JP7423247B2 - Positive electrode resin composition, positive electrode and secondary battery - Google Patents
Positive electrode resin composition, positive electrode and secondary battery Download PDFInfo
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- JP7423247B2 JP7423247B2 JP2019192255A JP2019192255A JP7423247B2 JP 7423247 B2 JP7423247 B2 JP 7423247B2 JP 2019192255 A JP2019192255 A JP 2019192255A JP 2019192255 A JP2019192255 A JP 2019192255A JP 7423247 B2 JP7423247 B2 JP 7423247B2
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- positive electrode
- resin composition
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- conductive material
- dispersant
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- 239000011342 resin composition Substances 0.000 title claims description 49
- 239000004020 conductor Substances 0.000 claims description 47
- 239000002270 dispersing agent Substances 0.000 claims description 42
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 34
- 239000006229 carbon black Substances 0.000 claims description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 40
- 229910001416 lithium ion Inorganic materials 0.000 description 40
- 235000019241 carbon black Nutrition 0.000 description 31
- 239000007787 solid Substances 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 239000011149 active material Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012982 microporous membrane Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 241000872198 Serjania polyphylla Species 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910013275 LiMPO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910015868 MSiO Inorganic materials 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910014195 BM-400B Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- DBUPOCYLUHVFHU-UHFFFAOYSA-N carboxyoxy 2,2-diethoxyethyl carbonate Chemical compound CCOC(OCC)COC(=O)OOC(O)=O DBUPOCYLUHVFHU-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、正極樹脂組成物、正極及び二次電池に関する。 The present invention relates to a positive electrode resin composition, a positive electrode, and a secondary battery.
環境・エネルギー問題の高まりから、化石燃料への依存度を減らす低炭素社会の実現に向けた技術の開発が盛んに行われている。このような技術開発の例としては、ハイブリッド電気自動車や電気自動車等の低公害車の開発、太陽光発電や風力発電等の自然エネルギー発電・蓄電システムの開発、電力を効率よく供給し、送電ロスを減らす次世代送電網の開発等があり、多岐に渡っている。 Due to increasing environmental and energy issues, there is active development of technologies aimed at reducing dependence on fossil fuels and realizing a low-carbon society. Examples of such technological developments include the development of low-pollution vehicles such as hybrid electric vehicles and electric vehicles, the development of natural energy generation and storage systems such as solar power generation and wind power generation, and the efficient supply of electricity and reduction of transmission losses. There is a wide range of projects, including the development of next-generation power transmission networks that will reduce the amount of electricity generated.
これらの技術に共通して必要となるキーデバイスの一つが電池であり、このような電池に対しては、システムを小型化するための高いエネルギー密度が求められる。また、使用環境温度に左右されずに安定した電力の供給を可能にするための高いレート特性が求められる。さらに、長期間の使用に耐えうる良好なサイクル特性等も求められている。そのため、従来の鉛蓄電池、ニッケル－カドミウム電池、ニッケル－水素電池から、より高いエネルギー密度、レート特性およびサイクル特性を有するリチウムイオン二次電池（以下、「リチウムイオン電池」ともいう。）への置き換えが急速に進んでいる。 One of the key devices commonly required by these technologies is a battery, and such batteries are required to have high energy density in order to miniaturize the system. In addition, high rate characteristics are required to enable stable power supply regardless of the operating environment temperature. Furthermore, good cycle characteristics that can withstand long-term use are also required. Therefore, conventional lead-acid batteries, nickel-cadmium batteries, and nickel-hydrogen batteries are being replaced with lithium-ion secondary batteries (hereinafter also referred to as "lithium-ion batteries") that have higher energy density, rate characteristics, and cycle characteristics. is progressing rapidly.
従来、リチウムイオン二次電池の正極は、正極活物質、導電材及びバインダー（結着材）を含有する正極ペーストを、集電体に塗工することにより製造されている。正極活物質としては、コバルト酸リチウム、マンガン酸リチウム等のリチウム含有複合酸化物が用いられてきた。活物質自体は導電性に乏しいことから、導電性を付与する目的で、アグリゲート（一次粒子が複数融着した構造：一次凝集体）が発達したカーボンブラックや、異方性で結晶が発達した黒鉛等の導電材を添加することが行われてきた（特許文献１）。 Conventionally, a positive electrode of a lithium ion secondary battery is manufactured by applying a positive electrode paste containing a positive electrode active material, a conductive material, and a binder to a current collector. As positive electrode active materials, lithium-containing composite oxides such as lithium cobalt oxide and lithium manganate have been used. Since the active material itself has poor conductivity, carbon black with developed aggregates (a structure in which multiple primary particles are fused together: primary aggregate) and carbon black with anisotropically developed crystals are used for the purpose of imparting conductivity. Addition of a conductive material such as graphite has been practiced (Patent Document 1).
導電材の基本的な役割は、導電性の乏しい活物質に、充放電時に正極活物質が繰り返し膨張収縮しても、損なわれることの少ない安定した導電性を付与することである。そのため、正極作製において、導電材として使用されるカーボンブラックは、アグリゲートの大きさがある範囲内に制御されていることが重要である。制御が十分でない場合や活物質間での分散が悪い場合には、活物質とカーボンブラックの接触が十分得られず、導電パスが確保できなくなり、活物質であるリチウム含有複合酸化物の性能を十分に引き出せないという問題が生じる。結果として、正極内に導電性の劣る部分が局所的に現れ、活物質が有効に利用されずに放電容量が低下、電池の寿命が短くなる原因となっている。 The basic role of a conductive material is to provide an active material with poor conductivity with stable conductivity that is not easily impaired even if the positive electrode active material repeatedly expands and contracts during charging and discharging. Therefore, in producing a positive electrode, it is important that the aggregate size of carbon black used as a conductive material is controlled within a certain range. If the control is insufficient or the dispersion between the active materials is poor, sufficient contact between the active material and carbon black will not be obtained, making it impossible to secure a conductive path, which will affect the performance of the lithium-containing composite oxide, which is the active material. The problem arises that it is not possible to draw out enough. As a result, portions with poor conductivity appear locally within the positive electrode, and the active material is not effectively utilized, resulting in a decrease in discharge capacity and a shortened battery life.
そこで、特許文献２には、スラリー中のカーボンブラックの分散性を改善するため、分散剤であるポリビニルピロリドンの存在下でカーボンブラックを高圧ジェットミルにより溶剤にサブミクロンオーダーで分散させる方法が行われている。特許文献２によれば、分散状態が安定したカーボンブラックを正極に使用することで、高容量で、かつサイクル特性が優れたリチウムイオン二次電池を得ることができることが記載されている。 Therefore, in order to improve the dispersibility of carbon black in a slurry, Patent Document 2 discloses a method in which carbon black is dispersed in a submicron order in a solvent using a high-pressure jet mill in the presence of polyvinylpyrrolidone as a dispersant. ing. Patent Document 2 describes that a lithium ion secondary battery with high capacity and excellent cycle characteristics can be obtained by using carbon black in a stable dispersion state for the positive electrode.
特許文献３には、リチウムイオン二次電池用正極において、分散安定性と少量添加で優れた導電性を発揮する導電材について記載されている。具体的には、Ｎ－メチル－２－ピロリドンを分散媒とし、これに平均粒径０．１～１μｍのカーボンブラックを３～３０質量％の割合で懸濁させると共に、ビニルピロリドン系ポリマーを０．１～１０質量％添加してなることを特徴とするカーボンブラックスラリーが提案されている。特許文献３の実施例には、レーザー回折・散乱分光法により求めた平均粒径が０．３μｍであるカーボンブラックが記載されており、当該カーボンブラックを正極の導電材として用いて作製したリチウムイオン二次電池は放電容量が高かったことが示されている。 Patent Document 3 describes a conductive material that exhibits dispersion stability and excellent conductivity when added in a small amount in a positive electrode for a lithium ion secondary battery. Specifically, N-methyl-2-pyrrolidone is used as a dispersion medium, carbon black with an average particle size of 0.1 to 1 μm is suspended in it at a ratio of 3 to 30% by mass, and a vinylpyrrolidone polymer is suspended in a proportion of 3 to 30% by mass. A carbon black slurry characterized by adding .1 to 10% by mass has been proposed. Examples of Patent Document 3 describe carbon black with an average particle size of 0.3 μm determined by laser diffraction/scattering spectroscopy, and lithium ions produced using the carbon black as a conductive material for a positive electrode. It has been shown that the secondary battery had a high discharge capacity.
