JP2023516191A - 正極活物質前駆体材料およびリチウム二次電池用正極活物質の製造方法、およびこれによって製造されたリチウム二次電池用正極活物質 - Google Patents
正極活物質前駆体材料およびリチウム二次電池用正極活物質の製造方法、およびこれによって製造されたリチウム二次電池用正極活物質 Download PDFInfo
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- JP2023516191A JP2023516191A JP2022551772A JP2022551772A JP2023516191A JP 2023516191 A JP2023516191 A JP 2023516191A JP 2022551772 A JP2022551772 A JP 2022551772A JP 2022551772 A JP2022551772 A JP 2022551772A JP 2023516191 A JP2023516191 A JP 2023516191A
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- active material
- positive electrode
- electrode active
- lithium secondary
- secondary battery
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 88
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000002243 precursor Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 239000006182 cathode active material Substances 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 96
- 150000003839 salts Chemical class 0.000 claims description 54
- 239000000126 substance Substances 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 229910052759 nickel Inorganic materials 0.000 claims description 44
- 239000011572 manganese Substances 0.000 claims description 42
- 238000000638 solvent extraction Methods 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 238000002386 leaching Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 7
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- DFTMMVSDKIXUIX-KQQUZDAGSA-N (NE)-N-[(4E)-4-hydroxyiminohexan-3-ylidene]hydroxylamine Chemical compound CC\C(=N/O)\C(\CC)=N\O DFTMMVSDKIXUIX-KQQUZDAGSA-N 0.000 claims description 2
- AACZKKTXNWTCOF-UHFFFAOYSA-N N-(2-hydroxyiminopentan-3-ylidene)hydroxylamine Chemical compound CCC(=NO)C(C)=NO AACZKKTXNWTCOF-UHFFFAOYSA-N 0.000 claims description 2
- WXRLRVISPKDAAE-UHFFFAOYSA-N N-(5-hydroxyiminooctan-4-ylidene)hydroxylamine Chemical compound CCCC(=NO)C(CCC)=NO WXRLRVISPKDAAE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims 1
- UMTJFKXZVNTLFZ-UHFFFAOYSA-N bis(2-ethylhexyl) hydrogen phosphate Chemical compound C(C)C(COP(OCC(CCCC)CC)(O)=O)CCCC.C(C)C(COP(OCC(CCCC)CC)(O)=O)CCCC UMTJFKXZVNTLFZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 description 59
- 239000000243 solution Substances 0.000 description 43
- 239000010941 cobalt Substances 0.000 description 24
- 229910017052 cobalt Inorganic materials 0.000 description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 24
- -1 cobalt Chemical class 0.000 description 20
- 238000005406 washing Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
