JP6068973B2 - Electrode binder composition - Google Patents
Electrode binder composition Download PDFInfo
- Publication number
- JP6068973B2 JP6068973B2 JP2012279173A JP2012279173A JP6068973B2 JP 6068973 B2 JP6068973 B2 JP 6068973B2 JP 2012279173 A JP2012279173 A JP 2012279173A JP 2012279173 A JP2012279173 A JP 2012279173A JP 6068973 B2 JP6068973 B2 JP 6068973B2
- Authority
- JP
- Japan
- Prior art keywords
- binder composition
- parts
- electrode
- ethylenically unsaturated
- unsaturated carboxylic
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 86
- 239000011883 electrode binding agent Substances 0.000 title claims description 7
- 239000002002 slurry Substances 0.000 claims description 91
- 239000011230 binding agent Substances 0.000 claims description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 61
- 239000007773 negative electrode material Substances 0.000 claims description 45
- 239000007774 positive electrode material Substances 0.000 claims description 40
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- 239000011267 electrode slurry Substances 0.000 claims description 29
- -1 acryloyloxy Chemical group 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003990 capacitor Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000003458 sulfonic acid derivatives Chemical class 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000006230 acetylene black Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 6
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 3
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 claims description 3
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910011281 LiCoPO 4 Inorganic materials 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 3
- 229910013086 LiNiPO Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 description 32
- 238000011156 evaluation Methods 0.000 description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 24
- 229910001416 lithium ion Inorganic materials 0.000 description 24
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 239000011149 active material Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 235000019241 carbon black Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000002482 conductive additive Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229940052303 ethers for general anesthesia Drugs 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000652 nickel hydride Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- NLILVWPVOORXHM-UHFFFAOYSA-N (1-hydroxycyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(O)CCCCC1 NLILVWPVOORXHM-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
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- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
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- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
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- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、電極用バインダー組成物、このバインダー組成物を用いた電極用スラリー、並びにこれを利用する電極、二次電池、電気二重層キャパシタに関する。 The present invention relates to an electrode binder composition, an electrode slurry using the binder composition, an electrode using the same, a secondary battery, and an electric double layer capacitor.
近年、電子機器において、充電により繰り返し使用が可能である、リチウムイオン二次電池、ニッケル水素二次電池、ニッケルカドミウム二次電池等の二次電池や電気二重層キャパシタ等のキャパシタが用いられている。
これらの二次電池やキャパシタは一般に、電極、セパレーター、電解質を含む電解液から構成される。電極は、樹脂バインダー(結着剤)が溶解または膨潤した溶媒中に電極活物質を分散させた電極用スラリーを電極集電体用金属板上に塗工・乾燥させて、集電体とすることで製造される。
In recent years, in electronic devices, secondary batteries such as lithium ion secondary batteries, nickel hydride secondary batteries, nickel cadmium secondary batteries and capacitors such as electric double layer capacitors that can be repeatedly used by charging have been used. .
These secondary batteries and capacitors are generally composed of an electrolytic solution containing an electrode, a separator, and an electrolyte. The electrode is made by coating and drying an electrode slurry, in which an electrode active material is dispersed in a solvent in which a resin binder (binder) is dissolved or swollen, on a metal plate for an electrode current collector to form a current collector. It is manufactured by.
従来からリチウムイオン二次電池電極用の樹脂バインダーとしてポリフッ化ビニリデン(以下、PVDFという)が工業的に使用されているが、表面エネルギーが小さく、集電体用金属板や活物質との接着性が不十分という課題があった。 Conventionally, polyvinylidene fluoride (hereinafter referred to as PVDF) has been industrially used as a resin binder for lithium ion secondary battery electrodes, but it has low surface energy and adhesion to current collector metal plates and active materials. There was a problem of insufficient.
そこで、PVDFに代わり、SBRやアクリル系共重合体のバインダーが提案されている。これらのバインダーは、乳化重合によりゲル状の数100nmの粒子として存在するため、活物質への接着面積が増大し、電極と活物質との接着性を向上できるメリットがある。 Therefore, SBR and an acrylic copolymer binder have been proposed instead of PVDF. Since these binders exist as gel-like particles of several hundreds of nanometers by emulsion polymerization, there is an advantage that the adhesion area to the active material is increased and the adhesion between the electrode and the active material can be improved.
乳化重合では、重合時に乳化安定性が低下し、重合過程で粗大な凝集物を発生する場合がある。これが電極表面に露出し、バインダー塗工後の集電体平滑性に悪影響を与える場合があった。 In emulsion polymerization, the emulsion stability decreases during the polymerization, and coarse aggregates may be generated during the polymerization process. This may be exposed on the electrode surface and adversely affect the current collector smoothness after binder coating.
そこで、特許文献1には、ろ過処理により、粒子の球体積相当径が3μm以上である粗大粒子および/または凝集物の濃度が2000ppm以下である電極用バインダー組成物が報告されている。しかしながらこの方法では、ろ過時に目詰まりを生じ、ろ過作業が困難となる場合があった。 Therefore, Patent Document 1 reports a binder composition for an electrode in which the concentration of coarse particles and / or aggregates having a sphere volume equivalent diameter of 3 μm or more is 2000 ppm or less by filtration. However, this method may cause clogging during filtration, which may make filtration work difficult.
また、特許文献2には、ゲル含有量が50%以上のポリマーとセルロース系化合物からなるバインダー組成物、特許文献3には、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウムを用いて乳化重合したゲル含量が50%以上のポリマーと、エチレン−ビニルアルコール共重合体からなるバインダー組成物が提案されている。しかしながら、これらの方法では、いずれもバインダーの媒体が760mmHgでの沸点が80℃以上の液状有機物である。この結果、集電体の平滑性は得られるものの、高沸点の有機溶剤を使用するため乾燥工程が複雑になること、さらには乾燥時に発生する溶媒蒸気をそのまま大気に解放すると環境上問題となるため、回収設備が必要となる課題があった。 Patent Document 2 discloses a binder composition comprising a polymer having a gel content of 50% or more and a cellulose compound, and Patent Document 3 includes a gel content obtained by emulsion polymerization using sodium alkyldiphenyl ether disulfonate as an emulsifier. A binder composition comprising at least% polymer and an ethylene-vinyl alcohol copolymer has been proposed. However, in any of these methods, the binder medium is a liquid organic material having a boiling point of 80 ° C. or higher at 760 mmHg. As a result, although the smoothness of the current collector can be obtained, the drying process becomes complicated because an organic solvent having a high boiling point is used, and further, if the solvent vapor generated during drying is released to the atmosphere as it is, there is an environmental problem. Therefore, there is a problem that a recovery facility is required.
本発明は、上記問題と実状に鑑み、スラリーの貯蔵安定性、スラリー調製時の脱泡性、塗膜の平滑性に優れた電極用バインダー組成物、およびこれを用いた電極用スラリーを提供することを目的とする。さらに、この電極用スラリーを用いて製造される電極、並びに、この電池を用いて製造される、放電レート特性、サイクル特性に優れた二次電池および電気二重層キャパシタを提供することを目的とする。 The present invention provides a binder composition for an electrode excellent in storage stability of slurry, defoaming property at the time of slurry preparation, and smoothness of a coating film, and an electrode slurry using the same in view of the above problems and actual conditions. For the purpose. Furthermore, it aims at providing the secondary battery and electric double layer capacitor which were manufactured using this electrode slurry, and were excellent in the discharge rate characteristic and cycle characteristic which were manufactured using this battery. .
すなわち、上記課題を解決する本発明は、下記より構成される。
(1)(a)エチレン性不飽和カルボン酸エステルと、(b)(メタ)アクリロイル基を有するスルホン酸誘導体と、(c)エチレン性不飽和カルボン酸と、を共重合して得られる共重合体が水に分散してなる電極用バインダー組成物であって、(a)エチレン性不飽和カルボン酸エステル、(b)(メタ)アクリロイル基を有するスルホン酸誘導体および(c)エチレン性不飽和カルボン酸の総和100質量部中、(b)(メタ)アクリロイル基を有するスルホン酸誘導体が1〜8質量部であり、(c)エチレン性不飽和カルボン酸が0.1〜2質量部であり、(a)エチレン性不飽和カルボン酸エステルが、以下の(a1)〜(a3)からなる電極用バインダー組成物。
(a1)化1で表わされる構造単位において、R2は炭素数1〜20のアルキル基である単量体。
(a2)化2で表わされる構造単位において、R3は炭素数1〜7のメチレン鎖である単量体。
(a3)メタクリル酸アリル、ジメタクリル酸エチレングリコール、ジメタクリル酸プロピレングリコール、ジメタクリル酸テトラメチレングリコールおよびジメタクリル酸−1,3−ブチレングリコールから選択される、
1種以上の多官能単量体。
(2)(b)(メタ)アクリロイル基を有するスルホン酸誘導体が、(メタ)アクリロイルオキシポリオキシプロピレンスルホン酸ナトリウムであり、(c)エチレン性不飽和カルボン酸が、メタクリル酸である、(1)に記載の電極用バインダー組成物。
(3)(a1)化1で表わされる構造単位が、アクリル酸2−エチルヘキシル、およびメタクリル酸メチルである、(1)または(2)に記載の電極用バインダー組成物。
(4)(a)エチレン性不飽和カルボン酸エステルが、(a1)77〜92質量部、(a2)3〜8質量部、(a3)1〜5質量部である、(1)〜(3)の何れか一つに記載の電極用バインダー組成物。
(5)(c)エチレン性不飽和カルボン酸が、(a)エチレン性不飽和カルボン酸エステル、(b)(メタ)アクリロイル基を有するスルホン酸誘導体、および(c)エチレン性不飽和カルボン酸の総和100質量部中、0.1〜1質量部である、(1)〜(4)の何れか一つに記載の電極用バインダー組成物。
(6)(1)〜(5)のいずれか一つに記載の電極用バインダー組成物に、正極活物質、導電助剤を含有してなる電極用スラリー。
(7)(1)〜(5)のいずれか一つに記載の電極用バインダー組成物に、負極活物質、導電助剤を含有してなる電極用スラリー。
(8)正極活物質が、LiFePO4、LiMnPO4、LiMnXFe(1−X)PO4(但し、0<X<1)、LiCoPO4又はLi3V2(PO4)3、LiNiPO4からなる群から選択される少なくとも1種のリチウム含有リン酸塩である、(6)に記載の電極用スラリー。
(9)正極活物質が、LiCoO2、LiMn2O4、LiNiO2、Li(MnXNiYCoZ)O2又はLi(AlXNiYCoZ)O2からなる群から選択される少なくとも1種類のリチウム塩である、(6)に記載の電極用スラリー。但し、Li(MnXNiYCoZ)O2中又はLi(AlXNiYCoZ)O2中のX、Y及びZは、X+Y+Z=1と
いう関係を満たしかつ0<X<1、0<Y<1、0<Z<1という関係を満たす。
(10)負極活物質が、炭素質材料である、(7)に記載の電極用スラリー。
(11)負極活物質がLi4Ti5O12、金属スズを内包したスズ酸化物または金属シリコンを内包したシリコン酸化物からなる群から選択される少なくとも1種類である(7)に記載の電極用スラリー。
(12)導電助剤が、(i)繊維状炭素、(ii)カーボンブラック、(iii)繊維状炭素とカーボンブラックが相互に連結した炭素複合体から選択される少なくとも1種である、(6)〜(11)のいずれか一つに記載の電極用スラリー。
(13)(i)繊維状炭素が、平均繊維径が5〜50nmであり、かつ比表面積が50〜400m2/gである、(12)に記載の電極用スラリー。
(14)(ii)カーボンブラックが、平均粒径10〜100nmの一次粒子が鎖状に結合してなるアセチレンブラックである、(12)又は(13)に記載の電極用スラリー。
(15)(6)〜(14)のいずれか一つに記載の電極用スラリーを用いて製造される電極。
(16)(15)に記載の電極を用いて製造される二次電池。
(17)(15)に記載の電極を用いて製造される電気二重層キャパシタ。
That is, this invention which solves the said subject is comprised from the following.