導電材の分散不良を克服する手段として、ポリビニルピロリドン系高分子とノニオン系界面活性剤を分散剤として添加する方法もある（特許文献４）。 As a means to overcome poor dispersion of the conductive material, there is also a method of adding a polyvinylpyrrolidone polymer and a nonionic surfactant as a dispersant (Patent Document 4).
特許文献５には、カーボンブラックと、分散剤としてのポリビニルアルコールと、溶剤としてのＮ－メチル－２－ピロリドンとを含んでなるカーボンブラック分散液を用い、電池正極合材層の表面抵抗および５０サイクル後の放電容量維持率が良好になることが記されている。 Patent Document 5 discloses that a carbon black dispersion containing carbon black, polyvinyl alcohol as a dispersant, and N-methyl-2-pyrrolidone as a solvent is used to improve the surface resistance of a battery positive electrode composite layer and It is noted that the discharge capacity retention rate after cycling is improved.
このように、分散剤として高分子を用いる方法が従来提案されてきたが、未だ十分な分散性を有しているとは言えない。例えば特許文献４に記載の分散剤により、導電材の分散不良を改善できるものの、この分散剤を含有した正極をリチウムイオン電池として使用した際に４．３５Ｖのフロート充電後に放電容量が極端に低下するといった問題があった。しかしながら、現在のリチウムイオン二次電池市場では、同電池の耐電圧性が望まれており、分散性と耐電圧性を両立した正極用導電性樹脂組成物が必要不可欠である。 As described above, methods using polymers as dispersants have been proposed in the past, but it cannot be said that they have sufficient dispersibility yet. For example, the dispersant described in Patent Document 4 can improve poor dispersion of the conductive material, but when a positive electrode containing this dispersant is used as a lithium ion battery, the discharge capacity is extremely reduced after float charging at 4.35V. There was a problem with doing so. However, in the current lithium ion secondary battery market, the voltage resistance of the battery is desired, and a conductive resin composition for a positive electrode that has both dispersibility and voltage resistance is essential.
本発明は、上記問題と実情に鑑み、分散性及び耐電圧性に優れた正極樹脂組成物を提供することを目的とする。加えて、この正極樹脂組成物を用いて製造される極板抵抗が低い正極、更にこの正極を用いて製造される耐電圧性、放電レート特性及びサイクル特性に優れた二次電池を提供することを目的とする。 In view of the above problems and actual circumstances, the present invention aims to provide a positive electrode resin composition having excellent dispersibility and voltage resistance. In addition, to provide a positive electrode with low plate resistance manufactured using this positive electrode resin composition, and a secondary battery manufactured using this positive electrode with excellent voltage resistance, discharge rate characteristics, and cycle characteristics. With the goal.
本発明者等は、上記目的を達成するために鋭意研究した結果、特定の鹸化度を有するポリビニルアルコールを分散剤として含有し、且つ、特定の平均一次粒子径を有するカーボンブラックを含有する正極樹脂組成物を用いることにより、上記課題が解決できることを見出した。
具体的には、本発明者は、導電材としてカーボンブラック、結着材、及び分散剤として特定の鹸化度を有するポリビニルアルコールを含有する正極樹脂組成物を用いて製造した正極は、極板抵抗が低く、加えて、この正極を用いて製造した二次電池は、耐電圧性、放電レート特性及びサイクル特性に優れることを見出した。本発明者当該知見に基づき、完成されたものである。
As a result of intensive research to achieve the above object, the present inventors have developed a positive electrode resin containing polyvinyl alcohol having a specific degree of saponification as a dispersant and carbon black having a specific average primary particle diameter. It has been found that the above problems can be solved by using the composition.
Specifically, the present inventor has discovered that a positive electrode manufactured using a positive electrode resin composition containing carbon black as a conductive material, a binder, and polyvinyl alcohol having a specific degree of saponification as a dispersant has a high plate resistance. In addition, the secondary battery manufactured using this positive electrode was found to have excellent voltage resistance, discharge rate characteristics, and cycle characteristics. This invention was completed based on the knowledge of the present inventor.
すなわち、上記課題を解決する本発明は、下記に例示される。
［１］
導電材、結着材及び分散剤を含有する正極樹脂組成物であって、前記分散剤が少なくともポリビニルアルコールを含み、前記導電材が少なくともカーボンブラックを含み、前記ポリビニルアルコールの鹸化度が８５．５～９６．５モル％であり、前記カーボンブラックの平均一次粒子径が１８ｎｍ～４０ｎｍであることを特徴とする正極樹脂組成物。
［２］
前記ポリビニルアルコールの平均重合度が５００～１５００であることを特徴とする［１］に記載の正極樹脂組成物。
［３］
前記カーボンブラックのＤＢＰ吸収量が２５０～３１０ｍｌ／１００ｇであることを特徴とする［１］又は［２］に記載の正極樹脂組成物。
［４］
前記分散剤と導電材の質量比｛分散剤の質量／導電材の質量｝が０．０３～０．１５であることを特徴とする［１］～［３］のいずれか１項に記載の正極樹脂組成物。
［５］
前記結着材がポリフッ化ビニリデンであることを特徴とする［１］～［４］のいずれか１項に記載の正極樹脂組成物。
［６］
［１］～［５］のいずれか１項に記載の正極樹脂組成物を含む正極。
［７］
［６］に記載の正極を備えた二次電池。
なお、本明細書において、特にことわりがない限り、「～」という記号は両端の値「以上」および「以下」の範囲を意味する。例えば、「Ａ～Ｂ」というのは、Ａ以上、Ｂ以下であるという意味である。
That is, the present invention that solves the above problems is illustrated below.
[1]
A positive electrode resin composition containing a conductive material, a binder, and a dispersant, wherein the dispersant contains at least polyvinyl alcohol, the conductive material contains at least carbon black, and the saponification degree of the polyvinyl alcohol is 85.5. 96.5 mol %, and the carbon black has an average primary particle size of 18 nm to 40 nm.
[2]
The positive electrode resin composition according to item [1], wherein the polyvinyl alcohol has an average degree of polymerization of 500 to 1,500.
[3]
The positive electrode resin composition according to [1] or [2], wherein the carbon black has a DBP absorption amount of 250 to 310 ml/100 g.
[4]
The method according to any one of [1] to [3], wherein the mass ratio of the dispersant to the conductive material {mass of the dispersant/mass of the conductive material} is 0.03 to 0.15. Positive electrode resin composition.
[5]
The positive electrode resin composition according to any one of [1] to [4], wherein the binder is polyvinylidene fluoride.
[6]
A positive electrode comprising the positive electrode resin composition according to any one of [1] to [5].
[7]
A secondary battery comprising the positive electrode according to [6].
In this specification, unless otherwise specified, the symbol "~" means a range of "more than" and "less than" the values at both ends. For example, "A to B" means that the number is greater than or equal to A and less than or equal to B.
本発明の一実施形態によれば、分散性及び耐電圧性に優れた正極樹脂組成物を提供することができる。
本発明の一実施形態によれば、極板抵抗が低い正極を提供することができる。
本発明の一実施形態によれば、耐電圧性、レート特性及びサイクル特性に優れた二次電池を提供することができる。
また、本発明の好適な実施態様によれば、エネルギー密度が高く、耐電圧性、レート特性、サイクル特性に優れた二次電池を簡便に得ることができる正極を提供することができる。
According to one embodiment of the present invention, a positive electrode resin composition having excellent dispersibility and voltage resistance can be provided.
According to one embodiment of the present invention, a positive electrode with low plate resistance can be provided.
According to one embodiment of the present invention, it is possible to provide a secondary battery with excellent voltage resistance, rate characteristics, and cycle characteristics.
Further, according to a preferred embodiment of the present invention, it is possible to provide a positive electrode from which a secondary battery with high energy density and excellent voltage resistance, rate characteristics, and cycle characteristics can be easily obtained.
以下、本発明を詳細に説明する。なお、本発明は、以下に説明する実施形態に限定されるものではない。 The present invention will be explained in detail below. Note that the present invention is not limited to the embodiments described below.
以下、本発明の構成材料について詳細に説明する。 Hereinafter, the constituent materials of the present invention will be explained in detail.
