WO2022097653A1 - Method of producing modified lithium nickel manganese cobalt composite oxide particles - Google Patents
Method of producing modified lithium nickel manganese cobalt composite oxide particles Download PDFInfo
- Publication number
- WO2022097653A1 WO2022097653A1 PCT/JP2021/040449 JP2021040449W WO2022097653A1 WO 2022097653 A1 WO2022097653 A1 WO 2022097653A1 JP 2021040449 W JP2021040449 W JP 2021040449W WO 2022097653 A1 WO2022097653 A1 WO 2022097653A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite oxide
- lithium nickel
- oxide particles
- cobalt composite
- manganese cobalt
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 312
- 239000002131 composite material Substances 0.000 title claims abstract description 239
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical class [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 238000000034 method Methods 0.000 title abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 185
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000013522 chelant Substances 0.000 claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000004381 surface treatment Methods 0.000 claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 49
- 125000004429 atom Chemical group 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 31
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 229910013200 LiNiMnCo Inorganic materials 0.000 abstract 4
- 229910014174 LixNiy Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 28
- 229910052759 nickel Inorganic materials 0.000 description 28
- 229910052748 manganese Inorganic materials 0.000 description 26
- 238000010304 firing Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 229910017052 cobalt Inorganic materials 0.000 description 22
- 239000010941 cobalt Substances 0.000 description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- YSLYUVMQXOBAFV-UHFFFAOYSA-N [Co].[Mn].[Ni].[Li].[Co] Chemical compound [Co].[Mn].[Ni].[Li].[Co] YSLYUVMQXOBAFV-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 9
- 238000013507 mapping Methods 0.000 description 9
- 150000002815 nickel Chemical group 0.000 description 9
- -1 oxides Chemical class 0.000 description 9
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 9
- WMAZTIKEPKCNRG-UHFFFAOYSA-N [Ni].[Co].[Mn].[Ni].[Li] Chemical compound [Ni].[Co].[Mn].[Ni].[Li] WMAZTIKEPKCNRG-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000006072 paste Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 238000000790 scattering method Methods 0.000 description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- AGCSFOPWOBXNNP-UHFFFAOYSA-N [Mn].[Co].[Ni].[Mn].[Li] Chemical compound [Mn].[Co].[Ni].[Mn].[Li] AGCSFOPWOBXNNP-UHFFFAOYSA-N 0.000 description 2
- YTXOOYOXJTVFEG-UHFFFAOYSA-N [Mn].[Ni].[Ni].[Li] Chemical compound [Mn].[Ni].[Ni].[Li] YTXOOYOXJTVFEG-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- XRASGLNHKOPXQL-UHFFFAOYSA-L azane 2-oxidopropanoate titanium(4+) dihydrate Chemical compound N.N.O.O.[Ti+4].CC([O-])C([O-])=O.CC([O-])C([O-])=O XRASGLNHKOPXQL-UHFFFAOYSA-L 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000006309 butyl amino group Chemical group 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 125000006316 iso-butyl amino group Chemical group [H]N(*)C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 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 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000006308 propyl amino group Chemical group 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N isocitric acid Chemical compound OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Definitions
- the present invention relates to a method for producing modified lithium nickel manganese cobalt composite oxide particles.
- lithium cobalt oxide has been used as the positive electrode active material of a lithium secondary battery.
- cobalt is a rare metal
- lithium nickel-manganese-cobalt composite oxides having a low cobalt content have been developed (see, for example, Patent Documents 1 and 2).
- Lithium-nickel-manganese-cobalt composite oxide-based lithium secondary batteries can be reduced in cost by adjusting the atomic ratios of nickel, manganese, and cobalt contained in the composite oxide. It is known that the capacity is higher than that of lithium cobalt oxide (see, for example, Patent Document 3).
- the lithium secondary battery using the lithium nickel manganese cobalt composite oxide as the positive electrode active material still has a problem of deterioration of cycle characteristics.
- Patent Documents 4 and 5 describe an alkoxide monomer or oligomer made of an organic metal compound such as Ti and an alcohol such as 2-propanol. After mixing, a chelating agent such as acetylacetone was added, and water was further added to prepare a dispersion in which a precursor of fine particles containing Ti having an average particle of 1 to 20 nm was dispersed, and the dispersion was used to prepare lithium nickel manganese.
- a method has been proposed in which the surface of particles of a cobalt composite oxide is coated and then heat-treated.
- lithium secondary batteries have been studied for use in the automobile field such as electric vehicles, hybrid vehicles, and plug-in hybrid vehicles. Therefore, in a lithium secondary battery using a lithium nickel manganese cobalt composite oxide as a positive electrode active material, further improvement of cycle characteristics is required.
- an object of the present invention is to provide lithium nickel-manganese-cobalt composite oxide particles capable of enhancing cycle characteristics when used as a positive electrode active material of a lithium secondary battery.
- heat treatment is performed to obtain modified lithium nickel-manganese-cobalt composite oxide particles, and the modified lithium nickel-manganese-cobalt composite oxide particles are used as a positive electrode active material for lithium secondary.
- the battery has been found to have excellent cycle characteristics, and the present invention has been completed.
- the present invention (1) has the following general formula (1): Li x Ny Mn z Cot M p O 1 + x (1)
- M is selected from Mg, Al, Ti, Zr, Cu, Fe, Sr, Ca, V, Mo, Bi, Nb, Si, Zn, Ga, Ge, Sn, Ba, W, Na and K. 1 or more kinds of metal elements are shown.
- X is 0.98 ⁇ x ⁇ 1.20
- y is 0.30 ⁇ y ⁇ 1.00
- z is 0 ⁇ z ⁇ 0.50
- t is 0.
- the lithium nickel manganese cobalt composite oxide particles represented by (1) are brought into contact with a surface treatment liquid containing a titanium chelate compound to obtain coated particles having the titanium chelate compound adhered to the particle surface of the lithium nickel manganese cobalt composite oxide particles. Then, the coated particles are heat-treated to obtain modified lithium nickel-manganese cobalt composite oxide particles.
- the titanium chelate compound has the following general formula (2): Ti (R 1 ) m L n (2)
- R 1 represents an alkoxy group, a hydroxyl group, a halogen atom, an amino group or phosphines, and when a plurality of them are present, they may be the same or different.
- L is derived from hydroxycarboxylic acid. When there are a plurality of groups, they may be the same or different.
- M indicates a number of 0 or more and 3 or less, n indicates a number of 1 or more and 3 or less, and m + n is 3 to 6. be.
- the present invention provides a method for producing modified lithium nickel-manganese-cobalt composite oxide particles.
- the present invention (2) provides the method for producing the modified lithium nickel manganese cobalt composite oxide particles of (1), which is characterized in that the temperature of the heat treatment is 400 to 1000 ° C. ..
- the present invention (3) is characterized in that L in the general formula (2) is a monovalent carboxylic acid, and the modified lithium nickel manganese cobalt composite oxide particles according to (1) or (2). It provides a manufacturing method of.
- the present invention (4) is a method for producing the modified lithium nickel manganese cobalt composite oxide particles according to (1) or (2), wherein L in the general formula (2) is lactic acid. It is to provide.
- the present invention (5) provides a method for producing the modified lithium nickel manganese cobalt composite oxide particles according to any one of (1) to (4), wherein the pH of the surface treatment liquid is 7 or more. It is something to do.
- the amount of the titanium chelate compound adhered to the coated particles is 0 . It is intended to provide the method for producing the modified lithium nickel manganese cobalt composite oxide particles according to any one of (1) to (5), which is 1 to 150 mg.
- the present invention (7) is characterized in that the amount of residual alkali in the lithium nickel-manganese-cobalt composite oxide particles represented by the general formula (1) is 1.2% by mass or less (1).
- the present invention (8) is characterized in that the amount of residual alkali in the modified lithium nickel manganese cobalt composite oxide particles is 1.2% by mass or less, whichever is (1) to (7). It provides a method for producing modified lithium nickel-manganese-cobalt composite oxide particles.
- the surface modification liquid was added to the surface modifier with an addition amount such that the Ti content per 1 m 2 of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) was 0.1 to 150 mg in terms of Ti atoms. Add to lithium nickel manganese cobalt composite oxide particles represented by the general formula (1), mix, and dry the whole amount.
- the present invention provides a method for producing the modified lithium nickel manganese cobalt composite oxide particles according to any one of (1) to (8).
- a method for producing a positive electrode active material for a lithium secondary battery which comprises a step of mixing small particles having an average particle diameter of 0.5 to 7.5 ⁇ m obtained by the production method according to any one of (1). Is to provide.
- lithium nickel-manganese-cobalt composite oxide particles capable of enhancing cycle characteristics when used as a positive electrode active material of a lithium secondary battery.
- the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) are converted into a titanium chelate represented by the general formula (2) or a general method.
