JP2015069745A - Aromatic polyamide bag-shaped separator - Google Patents
Aromatic polyamide bag-shaped separator Download PDFInfo
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- JP2015069745A JP2015069745A JP2013201178A JP2013201178A JP2015069745A JP 2015069745 A JP2015069745 A JP 2015069745A JP 2013201178 A JP2013201178 A JP 2013201178A JP 2013201178 A JP2013201178 A JP 2013201178A JP 2015069745 A JP2015069745 A JP 2015069745A
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- Prior art keywords
- aromatic polyamide
- separator
- bag
- film
- porous membrane
- Prior art date
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- 239000004760 aramid Substances 0.000 abstract description 89
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 89
- 230000008859 change Effects 0.000 abstract description 12
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 description 58
- 239000010408 film Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 22
- 239000011550 stock solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 229920001477 hydrophilic polymer Polymers 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- -1 for example Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- MSWAXXJAPIGEGZ-UHFFFAOYSA-N 2-chlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1 MSWAXXJAPIGEGZ-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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 101000804816 Xenopus laevis Werner syndrome ATP-dependent helicase homolog Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- VJLOFJZWUDZJBX-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;chloride Chemical compound [Cl-].OCC[NH2+]CCO VJLOFJZWUDZJBX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 230000009466 transformation Effects 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
Landscapes
- Cell Separators (AREA)
Abstract
Description
本発明は、芳香族ポリアミドからなる袋状セパレータに関するものであり、特に電池などの蓄電デバイスのセパレータとして好適に使用できる芳香族ポリアミド袋状セパレータに関するものである。 The present invention relates to a bag-like separator made of an aromatic polyamide, and more particularly to an aromatic polyamide bag-like separator that can be suitably used as a separator for an electricity storage device such as a battery.
リチウムイオン二次電池（ＬＩＢ）などの非水系二次電池は、携帯機器用途を中心に広範に普及しており、現在、さらなる高容量化、高出力化、高安全化に向けた研究開発が進められている。それに伴い、セパレータにもイオン透過性、電解液保持性、化学的安定性などに加え、耐熱性や耐短絡性などの安全性が、高い領域で同時に求められている。 Non-aqueous secondary batteries such as lithium ion secondary batteries (LIBs) are widely used mainly for portable devices, and research and development for higher capacity, higher output, and higher safety are now underway. It is being advanced. Accordingly, separators are also required to have safety such as heat resistance and short circuit resistance simultaneously in a high region in addition to ion permeability, electrolyte solution retention, chemical stability, and the like.
また、上記に加えて、正負極活物質や電解液などのセパレータ以外の構成部材との組み合わせに対する適応性も重要となる。 In addition to the above, applicability to combinations with constituent members other than separators such as positive and negative electrode active materials and electrolytes is also important.
例えば、負極材料においては、一般的に用いられている炭素材料に替わり、シリコン系、スズ系のような高容量化が期待できる合金系負極が検討されているが、これらの合金系負極は、リチウム吸蔵量が多くなると著しい体積膨張を示す。そのため、セパレータにも、負極の体積変化に対する適応性の高いものを選択する必要がある。 For example, in the negative electrode material, instead of a commonly used carbon material, an alloy-based negative electrode that can be expected to have a high capacity, such as silicon-based and tin-based materials, has been studied. When the amount of lithium occlusion increases, the volume expansion becomes remarkable. Therefore, it is necessary to select a separator having high adaptability to the volume change of the negative electrode.
電解液においては、エチレンカーボネートや、電解質としてイオン液体を用いることで有機溶媒の電解液を廃し、不揮発性、難燃性、不燃性を高める検討が行われているが、これら材料は多くが室温にて固体であり、電池して使用する場合、駆動時は融点以上の温度になり、停止時は固体化する。そのため、セパレータにも耐熱性と、寸法安定性を兼ね備えたものを選択する必要がある。 With regard to the electrolytic solution, studies have been made to eliminate the organic solvent electrolytic solution by using ethylene carbonate or an ionic liquid as an electrolyte, and to increase the non-volatility, flame retardancy, and non-flammability. When the battery is used as a battery, the temperature is higher than the melting point during driving and solidifies when stopped. Therefore, it is necessary to select a separator that has both heat resistance and dimensional stability.
さらには、高容量化に伴い、電池の異常時の発熱量が一段と大きくなると考えられ、セパレータにも、より一層の耐熱性が求められる。 Furthermore, as the capacity increases, it is considered that the amount of heat generated when the battery is abnormal increases further, and the separator is also required to have higher heat resistance.
セパレータの耐熱性を向上させる取り組みとして、ポリオレフィン多孔質膜の片面または両面に耐熱保護層（ＨＲＬ）を設けたセパレータが開示されている（例えば、特許文献１、２）。しかしながら、このＨＲＬの効果は限定的で、基材であるポリオレフィン層の収縮や溶融が起きた際に、セパレータ全体の収縮を有効に阻止できないことがある。さらに、積層体であるため、一般的に薄膜化が困難である。 As an effort to improve the heat resistance of the separator, a separator provided with a heat-resistant protective layer (HRL) on one side or both sides of a polyolefin porous membrane has been disclosed (for example, Patent Documents 1 and 2). However, the effect of this HRL is limited. When shrinkage or melting of the polyolefin layer as the base material occurs, shrinkage of the entire separator may not be effectively prevented. Furthermore, since it is a laminate, it is generally difficult to reduce the thickness.
また、先の耐熱保護層付きを設けたセパレータのポリオレフィン層同士や、耐熱保護層とポリオレフィン層を熱融着することで袋状としたセパレータが開示されている（特許文献３、４）。セパレータを袋状にすることで、極板の位置決めを容易にし、外部からの衝撃による極板の移動も最小限とすることを目的としている。しかしながら、これらもポリオレフィン層が溶融してしまうと、袋全体の収縮、熱融着部の剥離が発生してしまうことがある。 Moreover, the separator made into the bag shape by heat-seal | fusing the polyolefin layers of the separator which provided the heat-resistant protective layer with the heat-resistant protective layer and the polyolefin layer is disclosed (patent documents 3 and 4). The purpose is to facilitate positioning of the electrode plate by making the separator into a bag shape, and to minimize the movement of the electrode plate due to external impact. However, when the polyolefin layer is melted, the shrinkage of the entire bag and the peeling of the heat-sealed portion may occur.
このことから、電池の安全性を高めるためには、セパレータとして、耐熱性に優れる材料を用いた単膜を用いることが好ましい。 For this reason, in order to improve the safety of the battery, it is preferable to use a single film made of a material having excellent heat resistance as the separator.
耐熱性材料からなる単膜セパレータとして、特許文献５に、アラミド不織布やアラミドペーパーのセパレータとしての用途を開示した例がある。 As a single membrane separator made of a heat-resistant material, Patent Document 5 discloses an example in which an application as a separator for an aramid nonwoven fabric or an aramid paper is disclosed.
しかしながら、特許文献５に記載された不織布や紙状シートでは、繊維が厚み方向に折り重なった構造のため、厚み方向に圧縮を受けやすく、圧縮された際に空隙が消失し、抵抗が大きくなる懸念がある。また、繊維の大部分が面方向に連接しているために、たとえば捲回して用いる場合、長さ方向に引っ張られることで、幅方向は収縮してしまう。電池作成当初はセパレータの幅を広く取る事で対応することが可能だが、合金系負極などの体積変化の大きい電極を用いた場合、その後使用することでも徐々に寸法変化が進んでしまい、いずれ短絡等が起こる危険性がある。このような微小な変形を袋状にすることで、改善することが可能であるが、アラミドは耐熱性が非常に高いために、熱融着により袋状にすることは困難である。 However, in the nonwoven fabric and paper-like sheet described in Patent Document 5, since the fibers are folded in the thickness direction, the fibers are easily compressed in the thickness direction, and when compressed, the voids disappear and the resistance increases. There is. In addition, since most of the fibers are connected in the plane direction, for example, when wound and used, the width direction contracts by being pulled in the length direction. Although it is possible to cope with wide separators at the beginning of battery creation, when using electrodes with large volume changes such as alloy negative electrodes, dimensional changes gradually progress after use, and eventually short-circuiting occurs. There is a risk that this happens. Although it is possible to improve by making such a minute deformation into a bag shape, since aramid has a very high heat resistance, it is difficult to make it into a bag shape by thermal fusion.
以上のように、芳香族ポリアミド多孔質膜において、合金系負極などの体積変化の大きい電極を用いたリチウムイオン二次電池への適応には、なお改良の余地を有する。 As described above, there is still room for improvement in adaptation to a lithium ion secondary battery using an electrode having a large volume change such as an alloy-based negative electrode in an aromatic polyamide porous film.
本発明は上記事情に鑑み、合金系負極などの体積変化の大きい電極と共に使用した場合であっても、高い出力と長期間の優れたサイクル特性が得られ、かつ、優れた耐熱性を有する芳香族ポリアミド袋状セパレータを提供することを目的とする。 In view of the above circumstances, the present invention provides a high output and long-term excellent cycle characteristics even when used with an electrode having a large volume change such as an alloy-based negative electrode, and has an excellent heat resistance. It aims at providing a group polyamide bag-like separator.
上記目的を達成するための本発明は、以下の構成からなる。 In order to achieve the above object, the present invention has the following configuration.
（１）多孔質膜の少なくとも２辺を結合してなる矩形の袋状セパレータにおいて、多孔質膜が芳香族ポリアミドからなることを特徴とする、袋状セパレータ。 (1) A rectangular bag-like separator formed by bonding at least two sides of a porous membrane, wherein the porous membrane is made of an aromatic polyamide.
（２）矩形のすべての辺の２００℃における熱収縮率が−１．５〜１．０％である、請求項１に記載の袋状セパレータ。 (2) The bag-shaped separator according to claim 1, wherein the heat shrinkage rate at 200 ° C of all sides of the rectangle is -1.5 to 1.0%.
（３）芳香族ポリアミドのみからなることを特徴とする、請求項１または２に記載の袋状セパレータ。 (3) The bag-like separator according to claim 1 or 2, comprising only an aromatic polyamide.