(1) (a) an ethylenically unsaturated carboxylic acid ester, (b) (meth) and a sulfonic acid derivative having an acryloyl group, co obtained by copolymerizing a (c) an ethylenically unsaturated carboxylic acid weight A binder composition for an electrode in which a coalescence is dispersed in water , comprising: (a) an ethylenically unsaturated carboxylic acid ester, (b) a sulfonic acid derivative having a (meth) acryloyl group, and (c) an ethylenically unsaturated carboxylic acid In 100 parts by mass of the total acid, (b) the sulfonic acid derivative having a (meth) acryloyl group is 1 to 8 parts by mass, (c) the ethylenically unsaturated carboxylic acid is 0.1 to 2 parts by mass, (A) The binder composition for electrodes whose ethylenically unsaturated carboxylic acid ester consists of the following (a1)-(a3).
(A1) In the structural unit represented by Chemical Formula 1, a monomer in which R 2 is an alkyl group having 1 to 20 carbon atoms.
(A2) In the structural unit represented by Chemical Formula 2, a monomer in which R 3 is a methylene chain having 1 to 7 carbon atoms.
(A3) selected from allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate,
One or more polyfunctional monomers.
(2) (b) (meth) sulfonic acid derivative having an acryloyl group, a (meth) acryloyloxy polyoxypropylene sodium sulfonate, is (c) an ethylenically unsaturated carboxylic acid, methacrylic acid, (1 The binder composition for electrodes as described in ) .
(3) The binder composition for an electrode according to (1) or ( 2) , wherein the structural unit represented by (a1) Chemical formula 1 is 2-ethylhexyl acrylate and methyl methacrylate.
(4) (a) Ethylenically unsaturated carboxylic acid ester is (a1) 77-92 parts by mass, (a2) 3-8 parts by mass, (a3) 1-5 parts by mass, (1)-( 3 The binder composition for electrodes as described in any one of these.
(5) (c) the ethylenically unsaturated carboxylic acid is (a) an ethylenically unsaturated carboxylic acid ester, (b) a sulfonic acid derivative having a (meth) acryloyl group, and (c) an ethylenically unsaturated carboxylic acid The binder composition for electrodes according to any one of (1) to ( 4) , which is 0.1 to 1 part by mass in a total of 100 parts by mass.
(6) A slurry for an electrode comprising a positive electrode active material and a conductive additive in the electrode binder composition according to any one of (1) to ( 5) .
(7) A slurry for an electrode comprising the binder composition for an electrode according to any one of (1) to ( 5) , a negative electrode active material and a conductive additive.
(8) The positive electrode active material is LiFePO 4 , LiMnPO 4 , LiMn X Fe (1-X) PO 4 (where 0 <X <1), LiCoPO 4, or Li 3 V 2 (PO 4 ) 3 , LiNiPO 4 The electrode slurry according to ( 6) , which is at least one lithium-containing phosphate selected from the group consisting of:
(9) at least a positive electrode active material is selected from LiCoO 2, LiMn 2 O 4, LiNiO 2, Li (Mn X Ni Y Co Z) O 2 or Li (Al X Ni Y Co Z ) group consisting of O 2 The slurry for an electrode according to ( 6) , which is one type of lithium salt. However, Li (Mn X Ni Y Co Z) O 2 in or Li (Al X Ni Y Co Z ) O 2 in the X, Y and Z, X + Y + Z = 1 and satisfies the relationship of 0 <X <1, 0 The relationship of <Y <1, 0 <Z <1 is satisfied.
(10) The electrode slurry according to ( 7) , wherein the negative electrode active material is a carbonaceous material.
(11) The electrode according to the negative electrode active material is Li 4 Ti 5 O 12, it is at least one selected from the group consisting of silicon oxide containing therein the tin oxide or metal silicon encapsulating the metallic tin (7) Slurry.
(12) conductive additive is at least one selected from (i) fibrous carbon, (ii) carbon black, (iii) a carbon composite fibrous carbon and carbon black are interconnected, (6 ] The slurry for electrodes as described in any one of-( 11) .
(13) The slurry for electrodes according to ( 12) , wherein (i) fibrous carbon has an average fiber diameter of 5 to 50 nm and a specific surface area of 50 to 400 m 2 / g.
(14) The slurry for electrodes according to ( 12) or ( 13) , wherein the carbon black is acetylene black formed by binding primary particles having an average particle diameter of 10 to 100 nm in a chain form.
(15) An electrode manufactured using the electrode slurry according to any one of ( 6) to ( 14) .
(16) A secondary battery manufactured using the electrode according to ( 15) .
(17) An electric double layer capacitor produced using the electrode according to ( 15) .
本発明では、特定のエチレン性不飽和カルボン酸エステルと、(メタ)アクリロイル基を有するスルホン酸誘導体と、エチレン性不飽和カルボン酸とを共重合することで、電極用バインダー組成物のスラリーの貯蔵安定性、スラリー調製時の脱泡性が顕著に改善されることを見出した。また、脱泡性の改善により、気泡に起因する塗膜表面の欠陥が低減され、平滑性が良好となる。このため、本発明の電極用バインダー組成物を用いて電極用スラリーを作製し、これを用いた電極により作製した二次電池および電気二重層キャパシタは、放電レート特性や、サイクル特性等の電気特性に優れる。 In the present invention, a specific ethylenically unsaturated carboxylic acid ester, a sulfonic acid derivative having a (meth) acryloyl group, and an ethylenically unsaturated carboxylic acid are copolymerized to store the slurry of the electrode binder composition. It was found that the stability and the defoaming property during slurry preparation were remarkably improved. Moreover, the improvement of defoaming property reduces defects on the surface of the coating film due to air bubbles and improves smoothness. Therefore, an electrode slurry is prepared using the electrode binder composition of the present invention, and a secondary battery and an electric double layer capacitor prepared by using the electrode slurry have electrical characteristics such as discharge rate characteristics and cycle characteristics. Excellent.
<バインダー組成物>
本発明の電極用バインダー組成物(以下、単に「バインダー組成物」ということがある)は、(a)エチレン性不飽和カルボン酸エステルと、(b)(メタ)アクリロイル基を有するスルホン酸誘導体と、(c)エチレン性不飽和カルボン酸と、を共重合させ、(a)エチレン性不飽和カルボン酸エステルが、以下の(a1)〜(a3)からなるものである。
(a1)化1で表わされる構造単位において、R2は炭素数1〜20のアルキル基である単量体。
(a2)化2で表わされる構造単位において、R3は炭素数1〜7のメチレン鎖である単量体。
(a3)(メタ)アクリロイル基および(メタ)アリル基から選択される少なくとも1種類のエチレン性不飽和基を、分子中に二つ以上含有する多官能単量体。
<Binder composition>
The electrode binder composition of the present invention (hereinafter sometimes simply referred to as “binder composition”) includes (a) an ethylenically unsaturated carboxylic acid ester, and (b) a sulfonic acid derivative having a (meth) acryloyl group. (C) an ethylenically unsaturated carboxylic acid is copolymerized, and (a) the ethylenically unsaturated carboxylic acid ester is composed of the following (a1) to (a3).
(A1) In the structural unit represented by Chemical Formula 1, a monomer in which R 2 is an alkyl group having 1 to 20 carbon atoms.
(A2) In the structural unit represented by Chemical Formula 2, a monomer in which R 3 is a methylene chain having 1 to 7 carbon atoms.
(A3) A polyfunctional monomer containing at least one ethylenically unsaturated group selected from a (meth) acryloyl group and a (meth) allyl group in the molecule.
(a1)で表されるエチレン性不飽和カルボン酸エステルとしては、アルキル基の炭素数が1〜20であり、1〜10が好ましい。アルキル基は直鎖及び分岐鎖のいずれかのものを使用できるが、分岐鎖のものが好ましい。
(a1)の具体例としては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ペンチル、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ペンチル、メタクリル酸ヘキシル、メタクリル酸2−エチルヘキシル、メタクリル酸n−オクチル、メタクリル酸t−オクチル、メタクリル酸n−ドデシル、メタクリル酸n−オクタデシル、メタアクリル酸ノニル、メタアクリル酸イソノニル、メタクリル酸デシル、メタアクリル酸イソデシル、メタクリル酸ステアリル、アクリル酸ヘキシル、アクリル酸2−エチルヘキシル、アクリル酸n−オクチル、アクリル酸t−オクチル、アクリル酸n−ドデシル、アクリル酸n−オクタデシル、アクリル酸ノニル、アクリル酸イソノニル、アクリル酸デシル、アクリル酸イソデシル、アクリル酸ステアリル等が挙げられる。これらの中では、メタクリル酸メチル、メタクリル酸ブチル、アクリル酸メチル、アクリル酸ブチル、メタクリル酸2−エチルヘキシル、アクリル酸2−エチルヘキシルが好ましく、アクリル酸2−エチルヘキシルおよびメタクリル酸メチルの組み合わせがさらに好ましい。アクリル酸2−エチルヘキシルおよびメタクリル酸メチルは、(a)〜(c)の総和100質量部中、アクリル酸2−エチルヘキシルが82〜88質量部、メタクリル酸メチルが1〜7質量部が特に好ましい。
これらは、単独でも2種以上の組み合わせで使用することができる。
As the ethylenically unsaturated carboxylic acid ester represented by (a1), the alkyl group has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. The alkyl group can be either a straight chain or branched chain, but is preferably a branched chain.
Specific examples of (a1) include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and pentyl acrylate. , Hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, t-octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, meta Isodecyl acrylate, stearyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, t-octyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, acrylic Le acid nonyl, isononyl acrylate, decyl acrylate, isodecyl acrylate, and stearyl acrylate and the like. Among these, methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate and 2-ethylhexyl acrylate are preferable, and a combination of 2-ethylhexyl acrylate and methyl methacrylate is more preferable. 2-ethylhexyl acrylate and methyl methacrylate are particularly preferably 82 to 88 parts by mass of 2-ethylhexyl acrylate and 1 to 7 parts by mass of methyl methacrylate in a total of 100 parts by mass of (a) to (c).
These can be used alone or in combination of two or more.
(a1)の添加量は、(a)〜(c)の総和100質量部中、77〜92質量部であることが好ましく、82〜90質量部であることがさらに好ましい。添加量を77質量部以上とすることで、集電体の応力緩和性が向上し、得られる電池のサイクル特性が向上する。また、添加量を92質量部以下とすることで、塗膜の結着性及び平滑性が良好となる。 The addition amount of (a1) is preferably 77 to 92 parts by mass and more preferably 82 to 90 parts by mass in 100 parts by mass of the sum of (a) to (c). When the addition amount is 77 parts by mass or more, the stress relaxation property of the current collector is improved, and the cycle characteristics of the obtained battery are improved. Moreover, the binding property and smoothness of a coating film become favorable because an addition amount shall be 92 mass parts or less.
(a2)で表されるエチレン性不飽和カルボン酸エステルとしては、メチレン鎖の炭素数が1〜7であり、炭素数1〜3が好ましい。
(a2)の具体例としては、例えば、メタクリル酸2−ヒドロキシエチル、メタクリル酸3−ヒドロキシプロピル、メタクリル酸4−ヒドロキシブチル、メタクリル酸ヒドロキシシクロヘキシル、アクリル酸2−ヒドロキシエチル、メタクリル酸4−ヒドロキシブチル等が挙げられる。これらの中では、メタクリル酸2−ヒドロキシエチル、アクリル酸4−ヒドロキシブチルが好ましい。
これらは、単独でも2種以上の組み合わせでも使用することができる。
The ethylenically unsaturated carboxylic acid ester represented by (a2) has 1 to 7 carbon atoms in the methylene chain, and preferably 1 to 3 carbon atoms.
Specific examples of (a2) include, for example, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxycyclohexyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate. Etc. Among these, 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate are preferable.
These may be used alone or in combination of two or more.