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- 239000002184 metal Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 8
- 150000001868 cobalt Chemical class 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
- 150000002696 manganese Chemical class 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 239000004917 carbon fiber Substances 0.000 description 3
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
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- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
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- 229920005608 sulfonated EPDM Polymers 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910012722 Li3N-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012716 Li3N-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012734 Li3N—LiI—LiOH Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012047 Li4SiO4-LiI-LiOH Inorganic materials 0.000 description 1
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- 229910012057 Li4SiO4—LiI—LiOH Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
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- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
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- 229910021385 hard carbon Inorganic materials 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical class [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
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Abstract
Description
<正極活物質前駆体材料の製造方法>
本発明の正極活物質前駆体材料の製造方法は、(1)Mnと、Niと、Coとを含む廃リチウム二次電池の正極活物質を浸出させて浸出液を得るステップと、(2)第1抽出剤を用いて、前記浸出液を一次溶媒抽出してMn塩を得るステップと、(3)沈殿剤を用いて、前記溶媒抽出された浸出液を沈殿させてNi塩を得るステップと、(4)第2抽出剤を用いて、前記沈殿された浸出液を二次溶媒抽出してCo塩を得るステップと、を含む。また、本発明の正極活物質前駆体材料の製造方法は、リチウム塩を回収するステップをさらに含んでもよく、前記第1抽出剤および前記第2抽出剤はリン酸系物質を含み、前記沈殿剤はオキシム系物質を含む。
本発明のMn、NiおよびCoを含む廃リチウム二次電池の正極活物質は、下記化学式1で表される正極活物質を含むものであってもよい。
LiNixCoyMnzO2
前記化学式1において、0<x<10、0<y<10、および0<z<10であり、x+y+z=10であり、好ましくは、x=5、y=2、およびz=3であってもよいが、これに限定されるものではない。
本発明の正極活物質前駆体材料の製造方法は、前記Mn、NiおよびCoを含む廃リチウム二次電池の正極活物質を得るための前処理工程であって、廃リチウム二次電池を直ちに破砕した後、熱処理するステップをさらに含んでもよい。
[化学式1]
LiNixCoyMnzO2
前記化学式1において、0<x<10、0<y<10、および0<z<10であり、x+y+z=10であり、好ましくは、x=5、y=2、およびz=3であってもよいが、これに限定されるものではない。
本発明に係る正極活物質前駆体材料の製造方法は、第1リン酸系物質を用いて、前記浸出液を一次溶媒抽出してMn塩を得るステップを含み、酸性雰囲気下で行われてもよく、pH2~4で行われることが好ましく、pH3~4で行われることがさらに好ましく、約pH4で行われることが最も好ましい。
前記第1リン酸系物質は、マンガン塩の抽出剤であって、前記浸出液のpHが2~4、好ましくは、pH3~4、さらに好ましくは、pH4であるとき、Mn塩を80%以上の効率で抽出できる物質を含んでもよい。前記Mn塩の抽出効率は、80%以上であってもよく、好ましくは、85%以上、さらに好ましくは、90%以上であってもよい。