- a surface treatment liquid containing an ammonium salt of a titanium chelate represented by the formula (2) to obtain coated particles to which these titanium chelate compounds are attached to the particle surface of lithium nickel-manganese cobalt-cobalt composite oxide particles, and then to obtain coated particles.
- It has a modification step of obtaining modified lithium nickel manganese cobalt composite oxide particles by heat-treating the obtained coated particles.
- the titanium chelate represented by the general formula (2) and the ammonium salt of the titanium chelate represented by the general formula (2) may be generically referred to as “titanium chelate compound”.
- the method for producing a modified lithium nickel manganese cobalt composite oxide of the present invention basically has the following steps (A) to (B).
- modified lithium nickel manganese cobalt composite oxide particles (A) and “modified lithium nickel manganese cobalt composite oxide particles (B)” are collectively referred to as “modified lithium nickel manganese cobalt composite oxide particles (B)". It may be described as "object particles”.
- the coated particles are heat-treated to obtain modified lithium nickel-manganese-cobalt composite oxide particles (A) and modified lithium nickel-manganese-cobalt composite oxide particles (B).
- the modified lithium nickel manganese cobalt composite oxide particles (A) are present in which an oxide containing Ti adheres to the particle surface of the lithium nickel manganese cobalt composite oxide particles.
- the presence of the Ti-containing oxide adhering to the particle surface of the lithium nickel-manganese cobalt composite oxide particles means that the particle surface of the modified lithium nickel-manganese cobalt composite oxide particles is 10,000 to 30,000 times larger.
- the particle surface of the modified lithium nickel-manganese-cobalt composite oxide particles is made of Ti by SEM-EDX at a magnification of 10,000 to 30,000 times.
- Ti is observed in a uniformly distributed state like Co, Ni, Mn and the like.
- the present inventors preferentially proceed with the solid-dissolving reaction of Ti in the modified lithium-nickel-manganese-cobalt composite oxide particles (B), and Ti is solid-dissolved and contained in the lithium-nickel-manganese-cobalt composite oxide particles. Therefore, it is presumed that Ti is uniformly distributed on the particle surface of the lithium nickel manganese cobalt composite oxide particles in the same manner as Co, Ni, Mn and the like.
- the lithium nickel-manganese cobalt composite oxide particles represented by the general formula (1) to be modified are brought into contact with a surface treatment liquid containing a titanium chelate compound according to the present invention, and lithium nickel-nickel manganese cobalt
- a surface treatment liquid containing a titanium chelate compound according to the present invention lithium nickel-nickel manganese cobalt
- the titanium chelate compound on the particle surface of the lithium nickel manganese cobalt composite oxide particles may or may be partially coated on the entire particle surface of the lithium nickel manganese cobalt composite oxide particles. There may be. Covering a part of the particle surface means a state in which the particle surface has a portion where the surface of the object to be coated is exposed in addition to the titanium chelate compound.
- the lithium nickel-manganese-cobalt composite oxide particles to be modified are described by the following general formula (1): Li x Ny Mn z Cot M p O 1 + x (1)
- M is selected from Mg, Al, Ti, Zr, Cu, Fe, Sr, Ca, V, Mo, Bi, Nb, Si, Zn, Ga, Ge, Sn, Ba, W, Na and K. 1 or more kinds of metal elements are shown.
- X is 0.98 ⁇ x ⁇ 1.20
- y 0.30 ⁇ y ⁇ 1.00
- z is 0 ⁇ z ⁇ 0.50
- t is 0. ⁇ t ⁇ 0.50
- p indicates 0 ⁇ p ⁇ 0.05
- y + z + t + p 1.00.
- X in the general formula (1) is 0.98 ⁇ x ⁇ 1.20. It is preferable that x is 1.00 ⁇ x ⁇ 1.10 in that the initial capacity becomes high.
- y in the general formula (1) is 0.30 ⁇ y ⁇ 1.00. y is preferably 0.50 ⁇ y ⁇ 0.95, and particularly preferably 0.60 ⁇ y ⁇ 0.90, in terms of achieving both initial capacitance and cycle characteristics.
- z in the general formula (1) is 0 ⁇ z ⁇ 0.50. z is preferably 0.025 ⁇ z ⁇ 0.45 in terms of excellent safety.
- t is 0 ⁇ t ⁇ 0.50. t is preferably 0.025 ⁇ t ⁇ 0.45 in terms of excellent safety.
- y + z + t + p 1.00.
- y / z is preferably (y / z)> 1, particularly preferably (y / z) ⁇ 1.5, and more preferably 3 ⁇ (y / z) ⁇ 38.
- M in the formula is contained in the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1), if necessary, for the purpose of improving the battery performance such as cycle characteristics and safety. It is a metal element, and M includes Mg, Al, Ti, Zr, Cu, Fe, Sr, Ca, V, Mo, Bi, Nb, Si, Zn, Ga, Ge, Sn, Ba, W, Na and K. One or more kinds of metal elements selected from the above can be mentioned.
- p is 0 ⁇ p ⁇ 0.05, preferably 0.0001 ⁇ p ⁇ 0.045.
- the lithium nickel manganese cobalt composite oxide particles to be modified are granules of the lithium nickel manganese cobalt composite oxide represented by the general formula (1).
- the lithium nickel-manganese-cobalt composite oxide particles represented by the general formula (1) may be single particles in which primary particles are monodispersed or aggregated particles in which primary particles are aggregated to form secondary particles. good.
- the average particle size of the lithium nickel-manganese-cobalt composite oxide particles represented by the general formula (1) is a particle size (D50) of 50% in terms of volume in the particle size distribution obtained by the laser diffraction / scattering method, and is preferably 1. It is 0 to 30.0 ⁇ m, particularly preferably 3.0 to 25.0 ⁇ m.
- the BET specific surface area of the lithium nickel-manganese-cobalt composite oxide particles represented by the general formula (1) is preferably 0.05 to 2.00 m 2 / g, and particularly preferably 0.15 to 1.00 m 2 / g. g.
- the average particle size or the BET specific surface area of the lithium nickel-manganese-cobalt composite oxide particles is within the above range, the positive electrode mixture can be easily prepared and coated, and an electrode having a high filling property can be obtained.
- the amount of residual alkali in the lithium nickel-manganese-cobalt composite oxide particles of the general formula (1) to be reformed is preferably 1.2% by mass or less, and particularly preferably 1.0% by mass or less.
- the amount of residual alkali in the lithium nickel-manganese-cobalt composite oxide particles is within the above range, it is possible to suppress the expansion and deterioration of the battery caused by the generation of gas due to the residual alkali.
- the residual alkali indicates an alkali component eluted in water when the lithium nickel manganese cobalt composite oxide particles are stirred and dispersed in water at 25 ° C. Then, the residual alkali amount is obtained by weighing 5 g of lithium nickel manganese cobalt composite oxide particles and 100 g of pure water in a beaker, dispersing at 25 ° C. with a magnetic stirrer for 5 minutes, and then filtering this dispersion. It is determined by neutralizing and titrating the amount of alkali present in the filtrate. The amount of residual alkali is a value obtained by measuring the amount of lithium by titration and converting it into lithium carbonate.
- the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) to be reformed are, for example, mixed with a lithium source, a nickel source, a manganese source, a cobalt source and an M source to be added as necessary. It is produced by performing a raw material mixing step of preparing a raw material mixture and then a baking step of firing the obtained raw material mixture.
- the lithium source nickel source, manganese source, cobalt source and M source related to the raw material mixing step, for example, these hydroxides, oxides, carbonates, nitrates, sulfates, organic acid salts and the like are used.
- the average particle size of the lithium source, nickel source, manganese source, cobalt source and M source is 1.0 to 30.0 ⁇ m, preferably 2.0 to 25.0 ⁇ m, as the average particle size obtained by the laser / scattering method. It is preferable to have.
- the nickel source, manganese source and cobalt source related to the raw material mixing step may be a compound containing a nickel atom, a manganese atom and a cobalt atom.
- Examples of the compound containing a nickel atom, a manganese atom and a cobalt atom include a composite oxide containing these atoms, a composite hydroxide, a composite oxyhydroxide, a composite carbonate and the like.
- a known method is used as a method for preparing a compound containing a nickel atom, a manganese atom and a cobalt atom.
- a composite hydroxide it can be prepared by the coprecipitation method.
- the composite hydroxide can be coprecipitated by mixing an aqueous solution containing a predetermined amount of nickel atom, cobalt atom and manganese atom, an aqueous solution of a complexing agent and an aqueous solution of an alkali (). See JP-A-10-81521, JP-A-10-81520, JP-A-10-29820, JP-A-2002-201028, etc.).
- a solution containing nickel ion, manganese ion and cobalt ion (solution A) and a solution containing carbonate ion or hydrogen carbonate ion (solution B) are added to the reaction vessel to carry out the reaction.
- the method to be carried out Japanese Unexamined Patent Publication No. 2009-179545
- a solution containing a nickel salt, a manganese salt and a cobalt salt (solution A) and a solution containing a metal carbonate or a metal hydrogen carbonate solution B.