(a2)の添加量は、(a)〜(c)の総和100質量部中、3〜8質量部であることが好ましく、4〜6質量部であることがさらに好ましい。添加量を3質量部以上とすることで、電解液に対する耐膨潤性が向上し、電池のサイクル特性が良好となる。また、添加量を8質量部以下とすることで、スラリーの分散性が向上し、塗膜の平滑性が良好となる。 The added amount of (a2) is preferably 3 to 8 parts by mass, more preferably 4 to 6 parts by mass, in 100 parts by mass of the sum of (a) to (c). By making the addition amount 3 parts by mass or more, the swelling resistance to the electrolytic solution is improved, and the cycle characteristics of the battery are improved. Moreover, the dispersibility of a slurry improves and the smoothness of a coating film becomes favorable because an addition amount shall be 8 mass parts or less.
(a3)で表される(メタ)アクリロイル基および(メタ)アリル基から選択される少なくとも1種類のエチレン性不飽和基を、分子中に二つ以上含有する多官能単量体としては、メタクリル酸アリル、ジメタクリル酸エチレングリコール、ジメタクリル酸プロピレングリコール、ジメタクリル酸テトラメチレングリコール、ジメタクリル酸−1,3−ブチレングリコール等が挙げられる。これらの中では、メタクリル酸アリル及びジメタクリル酸エチレングリコール、およびメタクリル酸アリルが好ましく、ジメタクリル酸エチレングリコールが、特に好ましい。
これらは、単独でも2種以上を組み合わせても使用することができる。
As a polyfunctional monomer containing at least one kind of ethylenically unsaturated group selected from (meth) acryloyl group and (meth) allyl group represented by (a3) in the molecule, methacryl Examples include allyl acid, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate. Among these, allyl methacrylate and ethylene glycol dimethacrylate and allyl methacrylate are preferable, and ethylene glycol dimethacrylate is particularly preferable.
These can be used alone or in combination of two or more.
(a3)の添加量は、(a)〜(c)の総和100質量部中1〜5質量部であることが好ましく、1〜3質量部であることがさらに好ましい。添加量を1質量部以上とすることで、電解液に対する耐膨潤性が向上し、得られる電池のサイクル特性が良好となる。また、5質量部以下とすることで、集電体の応力緩和性を確保でき、塗膜の結着性が良好となる。 The addition amount of (a3) is preferably 1 to 5 parts by mass, more preferably 1 to 3 parts by mass, out of 100 parts by mass of the sum of (a) to (c). When the addition amount is 1 part by mass or more, the swelling resistance to the electrolytic solution is improved, and the cycle characteristics of the obtained battery are improved. Moreover, by setting it as 5 mass parts or less, the stress relaxation property of a collector can be ensured and the binding property of a coating film becomes favorable.
(b)で表される(メタ)アクリロイル基を有するスルホン酸誘導体の具体例としては、2−(メタクリロイルオキシ)エタンスルホン酸及びその塩、1‐(メタクリロイルオキシ)−2−メチル−1−プロパンスルホン酸及びその塩、4―[8−(メタクリロイルオキシ)オクチルオキシ]ベンゼンスルホン酸及びその塩、2−ヒドロキシ−3−(メタクリロイルオキシ)プロパン−1−スルホン酸およびその塩、メタクリロイルオキシポリオキシプロピレンスルホン酸およびその塩が挙げられる。塩としては、アルカリ金属塩(ナトリウム、カリウム等)や、アンモニウム塩等が挙げられる。
これらの中では、メタクリロイルオキシポリオキシプロピレンスルホン酸及びその塩、2−(メタクリロイルオキシ)エタンスルホン酸及びその塩が好ましく、メタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウムが、特に好ましい。なお、これらは単独で又は2種以上組み合わせて使用してもよい。
Specific examples of the sulfonic acid derivative having a (meth) acryloyl group represented by (b) include 2- (methacryloyloxy) ethanesulfonic acid and salts thereof, 1- (methacryloyloxy) -2-methyl-1-propane Sulfonic acid and its salt, 4- [8- (methacryloyloxy) octyloxy] benzenesulfonic acid and its salt, 2-hydroxy-3- (methacryloyloxy) propane-1-sulfonic acid and its salt, methacryloyloxypolyoxypropylene Examples include sulfonic acid and its salts. Examples of the salt include alkali metal salts (sodium, potassium, etc.) and ammonium salts.
Among these, methacryloyloxypolyoxypropylenesulfonic acid and its salt, 2- (methacryloyloxy) ethanesulfonic acid and its salt are preferable, and sodium methacryloyloxypolyoxypropylenesulfonic acid is particularly preferable. In addition, you may use these individually or in combination of 2 or more types.
(b)の添加量は、(a)〜(c)の総和100質量部中、1〜8質量部が好ましく、2〜4質量部であることがさらに好ましい。添加量を1質量部以上とすることで、真空脱泡性を向上できるため塗膜の平滑性を向上させることができる。また、8質量部以下とすることで、スラリーの分散性を確保し、塗膜の平滑性を確保できる。 The added amount of (b) is preferably 1 to 8 parts by mass and more preferably 2 to 4 parts by mass in 100 parts by mass of the sum of (a) to (c). By making the addition amount 1 mass part or more, the vacuum defoaming property can be improved, so that the smoothness of the coating film can be improved. Moreover, by setting it as 8 mass parts or less, the dispersibility of a slurry is ensured and the smoothness of a coating film is securable.
(c)で表されるエチレン性不飽和カルボン酸の具体例としては、メタクリル酸、アクリル酸、クロトン酸、3−ブテン酸などの不飽和モノカルボン酸、マレイン酸、フマル酸、イタコン酸などの不飽和ジカルボン酸が挙げられる。これらの中ではメタクリル酸、およびイタコン酸が好ましく、メタクリル酸が特に好ましい。なお、これらは単独で又は2種以上組み合わせて使用してもよい。 Specific examples of the ethylenically unsaturated carboxylic acid represented by (c) include unsaturated monocarboxylic acids such as methacrylic acid, acrylic acid, crotonic acid, and 3-butenoic acid, maleic acid, fumaric acid, and itaconic acid. An unsaturated dicarboxylic acid is mentioned. Among these, methacrylic acid and itaconic acid are preferable, and methacrylic acid is particularly preferable. In addition, you may use these individually or in combination of 2 or more types.
(c)の添加量は、(a)〜(c)の総和100質量部中、0.1〜2質量部が好ましく、0.5〜1質量部がさらに好ましい。添加量が0.1質量部以上とすることで活物質との結着性を向上させることができる。また、2質量部以下とすることでスラリーの貯蔵安定性を確保できる。 The addition amount of (c) is preferably 0.1 to 2 parts by mass, more preferably 0.5 to 1 part by mass, in 100 parts by mass of the sum of (a) to (c). When the addition amount is 0.1 parts by mass or more, the binding property with the active material can be improved. Moreover, the storage stability of a slurry is securable by setting it as 2 mass parts or less.
本発明では、本願発明の効果を損なうものでなければ、(a)〜(c)以外の単量体を併用することができる。(a)〜(c)以外の単量体の具体例としては、スチレン、アクリロニトリル、ブタジエン、イソプレン、(メタ)アクリルアミド、N−フェノルマレイミド等が挙げられる。 In the present invention, monomers other than (a) to (c) can be used in combination as long as the effects of the present invention are not impaired. Specific examples of monomers other than (a) to (c) include styrene, acrylonitrile, butadiene, isoprene, (meth) acrylamide, N-phenol maleimide and the like.
本発明のバインダー組成物の製造方法は特に制限されず、乳化重合法や懸濁重合法、乳化分散法等の公知方法によって製造することができる。これらの中では、製造が容易な点で乳化重合が好ましい。乳化重合では、単量体、水、乳化剤、重合開始剤の全てを一括して添加してもよいが、これらの一部を事前に混合分散し、重合中に分添することもできる。 The method for producing the binder composition of the present invention is not particularly limited, and can be produced by a known method such as an emulsion polymerization method, a suspension polymerization method, or an emulsion dispersion method. Among these, emulsion polymerization is preferable in terms of easy production. In emulsion polymerization, all of the monomer, water, emulsifier, and polymerization initiator may be added all at once, but some of these may be mixed and dispersed in advance and added during the polymerization.
バインダー組成物の調製に使用できる重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸の無機塩、t−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、p−メンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド等のハイドロパーオキサイド類、t−ブチルパーオキシベンゾエート、t−ブチルパーオキシデカノエート等のパーオキシエステル類が挙げられる。これらの中では、過硫酸カリウム、過硫酸アンモニウムがポリマーのゲル化度が調整し易い点で好ましい。重合開始剤の量は、全単量体100質量部に対し、0.01〜3質量部の割合で添加される。 Examples of the polymerization initiator that can be used for preparing the binder composition include inorganic salts of persulfuric acid such as potassium persulfate, ammonium persulfate, and sodium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide. And hydroperoxides such as cumene hydroperoxide and diisopropylbenzene hydroperoxide, and peroxyesters such as t-butyl peroxybenzoate and t-butyl peroxydecanoate. Among these, potassium persulfate and ammonium persulfate are preferable because the degree of gelation of the polymer can be easily adjusted. The amount of the polymerization initiator is added at a ratio of 0.01 to 3 parts by mass with respect to 100 parts by mass of all monomers.
バインダー組成物の調製に使用できる乳化剤は、本発明における(b)で表される(メタ)アクリロイル基を有するスルホン酸誘導体を、単独で使用しても良好なバインダー組成物を得ることができるが、他の乳化剤を併用してもよい。他の乳化剤としてはドデシルベンゼンスルホン酸塩、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ジアルキルスルフォサクシネート塩類、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類等が挙げられる。 The emulsifier that can be used for preparing the binder composition can obtain a good binder composition even if the sulfonic acid derivative having a (meth) acryloyl group represented by (b) in the present invention is used alone. Other emulsifiers may be used in combination. Other emulsifiers include dodecylbenzene sulfonate, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, And oxyethylene alkylphenyl ethers.
バインダー組成物の調製では、分子量を調整する目的として、メルカプタンやテルペンなどの連鎖移動剤を使用することも可能である。連鎖移動剤の具体例としては、n−オクチルメルカプタン、t−ドデシルメルカプタン、n−ドデシルメルカプタン、n−テトラデシルメルカプタン、n−オクタデシルメルカプタンおよびテルピノレンなどが挙げられる。これらの中では、n−オクチルメルカプタン、t−ドデシルメルカプタンおよびn−ドデシルメルカプタンが好ましく用いられる。なお、これらは、単独で又は2種以上組み合わせて使用してもよい。 In the preparation of the binder composition, chain transfer agents such as mercaptans and terpenes can be used for the purpose of adjusting the molecular weight. Specific examples of the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene. Among these, n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used. In addition, you may use these individually or in combination of 2 or more types.
バインダー組成物には、必要に応じて、老化防止剤等を添加することができる。 An anti-aging agent etc. can be added to a binder composition as needed.
バインダー組成物は、平均粒子径が100〜300nmであることが好ましい。平均粒子径を100nm以上とすることで、バインダー組成物の粘度上昇を抑えることができ、スラリー調製時の作業性を向上することができる。また、平均粒子径を300nm以下とすることで、バインダー組成物の粒子が活物質の間隙に入り込み易くなるため、活物質との接着面積を増大することができる。 The binder composition preferably has an average particle size of 100 to 300 nm. By setting the average particle size to 100 nm or more, an increase in the viscosity of the binder composition can be suppressed, and workability during slurry preparation can be improved. Moreover, since the particle | grains of a binder composition become easy to enter the gap | interval of an active material because an average particle diameter shall be 300 nm or less, an adhesion area with an active material can be increased.
