JP7461352B2 - リチウムイオン電池のセルのカソード用電極組成物、カソードスラリー組成物、カソード、及びそれを含む電池 - Google Patents
リチウムイオン電池のセルのカソード用電極組成物、カソードスラリー組成物、カソード、及びそれを含む電池 Download PDFInfo
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- JP7461352B2 JP7461352B2 JP2021531401A JP2021531401A JP7461352B2 JP 7461352 B2 JP7461352 B2 JP 7461352B2 JP 2021531401 A JP2021531401 A JP 2021531401A JP 2021531401 A JP2021531401 A JP 2021531401A JP 7461352 B2 JP7461352 B2 JP 7461352B2
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- weight
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- copolymer
- lithium
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- 239000000203 mixture Substances 0.000 title claims description 110
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 51
- 239000006257 cathode slurry Substances 0.000 title claims description 28
- 125000003700 epoxy group Chemical group 0.000 claims description 127
- 229920001577 copolymer Polymers 0.000 claims description 85
- 239000000178 monomer Substances 0.000 claims description 73
- -1 polysiloxanes Polymers 0.000 claims description 65
- 229920000459 Nitrile rubber Polymers 0.000 claims description 54
- 239000011230 binding agent Substances 0.000 claims description 43
- 239000006182 cathode active material Substances 0.000 claims description 39
- 239000004020 conductor Substances 0.000 claims description 31
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- 238000000034 method Methods 0.000 claims description 28
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 21
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
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- 239000010949 copper Substances 0.000 claims description 10
- 241001441571 Hiodontidae Species 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011651 chromium Substances 0.000 claims description 8
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- 239000011777 magnesium Substances 0.000 claims description 8
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- 239000003960 organic solvent Substances 0.000 claims description 8
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 8
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