- Japanese Patent Laid-Open No. 2009-179544 Japanese Patent Laid-Open No. 2009-179544
- the compound containing a nickel atom, a manganese atom and a cobalt atom may be a commercially available product.
- the average particle size of the compound containing nickel atom, cobalt atom and manganese atom is 1.0 to 100 ⁇ m, preferably 2.0 to 80.0 ⁇ m, which is the average particle size obtained by the laser / scattering method.
- a composite hydroxide containing a nickel atom, a cobalt atom and a manganese atom may be used as the nickel source, the manganese source and the cobalt source. , It is preferable in that the reactivity becomes good.
- the mixing ratio of the lithium source and the nickel source, manganese source, cobalt source and M source added as needed increases the discharge capacity, and Ni in the nickel source, manganese source and cobalt source.
- the molar ratio of Li atoms (Li / (Ni + Mn + Co + M)) to the total number of moles of atoms, Mn atoms, Co atoms and M atoms (Ni + Mn + Co + M) is 0.98 to 1.20, preferably 1.00 to 1.10. be.
- the mixing ratio of each raw material of the nickel source, the manganese source, the cobalt source and the M source to be added as needed is the nickel, manganese, cobalt and M represented by the general formula (1). It may be adjusted so as to have an atomic molar ratio of.
- the production history of the raw materials lithium source, nickel source, manganese source, cobalt source and M source is not limited, but the impurity content is as much as possible in order to produce high-purity lithium nickel-manganese-cobalt composite oxide particles. It is preferable that the amount is small.
- the means for mixing the lithium source, the nickel source, the manganese source, the cobalt source, and the M source to be added as needed may be either a dry method or a wet method, but the dry method is easy to manufacture. Mixing with is preferable.
- the mixing device include a high-speed mixer, a super mixer, a turbosphere mixer, an Erich mixer, a Henschel mixer, a Nauter mixer, a ribbon blender, a V-type mixer, a conical blender, a jet mill, a cosmomizer, a paint shaker, and a bead mill. , Ball mill and the like.
- a home mixer is sufficient.
- the mixing device In the case of wet mixing, it is preferable to use a media mill as the mixing device because it is possible to prepare a slurry in which each raw material is uniformly dispersed. Further, the slurry after the mixing treatment is preferably spray-dried from the viewpoint of obtaining a raw material mixture having excellent reactivity and uniformly dispersed raw materials.
- the firing step is a step of obtaining a lithium nickel-manganese-cobalt composite oxide by firing a raw material mixture obtained by performing a raw material mixing step.
- the firing temperature when the raw material mixture is fired and the raw materials are reacted is 600 to 1000 ° C, preferably 700 to 950 ° C.
- the reason for this is that if the firing temperature is less than 600 ° C, the reaction is insufficient and a large amount of unreacted lithium tends to remain, while if it exceeds 1000 ° C, the lithium nickel-manganese-cobalt composite oxide once formed will decompose. Because there is a tendency.
- the firing time in the firing step is 3 hours or more, preferably 5 to 30 hours.
- the firing atmosphere in the firing step is an oxidizing atmosphere of air and oxygen gas.
- firing may be performed in a multi-stage system.
- multi-stage firing modified lithium nickel-manganese-cobalt composite oxide particles having further excellent cycle characteristics can be obtained.
- firing in multiple stages firing in the range of 650 to 800 ° C. for 1 to 10 hours, then raising the temperature to 800 to 950 ° C. so as to be higher than the firing temperature, and firing as it is for 5 to 30 hours. Is preferable.
- the lithium nickel manganese cobalt composite oxide thus obtained may be subjected to a plurality of firing steps as needed.
- the lithium nickel-nickel-manganese composite oxide particles having the residual alkali amount in the above range are the nickel source and the manganese source in the raw material mixing step of the lithium source, the nickel source, the manganese source, the cobalt source and the M source added as needed.
- the molar ratio of Li atoms (Li / (Ni + Mn + Co + M)) to the total number of moles of Ni atoms, Mn atoms, Co atoms and M atoms in the cobalt source and M source is 0.98 to 1.20. After being subjected to a firing reaction at 700 ° C. or higher, preferably 750 to 1000 ° C.
- the lithium source, nickel source, manganese source, cobalt source and, if necessary, are sufficiently subjected to the firing reaction. It can be produced by reacting with the added M source.
- the firing is performed by the above-mentioned multi-stage method, so that lithium nickel-nickel-manganese composite oxide particles having a further reduced amount of residual alkali can be produced.
- the surface treatment liquid according to the step (A) is a titanium chelate compound, that is, a titanium chelate represented by the general formula (2) or an ammonium salt of the titanium chelate represented by the general formula (2) in water and / or organic. It is dissolved or dispersed in a solvent.
- the titanium chelate according to the step (A) has the following general formula (2): Ti (R 1 ) m L n (2)
- R 1 represents an alkoxy group, a hydroxyl group, a halogen atom, an amino group or phosphines, and when a plurality of them are present, they may be the same or different.
- L is derived from hydroxycarboxylic acid. When there are a plurality of groups, they may be the same or different.
- M indicates a number of 0 or more and 3 or less, n indicates a number of 1 or more and 3 or less, and m + n is 3 to 6. be.
- alkoxy group according to R 1 a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.
- the halogen atom related to R 1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the amino group according to R 1 include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a tert-butylamino group, a pentylamino group and the like.
- Examples of the phosphines related to R 1 include trimethylphosphine, triethylphosphine, tributylphosphine, tris-tert-butylphosphine, triphenylphosphine and the like.
- Examples of the group derived from the hydroxycarboxylic acid according to L include a group in which the oxygen atom of the hydroxyl group in the hydroxycarboxylic acid or the oxygen atom of the carboxyl group in the hydroxycarboxylic acid is coordinated with the titanium atom.
- Examples of the group derived from the hydroxycarboxylic acid according to L include a group in which the oxygen atom of the hydroxyl group in the hydroxycarboxylic acid and the oxygen atom of the carboxyl group in the hydroxylcarboxylic acid are coordinated with the titanium atom in two loci. Be done.
- the oxygen atom of the hydroxyl group in the hydroxycarboxylic acid and the oxygen atom of the carboxyl group in the hydroxycarboxylic acid are groups coordinated with the titanium atom in two loci.
- m + n is preferably 3, and when m is 1 or more and 3 or less, m + n is preferably 4 or 5.
- a diluted solution is obtained by diluting titanium alkoxide with a solvent, and the diluted solution is mixed with a hydroxycarboxylic acid to obtain a solution containing the titanium chelate (WO2019 / 138989). See the pamphlet).
- the solution containing the titanium chelate obtained by the above method for producing the titanium chelate can be used as it is as the surface treatment liquid in the step (A).
- water may be added to the solution containing the titanium chelate and used as a surface treatment liquid.
- a surface treatment liquid a dispersion liquid or a dissolution liquid of a water-containing solvent of titanium chelate can be obtained.
- titanium alkoxide examples include tetramethoxytitanium (IV), tetraethoxytitanium (IV), tetra-n-propoxytitanium (IV), tetraisopropoxytitanium (IV), and tetra-n-butoxytitanium (IV). ) And tetraisobutoxytitanium (IV) and the like.
- hydroxycarboxylic acid examples include monovalent carboxylic acids such as lactic acid, glucolic acid, glyceric acid and hydroxybutyric acid, divalent carboxylic acids such as tartronic acid, malic acid and tartrate acid, citric acid and isocitrate. Examples thereof include trivalent carboxylic acids of the above.
- lactic acid is preferable from the viewpoint that it easily becomes a solution at room temperature, is easily mixed with the titanium alkoxide diluted solution, and a titanium chelate can be easily produced.
- alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tert-butanol and n-pentane can be preferably used.
- a ligand compound may be added.
- a ligand compound include a halogen atom-containing compound, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a t-butylamino group, a pentylamino and the like.
- Examples thereof include amines having the above functional groups, trimethylphosphine, triethylphosphine, tributylphosphine, tris-tert-butylphosphine, triphenylphosphine and the like.
- titanium lactate ammonium salt Ti (OH) 2 [(OCH (CH 3 ) COO ⁇ )] 2 (NH 4 + ) 2 ) is preferable.
- titanium chelate and its ammonium salt are partially commercially available from Matsumoto Fine Chemical Co., Ltd., and commercially available products may be used.
- the Ti concentration in the surface treatment liquid according to the step (A) is 0.1 to 1500 mmol / L, preferably 0.2 to 1000 mmol / L as Ti atoms, which is the stability and coating of the Ti solution. It is preferable from the viewpoint of facilitating the operability of the process.
- the pH of the surface treatment liquid according to the step (A) is 7 or more, preferably 8 or more and 11 or less, particularly preferably more than 8 and 10 or less. It is preferable in that the elution of Li from the lithium nickel-manganese cobalt composite oxide particles is suppressed when they come into contact with each other.