＜導電材＞
本発明における導電材は、少なくともカーボンブラックを含有する。導電材中のカーボンブラックの含有濃度は例えば５０質量％以上とすることができ、好ましくは７０質量％以上とすることができ、より好ましくは９０質量％以上とすることができる。導電材としてカーボンブラックのみを使用することもできる。カーボンブラックは、一般の電池用導電材としてのカーボンブラック同様、アセチレンブラック、ファーネスブラック、チャンネルブラックなどの中から選ばれるものである。中でも、結晶性及び純度に優れるアセチレンブラックが好ましい。
<Conductive material>
The conductive material in the present invention contains at least carbon black. The concentration of carbon black in the conductive material can be, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. Carbon black alone can also be used as the conductive material. Carbon black is selected from acetylene black, furnace black, channel black, etc., like carbon black used as a general conductive material for batteries. Among these, acetylene black is preferred because of its excellent crystallinity and purity.
本発明におけるカーボンブラックの平均一次粒子径は１８～４０ｎｍである。平均一次粒子径を４０ｎｍ以下とすることで、活物質及び集電体との電気的接点が多くなり、良好な導電性付与効果が得られる。平均一次粒子径を１８ｎｍ以上とすることで、粒子間の相互作用が抑制されるため、正極活物質の間に均一に分散され、良好な導電経路が得られる。この観点から、カーボンブラックの平均一次粒子径は２０～３５ｎｍであることがより好ましい。なお、本発明において、カーボンブラックの平均一次粒子径は、透過型電子顕微鏡などで撮影した写真をもとに測定した粒子径を平均した値である。具体的には、透過電子顕微鏡ＪＥＭ－２０００ＦＸ（日本電子社製）を用いて１０万倍の画像５枚を撮影し、無作為に抽出した２００個以上の１次粒子について画像解析により粒子径を求め、それらの個数平均を算出することによって測定した。なお、粒子径とは、一次粒子の円相当径のことである。 The average primary particle size of carbon black in the present invention is 18 to 40 nm. By setting the average primary particle diameter to 40 nm or less, the number of electrical contacts between the active material and the current collector increases, and a good conductivity imparting effect can be obtained. By setting the average primary particle diameter to 18 nm or more, interaction between particles is suppressed, so that the particles are uniformly dispersed between the positive electrode active materials and a good conductive path is obtained. From this point of view, the average primary particle diameter of carbon black is more preferably 20 to 35 nm. In the present invention, the average primary particle diameter of carbon black is the average value of particle diameters measured based on photographs taken with a transmission electron microscope or the like. Specifically, five images were taken at a magnification of 100,000 times using a transmission electron microscope JEM-2000FX (manufactured by JEOL Ltd.), and the particle diameters of more than 200 randomly selected primary particles were determined by image analysis. It was measured by calculating the number average. Note that the particle diameter refers to the equivalent circular diameter of the primary particle.
本発明におけるカーボンブラックのＤＢＰ吸収量は２５０～３１０ｍｌ／１００ｇであることが好ましい。ＤＢＰ吸収量を２５０ｍｌ／１００ｇ以上とすることで、導電材として使用される際のアグリゲートが十分な長さと広がりを持ち、良好な導電経路と非水電解液の保液性が得られる。また、３１０ｍｌ／１００ｇ以下とすることで、アグリゲート同士の絡み合いによる凝集が抑えられるため、正極活物質の間に均一に分散され、良好な導電経路の形成と十分な非水電解液の保液性を両立することができる。なお、本発明において、ＤＢＰ吸収量は、ＪＩＳ Ｋ６２１７－４：２００８に準拠して測定した値である。 The DBP absorption amount of carbon black in the present invention is preferably 250 to 310 ml/100 g. By setting the DBP absorption amount to 250 ml/100 g or more, the aggregate has sufficient length and spread when used as a conductive material, and a good conductive path and non-aqueous electrolyte retention property are obtained. In addition, by setting the amount to 310 ml/100 g or less, aggregation due to entanglement between aggregates is suppressed, so that the positive electrode active material is uniformly dispersed, forming a good conductive path and retaining sufficient non-aqueous electrolyte. You can balance your sexuality. In the present invention, the DBP absorption amount is a value measured in accordance with JIS K6217-4:2008.
本発明におけるカーボンブラックの体積抵抗率はとくに限定されるものではないが、導電性の観点から低いほど好ましい。具体的には、７．５ＭＰａ圧縮下で測定した体積抵抗率は０．３０Ω・ｃｍ以下が好ましく、０．２５Ω・ｃｍ以下がより好ましい。 Although the volume resistivity of carbon black in the present invention is not particularly limited, it is preferably as low as possible from the viewpoint of electrical conductivity. Specifically, the volume resistivity measured under 7.5 MPa compression is preferably 0.30 Ω·cm or less, more preferably 0.25 Ω·cm or less.
本発明におけるカーボンブラックの灰分及び水分は特に限定されるものではないが、副反応の抑制の観点から、どちらも少ないほど好ましい。具体的には、灰分は０．０４質量％以下が好ましく、水分は０．１０質量％以下が好ましい。 The ash content and water content of the carbon black in the present invention are not particularly limited, but from the viewpoint of suppressing side reactions, it is preferable that both are as small as possible. Specifically, the ash content is preferably 0.04% by mass or less, and the water content is preferably 0.10% by mass or less.
＜結着材＞
本発明で用いる結着材は、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、スチレンブタジエン共重合体、（メタ）アクリル酸エステル共重合体が挙げられる。結着材としてのポリマーの構造には制約がなく、ランダム共重合体、交互共重合体、グラフト共重合体、ブロック共重合体なども使用できる。これらの中では、耐電圧性の点でポリフッ化ビニリデンが好ましい。
<Binder>
Examples of the binder used in the present invention include polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene copolymer, and (meth)acrylic acid ester copolymer. There are no restrictions on the structure of the polymer used as the binder, and random copolymers, alternating copolymers, graft copolymers, block copolymers, etc. can also be used. Among these, polyvinylidene fluoride is preferred in terms of voltage resistance.
＜分散剤＞
本発明で用いる分散剤は、少なくともポリビニルアルコール（以下、ＰＶＡと略すことがある。）を含有する。分散剤中のＰＶＡの含有濃度は例えば５０質量％以上とすることができ、好ましくは７０質量％以上とすることができ、より好ましくは９０質量％以上とすることができる。分散剤としてＰＶＡのみを使用することもできる。ＰＶＡはそれ自体既知の重合方法、例えば、酢酸ビニルに代表される脂肪酸ビニルエステルを重合し、加水分解することにより得ることができる。
<Dispersant>
The dispersant used in the present invention contains at least polyvinyl alcohol (hereinafter sometimes abbreviated as PVA). The concentration of PVA in the dispersant can be, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more. It is also possible to use PVA alone as a dispersant. PVA can be obtained by a known polymerization method, for example, by polymerizing and hydrolyzing a fatty acid vinyl ester typified by vinyl acetate.
上記脂肪酸ビニルエステルとしては、例えば、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニルおよびその他の直鎖または分岐状の飽和脂肪酸ビニルエステルが挙げられる。なかでも酢酸ビニルが好ましい。 Examples of the fatty acid vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, and other linear or branched saturated fatty acid vinyl esters. can be mentioned. Among them, vinyl acetate is preferred.
上記ポリビニルアルコールは、脂肪酸ビニルエステル以外の重合性不飽和モノマーと共重合して得ることもできる。脂肪酸ビニルエステルと共重合可能な重合性不飽和モノマーとしては、例えば、エチレン、プロピレンなどのオレフィン類；アルキル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート等などの（メタ）アクリロイル基含有モノマー；アリルグリシジルエーテルなどのアリルエーテル；塩化ビニル、塩化ビニリデン、フッ化ビニルなどのハロゲン化ビニル系化合物；アルキルビニルエーテル、４－ヒドロキシビニルエーテルなどのビニルエーテルなどが挙げられる。これらは１種を単独で又は２種以上を併用して用いることができる。 The above polyvinyl alcohol can also be obtained by copolymerizing with polymerizable unsaturated monomers other than fatty acid vinyl ester. Examples of polymerizable unsaturated monomers that can be copolymerized with fatty acid vinyl esters include olefins such as ethylene and propylene; Examples include meth)acryloyl group-containing monomers; allyl ethers such as allyl glycidyl ether; halogenated vinyl compounds such as vinyl chloride, vinylidene chloride, and vinyl fluoride; vinyl ethers such as alkyl vinyl ether and 4-hydroxy vinyl ether. These can be used alone or in combination of two or more.