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- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000843 powder Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- YPXCVTQZYYXWFJ-UHFFFAOYSA-N 2-(2-ethenoxyethyl)-3-propyloxirane Chemical compound CCCC1OC1CCOC=C YPXCVTQZYYXWFJ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000004452 carbocyclyl group Chemical group 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 125000004043 oxo group Chemical group O=* 0.000 claims description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000000464 thioxo group Chemical group S=* 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- NCWSYEUMCNBLPU-UHFFFAOYSA-N 1-(oxiran-2-yl)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CC)C1CO1 NCWSYEUMCNBLPU-UHFFFAOYSA-N 0.000 claims description 2
- HPRNPSLJNKWKCO-UHFFFAOYSA-N 1-(oxiran-2-yl)propyl prop-2-enoate Chemical group C=CC(=O)OC(CC)C1CO1 HPRNPSLJNKWKCO-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- ONCOIMJOLUOSDB-UHFFFAOYSA-N 2-(5-ethenoxypentyl)oxirane Chemical compound C=COCCCCCC1CO1 ONCOIMJOLUOSDB-UHFFFAOYSA-N 0.000 claims description 2
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 claims description 2
- PTBAHIRKWPUZAM-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1CO1 PTBAHIRKWPUZAM-UHFFFAOYSA-N 0.000 claims description 2
- CBKJLMZJKHOGEQ-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1CO1 CBKJLMZJKHOGEQ-UHFFFAOYSA-N 0.000 claims description 2
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 claims description 2
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 claims description 2
- FDWQGNULGGFFDP-UHFFFAOYSA-N 5-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C=CC1CCCC2OC12 FDWQGNULGGFFDP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000925 Cd alloy Inorganic materials 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- NNBZRMINUVCKKA-UHFFFAOYSA-N S(=O)(O)OSS(=O)(=O)O Chemical compound S(=O)(O)OSS(=O)(=O)O NNBZRMINUVCKKA-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 2
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- 150000004676 glycans Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- NONOKGVFTBWRLD-UHFFFAOYSA-N isocyanatosulfanylimino(oxo)methane Chemical compound O=C=NSN=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
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- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
