔質膜とポリオレフィン膜を積層した複合多孔質膜を用いることによりシャットダウン特性とメルトダウン特性のバランスに優れたリチウムイオン二次電池用セパレーターを提供できる。 The present invention provides lithium ion excellent in balance between shutdown characteristics and meltdown characteristics by using a polyamideimide resin porous film having a specific structure or a composite porous film in which a polyamideimide resin porous film and a polyolefin film are laminated. A separator for a secondary battery can be provided.
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