ポリビニルアルコールの重合方法は、それ自体既知の重合方法、例えば、酢酸ビニルをアルコール系有機溶媒中で溶液重合してポリ酢酸ビニルを製造し、これを鹸化する等の方法により製造することができるが、これに限られるものではなく、例えば、バルク重合や乳化重合や懸濁重合等でもよい。溶液重合を行う場合には、連続重合でもよいしバッチ重合でもよく、単量体は一括して仕込んでもよいし、分割して仕込んでもよく、あるいは連続的又は断続的に添加してもよい。 Polyvinyl alcohol can be produced by a known polymerization method, for example, by solution polymerizing vinyl acetate in an alcoholic organic solvent to produce polyvinyl acetate, which is then saponified. However, the method is not limited to this, and may be, for example, bulk polymerization, emulsion polymerization, suspension polymerization, or the like. When solution polymerization is carried out, it may be continuous or batch polymerization, and the monomers may be charged all at once, divided into portions, or added continuously or intermittently.
溶液重合において使用する重合開始剤は、特に限定するものではないが、アゾビスイソブチロニトリル、アゾビス－２，４－ジメチルバレロニトリル、アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）等のアゾ化合物；アセチルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アセチルシクロヘキシルスルホニルパーオキシド、２，４，４－トリメチルペンチル－２－パーオキシフェノキシアセテート等の過酸化物；ジイソプロピルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネート等のパーカーボネート化合物；ｔ－ブチルパーオキシネオデカネート、α－クミルパーオキシネオデカネート、ｔ－ブチルパーオキシネオデカネート等のパーエステル化合物；アゾビスジメチルバレロニトリル、アゾビスメトキシバレロニトリル等の公知のラジカル重合開始剤を使用することができる。 Polymerization initiators used in solution polymerization are not particularly limited, but include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), etc. azo compounds; peroxides such as acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxy acetate; diisopropyl peroxydicarbonate, - Percarbonate compounds such as 2-ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, α-cumyl peroxyneodecanate, t-butyl peroxyneodecanate, etc. Perester compound: Known radical polymerization initiators such as azobisdimethylvaleronitrile and azobismethoxyvaleronitrile can be used.
重合反応温度は、特に限定するものではないが、通常３０～１５０℃程度の範囲で設定することができる。 The polymerization reaction temperature is not particularly limited, but can usually be set within a range of about 30 to 150°C.
ポリビニルアルコールを製造する際の鹸化条件は特に限定されず、公知の方法で鹸化することができる。一般的には、メタノール等のアルコール溶液中において、アルカリ触媒又は酸触媒の存在下で、分子中のエステル部を加水分解することで行うことができる。アルカリ触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート等のアルカリ金属の水酸化物や、アルコラート等を用いることができる。酸触媒としては、例えば、塩酸、硫酸等の無機酸水溶液、ｐ－トルエンスルホン酸等の有機酸を用いることができるが、水酸化ナトリウムを用いることが望ましい。鹸化反応の温度は、特に限定されないが、好ましくは１０～７０℃、より好ましくは３０～４０℃の範囲であることが望ましい。反応時間は、特に限定されないが、３０分～３時間の範囲で行なうことが望ましい。 Saponification conditions for producing polyvinyl alcohol are not particularly limited, and saponification can be performed by a known method. Generally, this can be carried out by hydrolyzing the ester moiety in the molecule in an alcohol solution such as methanol in the presence of an alkali catalyst or an acid catalyst. As the alkali catalyst, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, alcoholates, etc. can be used. As the acid catalyst, for example, an aqueous solution of an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as p-toluenesulfonic acid can be used, but sodium hydroxide is preferably used. The temperature of the saponification reaction is not particularly limited, but is preferably in the range of 10 to 70°C, more preferably 30 to 40°C. The reaction time is not particularly limited, but it is preferably carried out within a range of 30 minutes to 3 hours.
本発明におけるポリビニルアルコールの鹸化度は８５．５～９６．５モル％である。鹸化度を９６．５モル％以下とすることで、Ｎ－メチル－２－ピロリドン等の溶媒への溶解性が高まるため、導電材の分散性が向上し、均一で低粘度の正極樹脂組成物を含むスラリーが得られ易くなる。鹸化度を８５．５モル％以上とすることで、高い耐電圧性を得られ易くなる。尚、ここでいうポリビニルアルコールの鹸化度は、ＪＩＳ Ｋ ６７２６：１９９４に準ずる方法で測定される値である。 The degree of saponification of polyvinyl alcohol in the present invention is 85.5 to 96.5 mol%. By setting the degree of saponification to 96.5 mol% or less, the solubility in solvents such as N-methyl-2-pyrrolidone increases, improving the dispersibility of the conductive material and creating a uniform and low-viscosity positive electrode resin composition. It becomes easier to obtain a slurry containing . By setting the degree of saponification to 85.5 mol% or more, high voltage resistance can be easily obtained. The degree of saponification of polyvinyl alcohol referred to herein is a value measured by a method according to JIS K 6726:1994.
本発明におけるポリビニルアルコールの平均重合度は５００～１５００であることが好ましい。平均重合度を１５００以下とすることで、Ｎ－メチル－２－ピロリドン等の溶媒への溶解性が高まるため、導電材の分散性が向上し、均一で低粘度の正極樹脂組成物を含むスラリーが得られ易くなる。平均重合度を５００以上とすることで、活物質及び導電材の分散性が高まり、良好な導電経路が得られ易くなる。 The average degree of polymerization of polyvinyl alcohol in the present invention is preferably 500 to 1,500. By setting the average degree of polymerization to 1500 or less, the solubility in solvents such as N-methyl-2-pyrrolidone increases, which improves the dispersibility of the conductive material and creates a slurry containing a homogeneous and low-viscosity positive electrode resin composition. becomes easier to obtain. By setting the average degree of polymerization to 500 or more, the dispersibility of the active material and the conductive material increases, making it easier to obtain a good conductive path.
＜活物質＞
本発明で用いる活物質は、リチウム含有複合酸化物またはリチウム含有ポリアニオン化合物であり、カチオンを可逆的に吸蔵放出可能な正極活物質のことである。例えば、ＬｉＣｏＯ2、ＬｉＭｎ2Ｏ4、ＬｉＮｉＯ2、ＬｉＭＰＯ4、Ｌｉ2ＭＳｉＯ4、ＬｉＮｉXＭｎ(2-X)Ｏ4、Ｌｉ(ＭｎXＮｉYＣｏZ)Ｏ2、Ｌｉ(ＡｌXＮｉYＣｏZ)Ｏ2またはｘＬｉ2ＭｎＯ3－（１－ｘ）ＬｉＭＯ2などがあげられる。但し、ＬｉＮｉXＭｎ(2-X)Ｏ4中のＸは０＜Ｘ＜２という関係を満たし、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という関係を満たし、ｘＬｉ2ＭｎＯ3－（１－ｘ）ＬｉＭＯ2中のｘは０＜ｘ＜１という関係を満たし、さらにＬｉＭＰＯ4中、Ｌｉ2ＭＳｉＯ4中又はｘＬｉ2ＭｎＯ3－（１－ｘ）ＬｉＭＯ2中のＭはＦｅ、Ｃｏ、Ｎｉ、Ｍｎから選ばれる元素の１種以上であることが好ましい。
<Active material>
The active material used in the present invention is a lithium-containing composite oxide or a lithium-containing polyanion compound, and is a positive electrode active material that can reversibly intercalate and release cations. For example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiMPO 4 , Li 2 MSiO 4 , LiNi x Mn (2-X) O 4 , Li(Mn x Ni Y Co Z )O 2 , Li(Al x Ni Y Examples include Co Z )O 2 or xLi 2 MnO 3 -(1-x)LiMO 2 . However , X in LiNi X Mn ( 2 - X) O 4 satisfies the relationship 0 < X, Y, and Z satisfy the relationship X+Y+Z=1, and the relationships 0<X<1, 0<Y<1, 0<Z<1, and xLi 2 MnO 3 -(1-x) x in LiMO 2 satisfies the relationship 0<x<1, and M in LiMPO 4 , Li 2 MSiO 4 or xLi 2 MnO 3 -(1-x)LiMO 2 is Fe, Co, Ni, Mn. It is preferable that it is one or more elements selected from.