本発明の芳香族ポリアミド袋状セパレータは、電極の位置決めが容易で、且つ、外部からの衝撃による電極の移動も最小限にとどめることが可能である。また、袋状とすることで、体積変化の大きい電極などと共に使用した場合であっても、セパレータ自体の幅、長さに影響を受けず、優れた追従性を示す。さらには、面方向への熱変形が小さく、高温においても連続して使用することが可能となる。そのため、リチウムイオン二次電池などの電池用セパレータに好適に用いることができる。 The aromatic polyamide bag-like separator of the present invention can easily position the electrode, and can minimize the movement of the electrode due to an impact from the outside. Moreover, even if it is a case where it is a case where it uses with an electrode etc. with a large volume change by making it into a bag shape, it is not influenced by the width | variety and length of separator itself, and shows outstanding followable | trackability. Furthermore, thermal deformation in the surface direction is small, and it can be used continuously even at high temperatures. Therefore, it can be suitably used for a battery separator such as a lithium ion secondary battery.
本発明の芳香族ポリアミド袋状セパレータを二次電池用セパレータとして用いた場合、電池の電極に合金系負極などの体積変化の大きい電極を用いた場合であっても、高い出力と長期間の優れたサイクル特性が得られる。さらに、本発明の芳香族ポリアミド袋状セパレータは、優れた耐熱性を有するため、得られた二次電池は高温でも使用可能となるのに加え、高い安全性を保持することが可能である。 When the aromatic polyamide bag separator of the present invention is used as a separator for a secondary battery, high output and long-term superiority can be obtained even when an electrode having a large volume change such as an alloy negative electrode is used as the battery electrode. Cycle characteristics can be obtained. Furthermore, since the aromatic polyamide bag-like separator of the present invention has excellent heat resistance, the obtained secondary battery can be used even at high temperatures and can also maintain high safety.
本発明において用いることができる芳香族ポリアミドとしては、次の化学式（１）および／または化学式（２）で表される繰り返し単位を有するものが好適である。
化学式（１）：
As the aromatic polyamide that can be used in the present invention, those having a repeating unit represented by the following chemical formula (1) and / or chemical formula (2) are preferable.
Chemical formula (1):
化学式（２）： Chemical formula (2):
ここで、Ａｒ１、Ａｒ２、Ａｒ３の基としては、例えば、次の化学式（３）〜（７）
化学式（３）〜（７）：
Here, examples of the groups Ar 1 , Ar 2 , and Ar 3 include the following chemical formulas (3) to (7):
Chemical formulas (3) to (7):
などが挙げられ、Ｘ、Ｙの基は、
Ａ群： −Ｏ−、−ＣＯ−、−ＣＯ２−、−ＳＯ２−、
Ｂ群： −ＣＨ２−、−Ｓ−、−Ｃ（ＣＨ３）２−
などから選択することができる。
The group of X and Y is
Group A: -O -, - CO -, - CO 2 -, - SO 2 -,
Group B: —CH 2 —, —S—, —C (CH 3 ) 2 —
Etc. can be selected.
さらに、これら芳香環上の水素原子の一部が、フッ素や臭素、塩素などのハロゲン基（特に塩素）、ニトロ基、メチルやエチル、プロピルなどのアルキル基（特にメチル基）、メトキシやエトキシ、プロポキシなどのアルコキシ基等の置換基で置換されているものが、吸湿率を低下させ湿度変化による寸法変化が小さくなるため好ましい。また、重合体を構成するアミド結合中の水素が他の置換基によって置換されていてもよい。 Furthermore, some of the hydrogen atoms on these aromatic rings are halogen groups such as fluorine, bromine and chlorine (especially chlorine), nitro groups, alkyl groups such as methyl, ethyl and propyl (especially methyl groups), methoxy and ethoxy, Those substituted with a substituent such as an alkoxy group such as propoxy are preferred because the moisture absorption rate is reduced and the dimensional change due to humidity change is reduced. In addition, hydrogen in the amide bond constituting the polymer may be substituted with another substituent.
本発明に用いられる芳香族ポリアミドは、上記の芳香環がパラ配向性を有しているものが、全芳香環の８０モル％以上を占めていることが好ましく、より好ましくは９０モル％以上を占めていることである。ここでいうパラ配向性とは、芳香核上主鎖を構成する２価の結合手が互いに同軸または平行にある状態をいう。このパラ配向性が８０モル％未満の場合、多孔質膜の剛性および耐熱性が不十分となる場合がある。さらに、芳香族ポリアミドが下記化学式（８）で表される繰り返し単位を６０モル％以上含有する場合、延伸性及び多孔質特性が特に優れることから好ましい。
化学式（８）：
In the aromatic polyamide used in the present invention, the above aromatic ring having para-orientation preferably accounts for 80 mol% or more of the total aromatic ring, more preferably 90 mol% or more. Is to occupy. Para-orientation here means a state in which the divalent bonds constituting the main chain on the aromatic nucleus are coaxial or parallel to each other. When this para orientation is less than 80 mol%, the rigidity and heat resistance of the porous membrane may be insufficient. Furthermore, when the aromatic polyamide contains 60 mol% or more of a repeating unit represented by the following chemical formula (8), it is preferable because stretchability and porous properties are particularly excellent.
Chemical formula (8):
本発明のセパレータは、芳香族ポリアミドからなる多孔質膜を、少なくとも２辺結合することで袋状としたことを特徴とする。帯状の多孔質膜の中央付近を２つに折り、２辺を結合する方法や、矩形に切り出した多孔質膜を、２枚重ね合わせ、３辺を結合する方法にて袋状にすることが可能である。袋状にすることで、正負極板の位置決めが容易になり、製造工程の簡便化が可能に、また、外部の衝撃による極板の移動も抑制することが可能となる。 The separator of the present invention is characterized in that a porous membrane made of an aromatic polyamide is formed into a bag shape by bonding at least two sides. The belt-shaped porous membrane can be folded into a bag shape by folding the central portion in two and joining the two sides, or by stacking two porous membranes cut into rectangles and joining the three sides. Is possible. By forming the bag shape, the positive and negative electrode plates can be easily positioned, the manufacturing process can be simplified, and the movement of the electrode plate due to external impact can be suppressed.
本発明の袋状セパレータは、矩形の全ての辺の２００℃における熱収縮率が−１．５〜１．０％であることが好ましい。より好ましくは−１．０〜０．５％、さらに好ましくは−０．５〜０．２％である。矩形の全ての辺の２００℃における熱収縮率を上記範囲内とすることで、電池用セパレータとして使用したときに、電極の膨張・収縮に追従することが可能となる。特に、リチウムイオン二次電池において、負極材としてシリコン系、スズ系のような高容量の合金系負極を用いた場合、充電によりリチウム吸蔵量が多くなると著しい体積膨張を示すため、高い寸法安定性を有することが好ましい。また、電極の膨張以外にも、充放電での発熱や、内部、外部短絡などによる異常発熱においても、上記範囲内とすることで、セパレータが収縮することなく、正負極が直接触れることを抑制することが可能となる。２００℃の熱収縮率が−１．５％未満となると、極板の熱膨張率を上回り、極板の間で曲がる、しわが入ることがあり、極間距離が変動し、電池抵抗が大きくなることがある。熱収縮率が１．０％を超えると、極板を押し縮めることで極板が変形し、極間距離が変動、電池抵抗が上昇することや、電池の異常発熱時にセパレータの収縮により、電池端部において短絡が起こることがある。 In the bag-shaped separator of the present invention, it is preferable that the heat shrinkage rate at 200 ° C. of all sides of the rectangle is −1.5 to 1.0%. More preferably, it is -1.0 to 0.5%, More preferably, it is -0.5 to 0.2%. By setting the thermal shrinkage rate at 200 ° C. of all the sides of the rectangle within the above range, it is possible to follow the expansion / contraction of the electrode when used as a battery separator. In particular, in lithium ion secondary batteries, when a high capacity alloy negative electrode such as silicon or tin is used as the negative electrode material, it shows significant volume expansion when the amount of lithium occlusion increases due to charging. It is preferable to have. Also, in addition to electrode expansion, heat generated during charging / discharging and abnormal heat generation due to internal and external short-circuits, etc., can be kept within the above range to prevent direct contact between the positive and negative electrodes without shrinking the separator. It becomes possible to do. When the thermal shrinkage rate at 200 ° C. is less than −1.5%, the thermal expansion coefficient of the electrode plates may be exceeded, the electrodes may bend or wrinkle, the distance between the electrodes may fluctuate, and the battery resistance may increase. There is. When the thermal shrinkage rate exceeds 1.0%, the electrode plate is deformed by compressing the electrode plate, the distance between the electrodes fluctuates, the battery resistance increases, or the battery contracts due to the shrinkage of the separator during abnormal battery heat generation. A short circuit may occur at the end.
本発明の袋状セパレータは、芳香族ポリアミドのみからなることが好ましい。芳香族ポリアミドからなる多孔質膜を袋状するには、少なくとも２辺を結合する必要がある。多孔質膜を結合する方法は、接着、熱融着、縫合など種々の方法が用いられるが、好ましくは多孔質膜に表面処理を施した後、圧縮、加熱により積層する方法、芳香族ポリアミドからなる糸、帯状の膜による縫合、多孔質膜から切り出された切り欠き同士を交差させる方法などが挙げられ、より好ましくは、低温プラズマ処理を施した後、圧縮、加熱により積層する方法である。芳香族ポリアミド多孔質膜の結合に、芳香族ポリアミド以外のもの、たとえば、アクリル系やエポキシ系に代表される接着剤を用いた接着や、ポリオレフィンなどの低融点の熱可塑性樹脂を用いた熱融着を行うと、ヤング率などの機械物性や、耐熱性、耐薬品性等、物性が低下したり、結合する対象が多孔質膜であるために、接着剤や熱可塑性樹脂が多孔質膜に含浸し、狙った部分より広い範囲が結合されてしまったり、接着剤や熱可塑性樹脂が不足し接着強度が低下する場合がある。 The bag-shaped separator of the present invention is preferably made of only aromatic polyamide. In order to form a porous membrane made of aromatic polyamide in a bag shape, it is necessary to bond at least two sides. Various methods such as adhesion, thermal fusion, and stitching are used as methods for bonding the porous membranes. Preferably, the porous membrane is subjected to surface treatment and then laminated by compression and heating, from aromatic polyamide. And a method of crossing notches cut out from the porous membrane, and more preferably, a method of laminating by compression and heating after performing a low temperature plasma treatment. Bonding of aromatic polyamide porous membranes can be performed by using adhesives other than aromatic polyamides, for example, adhesives typified by acrylic or epoxy resins, or heat melting using low melting point thermoplastic resins such as polyolefins. When wearing, mechanical properties such as Young's modulus, heat resistance, chemical resistance, and other physical properties deteriorate, or because the object to be bonded is a porous film, adhesives and thermoplastic resins become porous films. Impregnation may result in the bonding of a wider area than the target portion, or the adhesive strength may be lowered due to insufficient adhesive or thermoplastic resin.