バインダー組成物は集電体用金属板の腐食性や活物質の分散安定性等からpH5〜10が好ましく、より好ましくはpH6〜9である。pHの調整には、アンモニア、アルカリ金属水酸化物等が溶解している塩基性水溶液を加えて調整することができる。アルカリ金属水酸化物としては、例えば、水酸化ナトリウム、水酸化カリウム等が挙げられる。 The binder composition preferably has a pH of 5 to 10, more preferably a pH of 6 to 9, in view of the corrosiveness of the current collector metal plate, the dispersion stability of the active material, and the like. The pH can be adjusted by adding a basic aqueous solution in which ammonia, alkali metal hydroxide or the like is dissolved. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
<電極用スラリー>
本発明の電極用スラリーは、本発明のバインダー組成物と、活物質、導電助剤を、混合して得ることができる。また、本発明の電極用スラリーは、リチウムイオン二次電池、ニッケル水素二次電池及び電気二重層キャパシタ等における電極の形成に用いられるのが好ましく、特にリチウムイオン二次電池電極の形成に用いられるのが好ましい。
<Slurry for electrodes>
The slurry for electrodes of the present invention can be obtained by mixing the binder composition of the present invention, an active material, and a conductive additive. The electrode slurry of the present invention is preferably used for forming an electrode in a lithium ion secondary battery, a nickel hydride secondary battery, an electric double layer capacitor or the like, and particularly used for forming a lithium ion secondary battery electrode. Is preferred.
(正極活物質)
リチウムイオン二次電池の正極活物質としては、LiFePO4、LiMnPO4、LiMnXFe(1−X)PO4(但し、0<X<1)、LiCoPO4又はLi3V2(PO4)3、LiNiPO4等のリチウム含有リン酸塩が挙げられる。リチウム含有リン酸塩の中では、LiFePO4が、本技術のバインダー組成物に対して特に好適である。
(Positive electrode active material)
As the positive electrode active material of the lithium ion secondary battery, LiFePO 4 , LiMnPO 4 , LiMn X Fe (1-X) PO 4 (where 0 <X <1), LiCoPO 4 or Li 3 V 2 (PO 4 ) 3 And lithium-containing phosphates such as LiNiPO 4 . Of the lithium-containing phosphates, LiFePO 4 is particularly suitable for the binder composition of the present technology.
さらに、リチウムイオン二次電池の正極活物質としては、LiCoO2、LiMn2O4、LiNiO2、Li(MnXNiYCoZ)O2又はLi(AlXNiYCoZ)O2等のリチウム塩(但し、Li(MnXNiYCoZ)O2中又はLi(AlXNiYCoZ)O2中のX、Y及びZは、X+Y+Z=1という関係を満たしかつ0<X<1、0<Y<1、0<Z<1という関係を満たす。)が挙げられる。これらの中では、LiCoO2、LiMn2O4が、本技術のバインダー組成物に好適である。 Further, the lithium ion secondary battery as the positive electrode active material, LiCoO 2, LiMn 2 O 4 , LiNiO 2, Li (Mn X Ni Y Co Z) O 2 or Li (Al X Ni Y Co Z ) O 2 , etc. lithium salt (however, Li (Mn X Ni Y Co Z) O 2 in or Li (Al X Ni Y Co Z ) O 2 in the X, Y and Z, X + Y + Z = 1 and satisfies the relationship of 0 <X < 1 and 0 <Y <1, and 0 <Z <1). Among these, LiCoO 2 and LiMn 2 O 4 are suitable for the binder composition of the present technology.
また、リチウムイオン二次電池用以外の正極活物質としては、一般式として、AaMmZzOoNnFf(Aはアルカリ金属元素;Mは遷移金属元素(Fe、Mn、V、Ti、Mo、W、Zn)又はその複合物;Zは非金属元素(P、S、Se、As、Si、Ge、B);Oは酸素元素;Nは窒素元素;Fはフッ素元素;a、m、z、n、f≧0;o>0)で表される化合物、水酸化ニッケル、活性炭等が挙げられる。 Moreover, as a positive electrode active material other than for lithium ion secondary batteries, as a general formula, AaMmZzOoNnFf (A is an alkali metal element; M is a transition metal element (Fe, Mn, V, Ti, Mo, W, Zn) or its Composite; Z is a non-metallic element (P, S, Se, As, Si, Ge, B); O is an oxygen element; N is a nitrogen element; F is a fluorine element; a, m, z, n, f ≧ 0 A compound represented by o> 0), nickel hydroxide, activated carbon and the like.
(負極活物質)
リチウムイオン二次電池の負極活物質としては、炭素質材料が使用できる。これらの具体例としては、黒鉛、ポリアセン、ポリアセチレン等の炭素系化合物、ピレン、ペリレン等のアセン構造を含む芳香族炭化水素化合物が挙げられる。これらの中では、黒鉛が好ましい。
(Negative electrode active material)
A carbonaceous material can be used as the negative electrode active material of the lithium ion secondary battery. Specific examples thereof include carbon-based compounds such as graphite, polyacene, and polyacetylene, and aromatic hydrocarbon compounds including an acene structure such as pyrene and perylene. Of these, graphite is preferred.
炭素質材料以外のリチウムイオン二次電池用の負極活物質としては、負極活物質がLi4Ti5O12で表されるチタン酸リチウム、金属スズを内包したスズ酸化物または金属シリコンを内包したシリコン酸化物等が挙げられる。これらの中では、チタン酸リチウム、金属シリコンを内包したシリコン酸化物が好ましい。 As a negative electrode active material for lithium ion secondary batteries other than carbonaceous materials, the negative electrode active material included lithium titanate represented by Li 4 Ti 5 O 12 , tin oxide including metal tin, or metal silicon. Examples thereof include silicon oxide. Among these, lithium titanate and silicon oxide containing metal silicon are preferable.
リチウムイオン二次電池以外の負極活物質としては、例えば水素吸蔵合金を、ニッケル水素二次電池の負極活物質として使用することができる。また、電気二重層キャパシタの負極活物質としては、活性炭等が挙げられる。 As the negative electrode active material other than the lithium ion secondary battery, for example, a hydrogen storage alloy can be used as the negative electrode active material of the nickel hydrogen secondary battery. Moreover, activated carbon etc. are mentioned as a negative electrode active material of an electric double layer capacitor.
本発明の電極用スラリー中のバインダー組成物の量は、活物質100質量部に対して、0.1〜10質量部とすることが好ましい。バインダー組成物の量が0.1質量部以上であると、スラリー中に活物質が均一に分散し易くなり、塗工後の乾燥皮膜の強度が出やすい。また、バインダー組成物の量が10質量部以下であると内部抵抗を抑制できるため、レート特性の優れた電池を得ることができる。 It is preferable that the quantity of the binder composition in the slurry for electrodes of this invention shall be 0.1-10 mass parts with respect to 100 mass parts of active materials. When the amount of the binder composition is 0.1 parts by mass or more, the active material is easily dispersed uniformly in the slurry, and the strength of the dried film after coating is easily obtained. Moreover, since internal resistance can be suppressed as the quantity of a binder composition is 10 mass parts or less, the battery excellent in the rate characteristic can be obtained.
(導電助剤)
本発明の電極用スラリーには、導電助剤を添加することもできる。
(Conductive aid)
A conductive additive can also be added to the slurry for electrodes of the present invention.
導電助剤としては、アセチレンブラック、ケッチェンブラック(登録商標)、チャンネルブラック、ファーネスブラック、サーマルブラック等のカーボンブラック、カーボンナノチューブ、繊維状炭素、黒鉛粉末、各種グラファイトが挙げられる。これらは1種又は2種以上を組み合わせても良い。これらの中では、繊維状炭素、カーボンブラックが好ましい。 Examples of the conductive assistant include carbon black such as acetylene black, ketjen black (registered trademark), channel black, furnace black, and thermal black, carbon nanotube, fibrous carbon, graphite powder, and various graphites. These may be used alone or in combination of two or more. Among these, fibrous carbon and carbon black are preferable.
繊維状炭素の平均繊維径は、5〜50nmが好ましく、より好ましくは10〜30nmである。また、繊維状炭素の比表面積は50〜400m2/gが好ましく、より好ましくは100〜300m2/gである。繊維状炭素の平均繊維径が5〜50nm、比表面積が50〜400m2/gであると、より高い導電助剤としての効果が得られる。 5-50 nm is preferable and, as for the average fiber diameter of fibrous carbon, More preferably, it is 10-30 nm. The specific surface area of the fibrous carbon is preferably 50 to 400 m 2 / g, more preferably 100 to 300 m 2 / g. When the average fiber diameter of the fibrous carbon is 5 to 50 nm and the specific surface area is 50 to 400 m 2 / g, a higher effect as a conductive additive can be obtained.
カーボンブラックの中では、導電助剤としての効果の点から、平均粒径は10〜100nmの一次粒子が鎖状に結合したアセチレンブラックが、より好ましい。 Among carbon blacks, acetylene black in which primary particles having an average particle diameter of 10 to 100 nm are bonded in a chain form is more preferable from the viewpoint of the effect as a conductive additive.
(炭素複合体)
本発明の電極用スラリーには、導電助剤および活物質の導電性付与能力、導電性の向上の為、複数種の導電助剤や活物質を連結した炭素複合体を含有しても良い。例えば、リチウムイオン二次電池電極用スラリーの場合、繊維状炭素とカーボンブラックが連結された炭素複合体、さらにカーボンコートされたLiFePO4等のリチウム含有リン酸塩を、繊維状炭素、カーボンブラックと複合一体化させた複合体等が挙げられる。繊維状炭素とカーボンブラックが連結された炭素複合体は、例えば、繊維状炭素とカーボンブラックとの混合物を焼成することにより得られる。また、この炭素複合体と、リチウム含有リン酸塩等の活物質との混合物を、焼成したものを炭素複合体とすることもできる。
(Carbon composite)
The electrode slurry of the present invention may contain a carbon composite in which a plurality of conductive assistants and active materials are linked in order to improve the conductivity imparting ability and conductivity of the conductive assistant and the active material. For example, in the case of a slurry for a lithium ion secondary battery electrode, a carbon composite in which fibrous carbon and carbon black are linked, and a lithium-containing phosphate such as carbon-coated LiFePO 4 are used as fibrous carbon and carbon black. Examples include composites that are combined and integrated. A carbon composite in which fibrous carbon and carbon black are linked can be obtained, for example, by firing a mixture of fibrous carbon and carbon black. Moreover, what baked the mixture of this carbon composite and active materials, such as lithium containing phosphate, can also be made into a carbon composite.
(添加剤)
本発明の電極用スラリーには、必要に応じて、粘度調整剤を添加しても良い。
(Additive)
You may add a viscosity modifier to the slurry for electrodes of this invention as needed.
粘度調整剤としては、ポリビニルアルコール、カルボキシメチルセルロース、メチルセルロース、ポリメタクリル酸等の水溶性ポリマーや、その塩等が挙げられる。 As a viscosity modifier, water-soluble polymers, such as polyvinyl alcohol, carboxymethylcellulose, methylcellulose, polymethacrylic acid, its salt, etc. are mentioned.
電極用スラリーは、塗膜に欠陥が生じないようにして平滑性を確保するため、塗工前の段階で真空脱泡を行う。脱泡性が悪いと真空脱泡時に容器内でスラリーが膨張して液面が上昇するため真空脱泡ができなくなる。また、脱泡が不十分になるため、塗膜に欠陥が生じ、平滑性を損なう原因となる。 The electrode slurry is subjected to vacuum defoaming at a stage before coating in order to ensure smoothness without causing defects in the coating film. If the defoaming property is poor, the slurry expands in the container at the time of vacuum defoaming and the liquid level rises, so that the vacuum defoaming cannot be performed. Moreover, since defoaming becomes insufficient, a defect is generated in the coating film, which causes the smoothness to be impaired.
<電極>
電極は、本発明の電極用スラリーを金属板上に塗布し、乾燥して得た集電体を積層して得ることができる。なお、正極活物質を含む電極用スラリーにより正極が製造され、負極活物質を含む電極用スラリーにより負極が製造される。また、本発明の電極は、リチウムイオン二次電池、ニッケル水素二次電池及び電気二重層キャパシタの製造に用いられるのが好ましく、特にリチウムイオン二次電池の製造に用いられるのが好ましい。
<Electrode>
The electrode can be obtained by laminating a current collector obtained by applying the electrode slurry of the present invention on a metal plate and drying it. In addition, a positive electrode is manufactured with the slurry for electrodes containing a positive electrode active material, and a negative electrode is manufactured with the slurry for electrodes containing a negative electrode active material. The electrode of the present invention is preferably used for the production of a lithium ion secondary battery, a nickel hydrogen secondary battery and an electric double layer capacitor, and particularly preferably used for the production of a lithium ion secondary battery.
