JP6808208B1 - バインダ - Google Patents
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- JP6808208B1 JP6808208B1 JP2020514763A JP2020514763A JP6808208B1 JP 6808208 B1 JP6808208 B1 JP 6808208B1 JP 2020514763 A JP2020514763 A JP 2020514763A JP 2020514763 A JP2020514763 A JP 2020514763A JP 6808208 B1 JP6808208 B1 JP 6808208B1
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- Prior art keywords
- electrode
- inorganic particles
- active material
- binder
- binder according
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- 239000011230 binding agent Substances 0.000 title claims abstract description 70
- 239000010954 inorganic particle Substances 0.000 claims abstract description 74
- 239000007772 electrode material Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 239000002562 thickening agent Substances 0.000 claims abstract description 44
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims description 36
- 238000004132 cross linking Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229920003002 synthetic resin Polymers 0.000 claims description 19
- 239000000057 synthetic resin Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- -1 alginate ester Chemical class 0.000 claims description 13
- 239000011267 electrode slurry Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 229920006026 co-polymeric resin Polymers 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 235000010443 alginic acid Nutrition 0.000 claims description 8
- 229920000615 alginic acid Polymers 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 239000000454 talc Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000000783 alginic acid Substances 0.000 claims description 5
- 229960001126 alginic acid Drugs 0.000 claims description 5
- 150000004781 alginic acids Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 claims description 4
- PNNNRSAQSRJVSB-SLPGGIOYSA-N Fucose Natural products C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O PNNNRSAQSRJVSB-SLPGGIOYSA-N 0.000 claims description 4
- SHZGCJCMOBCMKK-DHVFOXMCSA-N L-fucopyranose Chemical compound C[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-DHVFOXMCSA-N 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 3
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 3
- 229920002307 Dextran Polymers 0.000 claims description 3
- 229920000855 Fucoidan Polymers 0.000 claims description 3
- 229920002148 Gellan gum Polymers 0.000 claims description 3
- 229920002581 Glucomannan Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940072056 alginate Drugs 0.000 claims description 3
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229930182830 galactose Natural products 0.000 claims description 3
- 235000010492 gellan gum Nutrition 0.000 claims description 3
- 239000000216 gellan gum Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 229940046240 glucomannan Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000010987 pectin Nutrition 0.000 claims description 3
- 229920001277 pectin Polymers 0.000 claims description 3
- 239000001814 pectin Substances 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229920000569 Gum karaya Polymers 0.000 claims description 2
- 241000934878 Sterculia Species 0.000 claims description 2