上記活物質の内、本発明で用いる活物質はレーザー光散乱法で測定した体積基準の粒度の累積分布から求められる平均粒子径（Ｄ５０）が２０μｍ以下、好ましくは５μｍ以下であることが好ましい。このような構成にすることで、正極樹脂組成物を含むスラリー粘度の低減効果が十分に発現され、導電材の分散性が向上した正極と高いサイクル特性を有する二次電池が得られ易くなる。 Among the above active materials, the active material used in the present invention preferably has an average particle diameter (D50) of 20 μm or less, preferably 5 μm or less, as determined from the cumulative distribution of volume-based particle size measured by a laser light scattering method. With such a configuration, the effect of reducing the viscosity of the slurry containing the positive electrode resin composition is sufficiently expressed, and it becomes easy to obtain a positive electrode with improved dispersibility of the conductive material and a secondary battery with high cycle characteristics.
＜正極樹脂組成物＞
本発明に用いる正極樹脂組成物の製造には公知の方法を用いることができる。例えば、活物質、導電材、結着材及び分散剤の溶媒分散溶液をボールミル、サンドミル、二軸混練機、自転公転式攪拌機、プラネタリーミキサー、ディスパーミキサー等により混合することで得られ、一般的には、スラリーにして用いられる。前記の活物質、導電材、結着材及び分散剤としては、既述したものを用いれば良い。正極樹脂組成物を含むスラリーの分散媒としては、水、Ｎ－メチル－２－ピロリドン、シクロヘキサン、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。高分子結着材としてポリフッ化ビニリデンを使用する際は、溶解性の点でＮ－メチル－２－ピロリドンが好ましく、スチレンブタジエン共重合体を使用する際は水が好ましい。
<Positive electrode resin composition>
A known method can be used to manufacture the positive electrode resin composition used in the present invention. For example, it can be obtained by mixing a solvent-dispersed solution of an active material, a conductive material, a binder, and a dispersant using a ball mill, sand mill, twin-screw kneader, rotation-revolution stirrer, planetary mixer, disper mixer, etc. It is used as a slurry. As the active material, conductive material, binder, and dispersant, those already described may be used. Examples of the dispersion medium for the slurry containing the positive electrode resin composition include water, N-methyl-2-pyrrolidone, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, and the like. When polyvinylidene fluoride is used as a polymer binder, N-methyl-2-pyrrolidone is preferred from the viewpoint of solubility, and when a styrene-butadiene copolymer is used, water is preferred.
本発明に用いる正極樹脂組成物中の分散剤と導電材の質量比｛分散剤の質量／導電材の質量｝は０．０３～０．１５であり、０．０４～０．１２がより好ましく、０．０５～０．１が最も好ましい。正極樹脂組成物中の分散剤と導電材の質量比を０．０３～０．１５にすることで分散剤が導電材に吸着し、より高い分散効果が得られ易くなり、０．０５～０．１にすることでより高い分散効果に加えて、過剰な分散剤が導電材表面を被覆し電荷移動反応を妨害する効果を抑え、電池の高抵抗化を抑制できる。 The mass ratio of the dispersant to the conductive material in the positive electrode resin composition used in the present invention {mass of the dispersant/mass of the conductive material} is 0.03 to 0.15, more preferably 0.04 to 0.12. , 0.05 to 0.1 are most preferred. By setting the mass ratio of the dispersant to the conductive material in the positive electrode resin composition to 0.03 to 0.15, the dispersant will be adsorbed to the conductive material, making it easier to obtain a higher dispersion effect. By setting the ratio to .1, in addition to a higher dispersion effect, it is possible to suppress the effect of excessive dispersant coating the surface of the conductive material and interfering with the charge transfer reaction, thereby suppressing the increase in resistance of the battery.
＜正極＞
本発明に用いる正極は以下の手順で作製可能である。まず、上記の正極樹脂組成物を含むスラリーをアルミニウム箔等の集電体上に塗布した後、加熱によりスラリーに含まれる溶媒を除去し、活物質が結着材を介して集電体表面に結着された多孔質体である正極合材層を形成する。次いで、集電体と正極合材層をロールプレス等により加圧して密着させることにより、目的とする正極を得ることができる。
<Positive electrode>
The positive electrode used in the present invention can be manufactured by the following procedure. First, a slurry containing the above positive electrode resin composition is applied onto a current collector such as aluminum foil, and then the solvent contained in the slurry is removed by heating, and the active material is applied to the surface of the current collector via the binder. A positive electrode composite material layer, which is a bound porous body, is formed. Next, the desired positive electrode can be obtained by pressurizing the current collector and the positive electrode composite material layer using a roll press or the like to bring them into close contact.
＜リチウムイオン電池＞
本発明に用いられるリチウムイオン電池の作製方法には、特に制限は無く、従来公知の電池の作製方法を用いて行えば良いが、例えば、図１に模式的に示した構成で、以下の方法により作製することもできる。すなわち、前記の正極を用いた正極１にアルミ製タブ５を溶接し、負極２にニッケル製タブ６を溶接した後、正極と負極の間に絶縁層となるポリオレフィン製微多孔膜３を配し、正極１、負極２およびポリオレフィン製微多孔膜３の空隙部分に非水電解液が十分に染込むまで注液し、外装４で封止することで作製することができる。
<Lithium ion battery>
There are no particular restrictions on the method for manufacturing the lithium ion battery used in the present invention, and any conventionally known battery manufacturing method may be used. It can also be produced by That is, after welding an aluminum tab 5 to the positive electrode 1 using the above-mentioned positive electrode and welding a nickel tab 6 to the negative electrode 2, a polyolefin microporous membrane 3 serving as an insulating layer is placed between the positive electrode and the negative electrode. , the nonaqueous electrolyte is injected into the voids of the positive electrode 1, the negative electrode 2, and the polyolefin microporous membrane 3 until it is sufficiently permeated, and then sealed with the exterior 4.
本発明のリチウムイオン電池の用途は、特に限定されないが、例えば、デジタルカメラ、ビデオカメラ、ポータブルオーディオプレイヤー、携帯液晶テレビ等の携帯ＡＶ機器、ノート型パソコン、スマートフォン、モバイルＰＣ等の携帯情報端末、その他、携帯ゲーム機器、電動工具、電動式自転車、ハイブリッド自動車、電気自動車、電力貯蔵システム等の幅広い分野において使用することができる。 Applications of the lithium ion battery of the present invention are not particularly limited, but include, for example, portable AV devices such as digital cameras, video cameras, portable audio players, and portable LCD televisions, portable information terminals such as notebook computers, smartphones, and mobile PCs, In addition, it can be used in a wide range of fields such as portable game devices, power tools, electric bicycles, hybrid cars, electric cars, and power storage systems.
以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明は、その趣旨を損なわない限り、以下に示す実施例に限定されるものではない。また、実施例および比較例ともに使用した正極は、吸着した水分を揮発させるために１７０℃で３時間真空乾燥を行った。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples; however, the present invention is not limited to the Examples shown below unless the spirit thereof is impaired. Further, the positive electrodes used in both Examples and Comparative Examples were vacuum dried at 170° C. for 3 hours in order to volatilize the adsorbed moisture.
＜実施例１＞
（正極樹脂組成物を含むスラリーの調製）
溶媒としてＮ－メチル－２－ピロリドン（関東化学社製、以下、ＮＭＰと記載）、結着材としてポリフッ化ビニリデン（アルケマ社製、「ＨＳＶ９００」、以下、ＰＶｄＦと記載）、導電材としてカーボンブラック（デンカ社製、「Ｌｉ－４３５」、以下、Ｌｉ－４３５と記載）、分散剤としてポリビニルアルコール（ポリビニルアルコールＡと記載）、活物質としてＬｉＮｉ0.5Ｍｎ0.3Ｃｏ0.2Ｏ2（ユミコア社製、「ＴＸ１０」平均粒子径（Ｄ５０）１０μｍ、以下、ＮＭＣ５３２と記載）をそれぞれ用意した。ＰＶｄＦが固形分で１．９質量％、Ｌｉ－４３５が固形分で１質量％、ポリビニルアルコールＡが固形分で０．１質量％（分散剤の質量／導電材の質量＝０．１）、ＮＭＣ５３２が固形分で９７質量％となるように秤量して混合し、この混合物に固形分含有量が６８質量％になるようにＮＭＰを添加し、自転公転式混合機（シンキー社製、あわとり練太郎ＡＲＶ－３１０）を用いて、均一になるまで混合し正極樹脂組成物を含むスラリーを得た。
<Example 1>
(Preparation of slurry containing positive electrode resin composition)
N-methyl-2-pyrrolidone (manufactured by Kanto Kagaku Co., Ltd., hereinafter referred to as NMP) as a solvent, polyvinylidene fluoride (manufactured by Arkema, "HSV900", hereinafter referred to as PVdF) as a binder, and carbon black as a conductive material. (manufactured by Denka Corporation, "Li-435", hereinafter described as Li-435), polyvinyl alcohol (described as polyvinyl alcohol A) as a dispersant, LiNi 0.5 Mn 0.3 Co 0.2 O 2 (manufactured by Umicore Corporation, "TX10'' average particle diameter (D50) 10 μm, hereinafter referred to as NMC532) were prepared. PVdF is 1.9% by mass in solid content, Li-435 is 1% by mass in solid content, polyvinyl alcohol A is 0.1% by mass in solid content (mass of dispersant / mass of conductive material = 0.1), NMC532 was weighed and mixed so that the solid content was 97% by mass, and NMP was added to this mixture so that the solid content was 68% by mass. Using a Rentaro ARV-310), the mixture was mixed until homogeneous to obtain a slurry containing a positive electrode resin composition.