本発明において用いる芳香族ポリアミド多孔質膜は、空孔率が５０〜８０％であることが好ましい。より好ましくは６０〜７０％である。空孔率が５０％未満であると、電池用セパレータとして用いたときに、電解液の保液量が少なく、急速充放電を行った際に、リチウムイオンが溶媒和するのに十分な溶媒分子を補うことができず、分極を起こすことがある。またさらに、充放電を繰り返した際に液枯れによる性能低下が起きることがある。空孔率が８０％を超えると、厚み方向の強度が不足し、極板を挿入するために開口部を広げたり、曲げる力がかかった時に、膜内での破壊が起こり、形状が保持出来ない場合がある。 The aromatic polyamide porous membrane used in the present invention preferably has a porosity of 50 to 80%. More preferably, it is 60 to 70%. When the porosity is less than 50%, when used as a battery separator, the amount of electrolyte solution is small, and sufficient solvent molecules are available for lithium ions to solvate when rapidly charged and discharged. Cannot be compensated for and may cause polarization. Furthermore, when charging / discharging is repeated, performance degradation may occur due to liquid erosion. If the porosity exceeds 80%, the strength in the thickness direction will be insufficient, and when a force is applied to widen or bend the opening to insert the electrode plate, it will break in the membrane and retain its shape. There may not be.
本発明において用いる芳香族ポリアミド多孔質膜は、ガーレ透気度が１〜５００秒／１００ｍｌであることが好ましい。より好ましくは５〜３００秒／１００ｍｌである。ガーレ透気度が１秒／１００ｍｌより小さいと強度が低下し、加工時にフィルムの破断が起きたり、電池用セパレータとして使用した際に電極間の短絡が起き易くなることがある。ガーレ透気度が５００秒／１００ｍｌより大きいと、抵抗が大きく、電池用セパレータとして使用した際に出力が低下しやすい。 The aromatic polyamide porous membrane used in the present invention preferably has a Gurley air permeability of 1 to 500 seconds / 100 ml. More preferably, it is 5 to 300 seconds / 100 ml. If the Gurley air permeability is less than 1 second / 100 ml, the strength decreases, and the film may be broken during processing, or a short circuit between the electrodes may easily occur when used as a battery separator. When the Gurley air permeability is greater than 500 seconds / 100 ml, the resistance is high, and the output is likely to decrease when used as a battery separator.
本発明において用いる芳香族ポリアミド多孔質膜の厚みは、３〜３０μｍであることが好ましく、より好ましくは５〜２０μｍである。３μｍ未満であると強度が低く、加工時にフィルムの破断が起きたり、耐電圧性が低く、セパレータとして使用した際に電極間が短絡する可能性がある。３０μｍを超えるとセパレータとして使用した際に内部抵抗の上昇により出力が低下したり、電池内に組み込める活物質層の厚みが薄くなり体積あたりの容量が小さくなることがある。多孔質膜の厚みは、芳香族ポリアミドのポリマー構造、重合度、製膜原液濃度、製膜原液粘度、製膜原液中の添加物、流延厚み、多孔化条件、湿式浴温度、熱処理時の温度および延伸条件など種々の条件により制御することができる。 The thickness of the aromatic polyamide porous membrane used in the present invention is preferably 3 to 30 μm, more preferably 5 to 20 μm. If it is less than 3 μm, the strength is low, the film breaks during processing, or the voltage resistance is low, and there is a possibility that the electrodes are short-circuited when used as a separator. When it exceeds 30 μm, when used as a separator, the output may decrease due to an increase in internal resistance, or the thickness of the active material layer that can be incorporated in the battery may become thin, and the capacity per volume may decrease. The thickness of the porous membrane is determined by the polymer structure of the aromatic polyamide, the degree of polymerization, the concentration of the film-forming stock solution, the viscosity of the film-forming stock solution, the additive in the film-forming stock solution, the casting thickness, the porosity condition, the wet bath temperature, and the heat treatment temperature. It can be controlled by various conditions such as temperature and stretching conditions.
本発明において用いる芳香族ポリアミド多孔質膜は、少なくとも一方向の破断点応力が３０ＭＰａ以上であることが好ましい。破断点応力が３０ＭＰａ未満の場合、加工時の高張力、張力変動などによりフィルムが破断し、生産性が低下することがある。生産性がより良くなることから、破断点応力は４０ＭＰａ以上であることがより好ましく、５０ＭＰａ以上であることがさらに好ましい。上限は特に定めることはないが、多孔質膜であれば一般的に１ＧＰａ程度が限界である。 The aromatic polyamide porous membrane used in the present invention preferably has a stress at break in at least one direction of 30 MPa or more. When the stress at break is less than 30 MPa, the film may be broken due to high tension and fluctuation in tension during processing, and productivity may be reduced. From the viewpoint of improving productivity, the stress at break is more preferably 40 MPa or more, and further preferably 50 MPa or more. The upper limit is not particularly defined, but generally about 1 GPa is the limit if it is a porous film.
本発明において用いる芳香族ポリアミド多孔質膜は、長手方向（ＭＤ）および幅方向（ＴＤ）の破断点伸度がいずれも１０％以上であることが好ましい。伸度が高いことにより、加工工程でのフィルム破れを低減することができ、高速で加工することが可能となる。また、電池用セパレータとして使用する際、充放電時の電極の膨張収縮に破断することなく追随でき、電池の耐久性や安全性が確保できる。加工性、耐久性および安全性がより向上することから、破断伸度は２０％以上であることがより好ましく、３０％以上であることがさらに好ましい。上限は特に定めることはないが、多孔質膜であれば一般的に２００％程度が限界である。 The aromatic polyamide porous membrane used in the present invention preferably has an elongation at break of 10% or more in the longitudinal direction (MD) and the width direction (TD). Since the elongation is high, film breakage in the processing step can be reduced, and processing at high speed becomes possible. Further, when used as a battery separator, the battery can follow the expansion and contraction of the electrode during charge and discharge without breaking, and the durability and safety of the battery can be ensured. Since workability, durability and safety are further improved, the breaking elongation is more preferably 20% or more, and further preferably 30% or more. The upper limit is not particularly defined, but generally about 200% is the limit for porous membranes.
次に、本発明において用いる芳香族ポリアミド多孔質膜の製造方法について、以下に説明する。まず、芳香族ポリアミドを、例えば、酸ジクロライドとジアミンを原料として重合する場合には、Ｎ−メチルピロリドン、Ｎ，Ｎ−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等の非プロトン性有機極性溶媒中で溶液重合により合成する方法や、水系媒体を使用する界面重合で合成する方法等をとることができる。ポリマーの分子量を制御しやすいことから、非プロトン性有機極性溶媒中での溶液重合が好ましい。 Next, the manufacturing method of the aromatic polyamide porous membrane used in the present invention will be described below. First, when an aromatic polyamide is polymerized using, for example, acid dichloride and diamine as raw materials, a solution in an aprotic organic polar solvent such as N-methylpyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethylsulfoxide, etc. A method of synthesis by polymerization, a method of synthesis by interfacial polymerization using an aqueous medium, or the like can be employed. Solution polymerization in an aprotic organic polar solvent is preferable because the molecular weight of the polymer can be easily controlled.
溶液重合の場合、分子量の高いポリマーを得るために、重合に使用する溶媒の水分率を５００ｐｐｍ以下（質量基準、以下同様）とすることが好ましく、２００ｐｐｍ以下とすることがより好ましい。使用する酸ジクロライドおよびジアミンの両者を等量用いると超高分子量のポリマーが生成することがあるため、モル比を、一方が他方の９５．０〜９９．５モル％になるように調整することが好ましい。また、芳香族ポリアミドの重合反応は発熱を伴うが、重合系の温度が上がると、副反応が起きて重合度が十分に上がらないことがあるため、重合中の溶液の温度を４０℃以下に冷却することが好ましい。重合中の溶液の温度は３０℃以下にすることがより好ましい。さらに、酸ジクロライドとジアミンを原料とする場合、重合反応に伴って塩化水素が副生するが、これを中和する場合には炭酸リチウム、炭酸カルシウム、水酸化カルシウムなどの無機の中和剤、あるいは、エチレンオキサイド、プロピレンオキサイド、アンモニア、トリエチルアミン、トリエタノールアミン、ジエタノールアミン等の有機の中和剤を使用するとよい。 In the case of solution polymerization, in order to obtain a polymer having a high molecular weight, the water content of the solvent used for the polymerization is preferably 500 ppm or less (mass basis, the same applies hereinafter), more preferably 200 ppm or less. If both the acid dichloride and diamine used are used in equal amounts, an ultra-high molecular weight polymer may be formed. Therefore, the molar ratio should be adjusted so that one is 95.0-99.5 mol% of the other. Is preferred. In addition, the polymerization reaction of the aromatic polyamide is exothermic, but if the temperature of the polymerization system rises, side reaction may occur and the degree of polymerization may not be sufficiently increased. It is preferable to cool. The temperature of the solution during polymerization is more preferably 30 ° C. or lower. Furthermore, when acid dichloride and diamine are used as raw materials, hydrogen chloride is produced as a by-product in the polymerization reaction, but when neutralizing this, an inorganic neutralizing agent such as lithium carbonate, calcium carbonate, calcium hydroxide, Alternatively, an organic neutralizer such as ethylene oxide, propylene oxide, ammonia, triethylamine, triethanolamine, diethanolamine may be used.