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- CYFLXLSBHQBMFT-UHFFFAOYSA-N sulfamoxole Chemical group O1C(C)=C(C)N=C1NS(=O)(=O)C1=CC=C(N)C=C1 CYFLXLSBHQBMFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
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- 239000000243 solution Substances 0.000 description 37
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- 238000006243 chemical reaction Methods 0.000 description 18
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- 238000005984 hydrogenation reaction Methods 0.000 description 15
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- 229920005596 polymer binder Polymers 0.000 description 15
- 239000002491 polymer binding agent Substances 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 14
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- 239000011149 active material Substances 0.000 description 13
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000006183 anode active material Substances 0.000 description 12
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
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- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 235000010935 mono and diglycerides of fatty acids Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OQAIUHLITJGRMM-UHFFFAOYSA-N n,n-di(propan-2-yl)hydroxylamine Chemical compound CC(C)N(O)C(C)C OQAIUHLITJGRMM-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WMRNGPYHLQSTDL-UHFFFAOYSA-N n-cyclohexyl-2-[[1-(cyclohexylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound C1CCCCC1NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC1CCCCC1 WMRNGPYHLQSTDL-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- WQSAJTZURUQYKX-UHFFFAOYSA-M sodium 2-methylprop-1-ene naphthalene-1-sulfonate Chemical compound [Na+].CC(C)=C.CC(C)=C.[O-]S(=O)(=O)c1cccc2ccccc12 WQSAJTZURUQYKX-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000011127 sodium aluminium sulphate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical class OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 235000019817 tetrapotassium diphosphate Nutrition 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
(i)少なくとも1つのカソード活物質と、
(ii)少なくとも1つのエポキシ基含有フッ素非含有コポリマーであって、