本発明において、前記第1リン酸系物質は、下記化学式2または下記化学式3で表される化合物から選択される1種以上の化合物を含むものであってもよい。
[化学式2]
[化学式3]
逆抽出:MR2+2H+→M2++2RH
(3)前記溶媒抽出された残液を沈殿させてニッケル(Ni)塩を得るステップ
本発明に係る正極活物質前駆体材料の製造方法は、オキシム系物質を用いて、前記溶媒抽出された残液を沈殿させてNi塩を得るステップを含み、酸性雰囲気下で行われてもよく、pH4~6で行われることが好ましく、pH5~6で行われることがより好ましく、約pH6で行われることが最も好ましい。
前記オキシム系物質は、ニッケル塩の沈殿剤であって、前記溶媒抽出された残液のpHが4~6、好ましくは、pH5~6、さらに好ましくは、pH6であるとき、Ni塩を80%以上の効率で浸出できる物質を含んでもよい。前記Ni塩の浸出効率は、80%以上であってもよく、好ましくは、85%以上、さらに好ましくは、90%以上であってもよい。
本発明に係る正極活物質前駆体材料の製造方法は、第2リン酸系物質を用いて、前記沈殿された浸出液を二次溶媒抽出してCo塩を得るステップを含み、酸性雰囲気下で行われてもよく、pH4~5.5で行われることが好ましく、pH4~5で行われることがさらに好ましく、約pH5で行われることが最も好ましい。
前記第2リン酸系物質は、コバルトの浸出剤であって、前記沈殿された浸出液のpHが4~5.5、好ましくは、pH4~5、さらに好ましくは、pH5であるとき、Co塩を80%以上の効率で抽出できる物質を含む。前記Co塩の抽出効率は、80%以上であってもよく、好ましくは、85%以上、さらに好ましくは、90%以上であってもよい。また、前記第2リン酸系物質がけん化したものを含んでもよい。
[化学式3]
また、本発明は、本発明に係る正極活物質前駆体材料の製造方法によって製造される正極活物質前駆体材料およびリチウム塩を混合してLiNixCoyMnzO2(前記式において、0≦x≦10、0≦y≦10、および0≦z≦10であり、x+y+z=10である。)で表される正極活物質を得ることを特徴とするリチウム二次電池用正極活物質の製造方法を提供する。
また、本発明は、本発明に係るリチウム二次電池用正極活物質の製造方法によって製造されたリチウム二次電池用正極活物質を提供する。本発明のリチウム二次電池用正極活物質は、本発明によって製造された正極活物質前駆体材料を用いる点を除いては、公知の製造方法によって製造することができる。
[発明の実施のための形態]
以下、実施例によって本発明をより詳細に説明する。しかし、下記の実施例は、本発明をより具体的に説明するためのものであって、本発明の範囲が下記の実施例によって限定されるものではない。
廃リチウム二次電池から分離したNCM523正極材900kgを破砕し、ミーリングで粒子大きさ2μm~5μmに粉砕処理した。前記得られた粉末を硫酸溶液で6時間以上反応させた後、Li、Mn、Co、およびNiが含まれた浸出液を得た。本実施例では、Mn塩、Ni塩、およびCo塩の順に抽出を行った。
前記実施例1および比較例1と同一の方法で、Li、Mn、Co、およびNiが含まれた浸出液を得ており、前記実施例1と同一の方法で、硫酸マンガン溶液を得た後、硫酸ニッケルを得た。
廃リチウム二次電池から分離したNCM523正極材900kgを破砕し、ミーリングで粉砕処理した。前記正極活物質粉末を硫酸溶液で6時間以上反応させた後、Li、Mn、Co、およびNiが含まれた浸出液を得た。本比較例では、Mn塩、Co塩、およびNi塩の順に抽出を行った。
前記実施例1および比較例1と同一の方法で、Li、Mn、Co、およびNiが含まれた浸出液を得た後、下記のような方法で、Mn塩、Ni塩およびCo塩を得た。
本比較例3は、前記実施例1において、コバルト塩の抽出とニッケル塩との抽出順序を異ならせたことを除き、前記実施例1と同一の方法で行い、すなわち、Mn塩、Co塩、およびNi塩の順に抽出を行った。
Claims (12)
- (1)Mnと、Niと、Coとを含む廃リチウム二次電池の正極活物質を浸出させて浸出液を得るステップと、
(2)第1リン酸系物質を用いて、前記浸出液を一次溶媒抽出してMn塩を得るステップと、
(3)オキシム系物質を用いて、前記溶媒抽出された残液を沈殿させてNi塩を得るステップと、
(4)第2リン酸系物質を用いて、前記沈殿された浸出液を二次溶媒抽出してCo塩を得るステップと、
を含む、正極活物質前駆体材料の製造方法。 - 前記廃リチウム二次電池の正極活物質は、下記化学式1で表される正極活物質を含むものである、請求項1に記載の正極活物質前駆体材料の製造方法。
[化学式1]
LiNixCoyMnzO2
(前記式1において、
0<x<10、0<y<10、および0<z<10であり、
x+y+z=10である。) - 前記第1リン酸系物質および前記第2リン酸系物質は、それぞれ独立して、ジ-(2-エチルヘキシル)リン酸(Di-(2-ethylhexyl)phosphoric acid)および2-エチルヘキシルホスホン酸モノ2-エチルヘキシルエステル(2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester)から選択される1種以上のものを含む、請求項3に記載の正極活物質前駆体材料の製造方法。
- 前記オキシム系物質は、ジメチルグリオキシム、ジエチルグリオキシム、ジプロピルグリオキシム、およびエチルメチルグリオキシムからなる群から選択される1種以上を含む、請求項1に記載の正極活物質前駆体材料の製造方法。
- 前記(1)~(3)ステップは、酸性雰囲気中で行われることを特徴とする、請求項1に記載の正極活物質前駆体材料の製造方法。
- 前記(1)ステップは、pH2~4で行われ、