- the pH of the surface treatment liquid can be adjusted by adding an acid or an alkali to the surface treatment liquid so that the pH is within the above range.
- the method of contacting the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) with the surface treatment liquid containing the titanium chelate compound is not particularly limited, but for example.
- a method of mixing and treating a surface treatment liquid containing a titanium nickel chelate compound and lithium nickel nickel manganese cobalt composite oxide particles represented by the general formula (1) can be mentioned.
- the mixture of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) and the surface treatment liquid containing the titanium chelate compound may be in the form of powder, paste or slurry. There may be.
- the amount of the surface treatment liquid containing the titanium chelate compound to the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) is prepared.
- Any form can be obtained.
- a powdery mixture of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) and the surface treatment liquid containing the titanium chelate compound is represented by the general formula (1). It is obtained by adding a surface treatment liquid containing a titanium chelate compound having a small volume of the liquid to the cobalt composite oxide particles, and also with the lithium nickel-manganese manganese cobalt composite oxide particles represented by the general formula (1).
- the contact between the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) and the solution containing the titanium chelate compound is the lithium nickel nickel manganese cobalt composite oxide particles represented by the general formula (1).
- the method of immersing in a solution containing a titanium chelate compound may be used.
- the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) and the surface treatment liquid containing a titanium chelate compound are used.
- a titanium chelate compound can be easily adhered to the entire surface of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1), and the mixture is in the form of a slurry. preferable.
- the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) are brought into contact with a surface treatment liquid containing a titanium chelate compound, and then the entire amount of the solvent is dried as it is, whereby the lithium nickel manganese cobalt composite oxide particles are represented by the general formula (1). It is preferable to obtain coated particles in which the particle surface of the lithium nickel manganese cobalt composite oxide particles is coated with a titanium chelate compound.
- the drying temperature at the time of drying is not particularly limited as long as it is a temperature at which the solvent evaporates, but is preferably 60 to 180 ° C, particularly preferably 90 to 150 ° C.
- the entire amount may be dried by a spray drying device, a rotary evaporator, a fluidized bed drying coating device, a vibration drying device, or the like.
- the entire amount of the solvent of the slurry containing the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) and the surface treatment liquid containing the titanium chelate compound is dried by a spray drying device. Is preferable in that it becomes easy to control the coating amount of the titanium chelate compound.
- the coated particles obtained in the step (A) are heat-treated to obtain a modified lithium nickel-manganese-cobalt composite oxide (A) or a modified lithium nickel-manganese-cobalt composite oxide (B). It is a process.
- the Ti atom is mainly in the state of an oxide containing Ti without being solid-dissolved in the lithium nickel manganese cobalt composite oxide particles, and the lithium nickel manganese cobalt. It exists on the surface of the composite oxide particles.
- a small amount of some Ti atoms may be solidly dissolved inside the lithium nickel manganese cobalt cobalt composite oxide particles.
- the Ti atom mainly exists in a solid-dissolved state inside the particles of the lithium nickel manganese cobalt cobalt composite oxide particles.
- the particle surface of the modified lithium nickel-manganese cobalt composite oxide particles was analyzed by elemental mapping analysis of Ti with SEM-EDX, Ti became Co. , Ni, Mn, etc., as long as it is observed in a uniformly distributed state, even if Ti atoms are present on the surface of the lithium nickel manganese cobalt composite oxide particles in the state of an oxide containing Ti. good.
- modified lithium nickel manganese cobalt composite oxide particles (A) or the modified lithium nickel manganese cobalt cobalt composite oxide particles (B) is an element of Ti on the particle surface of the sample particles by SEM-EDX. Confirmed by analysis by mapping analysis. That is, in the case of modified lithium nickel-manganese cobalt composite oxide particles (A), the particle surface of the sample particles is analyzed by elemental mapping analysis of Ti by SEM-EDX at a magnification of 10,000 to 30,000 times. At this time, it is observed that Ti is unevenly distributed and present on the surface of the sample particles such as uneven distribution.
- modified lithium nickel-manganese cobalt composite oxide particles B
- the particle surface of the sample particles is analyzed by elemental mapping analysis of Ti by SEM-EDX at a magnification of 10,000 to 30,000 times. When this is done, it is observed that Ti is uniformly distributed and present on the surface of the sample particles.
- the oxide containing Ti that coats the particle surface of the lithium nickel-manganese cobalt composite oxide particles is one selected from Ti oxide, Ti, and Li, Ni, Mn, Co, and M. Alternatively, it indicates a composite oxide or the like containing two or more kinds.
- the heat treatment temperature is 400 to 1000 ° C, preferably 450 to 950 ° C.
- the reason for this is that if the heat treatment temperature is less than 400 ° C, the titanium chelate for coating treatment is not sufficiently decomposed and oxidized to obtain a sufficient effect, while if the heat treatment temperature exceeds 1000 ° C, Ti and lithium are not obtained. Since the solid dissolution reaction with the nickel-manganese-cobalt composite oxide particles progresses too much and the solid dissolution of Ti progresses not only near the particle surface but also to the back, the amount of Ti near the particle surface is insufficient and the modification effect of the present invention is achieved. This is because it becomes difficult to obtain.
- the heat treatment time is not critical in the present production method, and is usually 1 hour or more, preferably 2 to 10 hours, and the modified lithium nickel manganese cobalt with satisfactory performance.
- Composite oxide particles can be obtained.
- the atmosphere of the heat treatment is preferably an oxidizing atmosphere of air, oxygen gas, or the like.
- the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) are subjected to a surface containing a titanium chelate compound. Since the entire amount of the solvent is dried as it is after contacting with the treatment liquid, the coating amount of the oxide containing Ti on the lithium nickel-nickel-manganese-cobalt composite oxide particles (A) (A). (Adhesion amount) and the solid solubility amount (content) of Ti in the lithium nickel manganese cobalt composite oxide particles in the modified lithium nickel manganese cobalt composite oxide particles (B) are the amount of the lithium nickel manganese cobalt composite oxide particles. It can be expressed as the theoretical coating amount (adhesion amount) and solid solubility amount (content) obtained from the Ti content in the surface treatment liquid containing the titanium chelate compound used.
- Ti per 1 m 2 of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) is set so as to be within the range of the adhesion amount of the oxide containing Ti described later.
- the surface modifier is added in an amount of 0.1 to 150 mg, preferably 0.5 to 120 mg in terms of Ti atom, and the lithium nickel manganese cobalt composite oxide represented by the general formula (1) is used. It is preferable to add the particles to the particles, mix them, and dry the whole amount, because it is easy to control the coating amount and the solid dissolution amount of the titanium chelate compound.
- the amount of the oxide adhering to Ti and the amount of solid solution of Ti (content) in the obtained modified lithium nickel-manganese cobalt composite oxide particles Is 0.1 to 150 mg, preferably 0.5 to 120 mg, in terms of Ti atoms, per 1 m 2 of lithium nickel manganese cobalt composite oxide particles.
- the modified lithium nickel-manganese cobalt composite oxide particles (constant lithium nickel manganese cobalt composite oxide particles) when the adhesion amount of the oxide containing Ti and the solid dissolution amount (content) of Ti in the modified lithium nickel manganese cobalt composite oxide particles are within the above ranges.
- the cycle characteristics are further improved, which is preferable. That is, in the method for producing the modified lithium nickel manganese cobalt composite oxide of the present invention, 0.1 to 150 mg, preferably 0.5, in terms of Ti atoms per 1 m 2 of the obtained modified lithium nickel manganese cobalt cobalt composite oxide particles.
- the residual alkali content in the modified lithium nickel manganese cobalt composite oxide particles obtained by the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention is 1.2% by mass or less, preferably 1. It is preferable that the content is 0% by mass or less because expansion and deterioration of the battery caused by gas generation due to residual alkali can be suppressed.
- the modified lithium nickel manganese cobalt composite oxide particles obtained by the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention are suitably used as a positive electrode active material for a lithium secondary battery, and the modified lithium nickel manganese manganese cobalt composite oxide particles are suitably used.
- Quality A lithium secondary battery using lithium nickel manganese cobalt composite oxide particles as a positive electrode active material is a case where lithium nickel manganese cobalt composite oxide particles having the same composition of unmodified Li, Ni, Mn and Co are used. Compared with, the cycle characteristics are higher.
- the large particles of the modified lithium nickel manganese cobalt composite oxide obtained by the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention and the modified lithium nickel manganese cobalt composite oxide particles of the present invention The capacity per volume can be improved by mixing with small particles of the modified lithium nickel manganese cobalt composite oxide obtained by the production method.
- the average particle size of the large particles is 7.5 to 30.0 ⁇ m, preferably 8.0 to 25.0 ⁇ m
- the average particle size of the small particles is 0.5 to 7.5 ⁇ m, preferably 1.0. It is preferably about 7.0 ⁇ m from the viewpoint of improving the capacity per volume.