(a)それぞれの場合でエポキシ基含有エチレン-酢酸ビニルコポリマーを基準として、
少なくとも25重量%の量の酢酸ビニル単位;及び
少なくとも5重量%の量のエチレン単位;及び
0.01~30重量%の量のエポキシ基含有モノマー単位を含む、
エポキシ基含有エチレン-酢酸ビニルコポリマーと;
(b)それぞれの場合でエポキシ基含有ニトリルゴムコポリマーを基準として、
5~60重量%の量のα,β-不飽和ニトリル単位;及び
10~94.99重量%の量の、任意選択的に完全又は部分的に水素化された共役ジエン単位;及び
0.01~30重量%の量のエポキシ基含有モノマー単位を含む、
エポキシ基含有ニトリルゴムコポリマーと;
から選択される、少なくとも1つのエポキシ基含有フッ素非含有コポリマーと、
を含む、電極組成物。
Li1+aNixCoyMnzMwO2 [式1]
(式中、Mは、アルミニウム(Al)、銅(Cu)、鉄(Fe)、バナジウム(V)、クロム(Cr)、チタン(Ti)、ジルコニウム(Zr)、亜鉛(Zn)、タンタル(Ta)、ニオブ(Nb)、マグネシウム(Mg)、ホウ素(B)、タングステン(W)、及びモリブデン(Mo)からなる群から選択される少なくとも1つであってよく、a、x、y、z、及びwは、それぞれの独立した元素の原子分率を表し、-0.5≦a≦0.5、0<x≦1、0<y≦1、0≦z≦1、0≦w≦1、及び0<x+y+z≦1である)
の化合物又はリン酸鉄リチウム(LFP)を含む。
(a)酢酸ビニル単位(VA)と、エチレン単位と、エポキシ基含有モノマー単位とを含む、少なくとも1つのエポキシ基含有エチレン-酢酸ビニルコポリマー、又は
(b)α,β-不飽和ニトリル単位と、任意選択的に完全又は部分的に水素化された共役ジエン単位と、エポキシ基含有モノマー単位とを含む、少なくとも1つのエポキシ基含有ニトリルゴムコポリマー、
を含む。
(a)それぞれの場合でエポキシ基含有エチレン-酢酸ビニルコポリマーを基準として、
少なくとも25重量%、好ましくは少なくとも30重量%、より好ましくは少なくとも35重量%、特に好ましくは少なくとも40重量%の量の酢酸ビニル単位と、
少なくとも5重量%、好ましくは少なくとも8重量%、より好ましくは少なくとも10重量%、特に好ましくは少なくとも15重量%の量のエチレン単位と、
0.01~30重量%、好ましくは0.05~25重量%、より好ましくは0.075~20重量%、さらにより好ましくは0.1~15重量%の量のエポキシ基含有モノマー単位と、
を含む少なくとも1つのエポキシ基含有エチレン-酢酸ビニルコポリマー;又は
(b)それぞれの場合で任意選択的に完全又は部分的に水素化されたエポキシ基含有ニトリルゴムコポリマーを基準として、
5~60重量%、好ましくは10~55重量%、さらにより好ましくは13~53重量%の量のα,β-不飽和ニトリル単位と、
10~94.99重量%、好ましくは20~89.95重量%、さらにより好ましくは36~86.9重量%の量の任意選択的に完全又は部分的に水素化された共役ジエン単位と、
0.01~30重量%、好ましくは0.05~25重量%、さらにより好ましくは0.1~15重量%の量のエポキシ基含有モノマー単位と、
を含む少なくとも1つのエポキシ基含有ニトリルゴムコポリマー、
である。
mは、0又は1であり、
Xは、O、O(CR2)p、(CR2)pO、C(=O)O、C(=O)O(CR2)p、C(=O)NR、(CR2)p、N(R)、N(R)(CR2)p、P(R)、P(R)(CR2)p、P(=O)(R)、P(=O)(R)(CR2)p、S、S(CR2)p、S(=O)、S(=O)(CR2)p、S(=O)2(CR2)p、又はS(=O)2であり、これらの基の中のRは、R1~R6と同じ定義を有することができ、
Yは、共役ジエン若しくは非共役ジエン、アルキン、及びビニル化合物を含む1つ以上、好ましくは1つの一不飽和又は多価不飽和モノマーから誘導される繰り返し単位を表す、又はポリエーテル、特にポリアルキレングリコールエーテル、及びポリアルキレンオキシド、ポリシロキサン、ポリオール、ポリカーボネート、ポリウレタン、ポリイソシアネート、多糖、ポリエステル、及びポリアミドを含むポリマーから誘導される構造要素を表し、
n及びpは、同じ又は異なるものであり、それぞれ0~10000の範囲内、好ましくは0~100の範囲内であり、特に好ましくはnは0~100の範囲内であり同時にp=0であり、
R、R1、R2、R3、R4、R5、及びR6は、同一又は異なるものであり、H、直鎖又は分岐、飽和又は一不飽和若しくは多価不飽和のアルキル基、飽和又は一不飽和若しくは多価不飽和のカルボ-若しくはヘテロシクリル基、アリール、ヘテロアリール、アリールアルキル、ヘテロアリールアルキル、アルコキシ、アリールオキシ、ヘテロアリールオキシ、アミノ、アミド、カルバモイル、アルキルチオ、アリールチオ、スルファニル、チオカルボキシル、スルフィニル、スルホノ(sulphono)、スルフィノ(sulphino)、スルフェノ、スルホン酸、スルファモイル、ヒドロキシイミノ、アルコキシカルボニル、F、Cl、Br、I、ヒドロキシル、ホスホナト、ホスフィナト、シリル、シリルオキシ、ニトリル、ボレート、セレネート、カルボニル、カルボキシル、オキシカルボニル、オキシスルホニル、オキソ、チオキソ、エポキシ、シアネート、チオシアネート、イソシアネート、チオイソシアネート、又はイソシアニドである)。