本発明において用いる芳香族ポリアミド多孔質膜を得るために、芳香族ポリアミドポリマーの対数粘度（ηｉｎｈ）は、１．８〜３．５ｄｌ／ｇであることが好ましく、２．２〜３．０ｄｌ／ｇであることがより好ましい。対数粘度が１．８ｄｌ／ｇ未満であると、ポリマー分子鎖の絡み合いによる鎖間の結合力が減少するため、靭性や強度などの機械特性が低下したり、熱収縮率が大きくなることがある。対数粘度が３．５ｄｌ／ｇを超えると、溶媒への溶解性が低下したり、芳香族ポリアミド分子が凝集し、多孔質膜を製膜することが困難になることがある。 In order to obtain the aromatic polyamide porous membrane used in the present invention, the logarithmic viscosity (η inh ) of the aromatic polyamide polymer is preferably 1.8 to 3.5 dl / g, and preferably 2.2 to 3.0 dl. / G is more preferable. When the logarithmic viscosity is less than 1.8 dl / g, the bond strength between the chains due to the entanglement of the polymer molecular chains decreases, so mechanical properties such as toughness and strength may decrease, and the thermal shrinkage rate may increase. . When the logarithmic viscosity exceeds 3.5 dl / g, the solubility in a solvent may be reduced, or aromatic polyamide molecules may aggregate and it may be difficult to form a porous membrane.
次に、本発明において用いる芳香族ポリアミド多孔質膜を製造する工程に用いる製膜原液（以下、単に製膜原液ということがある。）について、説明する。 Next, a film-forming stock solution used in the process for producing the aromatic polyamide porous membrane used in the present invention (hereinafter, simply referred to as a film-forming stock solution) will be described.
製膜原液には重合後のポリマー溶液をそのまま使用してもよく、あるいはポリマーを一度単離してから上述の非プロトン性有機極性溶媒や硫酸などの無機溶剤に再溶解して使用してもよい。芳香族ポリアミドを単離する方法としては、特に限定しないが、重合後の芳香族ポリアミド溶液を多量の水中に投入することで溶媒および中和塩を水中に抽出し、析出した芳香族ポリアミドのみを分離した後、乾燥させる方法などが挙げられる。また、再溶解時に溶解助剤として金属塩などを添加してもよい。金属塩としては、非プロトン性有機極性溶媒に溶解するアルカリ金属またはアルカリ土類金属のハロゲン化物が好ましく、例えば、塩化リチウム、臭化リチウム、塩化ナトリウム、臭化ナトリウム、塩化カリウム、臭化カリウムなどが挙げられる。 The polymer solution after polymerization may be used as it is for the film-forming stock solution, or it may be used after being isolated and then redissolved in an inorganic solvent such as the above-mentioned aprotic organic polar solvent or sulfuric acid. . The method for isolating the aromatic polyamide is not particularly limited, but the solvent and neutralized salt are extracted into water by introducing the polymerized aromatic polyamide solution into a large amount of water, and only the precipitated aromatic polyamide is removed. The method of drying after isolate | separating is mentioned. Further, a metal salt or the like may be added as a dissolution aid during re-dissolution. The metal salt is preferably an alkali metal or alkaline earth metal halide dissolved in an aprotic organic polar solvent, such as lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide, etc. Is mentioned.
製膜原液１００質量％中の芳香族ポリアミドの含有量は、５〜２０質量％が好ましく、より好ましくは９〜１５質量％である。製膜原液における芳香族ポリアミドの含有量が５質量％未満であると、孔構造の粗大化により、結合できる面積が少なくなり、十分な結合強度が得られず、曲げや温度変化で結合部が剥離してしまうことがある。また、靭性や強度などの機械特性が低下したり、熱収縮率が大きくなることがある。製膜原液における芳香族ポリアミドの含有量が２０質量％を超えると、多孔質膜の製造の際に芳香族ポリアミドポリマー同士の凝集が起こりやすくなり、無孔膜や、多孔構造を有しても、透気性の無い膜になる場合がある。 The content of the aromatic polyamide in 100% by mass of the film-forming stock solution is preferably 5 to 20% by mass, more preferably 9 to 15% by mass. If the content of the aromatic polyamide in the film-forming stock solution is less than 5% by mass, the area that can be bonded is reduced due to the coarsening of the pore structure, and sufficient bonding strength cannot be obtained. May peel. In addition, mechanical properties such as toughness and strength may decrease, and the thermal shrinkage rate may increase. When the content of the aromatic polyamide in the film-forming stock solution exceeds 20% by mass, the aromatic polyamide polymers tend to agglomerate during the production of the porous film, and even if there is a nonporous film or a porous structure In some cases, the film may be non-permeable.
製膜原液には孔形成能を向上させる目的で、親水性ポリマーを混合することが好ましい。混合する親水性ポリマーは製膜原液１００質量％に対して０．１〜１０質量％であることが好ましく、０．２〜５質量％であることがより好ましい。製膜原液における親水性ポリマーの含有量が０．１質量％未満の場合、多孔質膜を形成する過程において、芳香族ポリアミド分子が凝集し、多孔質膜を製膜することが困難になることがある。含有量が１０質量％を超える場合、得られる多孔質膜において、孔構造の粗大化や強度の低下が起きることがある。また、最終的に多孔質膜中に親水性ポリマーが残存し、耐熱性や剛性の低下、親水性ポリマーの電解液中への溶出などが起きることがある。 It is preferable to mix a hydrophilic polymer with the film-forming stock solution for the purpose of improving pore forming ability. The hydrophilic polymer to be mixed is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass with respect to 100% by mass of the film-forming stock solution. When the content of the hydrophilic polymer in the film-forming stock solution is less than 0.1% by mass, aromatic polyamide molecules aggregate in the process of forming the porous film, making it difficult to form the porous film. There is. When the content exceeds 10% by mass, the pore structure may be coarsened or the strength may be reduced in the resulting porous membrane. In addition, the hydrophilic polymer may eventually remain in the porous film, resulting in a decrease in heat resistance and rigidity, and elution of the hydrophilic polymer into the electrolytic solution.
親水性ポリマーとしては、非プロトン性有機極性溶媒に溶解するポリマーのうち、極性の置換基、特に、水酸基、アシル基およびアミノ基からなる群から選ばれる少なくとも１種の置換基を含有するポリマーであることが好ましい。このようなポリマーとして、例えば、ポリビニルピロリドン（以下、ＰＶＰと記すことがある。）、ポリエチレングリコール、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸、ポリエチレンイミン等が挙げられる。芳香族ポリアミドとの相溶性が良いＰＶＰを用いることが最も好ましい。ＰＶＰの重量平均分子量は、５０万〜３００万であることが好ましい。重量平均分子量が５０万未満であると、低分子量のＰＶＰが多孔質膜に残った場合、多孔質膜の耐熱性が低下したり、電池用セパレータとして使用した際にＰＶＰが電解液中に溶出したりする恐れがある。重量平均分子量が３００万を超えると、製膜原液の溶液粘度が高くなり過ぎることで多孔質膜を製膜することが困難になることがある。親水性ポリマーは重合後の芳香族ポリアミド溶液あるいは再溶解した芳香族ポリアミド溶液中に投入しても、単離した芳香族ポリアミドとともに非プロトン性有機極性溶媒中に投入して混練してもよい。 The hydrophilic polymer is a polymer containing at least one substituent selected from the group consisting of a polar substituent, particularly a hydroxyl group, an acyl group, and an amino group, among polymers that are soluble in an aprotic organic polar solvent. Preferably there is. Examples of such a polymer include polyvinyl pyrrolidone (hereinafter sometimes referred to as PVP), polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethyleneimine, and the like. It is most preferable to use PVP having good compatibility with the aromatic polyamide. The weight average molecular weight of PVP is preferably 500,000 to 3,000,000. When the weight average molecular weight is less than 500,000, when low molecular weight PVP remains in the porous membrane, the heat resistance of the porous membrane is reduced or the PVP is dissolved in the electrolyte when used as a battery separator. There is a risk of doing. When the weight average molecular weight exceeds 3 million, it may be difficult to form a porous film because the solution viscosity of the film forming stock solution becomes too high. The hydrophilic polymer may be put into the aromatic polyamide solution after polymerization or the re-dissolved aromatic polyamide solution, or may be put into an aprotic organic polar solvent together with the isolated aromatic polyamide and kneaded.
製膜原液には、得られる多孔質膜の表面に突起を形成して静摩擦係数を低減し加工性を向上させる目的で、無機粒子または有機粒子を添加してもよい。 In order to improve the processability by forming protrusions on the surface of the resulting porous membrane to improve the coefficient of static friction and improve the workability, inorganic or organic particles may be added to the stock solution.
製膜原液の溶液粘度は、Ｂ型粘度計を用いて３０℃、１０ｒｐｍにおいて測定される値が、１００〜８００Ｐａ・ｓであることが好ましい。より好ましくは２００〜６００Ｐａ・ｓである。溶液粘度が１００Ｐａ・ｓ未満であると、孔構造の粗大化により、厚み方向の圧縮変形弾性率や圧縮変形回復率が本発明の範囲内とならないことがある。また、靭性や強度などの機械特性が低下したり、熱収縮率が大きくなることがある。溶液粘度が８００Ｐａ・ｓを超えると、多孔質膜を製膜することが困難になることがある。 As for the solution viscosity of the film-forming stock solution, the value measured at 30 ° C. and 10 rpm using a B-type viscometer is preferably 100 to 800 Pa · s. More preferably, it is 200-600 Pa.s. When the solution viscosity is less than 100 Pa · s, the compression deformation elastic modulus and the compression deformation recovery rate in the thickness direction may not fall within the scope of the present invention due to the coarsening of the pore structure. In addition, mechanical properties such as toughness and strength may decrease, and the thermal shrinkage rate may increase. If the solution viscosity exceeds 800 Pa · s, it may be difficult to form a porous membrane.
上記のようにして調製された製膜原液を用いて、いわゆる溶液製膜法により、多孔質膜の製造が行われる。溶液製膜による多孔質膜の製造の方法として、代表的には湿式法、析出法などが挙げられるが、凝固浴を用いる湿式法では、形成される孔の粗大化や厚み方向の孔形状の不均一化が起きたり、孔間に隔壁が生じやすい場合がある。そのため、本発明の多孔質膜を得るには、孔構造を微細かつ均一に制御しやすい析出法で製膜することが好ましい。 A porous membrane is produced by a so-called solution casting method using the membrane-forming stock solution prepared as described above. Typical examples of the method for producing a porous film by solution casting include a wet method and a precipitation method. However, in a wet method using a coagulation bath, the pores formed in a coarse shape or a thickness direction are formed. In some cases, non-uniformity may occur or partition walls are likely to be formed between the holes. For this reason, in order to obtain the porous film of the present invention, it is preferable to form the film by a deposition method in which the pore structure can be controlled finely and uniformly.