- the pressurization density when the mixture is compressed at 0.65 tonf / cm 2 is 2.7 g / cm 3 or more, preferably 2.8 to 3.3 g / cm 3 , the capacity per volume. Is preferable in that the value becomes higher.
- the modified lithium nickel manganese cobalt composite oxide particles (A) are preferable as the large particles of the modified lithium nickel manganese cobalt composite oxide, and the modified lithium nickel manganese cobalt composite oxide particles (A) are preferred.
- the small particles of the lithium nickel-manganese-cobalt composite oxide are preferably modified lithium nickel-manganese-cobalt composite oxide particles (B) in that the cycle characteristics are further improved.
- the oxide containing the chelate compound and its thermal decomposition product Ti is easily highly dispersed without being uniformly bulky on the particle surface of the lithium nickel manganese cobalt composite oxide particles, and the titanium chelate compound adhered to the chelate compound by thermal decomposition.
- the reactivity of the titanium-containing oxide as a product with the lithium nickel manganese cobalt composite oxide particles is increased on the surface of the lithium nickel manganese cobalt composite oxide particles.
- the titanium chelate compound and the oxide containing Ti, which is a thermal decomposition product thereof, are more likely to be uniformly and more highly dispersed on the particle surface of the lithium nickel-nickel manganese cobalt composite oxide particles, and the titanium chelate compound adhered to the titanium chelate compound is thermally decomposed.
- the heat treatment temperature in the step (B) is the same. Even so, the smaller the average particle size of the lithium nickel-manganese cobalt composite oxide particles to which the titanium chelate compound is attached in the step (A), the easier it is for the modified lithium nickel-manganese cobalt composite oxide particles (B) to be produced. Become.
- the heat treatment temperature in the step (B) when the heat treatment temperature in the step (B) is higher, the reactivity between the oxide containing Ti, which is a thermal decomposition product of the adhered titanium chelate compound, and the lithium nickel manganese cobalt composite oxide particles is lithium nickel manganese. Since it is higher on the surface of the cobalt composite oxide particles, the higher the heat treatment temperature in the step (B), the easier it is for the modified lithium nickel-manganese cobalt composite oxide particles (B) to be produced.
- the attached titanium chelate compound and the oxide containing Ti, which is a thermal decomposition product thereof, are non-uniformly bulky and easily dispersed on the particle surface of the lithium nickel manganese cobalt composite oxide particles, and the attached titanium chelate compound is bulky.
- the oxide containing Ti which is a thermal decomposition product, has a low reactivity with the lithium nickel-nickel-manganese-cobalt composite oxide particles on the surface of the lithium-nickel-manganese-cobalt composite oxide particles.
- the modified lithium nickel manganese cobalt composite oxide particles (A) are produced when the average particle size of the lithium nickel manganese cobalt composite oxide particles to which the titanium chelate compound is attached in the step (A) is larger. It becomes easier to do. Further, as the heat treatment temperature in the step (B) is lower, the reactivity between the adhered titanium chelate compound and the lithium nickel manganese cobalt composite oxide particles becomes lower on the surface of the lithium nickel manganese cobalt composite oxide particles.
- the lower the heat treatment temperature in the step the easier it is for the modified lithium nickel manganese cobalt composite oxide particles (A) to be produced. Therefore, in the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention, the average particle size of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) used in the step (A) and (B). )
- the modified lithium nickel manganese cobalt cobalt composite oxide particles (A) and the modified lithium nickel manganese cobalt cobalt composite oxide particles (B) can be produced separately by appropriately selecting the combination of the heat treatment temperatures in the step). ..
- the modified lithium nickel-manganese cobalt-cobalt composite oxide particles (A) have an average particle diameter as the lithium nickel-manganese-cobalt composite oxide particles of the general formula (1) in the step (A).
- the above (B) has a heat treatment temperature of 750 ° C. or higher and 1000 ° C. or lower, preferably 750 ° C. or higher and 900 ° C. or lower, using particles having a thickness of 7.5 to 30.0 ⁇ m, preferably 8.0 to 25.0 ⁇ m. It can be manufactured by performing the steps A) and (B).
- the modified lithium nickel manganese cobalt composite oxide particles (B) have an average particle diameter of 0.5 to 7.5 ⁇ m as the lithium nickel manganese cobalt composite oxide particles of the general formula (1) in the step (A).
- Steps (A) and (B) above preferably using particles having a size of 1.0 to 7.0 ⁇ m and setting the heat treatment temperature in step (B) to 750 ° C. or higher and 1000 ° C. or lower, preferably 750 ° C. or higher and 900 ° C. or lower. It can be manufactured by performing.
- the resulting raw material mixture was then calcined in an alumina pot at 700 ° C. for 2 hours, followed by 850 ° C. for 10 hours in an air atmosphere. After the firing was completed, the fired product was crushed and classified. As a result of measuring the obtained fired product by XRD, it was confirmed that it was a single-phase lithium nickel-manganese-cobalt composite oxide.
- the obtained particles had an average particle diameter of 10.2 ⁇ m, a BET specific surface area of 0.21 m 2 / g, and secondarily aggregated spherical lithium nickel-manganese-cobalt composite oxide particles (LiNi 0.6 Mn 0 ). It was .2 Co 0.2 O 2 ).
- the obtained particles had an average particle diameter of 5.4 ⁇ m, a BET specific surface area of 0.69 m 2 / g, and secondarily aggregated spherical lithium nickel-manganese-cobalt composite oxide particles (LiNi 0.6 Mn 0 ). It was .2 Co 0.2 O 2 ).
- Table 1 shows various physical properties of the lithium nickel manganese cobalt composite oxide sample (LNMC sample) obtained above.
- the average particle size, residual alkali amount and pressure density of the LNMC sample were measured as follows. ⁇ Average particle size> The average particle size was determined by the laser diffraction / scattering method. ⁇ Measurement of residual alkali amount> Regarding the residual alkalinity of the LNMC sample, 5 g of the sample and 100 g of ultrapure water were weighed in a beaker and dispersed at 25 ° C. for 5 minutes using a magnetic stirrer.
- this dispersion is filtered, and 70 ml of the filtrate is titrated with 0.1N-HCl by an automatic titrator (model COMITE-2500), and the amount of residual alkali (lithium amount) present in the sample is measured. (Value converted to lithium carbonate) was calculated.
- Examples 1 to 6 Using the LNMC sample and the surface treatment liquid, the slurry was weighed so as to have the ratio shown in Table 3, and the slurry was prepared so that the solid content concentration was 25% by mass. Next, the slurry was supplied to a spray dryer whose outlet temperature was set to 120 ° C. at a slurry supply rate of 65 g / min to obtain coated particles in which titanium lactate chelate adhered to the particle surface of the LNMC sample. Next, the coated particles were heat-treated at 800 ° C. for 5 hours, and the modified LNMC sample (A) in which the oxide of Ti was attached to the particle surface of the LNMC sample and the modified LNMC sample in which Ti was dissolved and contained.
- the modified LNMC sample (A) in which the oxide of Ti was attached to the particle surface of the LNMC sample and the modified LNMC sample in which Ti was dissolved and contained.
- LNMC sample (B) An LNMC sample (B) was obtained. Whether the modified LNMC sample to which the Ti oxide is attached or the modified LNMC sample in which Ti is solid-dissolved and contained in the LNMC sample is determined by SEM on the particle surface of the sample particles at a magnification of 20,000 times. -It was confirmed by performing elemental mapping analysis of Ti with EDX (electron emission scanning electron microscope SU-8220 manufactured by Hitachi High-Technologies Co., Ltd. and energy dispersive X-ray analyzer XFlash5060 FlatQUAD manufactured by BRUKER Co., Ltd.). When LNMC sample 1 was used as the LNMC sample, the surface of the sample particles was analyzed by elemental mapping of Ti using SEM-EDX.
- the residual alkali amount is determined by the same method as for the LNMC sample. It was measured.
- the amount of the surface treatment liquid added in Table 3 is a calculated value that gives the Ti content in terms of Ti atoms per 1 m 2 of the LNMC sample when the surface treatment liquid is added, and was calculated by the following formula.
- k xx (1 / t) k: Ti content (mg) in terms of Ti atoms per 1 m 2 of LNMC sample x: Ti content in terms of Ti atom per 1 g of LNMC sample (mg) t: BET specific surface area of LNMC sample (m 2 / g)
- the battery performance test was conducted as follows. ⁇ Making a lithium secondary battery 1> 95% by mass of the modified LNMC sample, 2.5% by mass of graphite powder, and 2.5% by mass of polyvinylidene fluoride obtained in the examples were mixed to prepare a positive electrode agent, which was dispersed in N-methyl-2-pyrrolidinone. To prepare a kneaded paste. The kneaded paste was applied to an aluminum foil, dried and pressed, and punched into a disk having a diameter of 15 mm to obtain a positive electrode plate.
- a coin-type lithium secondary battery was manufactured using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution.