本発明により使用されるエポキシ基含有コポリマーは、エチレン及び酢酸ビニルの重合反応を開始した後に、エポキシ基含有モノマーが反応混合物に加えられる方法によって得ることができる。反応混合物は、1つ以上の前述のさらなるモノマーを開始時にさらに含むことができ、エポキシ基含有モノマーを既に含むことができる。この場合、この方法は、典型的には、バッチプロセスとして、例えば撹拌槽型反応器中で行われ、又は連続プロセスとして、例えばタンクカスケード又は管型反応器中で行われる。バッチプロセスにおける開始後のエポキシ基含有モノマーの添加は、反応を開始した後、エポキシ基含有モノマーは、数回に分けて、又は連続して、好ましくは連続して、反応混合物に加えられ、一方、連続プロセスでは、エポキシ基含有モノマーは、反応開始位置の下流に位置する少なくとも1つ、好ましくは2つ以上の場所で反応混合物に加えられる、ことを意味するものと理解されている。この場合、反応開始は、少なくとも酢酸ビニルとエチレンとの重合が最初に起こる時点又は位置である。
それぞれの場合で成分i)+ii)+iii)の合計を基準として、
i)1~80重量%、好ましくは5~70重量%のエチレンと、
ii)1~99重量%、好ましくは25~95重量%の酢酸ビニルと、
iii)0.01~30重量%のエポキシ基含有モノマーと、
を含む。
それぞれの場合で成分の合計(iv+v)を基準として
iv)5~95重量%の酢酸ビニルと、
v)5~95重量%のエポキシ基含有モノマーと、
を含み、
成分iv)+v)+極性有機溶媒の合計を基準として、20~60重量%の極性有機溶媒も含む。
エポキシ基含有ニトリルゴムコポリマーの重合
ニトリルゴムの乳化重合はよく知られており、典型的には、アニオン性乳化剤又は無電荷の乳化剤の水溶性塩が乳化剤として使用される。アニオン性乳化剤の使用が好ましい。
(1)エポキシ基含有フッ素非含有コポリマー(ii)を溶媒中に熔解させてバインダー溶液を形成するステップと;
(2)ステップ(1)からのバインダー溶液を、カソード活物質(i)、伝導性材料、及び任意選択的にさらなる添加剤と混合してカソードスラリー組成物を形成するステップと、
(3)ステップ(2)からのカソードスラリー組成物を集電体上に塗布してカソードシートを形成するステップと;
(4)ステップ(3)のカソードシートを乾燥させるステップと、
を含むことを特徴とする製造方法に関する。
ムーニー粘度 - ムーニー粘度(ML1+4、100℃)の値は、それぞれの場合で、DIN 53523/3又はASTM D 1646に準拠して100℃において剪断円板粘度計によって測定される。MSR(ムーニー応力緩和(Mooney Stress Relaxation))は、それぞれの場合で、ISO 289-4:2003(E)に準拠して100℃において剪断円板粘度計によって測定される。
A:容量保持が95%以上である
B:容量保持が85%以上及び95%未満である
C:容量保持が75%以上及び85%未満である
D:容量保持が75%未満である
エポキシ基含有完全水素化アクリロニトリルブタジエンコポリマーAの調製
以下の一連の実施例にバインダーとして使用されるエポキシ基含有完全水素化アクリロニトリルブタジエンコポリマーAを、表1中に明記される基本処方により生成し、すべての供給材料は、モノマー混合物100重量部を基準とした重量部の単位で記載される。表1には、それぞれの重合条件も明記している。
エポキシ基含有エチレン-酢酸ビニルコポリマーsB及びCを以下の手順により調製した。
5Lの撹拌オートクレーブ中で調製を行った。このために、693gのtert-ブタノール、1288gの酢酸ビニル、2.0gのメタクリル酸グリシジルからなる1983gの溶液、及び2.5gのADVNと250gの酢酸ビニル/tert-ブタノール溶液(酢酸ビニル20%)とからなる252.5gの活性剤溶液とからなる溶液を、RTにおいて5L反応器中に次々に注入した。反応器を窒素で不活性化し、次に1062gのエチレンを注入した。温度を61℃まで上昇させて、約380barの圧力を確立した。半時間後(この時点で変換は酢酸ビニルを基準として約10重量%となる)、122.2gのtert-ブタノールと、143.8gの酢酸ビニルと、40.0gのメタクリル酸グリシジルとからなる溶液を反応混合物中に0.6g/分の速度で計量供給した。反応時間全体にわたって、エチレンの注入によって圧力を約380barに維持した。10時間の反応時間の後、エチレンの計量供給を停止し、ポリマー溶液を5Lの反応器から停止用オートクレーブ中に急送した。溶媒及び残留モノマーを除去した後、100mg/kg未満の残留メタクリル酸グリシジル含有量を有するメタクリル酸グリシジル-エチレン-酢酸ビニルコポリマーを得た。