析出法による多孔質膜の製造を行う場合、まず、製膜原液を口金やダイコーターを用いて、支持体上にキャスト（流延）し、製膜原液のキャスト膜を得た後、ポリマーを析出させて多孔質膜を得る。支持体の素材は、特に限定しないが、ステンレス、ガラス、ポリエチレンテレフタレート（ＰＥＴ）などの樹脂などが挙げられる。キャスト膜からポリマーを析出させる方法として、調温調湿雰囲気下でキャスト膜を吸湿させてポリマーを析出させる方法、キャスト膜を冷却することによりポリマーの溶解性を低下させて相分離または析出させる方法、キャスト膜に霧状の水を吹き付けてポリマーを析出させる方法などが挙げられる。冷却する方法ではポリマーの析出までに時間を要し、孔形状の不均一化が起きやすかったり、生産性が低下することがある。一方、霧状の水を吹き付ける方法では、表面に緻密な層が形成されることがある。これらのことから、調温調湿雰囲気下でキャスト膜に吸湿させる方法が、水の供給速度および量を任意に制御可能で、均質な多孔質構造を短時間で形成させることができることから好ましい。 When producing a porous film by the precipitation method, first, the film-forming stock solution is cast (cast) on a support using a die or a die coater to obtain a cast film of the film-forming stock solution, Precipitate to obtain a porous film. The material for the support is not particularly limited, and examples thereof include resins such as stainless steel, glass, and polyethylene terephthalate (PET). As a method for precipitating the polymer from the cast membrane, a method for precipitating the polymer by absorbing the cast membrane in a temperature-controlled humidity atmosphere, a method for reducing the solubility of the polymer by cooling the cast membrane and causing phase separation or precipitation. And a method of depositing a polymer by spraying mist water on a cast film. In the cooling method, it takes time to deposit the polymer, and the pore shape is likely to be nonuniform, and the productivity may be lowered. On the other hand, in the method of spraying mist-like water, a dense layer may be formed on the surface. For these reasons, the method of absorbing moisture into the cast film under a temperature-controlled humidity atmosphere is preferable because the supply rate and amount of water can be arbitrarily controlled and a homogeneous porous structure can be formed in a short time.
上記した多孔質膜の製造工程において、調温調湿雰囲気の容積絶対湿度は１０〜１８０ｇ／ｍ３とすることが好ましい。より好ましくは３０〜１００ｇ／ｍ３、さらに好ましくは４０〜９０ｇ／ｍ３である。また、この絶対湿度を満たす範囲内で、雰囲気の温度は２０〜７０℃、相対湿度は６０〜９５％ＲＨとすることが好ましい。より好ましくは、雰囲気の温度は３０〜６０℃、相対湿度は７０〜９０％ＲＨである。調温調湿雰囲気下での処理時間は０．５〜５分とすることが好ましく、０．５〜３分とすることがより好ましい。 In the manufacturing process of the porous membrane described above, the volume absolute humidity of the temperature-controlled and humidity-controlled atmosphere is preferably 10 to 180 g / m 3 . More preferably, it is 30-100 g / m < 3 >, More preferably, it is 40-90 g / m < 3 >. Moreover, within the range which satisfy | fills this absolute humidity, it is preferable that the temperature of atmosphere is 20-70 degreeC and a relative humidity shall be 60-95% RH. More preferably, the temperature of the atmosphere is 30 to 60 ° C., and the relative humidity is 70 to 90% RH. The treatment time in the temperature-controlled humidity atmosphere is preferably 0.5 to 5 minutes, and more preferably 0.5 to 3 minutes.
次に、析出させた芳香族ポリアミド多孔質膜を、支持体ごとあるいは支持体から剥離して湿式浴に導入し、溶媒、取り込まれなかった親水性ポリマー、および無機塩等の添加剤の除去を行う。浴組成は特に限定されないが、水、あるいは有機溶媒／水の混合系を用いることが、経済性および取扱いの容易さから好ましい。また、湿式浴中には無機塩が含まれていてもよい。湿式浴温度は、溶媒等を効率的に除去できることから、２０℃以上であることが好ましい。浴温度の上限は特に定めることはないが、水の蒸発や沸騰による気泡の発生の影響を考えると、９０℃までに抑えることが効率的である。導入時間は、１〜２０分にすることが好ましい。さらに、湿式浴中で多孔質膜の長手方向（ＭＤ）および幅方向（ＴＤ）に延伸を施してもよい。 Next, the deposited aromatic polyamide porous membrane is peeled off from the support or from the support and introduced into a wet bath to remove the solvent, the hydrophilic polymer not taken in, and additives such as inorganic salts. Do. The bath composition is not particularly limited, but it is preferable to use water or an organic solvent / water mixed system from the viewpoint of economy and ease of handling. Further, the wet bath may contain an inorganic salt. The wet bath temperature is preferably 20 ° C. or higher because the solvent and the like can be efficiently removed. Although the upper limit of the bath temperature is not particularly defined, it is efficient to suppress the temperature to 90 ° C. in consideration of the generation of bubbles due to water evaporation or boiling. The introduction time is preferably 1 to 20 minutes. Furthermore, you may extend | stretch in the longitudinal direction (MD) and width direction (TD) of a porous membrane in a wet bath.
次に、脱溶媒を終えた多孔質膜に、テンターなどを用いて熱処理を施す。この時、含水状態の多孔質膜から水分を乾燥させる前に、多孔質膜の長手方向（ＭＤ）および幅方向（ＴＤ）への延伸を完了させた後、芳香族ポリアミドのガラス転移温度を上回る温度で熱処理を施すことが好ましい。延伸を含水状態で施すことで、芳香族ポリアミドの分子鎖が延伸方向へ配向することを抑制でき、伸度の高い多孔質膜が得られる。また、熱処理を芳香族ポリアミドのガラス転移温度を上回る温度で施すことで、加工時や、電池セパレータとして使用する際の乾燥工程などの様々な温度の加熱においても、収縮、変形を抑制できる。 Next, the porous film that has been desolvated is subjected to heat treatment using a tenter or the like. At this time, after drying the porous film in the longitudinal direction (MD) and the width direction (TD) before drying the moisture from the water-containing porous film, the glass transition temperature of the aromatic polyamide is exceeded. Heat treatment is preferably performed at a temperature. By performing stretching in a water-containing state, the molecular chain of the aromatic polyamide can be suppressed from being oriented in the stretching direction, and a porous film having a high elongation can be obtained. Moreover, shrinkage | contraction and a deformation | transformation can be suppressed also in the heating of various temperature, such as a drying process at the time of a process, and using as a battery separator by performing heat processing at the temperature exceeding the glass transition temperature of aromatic polyamide.
次に、芳香族ポリアミド多孔質膜を袋状に結合する方法について説明する。芳香族ポリアミド多孔質膜同士を結合する場合、結合部分に、溶媒を塗布し貼り合わせ後、乾燥する方法、接着剤を用いる方法、結合部分にシート状にポリオレフィンなどの低融点の熱可塑性樹脂を挟み、加圧、熱処理する方法、多孔質膜に表面処理を施した後、圧縮、加熱により積層する方法、芳香族ポリアミドからなる糸、帯状の膜により縫合する方法、多孔質膜から切り出された切り欠き同士を交差させる方法などが挙げられるが、耐薬品性、耐熱性に優れ、袋状にした時の厚みが抑えられる、多孔質膜に表面処理を施した後、圧縮、加熱により積層する方法が好適である。多孔質膜への表面処理としては、コロナ放電処理（各種ガス雰囲気中のコロナ放電処理も含む）、常圧または低圧、高温、低温各種条件を組み合わせたプラズマ処理、化学薬品や紫外線、電子線等による酸化処理等が挙げられるが、表裏に接続する孔を有する多孔質膜が処理対象であることを考慮し、また、本発明の目的である芳香族ポリアミド多孔質膜の物性の低下を抑えるためには、比較的低温で加工できる各種ガス雰囲気下での低温プラズマ処理が特に好ましい。 Next, a method for bonding the aromatic polyamide porous membrane in a bag shape will be described. When bonding aromatic polyamide porous membranes to each other, a solvent is applied to the bonding portion, a method of drying after bonding, a method using an adhesive, and a low melting point thermoplastic resin such as polyolefin in a sheet shape at the bonding portion. A method of sandwiching, pressurizing and heat-treating, applying a surface treatment to a porous membrane, then laminating by compression and heating, a method of stitching with an aromatic polyamide thread, a strip-like membrane, cut out from a porous membrane The method of crossing notches is mentioned, but it is excellent in chemical resistance and heat resistance, the thickness when it is made into a bag shape can be suppressed, and after applying surface treatment to the porous film, it is laminated by compression and heating The method is preferred. Surface treatments for porous membranes include corona discharge treatment (including corona discharge treatment in various gas atmospheres), plasma treatment combining various conditions of normal pressure or low pressure, high temperature, and low temperature, chemicals, ultraviolet rays, electron beams, etc. In order to suppress deterioration of physical properties of the aromatic polyamide porous membrane, which is an object of the present invention, considering that the porous membrane having pores connected to the front and back is a target to be treated. In particular, low-temperature plasma treatment in various gas atmospheres that can be processed at a relatively low temperature is particularly preferable.
ここでいう低温プラズマ処理とは、芳香族ポリアミド多孔質膜の表面を、電極間に直流または交流の高電圧を印加することによって発生する放電にさらすことによってなされる処理で、該処理時の圧力は特に限定されることなく処理装置、放電形式なども適宜選定すればよい。処理雰囲気はアルゴン、ヘリウム、窒素、酸素、空気、二酸化炭素、水蒸気などが一般的に用いられるが、水蒸気含有雰囲気下が処理効率が良く、特に好ましい。また水蒸気は、アルゴン、ヘリウム、窒素、酸素、空気、二酸化炭素などの別のガスで希釈してもよい。この表面処理により、ポリマーのアミド基の分解や核置換基の脱離反応が起こって、フィルム表面にラジカルが発生し、次のプレス工程でラジカル同士が反応して接合が起こる。 The term “low temperature plasma treatment” as used herein refers to a treatment performed by exposing the surface of the aromatic polyamide porous membrane to a discharge generated by applying a direct or alternating high voltage between the electrodes. Is not particularly limited, and a processing apparatus, a discharge type, and the like may be appropriately selected. Argon, helium, nitrogen, oxygen, air, carbon dioxide, water vapor and the like are generally used as the treatment atmosphere, but a water vapor-containing atmosphere is particularly preferred because of good treatment efficiency. The water vapor may be diluted with another gas such as argon, helium, nitrogen, oxygen, air, carbon dioxide. By this surface treatment, decomposition of the amide group of the polymer and elimination reaction of the nucleus substituent occur, radicals are generated on the film surface, and the radicals react with each other in the next pressing step to cause bonding.