(集電体用金属板)
正極集電体の金属板としては、通常、アルミニウムが好ましく用いられる。また、負極集電体の金属板としては、通常、銅が好ましく用いられる。金属板の形状は、特に限定するものではないが、箔状が好ましい。金属板の厚さは、加工性を容易にする点から、厚さは5〜30μmが好ましい。
(Metal plate for current collector)
Usually, aluminum is preferably used as the metal plate of the positive electrode current collector. Moreover, as a metal plate of the negative electrode current collector, copper is usually preferably used. The shape of the metal plate is not particularly limited, but a foil shape is preferable. The thickness of the metal plate is preferably 5 to 30 μm from the viewpoint of facilitating workability.
(電極の製造方法)
電極用スラリーの塗布方法は、一般的な方法を用いることができる。例えば、リバースロール法、ダイレクトロール法、ブレード法、ナイフ法、エクストルージョン法、カーテン法、グラビア法、バー法、ディップ法及びスクイーズ法を挙げることができる。そのなかでもブレード法(コンマロールまたはダイカット)、ナイフ法及びエクストルージョン法が好ましい。この際、バインダーの溶液物性、乾燥性に合わせて塗布方法を選定することにより、良好な塗布層の表面状態を得ることができる。塗布は片面に施しても、両面に施してもよく、両面の場合、片面ずつ逐次でも両面同時でもよい。また、塗布は連続でも間欠でもストライプでもよい。電極用スラリーの塗布厚みや長さ、巾は、電池の大きさに合わせて適宜決定すればよい。例えば、電極用スラリーの塗布厚み、すなわち、集電体の厚さは、10μm〜500μmの範囲とすることができる。
(Method for manufacturing electrode)
As a method for applying the electrode slurry, a general method can be used. Examples thereof include a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, a dip method, and a squeeze method. Of these, blade method (comma roll or die cut), knife method and extrusion method are preferable. Under the present circumstances, the surface state of a favorable coating layer can be obtained by selecting a coating method according to the solution physical property and drying property of a binder. The application may be performed on one side or both sides, and in the case of both sides, each side may be sequentially or simultaneously. The application may be continuous, intermittent, or striped. The application thickness, length, and width of the electrode slurry may be appropriately determined according to the size of the battery. For example, the application thickness of the slurry for electrodes, that is, the thickness of the current collector can be in the range of 10 μm to 500 μm.
電極用スラリーの乾燥方法は、一般に採用されている方法を利用することができる。特に、熱風、真空、赤外線、遠赤外線、電子線および低温風を単独あるいは組み合わせて用いることが好ましい。本発明においては、水を媒体として調製した電極用スラリーを用いることで、50〜130℃程度の温度で乾燥を行うことができ、乾燥のためのエネルギーを少なくすることができる。 As a method for drying the electrode slurry, a generally adopted method can be used. In particular, it is preferable to use hot air, vacuum, infrared rays, far-infrared rays, electron beams and low-temperature air alone or in combination. In the present invention, by using an electrode slurry prepared using water as a medium, drying can be performed at a temperature of about 50 to 130 ° C., and energy for drying can be reduced.
電極は、必要に応じてプレスすることができる。プレス法は、一般に採用されている方法を用いることができるが、特に金型プレス法やカレンダープレス法(冷間または熱間ロール)が好ましい。カレンダープレス法でのプレス圧は、特に限定されないが、0.2〜3ton/cmが好ましい。 The electrode can be pressed as needed. As the pressing method, a generally adopted method can be used, and a die pressing method and a calendar pressing method (cold or hot roll) are particularly preferable. The press pressure in the calendar press method is not particularly limited, but is preferably 0.2 to 3 ton / cm.
<二次電池および電気二重層キャパシタ>
二次電池および電気二重層キャパシタは、本発明の電極を使用して得られるものである。二次電池としては、リチウムイオン二次電池、ニッケル水素二次電池等が挙げられる。このうち、本発明の電極は、特に、リチウムイオン二次電池への利用が好適である。また、本発明の二次電池や電気二重層キャパシタは、本発明の電極(正極及び負極)と、セパレーターと、電解質溶液(以下、単に「電解液」ということがある)とを有して構成されるものが好適である。なお、本発明の正極あるいは負極と、本発明以外の電極と組合せても良い。
<Secondary battery and electric double layer capacitor>
The secondary battery and the electric double layer capacitor are obtained using the electrode of the present invention. Examples of the secondary battery include a lithium ion secondary battery and a nickel hydride secondary battery. Among these, the electrode of the present invention is particularly suitable for use in a lithium ion secondary battery. Further, the secondary battery or electric double layer capacitor of the present invention comprises the electrode (positive electrode and negative electrode) of the present invention, a separator, and an electrolyte solution (hereinafter sometimes simply referred to as “electrolyte”). Are preferred. In addition, you may combine the positive electrode or negative electrode of this invention, and the electrode other than this invention.
(セパレーター)
セパレーターには、電気絶縁性の多孔質膜、網、不織布等、充分な強度を有するものであればどのようなものでも使用可能である。特に、電解液のイオン移動に対して低抵抗であり、かつ、溶液保持に優れたものを使用するとよい。材質は特に限定しないが、ガラス繊維等の無機物繊維または有機物繊維、ポリエチレン、ポリプロピレン、ポリエステル、ポリテトラフロオロエチレン、ポリフロン等の合成樹脂またはこれらの層状複合体等を挙げることができる。接着性および安全性の観点からポリエチレン、ポリプロピレンまたはこれらの層状複合膜が望ましい。
(separator)
Any separator can be used as long as it has sufficient strength, such as an electrically insulating porous film, a net, and a nonwoven fabric. In particular, it is preferable to use a material that has low resistance to ion migration of the electrolytic solution and excellent in solution holding. The material is not particularly limited, and examples thereof include inorganic fibers such as glass fibers or organic fibers, synthetic resins such as polyethylene, polypropylene, polyester, polytetrafluoroethylene, and polyflon, and layered composites thereof. From the viewpoint of adhesion and safety, polyethylene, polypropylene, or a layered composite film thereof is desirable.
(電解質)
電解質は、公知のリチウム塩がいずれも使用でき、LiClO4、LiBF4,LiBF6、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiB10Cl10、LiAlCl4、LiCl、LiBr、LiI、LiB(C2H5)4、LiCF3SO3、LiCH3SO3、LiCF3SO3、LiC4F9SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiC(CF3SO2)3、低級脂肪酸カルボン酸リチウム等が挙げられるが、特に限定されるものではない。
(Electrolytes)
Electrolyte, any known lithium salt can be used, LiClO 4, LiBF 4, LiBF 6, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, LiAlCl 4, LiCl LiBr, LiI, LiB (C 2 H 5 ) 4 , LiCF 3 SO 3 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , lithium lower fatty acid carboxylate and the like can be mentioned, but not particularly limited.
(電解液)
リチウムイオン二次電池の場合の電解液としては、リチウム塩の電解質を溶解する非水系の有機溶媒より構成されるものが好適である。これらの有機溶媒としては、カーボネート類、γ−ブチロラクトン等のラクトン類、エーテル類、ジメチルスルホキシド等のスルホキシド類、オキソラン類、含窒素化合物類、エステル類、無機酸エステル類、アミド類、グライム類、ケトン類、スルホラン等のスルホラン類、3−メチル−2−オキサゾリジノン等のオキサゾリジノン類、スルトン類等の1種又は2種以上の混合溶媒を用いることができる。
具体的には、カーボネート類としては、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等が挙げられる。
エーテル類としては、トリメトキシメタン、1,2−ジメトキシエタン、ジエチルエーテル、2−エトキシエタン、テトラヒドロフラン、2−メチルテトラヒドロフラン等が挙げられる。
オキソラン類としては、1,3−ジオキソラン、4−メチル−1,3−ジオキソラン等が挙げられる。
含窒素化合物類としては、アセトニトリル、ニトロメタン、N−メチル−2−ピロリドン等が挙げられる。
エステル類としては、ギ酸メチル、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、リン酸トリエステル等が挙げられる。
無機酸エステル類としては、硫酸エステル、硝酸エステル、塩酸エステル等が挙げられる。
アミド類としては、ジメチルホルムアミド、ジメチルアセトアミド等が挙げられる。
グライム類としては、ジグライム、トリグライム、テトラグライム等が挙げられる。
ケトン類としては、アセトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン等が挙げられる。
スルトン類としては、1,3−プロパンサルトン、4−ブタンスルトン、ナフタスルトン等が挙げられる。
(Electrolyte)
As the electrolyte in the case of a lithium ion secondary battery, an electrolyte composed of a non-aqueous organic solvent that dissolves an electrolyte of a lithium salt is suitable. Examples of these organic solvents include carbonates, lactones such as γ-butyrolactone, ethers, sulfoxides such as dimethyl sulfoxide, oxolanes, nitrogen-containing compounds, esters, inorganic acid esters, amides, glymes, One or two or more mixed solvents such as ketones, sulfolanes such as sulfolane, oxazolidinones such as 3-methyl-2-oxazolidinone, and sultone can be used.
Specific examples of carbonates include propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
Examples of ethers include trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran and the like.
Examples of oxolanes include 1,3-dioxolane and 4-methyl-1,3-dioxolane.
Nitrogen-containing compounds include acetonitrile, nitromethane, N-methyl-2-pyrrolidone and the like.
Examples of the esters include methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, and phosphoric acid triester.
Examples of inorganic acid esters include sulfate esters, nitrate esters, and hydrochloric acid esters.
Examples of amides include dimethylformamide and dimethylacetamide.
Examples of the glymes include diglyme, triglyme, and tetraglyme.
Examples of ketones include acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of sultone include 1,3-propane sultone, 4-butane sultone, naphtha sultone and the like.
これらのリチウムイオン二次電池の電解液の中では、カーボネート類にLiPF6を溶解した非水系の電解液が好ましく、電解質濃度は使用する電極、電解液によって異なるが、0.5〜3モル/Lが好ましい。 Among the electrolytes of these lithium ion secondary batteries, non-aqueous electrolytes in which LiPF 6 is dissolved in carbonates are preferred, and the electrolyte concentration varies depending on the electrodes and electrolytes used, but 0.5-3 mol / L is preferred.
ニッケル水素電池の場合の電解液としては、水酸化ナトリウム、水酸化リチウム、水酸化カリウム等の電解質の水溶液が挙げられる。電気二重層キャパシタの場合の電解液としては、アンモニウム塩、スルホニウム塩等の電解質を含む有機溶媒等の非水溶液系溶媒を有して構成される。この場合の有機溶媒としては、カーボネート類、アルコール類、ニトリル類、アミド類、エーテル類等の1種又は2種以上の混合溶媒を用いることができる。 Examples of the electrolytic solution in the case of a nickel metal hydride battery include aqueous solutions of electrolytes such as sodium hydroxide, lithium hydroxide, and potassium hydroxide. The electrolytic solution in the case of the electric double layer capacitor is configured to have a non-aqueous solvent such as an organic solvent containing an electrolyte such as an ammonium salt or a sulfonium salt. As the organic solvent in this case, one kind or two or more kinds of mixed solvents such as carbonates, alcohols, nitriles, amides and ethers can be used.
以下、本発明を実施例および比較例により具体的に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.