- 235000010494 karaya gum Nutrition 0.000 claims description 2
- 239000000231 karaya gum Substances 0.000 claims description 2
- 229940039371 karaya gum Drugs 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims 1
- 239000005715 Fructose Substances 0.000 claims 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000011149 active material Substances 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 150000001340 alkali metals Chemical class 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000002905 metal composite material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
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- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 4
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- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- MPHUYCIKFIKENX-UHFFFAOYSA-N methyl 2-ethenylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C=C MPHUYCIKFIKENX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 description 1
- 235000018342 monosodium citrate Nutrition 0.000 description 1
- 239000002524 monosodium citrate Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 125000002347 octyl 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])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
無機粒子によって被覆された再乳化性樹脂粉末と、
電極活物質由来の金属イオンと水系において架橋し、疎水性ゲルを形成する金属架橋増粘剤とを含有する、バインダ。
前記正極および前記負極の少なくとも一方は〔1〕〜〔9〕のいずれか1つに記載のバインダを含む、電気化学デバイス。
本発明の一実施形態に係るバインダは、電気化学デバイスの電極材料を連結させるバインダであって、無機粒子によって被覆された再乳化性樹脂粉末と、電極活物質由来の金属イオンと水系において架橋し、疎水性ゲルを形成する金属架橋増粘剤とを含有する。本明細書において「水系」とは、水が存在する環境を意味する。また、水系媒体とは、水を含有する媒体を意味する。
本発明の一実施形態に係るバインダは、再乳化性樹脂粉末を含有する。本明細書において、再乳化性樹脂粉末とは、合成樹脂エマルジョンを乾燥させることで得られる粉末であり、水系媒体(例えば水)と混合することで再乳化させるとエマルジョンを生成することができる粉末を意味する。再乳化性樹脂粉末は、乾燥された状態でも合成樹脂が乳化剤によって被覆された構造を有する。それゆえ、再乳化性樹脂粉末は、水系媒体と混合することで再乳化させることができる。
本発明の一実施形態に係るバインダにおいて、再乳化性樹脂粉末は、無機粒子によって被覆されている。すなわち、無機粒子は、再乳化性樹脂粉末の表面に存在する。具体的には、再乳化性樹脂粉末は、合成樹脂が乳化剤によって覆われ、その外側に更に無機粒子が存在する構造を取り得る。つまり、再乳化性樹脂粉末は、当該乳化剤を介して無機粒子が合成樹脂に結合している構造を取り得る。
本発明の一実施形態に係るバインダは、電極活物質由来の金属イオンと水系において架橋し、疎水性ゲルを形成する金属架橋増粘剤を含有する。本明細書において、「電極活物質由来の金属イオン」とは、電極活物質から生じ得る金属イオンであることを意味する。また、「金属架橋増粘剤」とは、前記金属イオンと水系において架橋されることによって増粘し、金属と結合して疎水性のゲルを形成する性質を有する物質を意味する。
本発明の一実施形態に係るバインダは、無機粒子によって被覆された再乳化性樹脂粉末と、金属架橋増粘剤とを、分散機を用いて均一に混合し、分散させることによって調製することができる。分散機は単純混合、粉砕混合のいずれの方式であってもよい。例えば、ジェットミル、サンドミル、ボールミル、ビーズミル、LMZミル、DCPパールミル、遊星ボールミル、ロッキングミル、V型混合機、ダブルコーンミキサー、コンテナブレンダー、リボンミキサー、ホモジナイザー、二軸混練機、薄膜旋回型高速ミキサー等の分散機を利用することができる。
本発明の一実施形態に係る電極用スラリーは、上述のバインダと、電極活物質と、水とを含有する。電極活物質は、正極活物質および負極活物質のいずれであってもよく、特にアルカリ金属複合酸化物であることが好ましい。
本発明の一実施形態に係る電気化学デバイス用電極は、本発明の一実施形態に係るバインダを含有する。例えば、本発明の一実施形態に係る電極用スラリーを電極基材(集電体)の表面に塗布し、乾燥させることによって、電極基材の表面に電極合材層が存在する、本発明の一実施形態に係る電気化学デバイス用電極を製造することができる。換言すれば、当該電気化学デバイス用電極は、上述のバインダと電極活物質とを含み、さらに導電助剤を含み得る電極合材層が電極基材上に形成された構造を有する。
本発明の一実施形態に係る電気化学デバイスは、正極および負極を備え、当該正極と当該負極との間に電解質を含む電気化学デバイスであって、前記正極および前記負極の少なくとも一方は上述のバインダを含む。また、本発明の一実施形態に係る電気化学デバイスは、前記正極および前記負極の少なくとも一方が上述の電気化学デバイス用電極であるとも言える。
再乳化性樹脂粉末の製造にあたり、水分散エマルジョンとしてスチレンブタジエンゴムエマルジョン(DIC株式会社、ラックスターDS−410)およびアクリルエマルジョン(村山化学研究所、F−35)を準備した。各実施例で用いた無機粒子および金属架橋増粘剤を、水分散エマルジョンとともに表1に示す。
活物質としてNCM111を93重量部、導電助剤としてアセチレンブラックを3重量部、正極向け水系バインダ(iElectrolyte、IEB−P01)4重量部を使用し、これらを混合した。得られた混合物に水を25重量部加えて、プラネタリミキサー(プライミクス社、TKハイビスミックス)を用いて混錬することで電極用スラリーを作製した。