更に、この表面処理の処理強度（印加電圧／（処理速度×電極幅）で計算した値）が１００Ｗ・ｍｉｎ／ｍ２以上であることが好ましい。１００Ｗ・ｍｉｎ／ｍ２未満では、ラジカルの発生が不十分で、結合が不十分となり、伸度や屈曲特性が低下することがある。処理強度が強すぎるとポリマーの分解が進み、耐熱性が低下することがあるため、上限は２，０００Ｗ・ｍｉｎ／ｍ２である。ポリマーの分解が進むことなく、必要な接合力が得られることから、処理強度は３００〜１，０００Ｗ・ｍｉｎ／ｍ２であることがより好ましい。 Furthermore, it is preferable that the treatment intensity of the surface treatment (applied voltage / (treatment speed × electrode width)) is 100 W · min / m 2 or more. If it is less than 100 W · min / m 2 , the generation of radicals is insufficient, the bonding becomes insufficient, and the elongation and bending properties may deteriorate. If the treatment strength is too strong, polymer decomposition proceeds and the heat resistance may decrease, so the upper limit is 2,000 W · min / m 2 . It is more preferable that the treatment strength is 300 to 1,000 W · min / m 2 , since the necessary bonding force can be obtained without the decomposition of the polymer.
次に、上記表面処理を行った芳香族ポリアミド多孔質膜を所定の形状に切り出し重ね合わせて、結合部を熱板プレス、真空プレス、加熱ロールプレス法等を行うことにより、ラジカル同士が反応して結合が起こる。熱処理の条件は、１８０〜３５０℃であると物性の低下を抑えながら、接合できるため好ましく、２００〜３００℃であることがより好ましい。また、プレス圧力は特に限定されないが１〜５０ｋｇ／ｃｍ２の範囲が一般的である。また、プレス時間は多孔質膜の厚さやプレス方法によって異なるが、熱処理時の温度で１分〜１０時間の範囲が一般的である。プレス後は徐冷してから取り出す方がフィルムの平面性の保持から好ましい。 Next, the surface-treated aromatic polyamide porous membrane is cut into a predetermined shape and superimposed, and the bonding part is subjected to hot plate press, vacuum press, heated roll press method, etc., so that the radicals react with each other. Bonding occurs. The heat treatment condition is preferably 180 to 350 ° C., since bonding can be performed while suppressing a decrease in physical properties, and more preferably 200 to 300 ° C. The pressing pressure is not particularly limited, but is generally in the range of 1 to 50 kg / cm2. The pressing time varies depending on the thickness of the porous film and the pressing method, but is generally in the range of 1 minute to 10 hours at the heat treatment temperature. After pressing, it is preferable to slowly cool and then remove from the viewpoint of maintaining the flatness of the film.
本発明の芳香族ポリアミド袋状セパレータは、電極の位置決めが容易で、且つ、外部からの衝撃による電極の移動も最小限にとどめることが可能である。また、袋状とすることで、体積変化の大きい電極などと共に使用した場合であっても、セパレータ自体の幅、長さに影響を受けず、優れた追従性を示す。さらには、面方向への熱変形が小さく、高温においても連続して使用することが可能となる。 The aromatic polyamide bag-like separator of the present invention can easily position the electrode, and can minimize the movement of the electrode due to an impact from the outside. Moreover, even if it is a case where it is a case where it uses with an electrode etc. with a large volume change by making it into a bag shape, it is not influenced by the width | variety and length of separator itself, and shows outstanding followable | trackability. Furthermore, thermal deformation in the surface direction is small, and it can be used continuously even at high temperatures.
本発明の芳香族ポリアミド袋状セパレータを用いた電池の例として、リチウムイオン二次電池が挙げられ、特に負極材料として、高容量ながら体積変化の大きい合金系負極活物質を用いた場合に、良好な電池性能を発揮させ得る。合金系負極活物質として、シリコン酸化物、シリコン合金、スズ合金、リチウム合金などが挙げられ、これらを２種以上混合して用いても良いし、黒鉛などの炭素系活物質と混合して用いてもよい。 As an example of a battery using the aromatic polyamide bag-like separator of the present invention, a lithium ion secondary battery can be mentioned. Battery performance can be demonstrated. Examples of the alloy-based negative electrode active material include silicon oxide, silicon alloy, tin alloy, and lithium alloy. These may be used as a mixture of two or more thereof, or may be used as a mixture with a carbon-based active material such as graphite. May be.
本発明の芳香族ポリアミド袋状セパレータを二次電池用セパレータとして用いた場合、電池の電極に合金系負極などの体積変化の大きい電極を用いた場合であっても、高い出力と長期間の優れたサイクル特性が得られる。さらに、本発明の芳香族ポリアミド袋状セパレータは、優れた耐熱性を有するため、得られた二次電池は高温でも使用可能となるのに加え、異常発熱を起こした場合も、高い安全性を保持することが可能である。従って、本発明の芳香族ポリアミド多孔質膜をセパレータとして用いた二次電池は、小型の電子機器を始め、電気自動車（ＥＶ）やハイブリッド車（ＨＥＶ）、プラグインハイブリッド車（ＰＨＥＶ）などの交通機関、産業用クレーンなどの大型の産業機器の動力源として好適に用いることができる。また、太陽電池、風力発電装置などにおける電力の平準化やスマートグリッドのための蓄電装置としても好適に用いることができる。 When the aromatic polyamide bag separator of the present invention is used as a separator for a secondary battery, high output and long-term superiority can be obtained even when an electrode having a large volume change such as an alloy negative electrode is used as the battery electrode. Cycle characteristics can be obtained. Furthermore, since the aromatic polyamide bag separator of the present invention has excellent heat resistance, the obtained secondary battery can be used even at high temperatures, and also has high safety even when abnormal heat generation occurs. It is possible to hold. Therefore, the secondary battery using the aromatic polyamide porous membrane of the present invention as a separator is used for traffic such as small electronic devices, electric vehicles (EV), hybrid vehicles (HEV), plug-in hybrid vehicles (PHEV) and the like. It can be suitably used as a power source for large-scale industrial equipment such as engines and industrial cranes. Further, it can be suitably used as a power storage device for leveling power or a smart grid in a solar cell, a wind power generator, or the like.
［物性の測定方法ならびに効果の評価方法］
実施例における物性の測定方法は次の方法に従って行った。
[Methods for measuring physical properties and methods for evaluating effects]
The physical properties were measured in the examples according to the following method.
（１）空孔率
２００ｍｍ角の試料の厚みと質量を測定し、多孔質膜の見かけの密度（かさ密度）ｄ１を求めた。これとポリマーの真密度ｄ０より、下式を用いて空孔率を算出した。
(1) the thickness and mass of the sample of porosity 200mm angle was measured to determine the apparent density of the porous membrane (bulk density) d 1. From this and the true density d 0 of the polymer, the porosity was calculated using the following equation.
空孔率（％）＝（１−ｄ１／ｄ０）×１００
（２）ガーレ透気度
Ｂ型ガーレーデンソメーター（安田精機製作所社製）を使用し、ＪＩＳ−Ｐ８１１７（１９９８）に規定された方法に従って、多孔質膜のガーレ透気度の測定を行った。試料の多孔質膜を直径２８．６ｍｍ、面積６４５ｍｍ２の円孔に締め付け、内筒により（内筒質量５６７ｇ）、筒内の空気を試験円孔部から筒外へ通過させ、空気１００ｍｌが通過する時間を測定することでガーレ透気度とした。
Porosity (%) = (1−d 1 / d 0 ) × 100
(2) Gurley air permeability A B-type Gurley densometer (manufactured by Yasuda Seiki Seisakusho) was used, and the Gurley air permeability of the porous film was measured according to the method defined in JIS-P8117 (1998). The porous membrane of the sample is clamped to a circular hole with a diameter of 28.6 mm and an area of 645 mm 2 , and the air inside the cylinder is passed from the test hole to the outside of the cylinder by the inner cylinder (inner cylinder mass 567 g), and 100 ml of air passes. The Gurley air permeability was determined by measuring the time to perform.
（３）厚み
定圧厚み測定器ＦＦＡ−１（尾崎製作所社製）を用いて多孔質膜の厚みを測定した。測定子径は５ｍｍ、測定荷重は１．２５Ｎである。幅方向に、２０ｍｍ間隔で１０箇所測定し、平均値を求めた。
(3) Thickness The thickness of the porous membrane was measured using a constant pressure thickness measuring device FFA-1 (manufactured by Ozaki Seisakusho). The probe diameter is 5 mm and the measurement load is 1.25 N. Ten points were measured at intervals of 20 mm in the width direction, and the average value was obtained.
（４）２００℃における熱収縮率
試料の芳香族ポリアミド袋状セパレータの矩形の辺の長さを測定しＬ１とした。２００℃の熱風オーブン中で１０分間、実質的に張力を掛けない状態で熱処理を行った後の矩形の辺の長さをＬ２とし、下式で熱収縮率を計算した。矩形の４辺についてそれぞれ測定し、同一の製造方法にて得られた芳香族ポリアミド袋状セパレータを５袋測定し、それぞれの辺の平均値を求めた。
(4) measure the length of the rectangular sides of the aromatic polyamide pouched separator thermal shrinkage sample at 200 ° C. and was L 1. 200 ° C. 10 min in a hot air oven at substantially the length of the rectangular sides after the heat treatment in the absence of tension and L 2, was calculated thermal shrinkage by the following formula. Four sides of the rectangle were measured, and five aromatic polyamide bag-like separators obtained by the same production method were measured, and the average value of each side was determined.