調製は、5Lの撹拌オートクレーブ中で行った。このために、564gのtert-ブタノール、1096gの酢酸ビニル、5.0gのメタクリル酸グリシジルからなる1665gの溶液、及び2.5gのADVNと250gの酢酸ビニル/tert-ブタノール溶液(酢酸ビニル20%)とからなる252.5gの活性剤溶液を、RTにおいて5L反応器中に次々に注入した。反応器を窒素で不活性化し、次に1178gのエチレンを注入した。温度を61℃まで上昇させて、約380barの圧力を確立した。半時間後(この時点で変換は酢酸ビニルを基準として約10重量%となる)、122.2gのtert-ブタノールと、101.8gの酢酸ビニルと、82.0gのメタクリル酸グリシジルとからなる溶液を反応混合物中に0.6g/分の速度で計量供給した。反応時間全体にわたって、エチレンの注入によって圧力を約380barに維持した。10時間の反応時間の後、エチレンの計量供給を停止し、ポリマー溶液を5Lの反応器から停止用オートクレーブ中に急送した。溶媒及び残留モノマーを除去した後、100mg/kg未満の残留メタクリル酸グリシジル含有量を有するメタクリル酸グリシジル-エチレン-酢酸ビニルコポリマーを得た。
ステップ(1) - 溶解:振盪機中室温において、ある量のコポリマーA~Hを溶媒(NMP)に終夜溶解させてバインダー溶液(5重量%)を形成する。
Claims (15)
- リチウムイオン電池のセルのカソード用電極組成物であって、
(i)少なくとも1つのカソード活物質と、
(ii)少なくとも1つのエポキシ基含有フッ素非含有コポリマーであって、
(a)それぞれの場合でエポキシ基含有エチレン-酢酸ビニルコポリマーを基準として、
少なくとも25重量%の量の酢酸ビニル単位;及び
少なくとも5重量%の量のエチレン単位;及び
0.1~15重量%の量のエポキシ基含有モノマー単位を含む、
前記エポキシ基含有エチレン-酢酸ビニルコポリマーと;
(b)それぞれの場合でエポキシ基含有ニトリルゴムコポリマーを基準として、
13~53重量%の量のα,β-不飽和ニトリル単位;及び
10~94.99重量%の量の、完全に水素化された共役ジエン単位;及び
0.1~15重量%の量のエポキシ基含有モノマー単位を含む、
前記エポキシ基含有ニトリルゴムコポリマーと;
から選択される、少なくとも1つのエポキシ基含有フッ素非含有コポリマーと、
を含み、
エポキシ基含有ニトリルゴムコポリマー(b)は、完全に不飽和のエポキシ基含有ニトリルゴムコポリマーの1%未満の残留二重結合を含む、電極組成物。 - 前記エポキシ基含有フッ素非含有コポリマー(ii)が、一般式(I)
mは、0又は1であり、
Xは、O、O(CR2)p、(CR2)pO、C(=O)O、C(=O)O(CR2)p、C(=O)NR、(CR2)p、N(R)、N(R)(CR2)p、P(R)、P(R)(CR2)p、P(=O)(R)、P(=O)(R)(CR2)p、S、S(CR2)p、S(=O)、S(=O)(CR2)p、S(=O)2(CR2)p、又はS(=O)2であり、これらの基の中のRは、R1~R6と同じ定義を有することができ、
Yは、共役ジエン若しくは非共役ジエン、アルキン、及びビニル化合物を含む1つ以上の一不飽和又は多価不飽和モノマーから誘導される繰り返し単位を表す、又はポリエーテル、特にポリアルキレングリコールエーテル、及びポリアルキレンオキシド、ポリシロキサン、ポリオール、ポリカーボネート、ポリウレタン、ポリイソシアネート、多糖、ポリエステル、及びポリアミドを含むポリマーから誘導される構造要素を表し、
n及びpは、同じ又は異なるものであり、それぞれ0~10000の範囲内であり、
R、R1、R2、R3、R4、R5、及びR6は、同一又は異なるものであり、H、直鎖又は分岐、飽和又は一不飽和若しくは多価不飽和のアルキル基、飽和又は一不飽和若しくは多価不飽和のカルボ若しくはヘテロシクリル基、アリール、ヘテロアリール、アリールアルキル、ヘテロアリールアルキル、アルコキシ、アリールオキシ、ヘテロアリールオキシ、アミノ、アミド、カルバモイル、アルキルチオ、アリールチオ、スルファニル、チオカルボキシル、スルフィニル、スルホノ、スルフィノ、スルフェノ、スルホン酸、スルファモイル、ヒドロキシイミノ、アルコキシカルボニル、F、Cl、Br、I、ヒドロキシル、ホスホナト、ホスフィナト、シリル、シリルオキシ、ニトリル、ボレート、セレネート、カルボニル、カルボキシル、オキシカルボニル、オキシスルホニル、オキソ、チオキソ、エポキシ、シアネート、チオシアネート、イソシアネート、チオイソシアネート、又はイソシアニドである)
の1つ以上のエポキシ基含有モノマーから誘導される繰り返し単位を含む、請求項1に記載の電極組成物。 - 共重合したエポキシ基含有モノマーが、アクリル酸2-エチルグリシジル、メタクリル酸2-エチルグリシジル、アクリル酸2-(n-プロピル)グリシジル、メタクリル酸2-(n-プロピル)グリシジル、アクリル酸2-(n-ブチル)グリシジル、メタクリル酸2-(n-ブチル)グリシジル、アクリル酸グリシジルメチル、メタクリル酸グリシジルメチル、メタクリル酸グリシジル、アクリル酸グリシジル、アクリル酸(3’,4’-エポキシヘプチル)-2-エチル、メタクリル酸(3’,4’-エポキシヘプチル)-2-エチル、アクリル酸6’,7’-エポキシヘプチル、メタクリル酸6’,7’-エポキシヘプチル、アリルグリシジルエーテル、アリル3,4-エポキシヘプチルエーテル、6,7-エポキシヘプチルアリルエーテル、ビニルグリシジルエーテル、ビニル3,4-エポキシヘプチルエーテル、3,4-エポキシヘプチルビニルエーテル、6,7-エポキシヘプチルビニルエーテル、o-ビニルベンジルグリシジルエーテル、m-ビニルベンジルグリシジルエーテル、p-ビニルベンジルグリシジルエーテル、3-ビニルシクロヘキセンオキシド、及びそれらの混合物からなる群から選択される、請求項1又は2に記載の電極組成物。