［分散性の評価（正極樹脂組成物を含むスラリーの粘度）］
正極樹脂組成物を含むスラリーの分散性をＪＩＳ Ｋ７２４４－１０に記載される回転型レオメータを用いた方法で粘度を評価した。具体的には、回転型レオメータ（アントンパール社製、ＭＣＲ３００）を用いて、固形分含有量が６８質量％の正極樹脂組成物を含むスラリー１ｇをディスク上に塗布し、測定温度を２５℃に設定し、せん断速度を１００ｓ-1から０．０１ｓ-1まで変化させて測定を行い、せん断速度１０ｓ-1の粘度を評価した。粘度の数値が低い程、良好な分散性を意味する。本実施例の粘度は、１．２４Ｐａ・ｓであった。
[Evaluation of dispersibility (viscosity of slurry containing positive electrode resin composition)]
The viscosity of the slurry containing the positive electrode resin composition was evaluated using a method using a rotational rheometer as described in JIS K7244-10. Specifically, using a rotary rheometer (manufactured by Anton Paar, MCR300), 1 g of slurry containing a positive electrode resin composition with a solid content of 68% by mass was applied onto a disk, and the measurement temperature was raised to 25°C. The measurement was carried out by changing the shear rate from 100 s -1 to 0.01 s -1 to evaluate the viscosity at a shear rate of 10 s -1 . A lower viscosity value means better dispersibility. The viscosity of this example was 1.24 Pa·s.
（正極の作製）
調製した正極樹脂組成物を含むスラリーを、厚さ１５μｍのアルミニウム箔（ＵＡＣＪ社製）の片面上に、アプリケータにて成膜し、乾燥機内に静置して１０５℃、一時間で予備乾燥させ、ＮＭＰ溶媒を完全に除去した。次に、ロールプレス機にて２００ｋｇ／ｃｍの線圧でプレスし、厚さ１５μｍのアルミニウム箔を含んだ塗膜の厚さが８０μｍになるように調製した。次いで、残留水分を完全に除去するため、１７０℃で３時間真空乾燥して正極を得た。
(Preparation of positive electrode)
The slurry containing the prepared positive electrode resin composition was formed into a film using an applicator on one side of a 15 μm thick aluminum foil (manufactured by UACJ), and left to stand in a dryer for pre-drying at 105°C for one hour. The NMP solvent was completely removed. Next, it was pressed using a roll press machine with a linear pressure of 200 kg/cm to prepare a coating film containing 15 μm thick aluminum foil to have a thickness of 80 μm. Next, in order to completely remove residual moisture, vacuum drying was performed at 170° C. for 3 hours to obtain a positive electrode.
［正極の極板抵抗評価］
作製した正極を直径１４ｍｍの円盤状に切り抜き、表裏をＳＵＳ３０４製平板電極によって挟んだ状態で、電気化学測定システム（ソーラトロン社製、ファンクションジェネレーター１２６０およびポテンショガルバノスタット１２８７）を用いて、振幅電圧１０ｍＶ、周波数範囲１Ｈｚ～１００ｋＨｚにて交流インピーダンスを測定した。得られた抵抗成分値に切り抜いた円盤状の面積を掛けた抵抗値を極板抵抗とした。本実施例の正極の極板抵抗は１２０Ω・ｃｍ2であった。
[Positive plate resistance evaluation]
The produced positive electrode was cut out into a disk shape with a diameter of 14 mm, and with the front and back sides sandwiched between SUS304 flat plate electrodes, an amplitude voltage of 10 mV was measured using an electrochemical measurement system (manufactured by Solartron, function generator 1260 and potentiogalvanostat 1287). AC impedance was measured in a frequency range of 1 Hz to 100 kHz. The resistance value obtained by multiplying the obtained resistance component value by the area of the cut out disk shape was defined as the plate resistance. The plate resistance of the positive electrode in this example was 120Ω·cm 2 .
（負極の作製）
溶媒として純水（関東化学社製）、負極活物質として人造黒鉛（日立化成社製、「ＭＡＧ－Ｄ」）、結着材としてスチレンブタジエンゴム（日本ゼオン社製、「ＢＭ－４００Ｂ」、以下、ＳＢＲと記載）、分散剤としてカルボキシメチルセルロース（ダイセル社製、「Ｄ２２００」、以下、ＣＭＣと記載）をそれぞれ用意した。次いで、ＣＭＣが固形分で１質量％、人造黒鉛が固形分で９７質量％となるように秤量して混合し、この混合物に純水を添加し、自転公転式混合機（シンキー社製、あわとり練太郎ＡＲＶ－３１０）を用いて、均一になるまで混合した。さらに、ＳＢＲが固形分で２質量％となるように秤量し、上記混合物に添加し、自転公転式混合機（シンキー社製、あわとり練太郎ＡＲＶ－３１０）を用いて、均一になるまで混合し、負極スラリーを得た。次いで、負極スラリーを、厚さ１０μｍの銅箔（ＵＡＣＪ社製）上にアプリケータにて成膜し、乾燥機内に静置して６０℃、一時間で予備乾燥させた。次に、ロールプレス機にて１００ｋｇ／ｃｍの線圧でプレスし、銅箔を含んだ塗膜の厚さが５０μｍになるように調製した。残留水分を完全に除去するため、１２０℃で３時間真空乾燥して負極を得た。
(Preparation of negative electrode)
Pure water (manufactured by Kanto Kagaku Co., Ltd.) as a solvent, artificial graphite (manufactured by Hitachi Chemical Co., Ltd., "MAG-D") as a negative electrode active material, and styrene-butadiene rubber (manufactured by Nippon Zeon Co., Ltd., "BM-400B", hereinafter referred to as a binder) , SBR) and carboxymethyl cellulose (manufactured by Daicel Corporation, "D2200", hereinafter referred to as CMC) were prepared as a dispersant. Next, CMC and artificial graphite were weighed and mixed to have a solid content of 1% by mass and 97% by mass, pure water was added to this mixture, and Using a Tori Rentaro ARV-310), the mixture was mixed until uniform. Furthermore, SBR was weighed to have a solid content of 2% by mass, added to the above mixture, and mixed until homogeneous using an autorotation-revolution mixer (Shinky Co., Ltd., Awatori Rentaro ARV-310). A negative electrode slurry was obtained. Next, the negative electrode slurry was formed into a film using an applicator on a copper foil having a thickness of 10 μm (manufactured by UACJ), and was left standing in a dryer to be pre-dried at 60° C. for one hour. Next, it was pressed using a roll press machine with a linear pressure of 100 kg/cm to prepare a coating film containing copper foil having a thickness of 50 μm. In order to completely remove residual moisture, vacuum drying was performed at 120° C. for 3 hours to obtain a negative electrode.