熱収縮率（％）＝（（Ｌ１−Ｌ２）／Ｌ１）×１００
（５）対数粘度（ηｉｎｈ）
臭化リチウム（ＬｉＢｒ）を２．５質量％添加したＮ−メチルピロリドン（ＮＭＰ）に、ポリマーを０．５ｇ／ｄｌの濃度で溶解させ、ウベローデ粘度計を使用して、３０℃にて流下時間を測定した。ポリマーを溶解させないブランクのＮＭＰの流下時間も同様に測定し、下式を用いて対数粘度（ηｉｎｈ）を算出した。
Thermal contraction rate (%) = ((L 1 −L 2 ) / L 1 ) × 100
(5) Logarithmic viscosity (η inh )
The polymer was dissolved at a concentration of 0.5 g / dl in N-methylpyrrolidone (NMP) to which 2.5% by mass of lithium bromide (LiBr) was added, and the flow-down time was 30 ° C. using an Ubbelohde viscometer. Was measured. The flow time of blank NMP in which the polymer was not dissolved was measured in the same manner, and the logarithmic viscosity (η inh ) was calculated using the following equation.
ηｉｎｈ（ｄｌ／ｇ）＝〔ｌｎ（ｔ／ｔ０）〕／０．５
ｔ０：ブランクの流下時間（秒）
ｔ：サンプルの流下時間（秒）
（６）芳香族ポリアミドのガラス転移温度
温度変調示差走査熱量測定（温度変調ＤＳＣ）法により、以下の条件で測定した。測定試料は、重合後の溶液から芳香族ポリアミドのみを単離したものを用いた。
η inh (dl / g) = [ln (t / t 0 )] / 0.5
t 0 : Blank flow time (seconds)
t: Sample flow time (seconds)
(6) Glass transition temperature of aromatic polyamide The glass transition temperature was measured by the temperature modulation differential scanning calorimetry (temperature modulation DSC) method under the following conditions. As the measurement sample, one obtained by isolating aromatic polyamide alone from the solution after polymerization was used.
測定装置：Ｑ１００（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製）
データ処理装置：Ｕｎｉｖｅｒｓａｌ Ａｎａｌｙｓｉｓ ２０００
（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製）
測定雰囲気：窒素流（５０ｍＬ／分）
温度・熱量校正：高純度インジウム
温度範囲：２５〜３５０℃
昇温速度：２℃／分
試料量：約５ｍｇ
（７）耐熱性
試料の芳香族ポリアミド袋状セパレータ５袋を、３００℃の熱風オーブン中で１０分間、実質的に張力を掛けない状態で加熱を行った後、結合部の剥がれ、しわ、変色を観察し、下記の基準で判定した。
Measuring device: Q100 (manufactured by TA Instruments)
Data processing device: Universal Analysis 2000
(Manufactured by TA Instruments)
Measurement atmosphere: Nitrogen flow (50 mL / min)
Temperature / calorie calibration: High purity indium Temperature range: 25-350 ° C
Temperature increase rate: 2 ° C / min Sample amount: Approximately 5mg
(7) Heat resistance After heating 5 samples of sample aromatic polyamide bag-like separators in a hot air oven at 300 ° C. for 10 minutes with substantially no tension applied, peeling, wrinkling, and discoloration of the bonded portion Was observed and judged according to the following criteria.
○：５袋とも変化無し
△：結合部の剥がれ、しわ、変色のうち１つがあるものが２袋以下。
○: No change in all five bags Δ: Two or less bags have one of peeling, wrinkle, and discoloration of the joint.
×：結合部の剥がれ、しわ、変色のうち１つあるものが３袋以上、２つ以上があるものが１袋以上。 X: Three or more bags having one of peeling, wrinkle, and discoloration of the connecting portion, and one or more bags having two or more.
以下に実施例に基づいて本発明をより具体的に説明するが、本発明はこれらに限定されるものでない。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto.
（実施例１）
脱水したＮ−メチルピロリドン（ＮＭＰ、三菱化学社製）に、ジアミン全量に対して２０モル％に相当する２−クロロ−１，４−フェニレンジアミン（日本化薬社製）と８０モル％に相当する４，４’−ジアミノジフェニルエーテル（東京化成社製）を窒素気流下で溶解させ、３０℃以下に冷却した。そこへ、系内を窒素気流下、３０℃以下に保った状態で、ジアミン全量に対して９９モル％に相当する２−クロロテレフタロイルクロライド（日本軽金属社製）を添加して、全量添加後、約２時間の撹拌を行い、芳香族ポリアミドを重合した。得られた重合溶液を、酸クロライド全量に対して９７モル％の炭酸リチウム（本荘ケミカル社製）および６モル％のジエタノールアミン（東京化成社製）により中和することで芳香族ポリアミドの溶液を得た。得られた芳香族ポリアミドの対数粘度ηｉｎｈは２．５ｄｌ／ｇ、ガラス転移温度は２５５℃であった。
Example 1
To dehydrated N-methylpyrrolidone (NMP, manufactured by Mitsubishi Chemical Corporation), 2-chloro-1,4-phenylenediamine (manufactured by Nippon Kayaku Co., Ltd.) corresponding to 20 mol% and 80 mol% corresponding to the total amount of diamine 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in a nitrogen stream and cooled to 30 ° C. or lower. Then, 2-chloroterephthaloyl chloride (manufactured by Nippon Light Metal Co., Ltd.) corresponding to 99 mol% was added to the total amount of diamine while maintaining the system at 30 ° C. or lower under a nitrogen stream, and the total amount was added Thereafter, the mixture was stirred for about 2 hours to polymerize the aromatic polyamide. The obtained polymerization solution was neutralized with 97 mol% lithium carbonate (Honjo Chemical Co., Ltd.) and 6 mol% diethanolamine (Tokyo Kasei Co., Ltd.) with respect to the total amount of acid chloride to obtain an aromatic polyamide solution. It was. The obtained aromatic polyamide had a logarithmic viscosity η inh of 2.5 dl / g and a glass transition temperature of 255 ° C.
次に、得られた芳香族ポリアミド溶液中にポリビニルピロリドン（ＰＶＰ、ＢＡＳＦ社製Ｋ９０）、ＲＯ水、および希釈用のＮＭＰを、以下の組成になるように添加し、６０℃で２時間撹拌を行うことで製膜原液を得た。製膜原液１００質量％に対するそれぞれの成分の最終的な含有量は、芳香族ポリアミド１０質量％、ＰＶＰ５質量％、水１０質量％であり、残りの７５質量％はＮＭＰおよび重合原液に含まれる中和塩（塩化リチウム、ジエタノールアミン塩酸塩）である。 Next, polyvinylpyrrolidone (PVP, BASF K90), RO water, and NMP for dilution are added to the obtained aromatic polyamide solution so as to have the following composition, followed by stirring at 60 ° C. for 2 hours. A film forming stock solution was obtained. The final content of each component with respect to 100% by mass of the film-forming stock solution is 10% by mass of aromatic polyamide, 5% by mass of PVP, and 10% by mass of water, and the remaining 75% by mass is contained in NMP and the polymerization stock solution. Japanese salt (lithium chloride, diethanolamine hydrochloride).
この製膜原液を、口金から支持体であるステンレス（ＳＵＳ３１６）ベルト上に膜状に塗布し、温度５０℃、相対湿度８５％ＲＨの調温調湿空気中で、塗布膜がベルトから剥離可能になるまで処理した。次に、塗布膜をベルトから剥離し、３０℃の水浴に導入することで、溶媒およびＰＶＰなどの抽出を行うとともに、定幅で長手方向（ＭＤ）に１．２０倍の延伸を施した。続いて、得られた含水状態の多孔質膜を、温度１５０℃のテンター室内に導入し、定長で幅方向（ＴＤ）に１．２０倍の延伸を施した。その後、定長定幅で温度２８０℃のテンター室内にて１分間の熱処理を施し、多孔質膜を得た。 This film-forming stock solution can be applied in the form of a film from a base to a stainless steel (SUS316) belt, which is a support, and the coating film can be peeled off from the belt in temperature-controlled air at a temperature of 50 ° C. and a relative humidity of 85% RH. Processed until Next, the coating film was peeled from the belt and introduced into a 30 ° C. water bath to extract the solvent, PVP, and the like, and at the same time, stretched 1.20 times in the longitudinal direction (MD). Subsequently, the obtained porous film in a water-containing state was introduced into a tenter chamber having a temperature of 150 ° C., and stretched 1.20 times in the width direction (TD) at a constant length. Thereafter, heat treatment was performed for 1 minute in a tenter chamber having a constant length and a constant width and a temperature of 280 ° C. to obtain a porous film.
得られた芳香族ポリアミド多孔質膜を、幅５０ｍｍ、長さ１４０ｍｍの帯状に切り出し、芳香族ポリアミド多孔質膜が幅方向両端のみ１０ｍｍずつ露出するよう、幅３０ｍｍのポリイミド製微粘着テープを貼り付けた。 The obtained aromatic polyamide porous membrane is cut into a strip shape having a width of 50 mm and a length of 140 mm, and a polyimide slightly adhesive tape with a width of 30 mm is applied so that the aromatic polyamide porous membrane is exposed only 10 mm at both ends in the width direction. It was.
この芳香族ポリアミド多孔質膜のポリイミド製微粘着テープを貼り付けた面に低温プラズマ処理を以下の方法、条件で施した。内部電極方式の低温プラズマ処理装置で、処理ガスにＡｒを用い、圧力は４０Ｐａ、処理速度は０．５ｍ／分、処理強度（印加電圧／（処理速度×電極幅）で計算した値）は１，０００Ｗ・ｍｉｎ／ｍ２とした。 A low-temperature plasma treatment was performed on the surface of the aromatic polyamide porous membrane on which the polyimide slightly adhesive tape was affixed under the following method and conditions. An internal electrode type low temperature plasma processing apparatus using Ar as a processing gas, a pressure of 40 Pa, a processing speed of 0.5 m / min, and a processing intensity (value calculated by applied voltage / (processing speed × electrode width)) of 1. , 000 W · min / m 2 .
上記の低温プラズマ処理した芳香族ポリアミド多孔質膜から、ポリイミド製微粘着テープを剥離し、処理面を内側にして、長さ方向７０ｍｍの位置から折り合わせ、温度２００℃、圧力５ｋｇ／ｃｍ２、０．５時間の条件で熱板プレス装置にて結合した。積層後は急に圧力を開放せず熱板の温度が３０℃まで冷却してから圧力を開放させ芳香族ポリアミド袋状セパレータを取り出した。 From the above-mentioned low-temperature plasma-treated aromatic polyamide porous film, the polyimide slightly adhesive tape is peeled off, and the treated surface is turned inside, and folded from a position in the length direction of 70 mm, temperature 200 ° C., pressure 5 kg / cm 2 , Bonding was performed by a hot plate press apparatus under the condition of 0.5 hour. After lamination, the pressure was released after the temperature of the hot plate was cooled to 30 ° C. without suddenly releasing the pressure, and the aromatic polyamide bag separator was taken out.