- ISO 289(ISO 289-1:2014-02)に準拠して100℃において剪断円板粘度計によって測定される、前記エポキシ基含有フッ素非含有コポリマー(ii)のムーニー粘度(ML(1+4)100℃)が≧5ムーニー単位(MU)である、請求項1~3のいずれか一項に記載の電極組成物。
- 20K/分の加熱速度でDSCによって測定して、前記エポキシ基含有フッ素非含有コポリマー(ii)が+40℃~-50℃の範囲内のガラス転移温度を有する、請求項1~4のいずれか一項に記載の電極組成物。
- 前記エポキシ基含有フッ素非含有コポリマー(ii)が、前記電極組成物の全重量を基準として0.1~15重量%の量で存在する、請求項1~5のいずれか一項に記載の電極組成物。
- 前記少なくとも1つのカソード活物質(i)が以下の式1:
Li1+aNixCoyMnzMwO2 [式1]
(式中、Mは、アルミニウム(Al)、銅(Cu)、鉄(Fe)、バナジウム(V)、クロム(Cr)、チタン(Ti)、ジルコニウム(Zr)、亜鉛(Zn)、タンタル(Ta)、ニオブ(Nb)、マグネシウム(Mg)、ホウ素(B)、タングステン(W)、及びモリブデン(Mo)からなる群から選択される少なくとも1つであってよく、a、x、y、z、及びwは、それぞれの独立した元素の原子分率を表し、-0.5≦a≦0.5、0<x≦1、0<y≦1、0≦z≦1、0≦w≦1、及び0<x+y+z≦1である)
の化合物又はリン酸鉄リチウム(LFP)を含む、請求項1~6のいずれか一項に記載の電極組成物。 - 請求項1~7のいずれか一項に記載の電極組成物と、
少なくとも1つの伝導性材料と、
少なくとも1つの溶媒と、
を含む、カソードスラリー組成物。 - 前記少なくとも1つの伝導性材料が、カーボンブラック、アセチレンブラック、Ketjenブラック、チャンネルブラック、ファーネスブラック、ランプブラック及びサマーブラック、天然グラファイト及び人造グラファイト、膨張グラファイト、伝導性繊維、金属粉末、及びカーボンナノチューブ、グラフェン、酸化グラフェン、並びにそれらの混合物からなる群から選択される、請求項8に記載のカソードスラリー組成物。
- 前記少なくとも1つの伝導性材料が、前記カソードスラリー組成物の全固体重量を基準として0.5~50重量%の量で存在する、請求項8又は9に記載のカソードスラリー組成物。
- 前記少なくとも1つの溶媒が、環状脂肪族炭化水素、芳香族炭化水素、ケトン、塩素系脂肪族炭化水素、エステル、アシロニトリル、エーテル、アルコール、ニトリル、又はアミドを含む、請求項8~10のいずれか一項に記載のカソードスラリー組成物。
- 集電体とカソード活物質層とを含むカソードであって、前記カソード活物質層が、請求項1~7のいずれか一項に記載の電極組成物、及び伝導性材料を含む、カソード。
- 前記集電体が、鉄、銅、アルミニウム、ニッケル、焼結炭素、ステンレス鋼、その表面上が炭素、チタン、タンタル、金、白金、チタン、若しくは銀で処理されたステンレス鋼;アルミニウム-カドミウム合金、その表面上が伝導性材料で処理された非伝導性ポリマー;伝導性ポリマー、又はNi、Al、Au、Ag、Pd、Cr、Ta、Cu、若しくはBaの金属粉末を含む金属ペーストからなる群から選択される、請求項12に記載のカソード。
- アノードと、請求項12又は13に記載のカソードと、セパレータと、リチウム塩及び有機溶媒をベースとする電解液とを含む少なくとも1つのセルを含む、リチウムイオン電池。
- 電池のセルのカソード用電極組成物中のバインダーとしての、請求項1~6のいずれか一項に記載のエポキシ基含有フッ素非含有コポリマーの使用。
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CN114335546B (zh) * | 2022-03-07 | 2022-05-10 | 北京壹金新能源科技有限公司 | 一种电池电极用粘结剂以及电池电极 |
WO2023227484A1 (en) * | 2022-05-27 | 2023-11-30 | Arlanxeo Deutschland Gmbh | Powderous rubbers with lithium stearate, and use thereof as an electrode binder |
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WO2024031448A1 (zh) * | 2022-08-10 | 2024-02-15 | 宁德时代新能源科技股份有限公司 | 聚合物及其制备方法、正极浆料、正极极片、二次电池、电池模块、电池包和用电装置 |
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