（リチウムイオン電池の作製）
露点－５０℃以下に制御したドライルーム内で、上記正極を４０×４０ｍｍに加工し、負極を４４×４４ｍｍに加工した後、正極にアルミ製タブ、負極にニッケル製タブを溶接した。正極と負極それぞれの合材塗工面が中央で対向するようにし、さらに正極と負極間に４５×４５ｍｍに加工したポリオレフィン微多孔質膜を配置した。次に７０×１４０ｍｍ角に切断・加工したシート状の外装を長辺の中央部で二つ折りにした。次いで、正極用アルミ製タブと負極用ニッケル製タブが外装の外部に露出するように外装を配置しながら、二つ折りにした外装によって正極－ポリオレフィン微多孔質膜負極の積層体を挟んだ。次にヒートシーラーを用いて、外装の正極用アルミ製タブと負極用ニッケル製タブが露出した辺を含む２辺を加熱融着した後、加熱融着していない一辺から、２ｇの電解液（キシダ化学製、エチレンカーボネート／ジエチルカーボネート＝１／２（体積比）＋１Ｍ ＬｉＰＦ6溶液、以下、電解液と記載）を注液し、正極、負極およびポリオレフィン微多孔膜に十分に染み込ませてから、真空ヒートシーラーにより、電池の内部を減圧しながら、外装の残り１辺を加熱融着してリチウムイオン電池を得た。
(Preparation of lithium ion battery)
In a dry room controlled at a dew point of −50° C. or lower, the positive electrode was processed into a size of 40×40 mm and the negative electrode was processed into a size of 44×44 mm, and then an aluminum tab was welded to the positive electrode and a nickel tab was welded to the negative electrode. The composite coated surfaces of the positive and negative electrodes faced each other at the center, and a polyolefin microporous membrane processed to a size of 45×45 mm was placed between the positive and negative electrodes. Next, the sheet-like exterior that had been cut and processed into a 70 x 140 mm square was folded in half at the center of the long side. Next, the laminate of the positive electrode and the polyolefin microporous membrane negative electrode was sandwiched between the folded outer case while arranging the outer case so that the aluminum tab for the positive electrode and the nickel tab for the negative electrode were exposed to the outside of the outer case. Next, use a heat sealer to heat-seal the two sides of the exterior including the exposed sides of the aluminum tab for the positive electrode and the nickel tab for the negative electrode, and then apply 2 g of the electrolyte ( After injecting ethylene carbonate/diethyl carbonate = 1/2 (volume ratio) + 1M LiPF 6 solution (hereinafter referred to as electrolyte solution) manufactured by Kishida Chemical Co., Ltd. and sufficiently soaking it into the positive electrode, negative electrode, and polyolefin microporous membrane, A lithium ion battery was obtained by heat-sealing the remaining side of the exterior while reducing the pressure inside the battery using a vacuum heat sealer.
作製したリチウムイオン電池について、以下の方法により電池性能を評価した。 The battery performance of the produced lithium ion battery was evaluated by the following method.
（リチウムイオン電池の評価）
［放電レート特性（３Ｃ放電時の放電容量維持率）］
作製したリチウムイオン電池を、２５℃において、４．３Ｖ、０．２Ｃ制限の定電流定電圧充電をした後、０．２Ｃの定電流で３．０Ｖまで放電した。次いで、再度４．３Ｖ、０．２Ｃ制限の定電流定電圧で回復充電した後、放電電流を０．２Ｃとして３．０Ｖまで放電させ、このときの放電容量を測定した。引き続き、前記の回復充電の条件は毎回保って充電し、一方で放電電流は０．５Ｃ、１Ｃ、２Ｃ、３Ｃと段階的に変化させながら、回復充電と放電とを繰り返し、各放電電流に対する放電容量を測定した。電池の放電レート特性の指標として、０．２Ｃ放電時に対する３Ｃ放電時の放電容量維持率を算出した。本実施例のリチウムイオン電池の３Ｃ放電時の放電容量維持率は８０．５％であった。
(Evaluation of lithium ion batteries)
[Discharge rate characteristics (discharge capacity retention rate during 3C discharge)]
The produced lithium ion battery was charged at 4.3 V and a constant current and voltage with a 0.2 C limit at 25° C., and then discharged to 3.0 V at a constant current of 0.2 C. Next, after recovery charging was performed again at 4.3 V and constant current and constant voltage with a 0.2 C limit, the battery was discharged to 3.0 V at a discharge current of 0.2 C, and the discharge capacity at this time was measured. Subsequently, the above-mentioned recovery charging conditions were maintained each time for charging, while recovery charging and discharging were repeated while changing the discharge current stepwise from 0.5C, 1C, 2C, and 3C, and the discharge for each discharge current was repeated. Capacity was measured. As an index of the discharge rate characteristics of the battery, the discharge capacity retention rate during 3C discharge compared to 0.2C discharge was calculated. The discharge capacity retention rate of the lithium ion battery of this example at 3C discharge was 80.5%.
［サイクル特性（サイクル後の放電容量維持率）］
作製したリチウムイオン電池を、２５℃において、４．３Ｖ、１Ｃ制限の定電流定電圧充電をした後、１Ｃの定電流で３．０Ｖまで放電した。上記充放電を５００サイクル繰り返し、各サイクルにおける放電容量を測定した。電池のサイクル特性の指標として、特に１サイクル後に対する５００サイクル後の放電容量維持率を算出した。本実施例のリチウムイオン電池のサイクル後の放電容量維持率は９０％であった。
[Cycle characteristics (discharge capacity retention rate after cycling)]
The produced lithium ion battery was charged at 4.3 V with a constant current and voltage limit of 1 C at 25° C., and then discharged to 3.0 V with a constant current of 1 C. The above charging and discharging was repeated 500 cycles, and the discharge capacity in each cycle was measured. As an index of the cycle characteristics of the battery, in particular, the discharge capacity retention rate after 500 cycles compared to after 1 cycle was calculated. The discharge capacity retention rate of the lithium ion battery of this example after cycling was 90%.
［耐電圧性（フロート充電後の放電容量維持率）］
作製したリチウムイオン電池を、２５℃において、４．３５Ｖ、０．５Ｃ制限の定電流定電圧で２時間フロート充電した後、０．５Ｃの定電流で３．０Ｖまで放電させ、このときの放電容量を測定した。次いで、再度４．３５Ｖ、０．５Ｃ制限の定電流定電圧で４８時間フロート充電した後、同様に０．５Ｃの定電流で３．０Ｖまで放電させ、このときの放電容量を測定した。電池の耐電圧性の指標として、２時間充電時に対する４８時間充電時のフロート充電後の容量維持率を算出した。本実施例のリチウムイオン電池のフロート充電後の容量維持率は９４％であった。
[Voltage resistance (discharge capacity retention rate after float charging)]
The prepared lithium ion battery was float charged at 25°C for 2 hours at 4.35V and a constant current and voltage with a 0.5C limit, and then discharged to 3.0V at a constant current of 0.5C. Capacity was measured. Next, the battery was float charged again for 48 hours at 4.35 V and a constant current and voltage limited to 0.5 C, and then similarly discharged to 3.0 V at a constant current of 0.5 C, and the discharge capacity at this time was measured. As an index of the voltage resistance of the battery, the capacity retention rate after float charging during 2-hour charging and 48-hour charging was calculated. The capacity retention rate of the lithium ion battery of this example after float charging was 94%.
実施例１～８、比較例１～４で使用したポリビニルアルコールの鹸化度及び平均重合度を表１に示す。また、実施例１～８、比較例１～６で使用したカーボンブラックの平均一次粒子径及びＤＢＰ吸油量を表２に示す。 Table 1 shows the saponification degree and average degree of polymerization of the polyvinyl alcohol used in Examples 1 to 8 and Comparative Examples 1 to 4. Table 2 also shows the average primary particle diameter and DBP oil absorption of the carbon blacks used in Examples 1 to 8 and Comparative Examples 1 to 6.
＜実施例２＞
実施例１の分散剤を、ポリビニルアルコールＢへ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 2>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the dispersant in Example 1 was changed to polyvinyl alcohol B, and each evaluation was performed. The results are shown in Table 3.
＜実施例３＞
実施例１の分散剤を、ポリビニルアルコールＣへ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 3>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the dispersant in Example 1 was changed to polyvinyl alcohol C, and each evaluation was performed. The results are shown in Table 3.
＜実施例４＞
実施例１の分散剤を、ポリビニルアルコールＤへ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 4>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the dispersant in Example 1 was changed to polyvinyl alcohol D, and each evaluation was performed. The results are shown in Table 3.
＜実施例５＞
実施例１の導電材を、ＳＡＢ（デンカ社製）へ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 5>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the conductive material in Example 1 was changed to SAB (manufactured by Denka Corporation), and each evaluation was performed. The results are shown in Table 3.