得られた芳香族ポリアミド袋状セパレータの、各辺の２００℃における熱収縮率は、すべての辺において０．２％以下であり、最大で０．０２％であった。３００℃での耐熱性は、結合部の剥がれ、しわ、変色は無く、良好であった。 The heat shrinkage rate at 200 ° C. of each side of the obtained aromatic polyamide bag-like separator was 0.2% or less on all sides, and 0.02% at the maximum. The heat resistance at 300 ° C. was good with no peeling, wrinkling, or discoloration of the bonded portion.
（実施例２）
実施例１と同様に作成した芳香族ポリアミド多孔質膜を、幅５０ｍｍ、長さ１４０ｍｍの帯状に１枚、幅５ｍｍ、長さ１４０ｍｍの帯状に２枚切り出した。幅５０ｍｍ、長さ１４０ｍｍの帯状に切り出したものを、長さ方向７０ｍｍの位置から折り合わせ、幅方向、両端から５ｍｍから１０ｍｍにかけて５ｍｍの切れ込みを長さ方向に５ｍｍ間隔に片側１３カ所、計２６カ所に入れた。この切れ込みに、幅５ｍｍ、長さ１４０ｍｍの帯状に切り出したものを通して縫合し、余剰部分は切り取り、芳香族ポリアミド袋状セパレータとした。
(Example 2)
An aromatic polyamide porous membrane prepared in the same manner as in Example 1 was cut into one strip having a width of 50 mm and a length of 140 mm, and two strips having a width of 5 mm and a length of 140 mm. Folded into a strip shape with a width of 50 mm and a length of 140 mm, folded from the position of 70 mm in the length direction, 5 mm incision from the width direction, 5 mm to 10 mm from both ends, 13 points on one side at intervals of 5 mm in the length direction, total 26 I put it in the place. This cut was sewn through a strip of 5 mm width and 140 mm length, and the surplus portion was cut off to obtain an aromatic polyamide bag separator.
得られた芳香族ポリアミド袋状セパレータの、各辺の２００℃における熱収縮率は、すべての辺において０．２％以下であり、最大で０．０３％であった。３００℃での耐熱性は、結合部の剥がれ、しわ、変色は無く、良好であった。 The heat shrinkage rate of each side of the obtained aromatic polyamide bag-like separator at 200 ° C. was 0.2% or less on all sides, and 0.03% at the maximum. The heat resistance at 300 ° C. was good with no peeling, wrinkling, or discoloration of the bonded portion.
（実施例３）
実施例１と同様に作成した芳香族ポリアミド多孔質膜を、幅５０ｍｍ、長さ１４０ｍｍの帯状に切り出し、幅方向両端の１０ｍｍにエポキシ樹脂の液体接着剤を８μｍの厚みになるようにハンドコートした。次に、この多孔質膜を８０℃で１分、１５０℃で２分オーブンに入れて仮乾燥させた。仮乾燥した多孔質膜をエポキシ樹脂の液体接着剤をコート下面を内側にし、長さ方向に７０ｍｍの位置から折り合わせ、１３０℃のロールを用いて、速度０．３ｍ／分でラミネートした。その後、１８０℃のオーブン内で３時間、２２０℃のオーブンで３０分乾燥し、芳香族ポリアミド袋状セパレータとした。
(Example 3)
An aromatic polyamide porous membrane prepared in the same manner as in Example 1 was cut into a strip having a width of 50 mm and a length of 140 mm, and a liquid adhesive of epoxy resin was hand-coated to a thickness of 8 μm at 10 mm at both ends in the width direction. . Next, this porous membrane was put into an oven at 80 ° C. for 1 minute and at 150 ° C. for 2 minutes, and was temporarily dried. The temporarily dried porous film was coated with an epoxy resin liquid adhesive with the bottom surface on the inside, folded from a position of 70 mm in the length direction, and laminated at a speed of 0.3 m / min using a 130 ° C. roll. Then, it was dried in an oven at 180 ° C. for 3 hours and in an oven at 220 ° C. for 30 minutes to obtain an aromatic polyamide bag-like separator.
得られた芳香族ポリアミド袋状セパレータの、各辺の２００℃における熱収縮率は、すべての辺において０．２％以下であり、最大で０．１８％であった。３００℃での耐熱性は、２袋が変色していた。 The heat shrinkage rate at 200 ° C. of each side of the obtained aromatic polyamide bag-like separator was 0.2% or less on all sides, and was 0.18% at the maximum. As for the heat resistance at 300 ° C., two bags were discolored.
（実施例４）
実施例１と同様に作成した芳香族ポリアミド多孔質膜を、幅５０ｍｍ、長さ１４０ｍｍの帯状に切り出し、長さ方向に７０ｍｍの位置から折り合わせ、幅方向両端の１０ｍｍの位置に、融点１１５℃、厚み１０μｍのポリエチレンフィルムを幅１０ｍｍ、長さ７０ｍｍに切り出したものを挟み込み、１３０℃のロールを用いて、速度０．３ｍ／分でラミネート、芳香族ポリアミド袋状セパレータとした。
Example 4
An aromatic polyamide porous membrane prepared in the same manner as in Example 1 was cut into a strip having a width of 50 mm and a length of 140 mm, folded from the position of 70 mm in the length direction, and melted at 115 ° C. at 10 mm positions at both ends in the width direction. A 10 μm thick polyethylene film cut into a width of 10 mm and a length of 70 mm was sandwiched, and a 130 ° C. roll was used to laminate at a speed of 0.3 m / min to obtain an aromatic polyamide bag separator.
得られた芳香族ポリアミド袋状セパレータの、各辺の２００℃における熱収縮率は、開口部のある辺と、それに向き合った辺は１％以下であったが、ポリエチレンフィルムを挟み込み結合した辺は１．０％を超えており、最大で２．６％であった。３００℃での耐熱性は、５袋すべて変色、そのうち２袋は結合部の剥がれがあった。 The thermal polyamide shrinkage rate at 200 ° C. of each side of the obtained aromatic polyamide bag-like separator was 1% or less for the side with the opening and the side facing it, but the side with the polyethylene film sandwiched and bonded was It exceeded 1.0%, and it was 2.6% at the maximum. The heat resistance at 300 ° C. was discolored in all 5 bags, of which 2 bags were peeled off at the joint.
（比較例１）
溶融製膜２軸延伸にて作製した、ポリプロピレン多孔質フィルム（厚みは２１μｍ、空孔率は６２％、ガーレ値２４０ｓｅｃ／１００ｃｃ、破断伸度は８３％、破断強度は５６ＭＰａ）を、幅５０ｍｍ、長さ１４０ｍｍの帯状に切り出し、長さ方向に７０ｍｍの位置から折り合わせ、幅方向両端の１０ｍｍを１８０℃のロールを用いて、速度０．３ｍ／分でラミネートし、ポリオレフィン袋状セパレータとした。
(Comparative Example 1)
A polypropylene porous film (thickness: 21 μm, porosity: 62%, Gurley value: 240 sec / 100 cc, elongation at break: 83%, break strength: 56 MPa) prepared by melt film biaxial stretching, width 50 mm, A strip of 140 mm in length was cut out, folded from the position of 70 mm in the length direction, and 10 mm at both ends in the width direction were laminated at a speed of 0.3 m / min using 180 ° C. rolls to obtain a polyolefin bag separator.
得られた芳香族ポリアミド袋状セパレータの、各辺の２００℃における熱収縮率は、すべての辺において１．０％を超えており、最大で６．８％であった。３００℃での耐熱性は、５袋すべてが溶融していた。 The heat shrinkage rate at 200 ° C. of each side of the obtained aromatic polyamide bag separator exceeded 1.0% on all sides, and was 6.8% at the maximum. As for the heat resistance at 300 ° C., all five bags were melted.
本発明の芳香族ポリアミド袋状セパレータは、電極の位置決めが容易で、且つ、外部からの衝撃による電極の移動も最小限にとどめることが可能である。また、袋状とすることで、体積変化の大きい電極などと共に使用した場合であっても、セパレータ自体の幅、長さに影響を受けず、優れた追従性を示す。さらには、面方向への熱変形が小さく、高温においても連続して使用することが可能となる。そのため、リチウムイオン二次電池などの電池用セパレータに好適に用いることができる。 The aromatic polyamide bag-like separator of the present invention can easily position the electrode, and can minimize the movement of the electrode due to an impact from the outside. Moreover, even if it is a case where it is a case where it uses with an electrode etc. with a large volume change by making it into a bag shape, it is not influenced by the width | variety and length of separator itself, and shows outstanding followable | trackability. Furthermore, thermal deformation in the surface direction is small, and it can be used continuously even at high temperatures. Therefore, it can be suitably used for a battery separator such as a lithium ion secondary battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017091929A (en) * | 2015-11-13 | 2017-05-25 | 日本電気株式会社 | Separator for battery, battery including the separator, method for manufacturing the separator, and method for manufacturing the battery |
| CN113571840A (en) * | 2021-07-16 | 2021-10-29 | 华中科技大学 | A kind of aramid fiber composite diaphragm based on in-situ modification, its preparation method and application |
| WO2023068312A1 (en) * | 2021-10-20 | 2023-04-27 | 東レ株式会社 | Polymer ion conductive membrane, polymer ion conductive membrane for secondary batteries, composite ion permeable membrane, electrode complex, and secondary battery |
-
2013
- 2013-09-27 JP JP2013201178A patent/JP2015069745A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017091929A (en) * | 2015-11-13 | 2017-05-25 | 日本電気株式会社 | Separator for battery, battery including the separator, method for manufacturing the separator, and method for manufacturing the battery |
| CN113571840A (en) * | 2021-07-16 | 2021-10-29 | 华中科技大学 | A kind of aramid fiber composite diaphragm based on in-situ modification, its preparation method and application |
| WO2023068312A1 (en) * | 2021-10-20 | 2023-04-27 | 東レ株式会社 | Polymer ion conductive membrane, polymer ion conductive membrane for secondary batteries, composite ion permeable membrane, electrode complex, and secondary battery |
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