- a metallic lithium foil was used for the negative electrode, and 1 liter of a 1: 1 mixed solution of ethylene carbonate and methyl ethyl carbonate was used as the electrolytic solution in which 61 mol of LiPF was dissolved.
- the performance of the obtained lithium secondary battery was evaluated. The results are shown in Table 4.
- the modified LCO sample prepared in Reference Example 1 the unmodified LNMC sample 1 (Comparative Example 1), and the LNMC sample 2 (Comparative Example 2)
- lithium secondary batteries were prepared in the same manner. Evaluation was made. The results are also shown in Table 4.
- ⁇ Battery performance evaluation 1> The produced coin-type lithium secondary battery was operated at room temperature under the following test conditions, and the following battery performance was evaluated.
- CCCV charging constant current / constant voltage charging
- CC discharge constant current discharge
- a positive electrode active material sample of 95% by mass, graphite powder of 2.5% by mass, and polyvinylidene fluoride 2.5% by mass were mixed to prepare a positive electrode agent, which was dispersed in N-methyl-2-pyrrolidinone to prepare a kneaded paste. ..
- the kneaded paste was applied to an aluminum foil, dried and pressed, and punched into a disk having a diameter of 15 mm to obtain a positive electrode plate.
- a coin-type lithium secondary battery was manufactured using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution.
- a metallic lithium foil was used for the negative electrode, and 1 liter of a 1: 1 mixed solution of ethylene carbonate and methyl ethyl carbonate was used as the electrolytic solution in which 61 mol of LiPF was dissolved.
- the performance of the obtained lithium secondary battery was evaluated. The results are also shown in Table 6.
- ⁇ Battery performance evaluation 2> The manufactured coin-type lithium secondary battery was operated at room temperature under the following test conditions, and cycle characteristics were evaluated, initial charge capacity, initial discharge capacity (per active material weight), initial charge capacity, initial discharge capacity (per active material weight), The capacity retention rate and the energy density retention rate were evaluated by the same method as in the performance evaluation 1 of the battery. Further, the discharge capacity per volume was also evaluated, and the results are shown in Table 6. The modified LNMC samples of Examples 2 and 5 were used as positive electrode active material samples, and evaluation was performed by the same method. The results are also shown in Table 6. (6) Discharge capacity per volume The discharge capacity per volume was calculated from the following formula based on the initial discharge capacity and the electrode density.
- Discharge capacity per volume (mAh / cm 3 ) Discharge capacity (mAh / g) in the first cycle x
- the positive electrode material is a mixture of 95% by mass of the positive electrode active material sample, 2.5% by mass of graphite powder, and 2.5% by mass of polyvinylidene fluoride, and the press pressure at the time of electrode production is 0.38 ton / cm in linear pressure. And said.
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Abstract
Description
LixNiyMnzCotMpO1+x (1)
(式中、Mは、Mg、Al、Ti、Zr、Cu、Fe、Sr、Ca、V、Mo、Bi、Nb、Si、Zn、Ga、Ge、Sn、Ba、W、Na及びKから選ばれる1種又は2種以上の金属元素を示す。xは0.98≦x≦1.20、yは0.30≦y<1.00、zは0<z≦0.50、tは0<t≦0.50、pは0≦p≦0.05を示し、y+z+t+p=1.00である。)
で表されるリチウムニッケルマンガンコバルト複合酸化物粒子を、チタンキレート化合物を含む表面処理液に接触させて、該リチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面にチタンキレート化合物が付着した被覆粒子を得、次いで、該被覆粒子を加熱処理することにより、改質リチウムニッケルマンガンコバルト複合酸化物粒子を得る改質工程を有し、
前記チタンキレート化合物が、下記一般式(2):
Ti(R1)mLn (2)
(式中、R1は、アルコキシ基、水酸基、ハロゲン原子、アミノ基又はホスフィン類を示し、複数存在する場合、同一であってもよく、異なっていてもよい。Lはヒドロキシカルボン酸に由来する基を表し、複数存在する場合、同一であってもよく、異なっていてもよい。mは0以上3以下の数を示し、nは1以上3以下の数を示し、m+nは3~6である。)
で表されるチタンキレート又はそのアンモニウム塩であること、
を特徴とする改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法を提供するものである。 That is, the present invention (1) has the following general formula (1):
Li x Ny Mn z Cot M p O 1 + x (1)
(In the formula, M is selected from Mg, Al, Ti, Zr, Cu, Fe, Sr, Ca, V, Mo, Bi, Nb, Si, Zn, Ga, Ge, Sn, Ba, W, Na and K. 1 or more kinds of metal elements are shown. X is 0.98 ≦ x ≦ 1.20, y is 0.30 ≦ y <1.00, z is 0 <z ≦ 0.50, and t is 0. <t≤0.50, p indicates 0≤p≤0.05, and y + z + t + p = 1.00.)
The lithium nickel manganese cobalt composite oxide particles represented by (1) are brought into contact with a surface treatment liquid containing a titanium chelate compound to obtain coated particles having the titanium chelate compound adhered to the particle surface of the lithium nickel manganese cobalt composite oxide particles. Then, the coated particles are heat-treated to obtain modified lithium nickel-manganese cobalt composite oxide particles.
The titanium chelate compound has the following general formula (2):
Ti (R 1 ) m L n (2)
(In the formula, R 1 represents an alkoxy group, a hydroxyl group, a halogen atom, an amino group or phosphines, and when a plurality of them are present, they may be the same or different. L is derived from hydroxycarboxylic acid. When there are a plurality of groups, they may be the same or different. M indicates a number of 0 or more and 3 or less, n indicates a number of 1 or more and 3 or less, and m + n is 3 to 6. be.)
Being a titanium chelate represented by or an ammonium salt thereof,
The present invention provides a method for producing modified lithium nickel-manganese-cobalt composite oxide particles.
前記一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子1m2当たりのTi含有量が、Ti原子換算で0.1~150mgとなる添加量で、前記表面改質液を、前記一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子に添加して混合し、全量乾燥させること、
を特徴とする(1)~(8)いずれかの改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法を提供するものである。 Further, according to the present invention (9), in the reforming step,
The surface modification liquid was added to the surface modifier with an addition amount such that the Ti content per 1 m 2 of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) was 0.1 to 150 mg in terms of Ti atoms. Add to lithium nickel manganese cobalt composite oxide particles represented by the general formula (1), mix, and dry the whole amount.
The present invention provides a method for producing the modified lithium nickel manganese cobalt composite oxide particles according to any one of (1) to (8).
本発明の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法は、一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子を、一般式(2)で表されるチタンキレート又は一般式(2)で表されるチタンキレートのアンモニウム塩を含む表面処理液に接触させて、リチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面に、これらのチタンキレート化合物が付着した被覆粒子を得、次いで、得られた被覆粒子を加熱処理することにより、改質リチウムニッケルマンガンコバルト複合酸化物粒子を得る改質工程を有する。以下、一般式(2)で表されるチタンキレート及び一般式(2)で表されるチタンキレートのアンモニウム塩を総称して、「チタンキレート化合物」ということがある。 Hereinafter, the present invention will be described based on a preferred embodiment.
In the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention, the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) are converted into a titanium chelate represented by the general formula (2) or a general method. Contact with a surface treatment liquid containing an ammonium salt of a titanium chelate represented by the formula (2) to obtain coated particles to which these titanium chelate compounds are attached to the particle surface of lithium nickel-manganese cobalt-cobalt composite oxide particles, and then to obtain coated particles. It has a modification step of obtaining modified lithium nickel manganese cobalt composite oxide particles by heat-treating the obtained coated particles. Hereinafter, the titanium chelate represented by the general formula (2) and the ammonium salt of the titanium chelate represented by the general formula (2) may be generically referred to as “titanium chelate compound”.
(A)工程:一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子、すなわち、改質対象のリチウムニッケルマンガンコバルト複合酸化物を、本発明に係るチタンキレート化合物を含む表面処理液に接触させ、リチウムニッケルマンガンコバルト複合酸化物粒子の表面にチタンキレート化合物が付着した被覆粒子を得る工程。
(B)工程:(A)工程を行い得られた被覆粒子を加熱処理して、後述する改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)、又は改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)を得る工程。
なお、以下では、「改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)」及び「改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)」を総称して、「改質リチウムニッケルマンガンコバルト複合酸化物粒子」と記載することがある。 The method for producing a modified lithium nickel manganese cobalt composite oxide of the present invention basically has the following steps (A) to (B).
(A) Step: A surface treatment liquid containing a titanium chelate compound according to the present invention, which is a lithium nickel manganese cobalt composite oxide particle represented by the general formula (1), that is, a lithium nickel manganese cobalt composite oxide to be modified. A step of obtaining coated particles in which a titanium chelate compound is adhered to the surface of lithium nickel-nickel-manganese-cobalt composite oxide particles.
Step (B): The coated particles obtained by performing the step (A) are heat-treated to obtain the modified lithium nickel-manganese-cobalt composite oxide particles (A) described later, or the modified lithium nickel-manganese-cobalt composite oxide particles ( B) The process of obtaining.