上記で作製した正極シートまたは負極シート、セパレータシートおよび金属リチウム箔をこの順に積層し、得られた積層体をCR2302型のコイン電池ケース内に配置した。このコイン電池ケース内に非水電解液を注液した。そしてコイン電池ケースの周囲に絶縁パッキンを配置した状態でステンレス製蓋を重ね、かしめ機によって加圧し密閉することでコイン型リチウムイオン電池を構築した。これを評価用セルとして用いた。なお、前記セパレータシートとしてはポリエチレン(PE)の両面にポリプロピレン(PP)が積層された三層構造を有し、厚み20μmであるセパレータシートを用いた。前記非水電解液としては、エチレンカーボネート(EC)とジメチルカーボネート(DMC)とをEC:DMC=1:1の体積比で含む混合溶媒に、支持塩としてのLiPF6を1.0mol/Lの濃度で溶解させた非水電解液を用いた。
従来技術に相当する比較例よりも実施例の耐熱性が向上していることを確認するため、上述の正極シートまたは負極シートを備えた各評価用セルに対して、高温保存特性を評価した。具体的には以下のようにして200時間後の放電容量維持率を算出し、比較した。評価した電極活物質と、各電極活物質を含む評価用セルの測定に用いた電流値および電圧範囲とを表2に示す。
まず、各評価セルを、充電電流値0.1Cに設定した定電流−定電圧モード(CC−CVモード)により充電した。なお、CVモードでは、電流値がCCモードでの設定電流値の10分の1になった時点で充電を終了した。
初回充放電試験を経た各評価セルを、充電電流値0.1C、保存電圧4.2Vに設定して充電しながら、200時間、80℃で保存した。
上述の初回充放電試験によって得られた初回サイクルの放電容量値および80℃保存試験によって得られた80℃保存後の放電容量値から下記式により放電容量維持率を算出した。
放電容量維持率[%]=(80℃保存後の放電容量値)/(初回サイクルの放電容量値)×100
また、算出した放電容量維持率を下記の基準で評価した。
S:放電容量維持率が95%以上
A:放電容量維持率が90%以上95%未満
B:放電容量維持率が88%以上90%未満
なお、S、Aが合格、Bは不合格である。
評価結果を表3に示す。
金属架橋増粘剤:再乳化性樹脂粉末の重量比を変更した正極シートを作製し、組成比の変更による耐熱性への影響を確認した。具体的には実施例1と同じ材料を用い、活物質としてはNCM111を使用し、実施例1と同様に実施例6および7の正極シートを作製した。ここで金属架橋増粘剤:再乳化性樹脂粉末の重量比を実施例6では85:15、実施例7では70:30に調整した。これらの正極シートを用いてコイン型リチウムイオン電池を構築し、評価試験1と同様に高温保存特性を評価した。
評価結果を表4に示す。
再乳化性樹脂粉末を用いている実施例1に対して、再乳化性樹脂粉末化する工程を介していない、換言すれば噴霧乾燥の工程を介していないバインダを比較例6として用いて特性差を確認した。すなわち比較例6では、実施例1と同じ水分散エマルジョン、無機粒子および金属架橋増粘剤を単に混合することにより得たバインダを用いた。この比較例6について、実施例1と同様の方法で各活物質を用いて正極シートおよび負極シートを作製し、また、コイン型リチウムイオン電池を構築した。実施例1および比較例6について、以下のように放電容量維持率を算出した。
まず、各評価セルを、充電電流値0.1Cに設定したCC−CVモードにより充電した。なお、CVモードでは、電流値がCCモードでの設定電流値の10分の1になった時点で充電を終了した。
初回充放電試験を経た各評価セルを、充電電流値0.1Cに設定したCC−CVモードにより充電した。なお、CVモードでは、電流値がCCモードでの設定電流値の10分の1になった時点で充電を終了した。
上述の初回充放電試験によって得られた初回サイクルの放電容量値および1.0Cレートでの放電容量特性評価によって得られた放電容量値から下記式により放電容量維持率を算出した。
放電容量維持率[%]=(1.0Cでの放電容量値)/(初回サイクルの放電容量値)×100
<評価結果>
評価結果を表5に示す。なお、表中の「初回容量」は「初回サイクルの放電容量値」を表し、「容量維持率」は「放電容量維持率」を表す。
Claims (10)
- 電気化学デバイスの電極材料を連結させるバインダであって、
無機粒子によって被覆された再乳化性樹脂粉末と、
電極活物質由来の金属イオンと水系において架橋し、疎水性ゲルを形成する金属架橋増粘剤とを含有し、
前記金属架橋増粘剤:前記再乳化性樹脂粉末の重量比は、65:35〜90:10であり、
前記金属架橋増粘剤は、アルギン酸もしくはその塩、フコイダン、アルギン酸エステル、カラヤガム、カラギナンもしくはその塩、ペクチン、ジェランガム、グルコマンナン、ローカストビンガム、キサンタンガム、グルコース、マンノース、ガラクトース、アラビノース、フコース、リボース、フルクトース、カルボキシメチルデンプン、デキストラン、ヒアルロン酸、またはそれらの混合物である、バインダ。 - 前記再乳化性樹脂粉末は、合成樹脂が乳化剤によって被覆された構造を有する、請求項1に記載のバインダ。
- 前記合成樹脂は、ガラス転移温度が−40℃〜25℃である、請求項2に記載のバインダ。
- 前記合成樹脂は、ポリアクリル酸共重合体樹脂または共役ジエン系重合体のエマルジョンである、請求項3に記載のバインダ。
- 前記無機粒子は、耐熱性を有する無機粒子である、請求項1〜4のいずれか1項に記載のバインダ。
- 前記再乳化性樹脂粉末および前記無機粒子の合計量100重量%に対する無機粒子の含有量は、1〜40重量%である、請求項1〜5のいずれか1項に記載のバインダ。
- 前記無機粒子は、炭酸カルシウム、タルク、マイカ、パイロフィライト、クレー、ドロマイト、無水珪酸、カオリン、二酸化珪素、珪酸アルミニウム、水酸化アルミニウム、酸化アルミニウム、酸化アルミニウムの水和物、酸化マグネシウム、酸化カルシウム、酸化チタン、チタン酸バリウム、もしくは酸化ジルコニウム、またはそれらの混合物である、請求項1〜6のいずれか1項に記載のバインダ。
- 請求項1〜7のいずれか1項に記載のバインダと、電極活物質と、水とを含有する、電極用スラリー。
- さらに中和剤を含有する、請求項8に記載の電極用スラリー。
- 正極および負極を備え、当該正極と当該負極との間に電解質を含む電気化学デバイスであって、
前記正極および前記負極の少なくとも一方は請求項1〜7のいずれか1項に記載のバインダを含む、電気化学デバイス。
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EP3840087B1 (en) | 2023-12-13 |
KR102270074B1 (ko) | 2021-06-25 |
TWI728809B (zh) | 2021-05-21 |
CN111971829A (zh) | 2020-11-20 |
JPWO2021084671A1 (ja) | 2021-11-18 |
US11223048B2 (en) | 2022-01-11 |
WO2021084671A1 (ja) | 2021-05-06 |
TW202115218A (zh) | 2021-04-16 |
EP3840087A4 (en) | 2021-06-23 |
US20210135226A1 (en) | 2021-05-06 |
KR20210053811A (ko) | 2021-05-12 |
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