＜実施例６＞
実施例１の導電材を、Ｌｉ－２５０（デンカ社製）へ変更し、ＰＶｄＦが固形分で１．９５質量％、Ｌｉ－２５０が固形分で１質量％、ポリビニルアルコールＡが固形分で０．０５質量％（分散剤の質量／導電材の質量＝０．０５）となるように秤量して混合した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 6>
The conductive material in Example 1 was changed to Li-250 (manufactured by Denka Corporation), and the solid content of PVdF was 1.95% by mass, the solid content of Li-250 was 1% by mass, and the solid content of polyvinyl alcohol A was 0. A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that they were weighed and mixed so that the amount was 0.05% by mass (mass of dispersant/mass of conductive material = 0.05). were prepared and various evaluations were conducted. The results are shown in Table 3.
＜実施例７＞
実施例１の導電材を、ＥＣＰ（ライオン社製）へ変更し、ＰＶｄＦが固形分で１．８４質量％、ＥＣＰが固形分で１質量％、ポリビニルアルコールＡが固形分で０．１６質量％（分散剤の質量／導電材の質量＝０．１６）となるように秤量して混合した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 7>
The conductive material of Example 1 was changed to ECP (manufactured by Lion Corporation), and PVdF was 1.84% by mass in solid content, ECP was 1% by mass in solid content, and polyvinyl alcohol A was 0.16% by mass in solid content. A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that they were weighed and mixed so that (mass of dispersant/mass of conductive material = 0.16). An evaluation was conducted. The results are shown in Table 3.
＜実施例８＞
実施例１の導電材を、Ｌｉ－２５０（デンカ社製）へ変更し、ＰＶｄＦが固形分で１．９８質量％、Ｌｉ－２５０が固形分で１質量％、ポリビニルアルコールＡが固形分で０．０２質量％（分散剤の質量／導電材の質量＝０．０２）となるように秤量して混合した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Example 8>
The conductive material in Example 1 was changed to Li-250 (manufactured by Denka Corporation), and the solid content of PVdF was 1.98% by mass, the solid content of Li-250 was 1% by mass, and the solid content of polyvinyl alcohol A was 0. A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that they were weighed and mixed so that the amount was 0.02% by mass (mass of dispersant/mass of conductive material = 0.02). were prepared and various evaluations were conducted. The results are shown in Table 3.
＜比較例１＞
実施例１の分散剤を、ポリビニルアルコールＥへ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Comparative example 1>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the dispersant in Example 1 was changed to polyvinyl alcohol E, and each evaluation was performed. The results are shown in Table 3.
＜比較例２＞
実施例１の分散剤を、ポリビニルアルコールＦへ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Comparative example 2>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the dispersant in Example 1 was changed to polyvinyl alcohol F, and each evaluation was performed. The results are shown in Table 3.
＜比較例３＞
実施例１の導電材を、＃３０４０Ｂ（三菱化学社製）へ変更し、ＰＶｄＦが固形分で１．９７質量％、＃３０４０Ｂが固形分で１質量％、ポリビニルアルコールＡが固形分で０．０３質量％（分散剤の質量／導電材の質量＝０．０３）となるように秤量して混合した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Comparative example 3>
The conductive material in Example 1 was changed to #3040B (manufactured by Mitsubishi Chemical Corporation), and the solid content of PVdF was 1.97% by mass, the solid content of #3040B was 1% by mass, and the solid content of polyvinyl alcohol A was 0.9% by mass. A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the composition was weighed and mixed so that the amount was 0.03% by mass (mass of dispersant/mass of conductive material = 0.03). and conducted each evaluation. The results are shown in Table 3.
＜比較例４＞
実施例１の導電材を、ＢｌａｃｋＰｅａｒｌｓ２０００（キャボット社製）へ変更し、ＰＶｄＦが固形分で１．８５質量％、ＢｌａｃｋＰｅａｒｌｓ２０００が固形分で１質量％、ポリビニルアルコールＡが固形分で０．１５質量％（分散剤の質量／導電材の質量＝０．１５）となるように秤量して混合した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Comparative example 4>
The conductive material in Example 1 was changed to BlackPearls 2000 (manufactured by Cabot), PVdF was 1.85% by mass in solid content, BlackPearls 2000 was 1% by mass in solid content, and polyvinyl alcohol A was 0.15% by mass in solid content. A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that they were weighed and mixed so that (mass of dispersant/mass of conductive material = 0.15). An evaluation was conducted. The results are shown in Table 3.
＜比較例５＞
実施例１の分散剤を、ポリビニルピロリドン（日本触媒社製、Ｋ－９０）へ変更した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Comparative example 5>
A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared in the same manner as in Example 1, except that the dispersant in Example 1 was changed to polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., K-90), and various evaluations were conducted. was carried out. The results are shown in Table 3.
＜比較例６＞
実施例１の分散剤を添加せずに、ＰＶｄＦが固形分で２質量％、Ｌｉ－４３５が固形分で１質量％となるように秤量して混合した以外は、実施例１と同様な方法で正極樹脂組成物、正極及びリチウムイオン電池を作製し、各評価を実施した。結果を表３に示す。
<Comparative example 6>
A method similar to Example 1, except that the dispersant of Example 1 was not added, and PVdF was weighed and mixed so that the solid content was 2% by mass and the Li-435 was 1% by mass. A positive electrode resin composition, a positive electrode, and a lithium ion battery were prepared using the following methods, and various evaluations were performed. The results are shown in Table 3.
実施例１～８の正極樹脂組成物は、比較例１～６の正極樹脂組成物に比べて分散性が高いことが明らかになった。これにより本発明の実施例の正極は極板抵抗が低くなり、放電時の電圧降下を抑えられることが分かった。 It was revealed that the positive electrode resin compositions of Examples 1 to 8 had higher dispersibility than the positive electrode resin compositions of Comparative Examples 1 to 6. As a result, it was found that the positive electrode of the example of the present invention had a low plate resistance, and the voltage drop during discharge could be suppressed.
さらに、実施例１～８のリチウムイオン電池は、比較例１～６のリチウムイオン電池に比べて放電レート特性が高く、サイクル特性も高く、耐電圧性が高いことが明らかになった。これにより本発明の正極樹脂組成物を用いたリチウムイオン電池は放電電流の増加に伴う放電レート特性の低下を抑えられ、高い寿命も兼ね備えていることが分かった。 Furthermore, it was revealed that the lithium ion batteries of Examples 1 to 8 had higher discharge rate characteristics, higher cycle characteristics, and higher voltage resistance than the lithium ion batteries of Comparative Examples 1 to 6. As a result, it was found that a lithium ion battery using the positive electrode resin composition of the present invention can suppress a decrease in discharge rate characteristics due to an increase in discharge current, and also has a long life.
１ リチウムイオン電池正極
２ リチウムイオン電池負極
３ ポリオレフィン製微多孔膜
４ アルミ製タブ
５ ニッケル製タブ
６ 外装
1 Lithium ion battery positive electrode 2 Lithium ion battery negative electrode 3 Polyolefin microporous membrane 4 Aluminum tab 5 Nickel tab 6 Exterior
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| JP2005268026A (en) | 2004-03-18 | 2005-09-29 | Dainippon Printing Co Ltd | Coating composite for active material layer, electrode plate for non-aqueous electrolytic liquid secondary battery, and non-aqueous electrolytic liquid secondary battery |
| JP2016046188A (en) | 2014-08-26 | 2016-04-04 | 東洋インキＳｃホールディングス株式会社 | Carbon black dispersion and use of the same |
| JP2017054650A (en) | 2015-09-08 | 2017-03-16 | 株式会社豊田自動織機 | Composition containing positive electrode active material, dispersant and solvent |
| WO2018021073A1 (en) | 2016-07-28 | 2018-02-01 | デンカ株式会社 | Conductive resin composition for electrodes, electrode composition, electrode using same and lithium ion battery |
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| JP2005268026A (en) | 2004-03-18 | 2005-09-29 | Dainippon Printing Co Ltd | Coating composite for active material layer, electrode plate for non-aqueous electrolytic liquid secondary battery, and non-aqueous electrolytic liquid secondary battery |
| JP2016046188A (en) | 2014-08-26 | 2016-04-04 | 東洋インキＳｃホールディングス株式会社 | Carbon black dispersion and use of the same |
| JP2017054650A (en) | 2015-09-08 | 2017-03-16 | 株式会社豊田自動織機 | Composition containing positive electrode active material, dispersant and solvent |
| WO2018021073A1 (en) | 2016-07-28 | 2018-02-01 | デンカ株式会社 | Conductive resin composition for electrodes, electrode composition, electrode using same and lithium ion battery |
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