In the following, "modified lithium nickel manganese cobalt composite oxide particles (A)" and "modified lithium nickel manganese cobalt composite oxide particles (B)" are collectively referred to as "modified lithium nickel manganese cobalt composite oxide particles (B)". It may be described as "object particles".
改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)は、Tiを含む酸化物がリチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面に付着して存在するものである。該Tiを含む酸化物がリチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面に付着して存在することは、改質リチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面を、10,000~30,000倍の拡大倍率でSEM-EDXによるTiの元素マッピング分析で分析したときに、リチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面にTiが偏在等の不均一に分布した状態で観察されることにより確認される。
一方、改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)では、改質リチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面を、10,000~30,000倍の拡大倍率でSEM-EDXによるTiの元素マッピング分析で分析したときに、TiがCo、Ni、Mn等と同様に均一に分布した状態で観察される。本発明者らは、改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)はTiの固溶反応が優先的に進行して、リチウムニッケルマンガンコバルト複合酸化物粒子にTiが固溶して含有されるため、Tiがリチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面でCo、Ni、Mn等と同様に均一に分布するものと推測している。 In the step (B), the coated particles are heat-treated to obtain modified lithium nickel-manganese-cobalt composite oxide particles (A) and modified lithium nickel-manganese-cobalt composite oxide particles (B).
The modified lithium nickel manganese cobalt composite oxide particles (A) are present in which an oxide containing Ti adheres to the particle surface of the lithium nickel manganese cobalt composite oxide particles. The presence of the Ti-containing oxide adhering to the particle surface of the lithium nickel-manganese cobalt composite oxide particles means that the particle surface of the modified lithium nickel-manganese cobalt composite oxide particles is 10,000 to 30,000 times larger. When analyzed by elemental mapping analysis of Ti with SEM-EDX at the magnification of, it was confirmed by observing Ti in a non-uniformly distributed state such as uneven distribution on the particle surface of lithium nickel manganese cobalt composite oxide particles. To.
On the other hand, in the modified lithium nickel-manganese-cobalt composite oxide particles (B), the particle surface of the modified lithium nickel-manganese-cobalt composite oxide particles is made of Ti by SEM-EDX at a magnification of 10,000 to 30,000 times. When analyzed by element mapping analysis, Ti is observed in a uniformly distributed state like Co, Ni, Mn and the like. The present inventors preferentially proceed with the solid-dissolving reaction of Ti in the modified lithium-nickel-manganese-cobalt composite oxide particles (B), and Ti is solid-dissolved and contained in the lithium-nickel-manganese-cobalt composite oxide particles. Therefore, it is presumed that Ti is uniformly distributed on the particle surface of the lithium nickel manganese cobalt composite oxide particles in the same manner as Co, Ni, Mn and the like.
LixNiyMnzCotMpO1+x (1)
(式中、Mは、Mg、Al、Ti、Zr、Cu、Fe、Sr、Ca、V、Mo、Bi、Nb、Si、Zn、Ga、Ge、Sn、Ba、W、Na及びKから選ばれる1種又は2種以上の金属元素を示す。xは0.98≦x≦1.20、yは0.30≦y<1.00、zは0<z≦0.50、tは0<t≦0.50、pは0≦p≦0.05を示し、y+z+t+p=1.00である。)
で表されるリチウムニッケルマンガンコバルト複合酸化物粒子である。 In the step (A), the lithium nickel-manganese-cobalt composite oxide particles to be modified are described by the following general formula (1):
Li x Ny Mn z Cot M p O 1 + x (1)
(In the formula, M is selected from Mg, Al, Ti, Zr, Cu, Fe, Sr, Ca, V, Mo, Bi, Nb, Si, Zn, Ga, Ge, Sn, Ba, W, Na and K. 1 or more kinds of metal elements are shown. X is 0.98 ≦ x ≦ 1.20, y is 0.30 ≦ y <1.00, z is 0 <z ≦ 0.50, and t is 0. <t≤0.50, p indicates 0≤p≤0.05, and y + z + t + p = 1.00.)
It is a lithium nickel manganese cobalt composite oxide particle represented by.
Ti(R1)mLn (2)
(式中、R1は、アルコキシ基、水酸基、ハロゲン原子、アミノ基又はホスフィン類を示し、複数存在する場合、同一であってもよく、異なっていてもよい。Lはヒドロキシカルボン酸に由来する基を表し、複数存在する場合、同一であってもよく、異なっていてもよい。mは0以上3以下の数を示し、nは1以上3以下の数を示し、m+nは3~6である。)
で表されるチタンキレートである。 The titanium chelate according to the step (A) has the following general formula (2):
Ti (R 1 ) m L n (2)
(In the formula, R 1 represents an alkoxy group, a hydroxyl group, a halogen atom, an amino group or phosphines, and when a plurality of them are present, they may be the same or different. L is derived from hydroxycarboxylic acid. When there are a plurality of groups, they may be the same or different. M indicates a number of 0 or more and 3 or less, n indicates a number of 1 or more and 3 or less, and m + n is 3 to 6. be.)
It is a titanium chelate represented by.
k=x×(1/t)
k:リチウムニッケルマンガンコバルト複合酸化物粒子1m2当たりのTi原子換算のTi含有量(mg)
x:リチウムニッケルマンガンコバルト複合酸化物1gに対するTi原子換算のTi含有量(mg)
t:リチウムニッケルマンガンコバルト複合酸化物粒子のBET比表面積(m2/g) In the present invention, the "Ti content in terms of Ti atoms per 1 m 2 of lithium nickel manganese cobalt composite oxide particles" is calculated by the following formula.
k = xx (1 / t)
k: Ti content (mg) in terms of Ti atoms per 1 m 2 of lithium nickel manganese cobalt composite oxide particles
x: Ti content (mg) in terms of Ti atom per 1 g of lithium nickel manganese cobalt composite oxide
t: BET specific surface area (m 2 / g) of lithium nickel manganese cobalt composite oxide particles
k’=x×(1/t)
k’:Tiを含む酸化物のリチウムニッケルマンガンコバルト複合酸化物粒子1m2当たりのTi原子換算の付着量(mg)
x:リチウムニッケルマンガンコバルト複合酸化物1gに対するTi原子換算のTi含有量(mg)
t:リチウムニッケルマンガンコバルト複合酸化物粒子のBET比表面積(m2/g) In the present invention, "the amount of adhesion of an oxide containing Ti in terms of Ti atoms per 1 m 2 of lithium nickel manganese cobalt composite oxide particles" is calculated by the following formula.
k'= xx (1 / t)
k': Ti atom-equivalent adhesion amount per 1 m 2 of lithium nickel-manganesium-cobalt composite oxide particles of an oxide containing Ti (mg)
x: Ti content (mg) in terms of Ti atom per 1 g of lithium nickel manganese cobalt composite oxide
t: BET specific surface area (m 2 / g) of lithium nickel manganese cobalt composite oxide particles
言い換えると、本発明の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法においては、(A)工程でチタンキレート化合物を付着させるリチウムニッケルマンガンコバルト複合酸化物粒子の平均粒子径が大きい方が、付着したチタンキレート化合物やその加熱分解生成物であるTiを含む酸化物がリチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面に不均一に嵩張って分散し易く、嵩張って付着したチタンキレート化合物の加熱分解生成物であるTiを含む酸化物は、リチウムニッケルマンガンコバルト複合酸化物粒子との反応性がリチウムニッケルマンガンコバルト複合酸化物粒子表面上で低くなるので、(B)工程での加熱処理温度が同じであっても、(A)工程でチタンキレート化合物を付着させるリチウムニッケルマンガンコバルト複合酸化物粒子の平均粒子径が大きい方が、改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)が生成し易くなる。また、(B)工程での加熱処理温度が低いほど、付着したチタンキレート化合物とリチウムニッケルマンガンコバルト複合酸化物粒子との反応性がリチウムニッケルマンガンコバルト複合酸化物粒子表面上で低くなるので、(B)工程での加熱処理温度が低いほど、改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)が生成し易くなる。
そのため、本発明の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法では、(A)工程で用いる一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子の平均粒子径と(B)工程での加熱処理温度の組み合わせを、適宜選択することにより、改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)と改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)を造り分けることができる。 In the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention, the smaller the average particle size of the lithium nickel manganese cobalt composite oxide particles to which the titanium chelate compound is attached in the step (A), the smaller the adhered titanium. The oxide containing the chelate compound and its thermal decomposition product Ti is easily highly dispersed without being uniformly bulky on the particle surface of the lithium nickel manganese cobalt composite oxide particles, and the titanium chelate compound adhered to the chelate compound by thermal decomposition. The reactivity of the titanium-containing oxide as a product with the lithium nickel manganese cobalt composite oxide particles is increased on the surface of the lithium nickel manganese cobalt composite oxide particles. Therefore, in the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention, the smaller the average particle size of the lithium nickel manganese cobalt cobalt composite oxide particles to which the titanium chelate compound is adhered in the step (A), the more adhered. The titanium chelate compound and the oxide containing Ti, which is a thermal decomposition product thereof, are more likely to be uniformly and more highly dispersed on the particle surface of the lithium nickel-nickel manganese cobalt composite oxide particles, and the titanium chelate compound adhered to the titanium chelate compound is thermally decomposed. Since the oxide containing Ti, which is a product, has a high reactivity with the lithium nickel manganese cobalt composite oxide particles on the surface of the lithium nickel manganese cobalt composite oxide particles, the heat treatment temperature in the step (B) is the same. Even so, the smaller the average particle size of the lithium nickel-manganese cobalt composite oxide particles to which the titanium chelate compound is attached in the step (A), the easier it is for the modified lithium nickel-manganese cobalt composite oxide particles (B) to be produced. Become. Further, when the heat treatment temperature in the step (B) is higher, the reactivity between the oxide containing Ti, which is a thermal decomposition product of the adhered titanium chelate compound, and the lithium nickel manganese cobalt composite oxide particles is lithium nickel manganese. Since it is higher on the surface of the cobalt composite oxide particles, the higher the heat treatment temperature in the step (B), the easier it is for the modified lithium nickel-manganese cobalt composite oxide particles (B) to be produced.