<参考例1>
(バインダー組成物の調製)
攪拌機付きの温度調節の可能な容器に、(a1)としてアクリル酸2−エチルヘキシル86.5質量部(以下、単に「部」という)、メタクリル酸メチル5.1部、(a2)としてメタクリル酸2−ヒドロキシエチル5部、(a3)としてジメタクリル酸エチレングリコール2部、(b)としてメタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウム(三洋化成工業株式会社製「エレミノール(登録商標) RS−3000」、以下同じ)0.6部、(c)としてメタクリル酸0.8部、さらにイオン交換水100部を加え容器内を窒素で置換した。次に、過硫酸アンモニウム0.2部により80℃で重合を開始し、重合率が99%になった時点で冷却し、バインダー組成物を得た。得られたバインダー組成物に、10%水酸化カリウム水溶液を加え、pHを7に調整した。得られたバインダー組成物の固形分は50質量%であり、平均粒子径は226nmであった。
< Reference Example 1 >
(Preparation of binder composition)
In a temperature-adjustable container equipped with a stirrer, (a1) 86.5 parts by mass of 2-ethylhexyl acrylate (hereinafter simply referred to as “part”), methyl methacrylate 5.1 parts, (a2) methacrylic acid 2 -5 parts of hydroxyethyl, 2 parts of ethylene glycol dimethacrylate as (a3), sodium methacryloyloxypolyoxypropylene sulfonate as (b) ("Eleminol (registered trademark) RS-3000" manufactured by Sanyo Chemical Industries Ltd.), and the same hereinafter ) 0.6 parts, 0.8 parts of methacrylic acid as (c) and 100 parts of ion-exchanged water were added, and the inside of the container was replaced with nitrogen. Next, polymerization was started at 80 ° C. with 0.2 part of ammonium persulfate, and when the polymerization rate reached 99%, cooling was performed to obtain a binder composition. A 10% aqueous potassium hydroxide solution was added to the obtained binder composition to adjust the pH to 7. The obtained binder composition had a solid content of 50% by mass and an average particle size of 226 nm.
(バインダー組成物の平均粒子径)
得られたバインダー組成物を純水で希釈し、レーザー散乱式粒度測定機(ベックマンコールター社製 LS−13−320)を用いて、体積平均粒子径を測定した。
(Average particle size of binder composition)
The obtained binder composition was diluted with pure water, and the volume average particle size was measured using a laser scattering particle size measuring device (LS-13-320, manufactured by Beckman Coulter, Inc.).
(正極材スラリーの調製)
正極剤スラリーの調製には、以下の原料を用いた。
・カルボキシメチルセルロース:株式会社ダイセル製「D2200」
エーテル化度0.8〜1.0、1%溶液粘度2,000mPa・s(25℃)
・LiFePO4:クラリアント株式会社製「P2」、平均一次粒子径600nm
・LiCoO2:日本化学工業株式会社製「C−10N」、平均一次粒子径12μm
・LiMn2O4:東ソー株式会社製、平均一次粒子径10μm
・アセチレンブラック:電気化学工業株式会社製「HS−100」、平均一次粒子径35n
m
・繊維状炭素:株式会社エムディーナノテック社製「MDCNF」、平均径15nm、比表
面積240m3/g
(Preparation of positive electrode material slurry)
The following raw materials were used for the preparation of the positive electrode slurry.
Carboxymethyl cellulose: “D2200” manufactured by Daicel Corporation
Etherification degree 0.8-1.0, 1% solution viscosity 2,000 mPa · s (25 ° C.)
LiFePO 4 : “P2” manufactured by Clariant Inc., average primary particle diameter 600 nm
LiCoO 2 : “C-10N” manufactured by Nippon Chemical Industry Co., Ltd., average primary particle size of 12 μm
LiMn 2 O 4 : manufactured by Tosoh Corporation, average primary particle size of 10 μm
Acetylene black: “HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd., average primary particle size 35 n
m
-Fibrous carbon: “MDCNF” manufactured by MD Nanotech Co., Ltd., average diameter 15 nm, specific surface area 240 m 3 / g
プラネタリーミキサー内で、得られたバインダー組成物を固形分で5部、カルボキシメチルセルロース2部、LiFePO4を84部、アセチレンブラック)7部、繊維状炭素2部とイオン交換水を混合し固形分42%の正極材スラリーを調製した。さらに、プラネタリーミキサー内で、得られた正極材スラリーをゲージ圧0mmHgの条件にて、15分間、真空脱泡処理した。 In planetary mixer, 5 parts of the resulting binder composition solids, carboxymethylcellulose 2 parts, LiFePO 4 and 84 parts of acetylene black) 7 parts of mixed solid fibrous carbon 2 parts of ion-exchanged water A 42% positive electrode material slurry was prepared. Furthermore, the obtained positive electrode material slurry was vacuum defoamed for 15 minutes under the condition of a gauge pressure of 0 mmHg in a planetary mixer.
(正極材スラリーの評価)
[スラリー調製時の脱泡性]
調整した正極材スラリー100mLをメスシリンダーに入れ、これをデシケーター内に密封し、ゲージ圧0mmHgの減圧下に15分間放置した。この間、液面が最高点に達した際の体積と、減圧処理前の体積比より脱泡性を評価した。評価は、体積比で3倍以上膨張した場合を「不可」、2倍以上3倍未満の場合を「可」、2倍未満の場合を「良」とした。
体積比=v2/v1
但し、v1:減圧前の体積、v2:減圧時の液面最高時の体積
(Evaluation of positive electrode material slurry)
[Defoamability during slurry preparation]
100 mL of the adjusted positive electrode material slurry was placed in a graduated cylinder, which was sealed in a desiccator and allowed to stand for 15 minutes under reduced pressure at a gauge pressure of 0 mmHg. During this time, the defoaming property was evaluated from the volume when the liquid level reached the highest point and the volume ratio before the pressure reduction treatment. In the evaluation, the case where the volume ratio was expanded by 3 times or more was “impossible”, the case where it was 2 times or more and less than 3 times was “good”, and the case where it was less than 2 times was “good”.
Volume ratio = v2 / v1
However, v1: Volume before decompression, v2: Volume at the highest liquid level during decompression
[スラリーの貯蔵安定性]
調製した正極材スラリーを23℃にて静置し、1週間後にスラリー性状の評価を行った。ゲルや凝集物が発生したもの及びスラリーの沈降が認められたものを「不可」、凝集物の発生、スラリーの沈降、粘度変化が観られなかったものを「良」、粘度変化は生じたが、凝集物の発生を生じなかったものを「可」とした。
[Slurry storage stability]
The prepared positive electrode slurry was allowed to stand at 23 ° C., and the slurry properties were evaluated after 1 week. “No” when gel or agglomerate was generated or sludge was found to be settled, “good” when agglomerate was generated, slurry was settled, no change in viscosity was observed, viscosity change occurred Those that did not cause the formation of aggregates were evaluated as “OK”.
(正極の作製)
厚み20μmのアルミニウム箔両面に、調製した正極材スラリーを、自動塗工機で片面ずつ140g/m2となるように塗布し、60℃、滞留時間15分で予備乾燥した。次に、ロールプレス機にて0.2〜3ton/cmの線圧でプレスし、正極集電体の厚さが両面で148μmになるように調製した。さらに集電体を54mm幅に切断して、短冊状の集電体シートを作製した。集電体シートの端部にアルミニウム製の集電体タブを超音波溶着した後、残留溶媒や吸着水分といった揮発成分を完全に除去するため、120℃で14時間真空乾燥して正極を得た。作製した正極について、以下の方法により、塗膜の平滑性、結着性、及び鉛筆硬度を評価した。
(Preparation of positive electrode)
The prepared positive electrode slurry was applied to both sides of an aluminum foil having a thickness of 20 μm by an automatic coating machine so that each side was 140 g / m 2 and pre-dried at 60 ° C. and a residence time of 15 minutes. Next, it pressed with the linear pressure of 0.2-3 ton / cm with the roll press machine, and prepared so that the thickness of a positive electrode electrical power collector might be 148 micrometers on both surfaces. Further, the current collector was cut into a width of 54 mm to produce a strip-shaped current collector sheet. After ultrasonically welding a current collector tab made of aluminum to the end of the current collector sheet, in order to completely remove volatile components such as residual solvent and adsorbed moisture, vacuum drying was performed at 120 ° C. for 14 hours to obtain a positive electrode. . About the produced positive electrode, the smoothness of a coating film, binding property, and pencil hardness were evaluated with the following method.
(正極の評価)
[塗膜の平滑性(欠陥数)]
54mm×100mmに切断した正極表面を目視にて観察し、欠陥数を数え塗膜の平滑性を評価した。3枚の正極表面について、径が0.1mm以上の欠陥数の算術平均を算出した。ここで、欠陥とは、活物質、導電助剤およびバインダー組成物の凝集物、さらには気泡の発生によって周囲とは不均一となって見える部分を指す。尚、それぞれの欠陥の径は、光学顕微鏡を用い、倍率を100倍として観察することで確認した。
(Evaluation of positive electrode)
[Smoothness of coating film (number of defects)]
The positive electrode surface cut to 54 mm × 100 mm was visually observed, the number of defects was counted, and the smoothness of the coating film was evaluated. The arithmetic average of the number of defects having a diameter of 0.1 mm or more was calculated for the three positive electrode surfaces. Here, the term “defect” refers to an active material, an agglomerate of a conductive additive and a binder composition, and a portion that appears to be non-uniform due to the generation of bubbles. In addition, the diameter of each defect was confirmed by observing a magnification as 100 times using an optical microscope.
[結着性]
作製した正極を用い、JIS K 5600−5−6に準じ、カット間隔2mmで格子パターン25マスのクロスカット法試験により、塗膜の結着性を評価した。評価は0〜5の6段階により行い、数字が少ないものほど塗膜の結着性が良好であることを示す。
[Binding property]
Using the produced positive electrode, according to JIS K 5600-5-6, the binding property of the coating film was evaluated by a cross-cut method test with a grid pattern of 25 squares at a cut interval of 2 mm. Evaluation is performed in 6 stages of 0 to 5, and the smaller the number, the better the binding property of the coating film.
(負極材スラリーの調製)
負極材スラリーの調製には、以下の原料を用いた。
・カルボキシメチルセルロース:株式会社ダイセル製「D2200」
エーテル化度0.8〜1.0、1%溶液粘度2,000mPa・s(25℃)
・黒鉛:株式会社クレハ製「カーボトロンP」、平均粒径9μm
・Li4Ti5O12:アルタイルナノテクノロジー社製、比表面積130m2/g
・SiO:株式会社大阪チタニウムテクノロジーズ社製「SiO」
・アセチレンブラック:電気化学工業株式会社製「HS−100」、平均一次粒子径35n
m
・繊維状炭素:株式会社エムディーナノテック社製「MDCNF」、平均径15nm、比表
面積240m3/g
(Preparation of negative electrode material slurry)
The following raw materials were used for the preparation of the negative electrode material slurry.
Carboxymethyl cellulose: “D2200” manufactured by Daicel Corporation
Etherification degree 0.8-1.0, 1% solution viscosity 2,000 mPa · s (25 ° C.)
Graphite: “Carbotron P” manufactured by Kureha Co., Ltd., average particle size 9 μm
Li 4 Ti 5 O 12 : manufactured by Altair Nanotechnology, specific surface area 130 m 2 / g
・ SiO: “SiO” manufactured by Osaka Titanium Technologies, Ltd.
Acetylene black: “HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd., average primary particle size 35 n
m
-Fibrous carbon: “MDCNF” manufactured by MD Nanotech Co., Ltd., average diameter 15 nm, specific surface area 240 m 3 / g
プラネタリーミキサー内で、負極活物質として黒鉛を98部、調整したバインダー組成物を固形分で1部、カルボキシメチルセルロースを1部混合し、全固形分が50質量%となるように適量の水を加えて混練し、負極材スラリーを調製した。さらに、プラネタリーミキサー内で、得られた負極材スラリーをゲージ圧0mmHgの条件にて、15分間、真空脱泡処理した。 In a planetary mixer, 98 parts of graphite as the negative electrode active material, 1 part of the prepared binder composition and 1 part of carboxymethylcellulose are mixed, and an appropriate amount of water is added so that the total solid content is 50% by mass. In addition, kneading was performed to prepare a negative electrode material slurry. Furthermore, the negative electrode material slurry obtained was vacuum defoamed for 15 minutes under the condition of a gauge pressure of 0 mmHg in a planetary mixer.