前記(2)ステップは、pH4~6で行われ、
前記(3)ステップは、pH4~5.5で行われることを特徴とする、請求項6に記載の正極活物質前駆体材料の製造方法。 - 前記(3)ステップで得たNi塩に硫酸を添加するステップをさらに含む、請求項1に記載の正極活物質前駆体材料の製造方法。
- 前記Mn塩は、硫酸マンガンを含み、前記Ni塩は、硫酸ニッケルを含み、前記Co塩は、硫酸コバルトを含むことを特徴とする、請求項1に記載の正極活物質前駆体材料の製造方法。
- 前記廃リチウム二次電池の正極活物質は、廃リチウム二次電池を破砕した後、熱処理して得られることを含む、請求項1に記載の正極活物質前駆体材料の製造方法。
- 請求項1~10のいずれか1項に記載の製造方法によって製造される正極活物質前駆体材料およびリチウム塩を混合し、LiNixCoyMnzO2(前記式において、0≦x≦10、0≦y≦10、および0≦z≦10であり、x+y+z=10である。)で表される正極活物質を得ることを特徴とする、リチウム二次電池用正極活物質の製造方法。
- 請求項11の製造方法によって製造された、リチウム二次電池用正極活物質。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009193778A (ja) * | 2008-02-13 | 2009-08-27 | Nippon Mining & Metals Co Ltd | Co,Ni,Mn含有リチウム電池滓からの有価金属回収方法 |
JP2013001916A (ja) * | 2011-06-13 | 2013-01-07 | Sumitomo Metal Mining Co Ltd | ニッケルの浸出方法 |
CN108193050A (zh) * | 2017-11-27 | 2018-06-22 | 中国人民解放军陆军防化学院 | 一种废旧三元动力电池中金属材料回收方法 |
WO2018181816A1 (ja) * | 2017-03-31 | 2018-10-04 | Jx金属株式会社 | リチウムイオン電池スクラップの処理方法 |
KR20190123524A (ko) * | 2018-04-24 | 2019-11-01 | (주)이엠티 | 리튬이온이차전지의 폐 양극재로부터 양극활물질 전구체용 원료를 재생하는 방법, 이에 의하여 재생된 양극활물질 전구체용 원료, 양극활물질 전구체, 양극활물질, 양극 및 리튬이온이차전지 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010011447A2 (en) | 2008-07-24 | 2010-01-28 | Crs Holdings, Inc. | High strength, high toughness steel alloy |
CN101580317A (zh) * | 2009-06-01 | 2009-11-18 | 邱致忠 | 一种含镍废水处理工艺 |
KR101392616B1 (ko) * | 2012-10-30 | 2014-05-07 | (주)이엠티 | 리튬 이온 전지의 폐 양극재를 이용한 전구체 원료의 재생 방법, 그 방법에 의해 재생된 원료를 사용하여 제조한 전구체, 양극재 및 리튬 이온 전지 |
WO2016115404A1 (en) * | 2015-01-15 | 2016-07-21 | Envia Systems, Inc. | Positive electrode active materials with composite coatings for high energy density secondary batteries and corresponding processes |
CN105789726A (zh) * | 2016-04-21 | 2016-07-20 | 苏州聚智同创环保科技有限公司 | 一种以废旧锂离子电池为原料制备镍钴锰三元材料前驱体的方法 |
KR102008582B1 (ko) * | 2017-12-05 | 2019-08-07 | 타운마이닝리소스주식회사 | 용매추출 공정을 적용하여 리튬이차전지 폐 양극재를 니켈-코발트-망간 복합 황산염 용액으로 재생하는 방법 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009193778A (ja) * | 2008-02-13 | 2009-08-27 | Nippon Mining & Metals Co Ltd | Co,Ni,Mn含有リチウム電池滓からの有価金属回収方法 |
JP2013001916A (ja) * | 2011-06-13 | 2013-01-07 | Sumitomo Metal Mining Co Ltd | ニッケルの浸出方法 |
WO2018181816A1 (ja) * | 2017-03-31 | 2018-10-04 | Jx金属株式会社 | リチウムイオン電池スクラップの処理方法 |
CN108193050A (zh) * | 2017-11-27 | 2018-06-22 | 中国人民解放军陆军防化学院 | 一种废旧三元动力电池中金属材料回收方法 |
KR20190123524A (ko) * | 2018-04-24 | 2019-11-01 | (주)이엠티 | 리튬이온이차전지의 폐 양극재로부터 양극활물질 전구체용 원료를 재생하는 방법, 이에 의하여 재생된 양극활물질 전구체용 원료, 양극활물질 전구체, 양극활물질, 양극 및 리튬이온이차전지 |
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