(負極の作製)
厚み10μmの銅箔の両面に、調製した負極材スラリーを、自動塗工機で片面ずつ70g/m2となるように塗布し、60℃、滞留時間10分で予備乾燥した。次に、ロールプレス機にて0.2〜3ton/cmの線圧でプレスし、負極集電体の厚さが両面で90μmになるように調製した。さらに負極集電体を54mm幅に切断して短細状の集電体シートを作製した。集電体シートの端部にニッケル製の集電体タブを超音波溶着した後、残留溶媒や吸着水分といった揮発成分を完全に除去するため、120℃で14時間真空乾燥して負極を得た。
(Preparation of negative electrode)
The prepared negative electrode material slurry was applied to both sides of a copper foil having a thickness of 10 μm by an automatic coater so that each side was 70 g / m 2, and preliminarily dried at 60 ° C. and a residence time of 10 minutes. Next, it pressed with the linear pressure of 0.2-3 ton / cm with the roll press machine, and prepared so that the thickness of a negative electrode electrical power collector might be 90 micrometers on both surfaces. Further, the negative electrode current collector was cut into a width of 54 mm to produce a short current collector sheet. After ultrasonically welding a nickel current collector tab to the end of the current collector sheet, the anode was obtained by vacuum drying at 120 ° C. for 14 hours in order to completely remove volatile components such as residual solvent and adsorbed moisture. .
(リチウムイオン二次電池の作製)
得られた正極と負極とを組合せ、厚み25μm、幅60mmのポリエチレン微多孔膜セパレーターを介して捲回し、スパイラル状の捲回群を作製した後、これを電池缶に挿入した。次いで、電解質としてLiPF6を1mol/Lの濃度で溶解した非水溶液系の電解液(エチレンカーボーネート/メチルエチルカーボネート=30/70(質量比)混合液)を電池容器に5ml注入した後、注入口をかしめて密閉し、直径18mm、高さ65mmの円筒形のリチウム二次電池(3.4V−940mAh)を作製した。作製したリチウムイオン二次電池について、以下の方法により電池性能を評価した。
(Production of lithium ion secondary battery)
The obtained positive electrode and negative electrode were combined and wound through a polyethylene microporous membrane separator having a thickness of 25 μm and a width of 60 mm to produce a spiral wound group, which was then inserted into a battery can. Next, after injecting 5 ml of a non-aqueous electrolyte solution (ethylene carbonate / methyl ethyl carbonate = 30/70 (mass ratio) mixed solution) in which LiPF 6 was dissolved at a concentration of 1 mol / L as an electrolyte, The inlet was caulked and sealed to produce a cylindrical lithium secondary battery (3.4 V-940 mAh) having a diameter of 18 mm and a height of 65 mm. About the produced lithium ion secondary battery, the battery performance was evaluated with the following method.
(リチウムイオン二次電池の評価)
作製したリチウムイオン二次電池を、25℃において4.0V、0.2ItA(188mA)制限の定電流定電圧充電をした後、0.2ItAの定電流で2.0Vまで放電した。
(Evaluation of lithium ion secondary battery)
The prepared lithium ion secondary battery was charged at a constant current and a constant voltage with a limit of 4.0 V and 0.2 ItA (188 mA) at 25 ° C., and then discharged to 2.0 V at a constant current of 0.2 ItA.
[放電レート特性(高率放電容量維持率)]
次いで、放電電流を0.2ItA、1ItAと変化させ、各放電電流に対する放電容量を測定した。各測定における回復充電は4.0V(1ItAカット)の定電流定電圧充電を行った。そして、0.2ItA放電時に対する1ItA放電時の高率放電容量維持率を計算した。
[Discharge rate characteristics (High rate discharge capacity maintenance rate)]
Next, the discharge current was changed to 0.2 ItA and 1 ItA, and the discharge capacity for each discharge current was measured. The recovery charge in each measurement was a constant current constant voltage charge of 4.0 V (1 ItA cut). And the high rate discharge capacity maintenance factor at the time of 1 ItA discharge with respect to the time of 0.2 ItA discharge was calculated.
[サイクル特性(サイクル容量維持率)]
環境温度25℃にて、充電電圧4.0V、1ItAの定電流定電圧充電と、放電終止電圧2.0Vの1ItAの定電流放電を行った。充電及び放電のサイクルを繰り返し行い、1サイクル目の放電容量に対する500サイクル目の放電容量の比率を求めてサイクル容量維持率とした。
[Cycle characteristics (cycle capacity retention rate)]
At an environmental temperature of 25 ° C., a constant current and constant voltage charge with a charge voltage of 4.0 V and 1 ItA and a constant current discharge of 1 ItA with a discharge end voltage of 2.0 V were performed. The cycle of charging and discharging was repeated, and the ratio of the discharge capacity at the 500th cycle to the discharge capacity at the first cycle was determined as the cycle capacity maintenance rate.
結果を、表1に示す。 The results are shown in Table 1.
<実施例2〜7、参考例8>
(a1)アクリル酸2−エチルヘキシルおよびメタクリル酸メチルと、(b)メタキリロイルオキシポリオキシプロピレレンスルホン酸ナトリウムの添加量を表1に示したものに変更した以外は、参考例1に示した方法でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表1に示す。
<Examples 2 to 7, Reference Example 8 >
It was shown in Reference Example 1 except that the addition amount of (a1) 2-ethylhexyl acrylate and methyl methacrylate and (b) sodium methacryloyloxypolyoxypropylene sulfonate was changed to those shown in Table 1. The binder composition was produced by the method. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 1.
<参考例9>
(a1)としてアクリル酸2−エチルヘキシル85.05部、メタクリル酸メチル4.9部、(b)としてメタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウム3部、(c)としてメタクリル酸0.05部に変更した以外は、参考例1に示した方法でバインダー組成物を作製した。平均粒子径は、174nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表2に示す。
< Reference Example 9 >
(A1) was changed to 2-ethylhexyl acrylate (85.05 parts), methyl methacrylate (4.9 parts), (b) sodium methacryloyloxypolyoxypropylene sulfonate (c) and (c) 0.05 parts methacrylic acid. Except for the above, a binder composition was prepared by the method shown in Reference Example 1 . The average particle size was 174 nm. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 2.
<実施例10〜15、参考例16>
(a1)アクリル酸2−エチルヘキシルおよびメタクリル酸メチルと、(c)メタクリル酸の添加量を表2に示したものに変更した以外は、参考例9と同様な配合でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表2に示す。
<Examples 10 to 15 and Reference Example 16 >
A binder composition was prepared in the same manner as in Reference Example 9 except that (a1) 2-ethylhexyl acrylate and methyl methacrylate and (c) the amount of methacrylic acid added were changed to those shown in Table 2. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 2.
<参考例17>
(a1)としてアクリル酸2−エチルヘキシル64.3部、メタクリル酸メチル3.7部、(a2)としてメタクリル酸2−ヒドロキシエチル10部、(a3)としてジメタクリル酸エチレングリコール7部、(b)としてメタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウム8部、(c)としてメタクリル酸7部に変更した以外は、参考例1に示した方法でバインダー組成物を作製した。平均粒子径は、155nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表3に示す。
< Reference Example 17 >
(A1) 6-part 2-ethylhexyl acrylate, 3.7 parts methyl methacrylate, (a2) 10 parts 2-hydroxyethyl methacrylate, (a3) 7 parts ethylene glycol dimethacrylate, (b) A binder composition was prepared by the method shown in Reference Example 1 except that 8 parts of sodium methacryloyloxypolyoxypropylene sulfonate was used and 7 parts of methacrylic acid was used as (c). The average particle size was 155 nm. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 3.
<実施例18〜26>
単量体を表3に示したものに変更した以外は、参考例1に示した方法でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表3に示す。
<Examples 18 to 26>
A binder composition was prepared by the method shown in Reference Example 1 except that the monomers were changed to those shown in Table 3. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 3.
<実施例27>
(a1)としてアクリル酸2−エチルヘキシル88.1部、メタクリル酸メチル5.1部、(a2)としてメタクリル酸2−ヒドロキシエチル1部、(a3)としてジメタクリル酸エチレングリコール2部、(b)としてメタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウム3部、(c)としてメタクリル酸0.8部に変更した以外は、参考例1に示した方法でバインダー組成物を作製した。平均粒子径は、155nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表4に示す。
<Example 27>
(A1) 2ethylhexyl acrylate 88.1 parts, methyl methacrylate 5.1 parts, (a2) 2-hydroxyethyl methacrylate 1 part, (a3) ethylene glycol dimethacrylate 2 parts, (b) A binder composition was prepared by the method shown in Reference Example 1 , except that 3 parts of sodium methacryloyloxypolyoxypropylene sulfonate was used and 3 parts of (c) was changed to 0.8 part of methacrylic acid. The average particle size was 155 nm. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 4.
<実施例28〜32>
単量体を表4に示したものに変更した以外は、参考例1に示した方法でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表4に示す。
<Examples 28 to 32>
A binder composition was prepared by the method shown in Reference Example 1 except that the monomers were changed to those shown in Table 4. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 4.
<実施例33>
(a1)としてアクリル酸2−エチルヘキシル85.7部、メタクリル酸メチル5部、(a2)としてメタクリル酸2−ヒドロキシエチル5部、(a3)としてジメタクリル酸エチレングリコール0.5部、(b)としてメタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウム3部、(c)としてメタクリル酸0.8部に変更した以外は、参考例1に示した方法でバインダー組成物を作製した。平均粒子径は、181nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表5に示す。
<Example 33>
(A1) 85.7 parts 2-ethylhexyl acrylate, 5 parts methyl methacrylate, (a2) 5 parts 2-hydroxyethyl methacrylate, (a3) 0.5 parts ethylene glycol dimethacrylate, (b) A binder composition was prepared by the method shown in Reference Example 1 , except that 3 parts of sodium methacryloyloxypolyoxypropylene sulfonate was used and 3 parts of (c) was changed to 0.8 part of methacrylic acid. The average particle size was 181 nm. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 5.
<実施例34〜37>
単量体を表5に示したものに変更した以外は、参考例1に示した方法でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表5に示す。
<Examples 34 to 37>
A binder composition was prepared by the method shown in Reference Example 1 except that the monomers were changed to those shown in Table 5. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 5.
<実施例38>
表6に示す組成に従い、(a1)メタクリル酸メチルを添加しなかった以外は、参考例1と同様な方法でバインダー組成物を作製した。平均粒子径は、183nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表6に示す。
<Example 38>
According to the composition shown in Table 6, a binder composition was prepared in the same manner as in Reference Example 1 except that (a1) methyl methacrylate was not added. The average particle size was 183 nm. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 6.
<実施例39〜43>
アクリル酸2−エチルヘキシルおよびメタクリル酸を、表6に示したものに変更した以外は、実施例38と同様な配合でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表6に示す。
<Examples 39 to 43>
A binder composition was prepared in the same manner as in Example 38 except that 2-ethylhexyl acrylate and methacrylic acid were changed to those shown in Table 6. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 6.
<実施例44>
(a1)としてアクリル酸2−エチルヘキシル39.2部、メタクリル酸2−エチルヘキシル50部、(a2)としてメタクリル酸2−ヒドロキシエチル5部、(a3)としてジメタクリル酸エチレングリコール2部、(b)としてメタクリロイルオキシポリオキシプロピレンスルホン酸ナトリウム3部、(c)としてメタクリル酸0.8部に変更した以外は、参考例1に示した方法でバインダー組成物を作製した。平均粒子径は、192nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表7に示す。
<Example 44>
(A1) 39.2 parts of 2-ethylhexyl acrylate, 50 parts of 2-ethylhexyl methacrylate, (a2) 5 parts of 2-hydroxyethyl methacrylate, (a3) 2 parts of ethylene glycol dimethacrylate, (b) A binder composition was prepared by the method shown in Reference Example 1 , except that 3 parts of sodium methacryloyloxypolyoxypropylene sulfonate was used and 3 parts of (c) was changed to 0.8 part of methacrylic acid. The average particle size was 192 nm. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 7.
<実施例45〜51>
単量体を表7に示したものに変更した以外は、参考例1に示した方法でバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表7に示す。
<Examples 45-51>
A binder composition was prepared by the method shown in Reference Example 1 except that the monomers were changed to those shown in Table 7. Furthermore, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 7.
<比較例1>
比較例1では、(a2)化2で表わされる単量体を添加しなかったバインダー組成物を作製した。平均粒子径は、188nmであった。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施したが、塗膜の平滑性に乏しく、かつ、高率放電容量維持率およびサイクル容量維持率も低い値であった。結果を表8に示す。
<Comparative Example 1>
In Comparative Example 1, a binder composition was prepared in which the monomer represented by (a2) Chemical Formula 2 was not added. The average particle size was 188 nm. Further, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. However, the smoothness of the coating film was poor, and the high rate discharge capacity maintenance rate and The cycle capacity retention rate was also low. The results are shown in Table 8.
<比較例2>
比較例2では、(a3)エチレン性不飽和基を分子中に二つ以上含有する多官能単量体を添加しなかったバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施したが、高率放電容量維持率およびサイクル容量維持率が低い値となった。結果を表8に示す。
<Comparative example 2>
In Comparative Example 2, a binder composition was prepared in which (a3) a polyfunctional monomer containing two or more ethylenically unsaturated groups in the molecule was not added. Further, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1 and evaluated, but the high rate discharge capacity retention rate and cycle capacity retention rate were low. . The results are shown in Table 8.
<比較例3>
比較例3では、(b)(メタ)アクリロイル基を有するスルホン酸誘導体の代わりに、アリルスルホン酸ナトリウム3部を添加しバインダー組成物を作製した。さらに、参考例1と同様な方法で、正極材スラリー、負極材スラリー、正極、負極を作製し、各評価を実施したが、スラリー調整時の真空脱泡性および塗膜の平滑性に劣る結果となった。結果を表8に示す。
<Comparative Example 3>
In Comparative Example 3, 3 parts of sodium allyl sulfonate was added in place of the sulfonic acid derivative having (b) (meth) acryloyl group to prepare a binder composition. Further, a positive electrode material slurry, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1 and evaluated, but the results were inferior in vacuum defoaming property and smoothness of the coating film during slurry adjustment. It became. The results are shown in Table 8.
<比較例4>
比較例4では、表8に示した配合に従い、参考例1と同様な方法で、(b)(メタ)アクリロイル基を有するスルホン酸誘導体を添加せず80℃で重合を試みたが、8時間経過後も重合が進行せず、バインダー組成物が調製できなかった。
<Comparative example 4>
In Comparative Example 4, in accordance with the formulation shown in Table 8, polymerization was attempted at 80 ° C. in the same manner as in Reference Example 1 without adding the sulfonic acid derivative having (b) (meth) acryloyl group. Polymerization did not proceed even after the lapse of time, and a binder composition could not be prepared.
<比較例5>
比較例5では、(c)エチレン性不飽和カルボン酸を添加せずバインダー組成物を作製したが、サイクル容量維持率が低い値となった。結果を表8に示す。
<Comparative Example 5>
In Comparative Example 5, a binder composition was prepared without adding (c) ethylenically unsaturated carboxylic acid, but the cycle capacity retention rate was low. The results are shown in Table 8.
<実施例52>
実施例4のバインダー組成物を使用し、正極活物質をLiCoO2とした以外は、全て参考例1と同様な方法で正極材スラリーを調製した。さらに、参考例1と同様な方法で、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表9に示す。
<Example 52>
A positive electrode material slurry was prepared in the same manner as in Reference Example 1 except that the binder composition of Example 4 was used and the positive electrode active material was LiCoO 2 . Further, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 9.
<実施例53>
実施例4のバインダー組成物を使用し、正極活物質をLiMn2O4とした以外は、全て参考例1と同様な方法で正極材スラリーを調製した。さらに、参考例1と同様な方法で、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表9に示す。
<Example 53>
A positive electrode material slurry was prepared in the same manner as in Reference Example 1 except that the binder composition of Example 4 was used and the positive electrode active material was LiMn 2 O 4 . Further, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 9.
<実施例54>
実施例4のバインダー組成物を使用し、負極活物質を金属シリコンを内包したシリコン酸化物(大阪チタニウムテクノロジーズ社製「SiO」)とした以外は、全て参考例1と同様な方法で負極材スラリーを調製した。さらに、参考例1と同様な方法で、正極材スラリー、正極、負極を作製し、各評価を実施した。結果を表9に示す。
<Example 54>
A negative electrode material slurry was produced in the same manner as in Reference Example 1 except that the binder composition of Example 4 was used and the negative electrode active material was silicon oxide containing metallic silicon ("SiO" manufactured by Osaka Titanium Technologies). Was prepared. Further, a positive electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 9.
<実施例55>
実施例4のバインダー組成物を使用し、負極活物質としてLi4Ti5O12を使用した以外は、全て参考例1と同様な方法で負極材スラリーを調製した。さらに、参考例1と同様な方法で、正極材スラリー、正極、負極を作製し、各評価を実施した。結果を表9に示す。
<Example 55>
A negative electrode material slurry was prepared in the same manner as in Reference Example 1 except that the binder composition of Example 4 was used and Li 4 Ti 5 O 12 was used as the negative electrode active material. Further, a positive electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 9.
<実施例56>
繊維状炭素1.9部、アセチレンブラック7.4部、LiFePO483.7部を、エタノール1000部に加え、アルミナ製ボールからなる撹拌媒体を用い、振動ミルで5時間湿式撹拌することによって、繊維状炭素とアセチレンブラックのメカノケミカル的複合化と、LiFePO4との混合を、同時に実施した。撹拌後、濾過によりエタノールを除去し、乾燥機で100℃、3時間保持して乾燥し、さらにらいかい機を用いて8時間解砕処理した。この混合物をマッフル炉に充填し、窒素ガスを流しながら700℃で1時間加熱処理を行い繊維状炭素、アセチレンブラック、LiFePO4からなる炭素複合体を焼成した。得られた炭素複合体93部に、実施例4で得られたバインダー組成物を固形分で5部、カルボキシメチルセルロース2部を混合し、正極材スラリーを調製した。さらに、参考例1と同様な方法で、負極材スラリー、正極、負極を作製し、各評価を実施した。結果を表9に示す。
<Example 56>
By adding 1.9 parts of fibrous carbon, 7.4 parts of acetylene black, and 83.7 parts of LiFePO 4 to 1000 parts of ethanol and using a stirring medium made of alumina balls, the mixture is wet-stirred with a vibration mill for 5 hours. The mechanochemical combination of fibrous carbon and acetylene black and mixing with LiFePO 4 were performed simultaneously. After stirring, the ethanol was removed by filtration, dried at 100 ° C. for 3 hours with a dryer, and further crushed for 8 hours using a rougher. The mixture was filled in a muffle furnace, and a carbon composite made of fibrous carbon, acetylene black, and LiFePO 4 was fired at 700 ° C. for 1 hour while flowing nitrogen gas. To 93 parts of the obtained carbon composite, 5 parts of the binder composition obtained in Example 4 and 2 parts of carboxymethyl cellulose were mixed to prepare a positive electrode material slurry. Further, a negative electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 9.
<実施例57>
繊維状炭素2部、アセチレンブラック3.9部、金属シリコンを内包したシリコン酸化物(以下、シリコン酸化物と略す)92.1部を、エタノール1000部に加え、アルミナ製ボールからなる撹拌媒体を用い、振動ミルで5時間湿式撹拌することによって、繊維状炭素とアセチレンブラックのメカノケミカル的複合化と、シリコン酸化物との混合を、同時に実施した。さらに、実施例37と同様な方法で焼成を行い、炭素複合体を得た。得られた炭素複合体98部に、実施例4で得られたバインダー組成物を固形分で1部、カルボキシメチルセルロースを1部混合し、全固形分が50質量%となるように適量の水を加えて混練し、負極材スラリーを調製した。さらに、参考例1と同様な方法で、正極材スラリー、正極、負極を作製し、各評価を実施した。結果を表9に示す。
<Example 57>
2 parts of fibrous carbon, 3.9 parts of acetylene black, 92.1 parts of silicon oxide containing metal silicon (hereinafter abbreviated as silicon oxide) are added to 1000 parts of ethanol, and a stirring medium made of alumina balls is added. The mixture was mixed with silicon oxide and mechanochemical composite of fibrous carbon and acetylene black by wet stirring with a vibration mill for 5 hours. Further, firing was performed in the same manner as in Example 37 to obtain a carbon composite. 98 parts of the obtained carbon composite is mixed with 1 part of the binder composition obtained in Example 4 and 1 part of carboxymethylcellulose, and an appropriate amount of water is added so that the total solid content is 50% by mass. In addition, kneading was performed to prepare a negative electrode material slurry. Further, a positive electrode material slurry, a positive electrode, and a negative electrode were prepared in the same manner as in Reference Example 1, and each evaluation was performed. The results are shown in Table 9.
尚、各種活物質を使用した負極材スラリー及び負極についても正極と同様の評価を行ったところ、活物質の違いによらず評価結果は良好だった。 In addition, when the negative electrode material slurry and the negative electrode using various active materials were evaluated in the same manner as the positive electrode, the evaluation results were good regardless of the difference in the active materials.
表1〜表9の結果から、本発明の実施例のリチウムイオン二次電池電極用バインダー組成物から得られた電極用スラリーは貯蔵安定性、スラリー調製時の脱泡性に優れ、塗膜の平滑性が良好であり、リチウムイオン二次電池の放電レート特性、サイクル特性が良好であることが示される。 From the results of Tables 1 to 9, the electrode slurry obtained from the binder composition for lithium ion secondary battery electrodes of the examples of the present invention is excellent in storage stability and defoaming property at the time of slurry preparation. It shows that the smoothness is good and the discharge rate characteristics and cycle characteristics of the lithium ion secondary battery are good.
本発明のバインダー組成物を含有する電極用スラリーを利用することで、スラリー調製時の脱泡作業が容易になり、塗膜の平滑性に優れた電極を得ることができる。これにより、放電レート特性及びサイクル特性に優れたリチウムイオン二次電池やニッケル水素二次電池、電気二重層キャパシタ等を得ることができる。
By utilizing the slurry for electrodes containing the binder composition of the present invention, the defoaming operation at the time of slurry preparation becomes easy, and an electrode excellent in the smoothness of the coating film can be obtained. Thereby, a lithium ion secondary battery, a nickel hydride secondary battery, an electric double layer capacitor, etc. excellent in discharge rate characteristics and cycle characteristics can be obtained.
Claims (17)
(a1)化1で表わされる構造単位において、R2は炭素数1〜20のアルキル基である単量体。
(a2)化2で表わされる構造単位において、R3は炭素数1〜7のメチレン鎖である単量体。
(a3)メタクリル酸アリル、ジメタクリル酸エチレングリコール、ジメタクリル酸プロピレングリコール、ジメタクリル酸テトラメチレングリコールおよびジメタクリル酸−1,3−ブチレングリコールから選択される、
1種以上の多官能単量体。
(A1) In the structural unit represented by Chemical Formula 1, a monomer in which R 2 is an alkyl group having 1 to 20 carbon atoms.
(A2) In the structural unit represented by Chemical Formula 2, a monomer in which R 3 is a methylene chain having 1 to 7 carbon atoms.
(A3) selected from allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate,
One or more polyfunctional monomers.
いう関係を満たしかつ0<X<1、0<Y<1、0<Z<1という関係を満たす。 The positive electrode active material, at least one selected from LiCoO 2, LiMn 2 O 4, LiNiO 2, Li (Mn X Ni Y Co Z) O 2 or Li (Al X Ni Y Co Z ) group consisting of O 2 The electrode slurry according to claim 6 , which is a lithium salt. However, Li (Mn X Ni Y Co Z) O 2 in or Li (Al X Ni Y Co Z ) O 2 in the X, Y and Z, X + Y + Z = 1 and satisfies the relationship of 0 <X <1, 0 The relationship of <Y <1, 0 <Z <1 is satisfied.
An electric double layer capacitor manufactured using the electrode according to claim 15 .
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