In other words, in the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention, the larger the average particle size of the lithium nickel manganese cobalt cobalt composite oxide particles to which the titanium chelate compound is attached in the step (A), the larger the average particle size. The attached titanium chelate compound and the oxide containing Ti, which is a thermal decomposition product thereof, are non-uniformly bulky and easily dispersed on the particle surface of the lithium nickel manganese cobalt composite oxide particles, and the attached titanium chelate compound is bulky. The oxide containing Ti, which is a thermal decomposition product, has a low reactivity with the lithium nickel-nickel-manganese-cobalt composite oxide particles on the surface of the lithium-nickel-manganese-cobalt composite oxide particles. The modified lithium nickel manganese cobalt composite oxide particles (A) are produced when the average particle size of the lithium nickel manganese cobalt composite oxide particles to which the titanium chelate compound is attached in the step (A) is larger. It becomes easier to do. Further, as the heat treatment temperature in the step (B) is lower, the reactivity between the adhered titanium chelate compound and the lithium nickel manganese cobalt composite oxide particles becomes lower on the surface of the lithium nickel manganese cobalt composite oxide particles. B) The lower the heat treatment temperature in the step, the easier it is for the modified lithium nickel manganese cobalt composite oxide particles (A) to be produced.
Therefore, in the method for producing the modified lithium nickel manganese cobalt composite oxide particles of the present invention, the average particle size of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) used in the step (A) and (B). ) The modified lithium nickel manganese cobalt cobalt composite oxide particles (A) and the modified lithium nickel manganese cobalt cobalt composite oxide particles (B) can be produced separately by appropriately selecting the combination of the heat treatment temperatures in the step). ..
また、改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)は、(A)工程において一般式(1)であるリチウムニッケルマンガンコバルト複合酸化物粒子として、平均粒子径が0.5~7.5μm、好ましくは1.0~7.0μmの粒子を用い、(B)工程の加熱処理温度を750℃以上1000℃以下、好ましくは750℃以上900℃以下として上記(A)工程及び(B)工程を行うことにより製造することができる。 For example, in a preferred embodiment of the present invention, the modified lithium nickel-manganese cobalt-cobalt composite oxide particles (A) have an average particle diameter as the lithium nickel-manganese-cobalt composite oxide particles of the general formula (1) in the step (A). The above (B) has a heat treatment temperature of 750 ° C. or higher and 1000 ° C. or lower, preferably 750 ° C. or higher and 900 ° C. or lower, using particles having a thickness of 7.5 to 30.0 μm, preferably 8.0 to 25.0 μm. It can be manufactured by performing the steps A) and (B).
Further, the modified lithium nickel manganese cobalt composite oxide particles (B) have an average particle diameter of 0.5 to 7.5 μm as the lithium nickel manganese cobalt composite oxide particles of the general formula (1) in the step (A). Steps (A) and (B) above, preferably using particles having a size of 1.0 to 7.0 μm and setting the heat treatment temperature in step (B) to 750 ° C. or higher and 1000 ° C. or lower, preferably 750 ° C. or higher and 900 ° C. or lower. It can be manufactured by performing.
<リチウムニッケルマンガンコバルト複合酸化物粒子(LNMC)試料の調製>
<LNMC試料1>
炭酸リチウム(平均粒子径5.7μm)及びニッケルマンガンコバルト複合水酸化物(Ni:Mn:Co=6:2:2(モル比)、平均粒子径9.8μm)を秤量し、家庭用ミキサーで十分混合処理し、Li/(Ni+Mn+Co)のモル比が1.01の原料混合物を得た。なお、ニッケルマンガンコバルト複合水酸化物は市販のものを用いた。
次いで、得られた原料混合物を、アルミナ製の鉢で700℃で2時間、つづいて850℃で10時間、大気雰囲気中で焼成した。焼成終了後、該焼成品を粉砕、分級した。得られた焼成品をXRDで測定した結果、単相のリチウムニッケルマンガンコバルト複合酸化物であることを確認した。また、得られたものは、平均粒子径が10.2μmで、BET比表面積が0.21m2/gで、二次凝集した球状のリチウムニッケルマンガンコバルト複合酸化物粒子(LiNi0.6Mn0.2Co0.2O2)であった。 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.
<Preparation of Lithium Nickel Manganese Cobalt Composite Oxide Particle (LNMC) Sample>
<LNMC sample 1>
Weigh lithium carbonate (average particle size 5.7 μm) and nickel-manganese-cobalt composite hydroxide (Ni: Mn: Co = 6: 2: 2 (molar ratio), average particle size 9.8 μm) with a household mixer. The mixture was sufficiently mixed to obtain a raw material mixture having a molar ratio of Li / (Ni + Mn + Co) of 1.01. A commercially available nickel-manganese-cobalt composite hydroxide was used.
The resulting raw material mixture was then calcined in an alumina pot at 700 ° C. for 2 hours, followed by 850 ° C. for 10 hours in an air atmosphere. After the firing was completed, the fired product was crushed and classified. As a result of measuring the obtained fired product by XRD, it was confirmed that it was a single-phase lithium nickel-manganese-cobalt composite oxide. The obtained particles had an average particle diameter of 10.2 μm, a BET specific surface area of 0.21 m 2 / g, and secondarily aggregated spherical lithium nickel-manganese-cobalt composite oxide particles (LiNi 0.6 Mn 0 ). It was .2 Co 0.2 O 2 ).
炭酸リチウム(平均粒子径5.7μm)及びニッケルマンガンコバルト複合水酸化物(Ni:Mn:Co=6:2:2(モル比)、平均粒子径3.7μm)を秤量し、家庭用ミキサーで十分混合処理し、Li/(Ni+Mn+Co)のモル比が1.01の原料混合物を得た。なお、ニッケルマンガンコバルト複合水酸化物は市販のものを用いた。
次いで、得られた原料混合物を、アルミナ製の鉢で700℃で2時間、つづいて850℃で10時間、大気雰囲気中で焼成した。焼成終了後、該焼成品を粉砕、分級した。得られた焼成品をXRDで測定した結果、単相のリチウムニッケルマンガンコバルト複合酸化物であることを確認した。また、得られたものは、平均粒子径が5.4μmで、BET比表面積が0.69m2/gで、二次凝集した球状のリチウムニッケルマンガンコバルト複合酸化物粒子(LiNi0.6Mn0.2Co0.2O2)であった。 <LNMC sample 2>
Weigh lithium carbonate (average particle size 5.7 μm) and nickel-manganese-cobalt composite hydroxide (Ni: Mn: Co = 6: 2: 2 (molar ratio), average particle size 3.7 μm) with a household mixer. The mixture was sufficiently mixed to obtain a raw material mixture having a molar ratio of Li / (Ni + Mn + Co) of 1.01. A commercially available nickel-manganese-cobalt composite hydroxide was used.
The resulting raw material mixture was then calcined in an alumina pot at 700 ° C. for 2 hours, followed by 850 ° C. for 10 hours in an air atmosphere. After the firing was completed, the fired product was crushed and classified. As a result of measuring the obtained fired product by XRD, it was confirmed that it was a single-phase lithium nickel-manganese-cobalt composite oxide. The obtained particles had an average particle diameter of 5.4 μm, a BET specific surface area of 0.69 m 2 / g, and secondarily aggregated spherical lithium nickel-manganese-cobalt composite oxide particles (LiNi 0.6 Mn 0 ). It was .2 Co 0.2 O 2 ).
なお、LNMC試料の平均粒子径、残存アルカリ量及び加圧密度は下記のようにして測定した。
<平均粒子径>
平均粒子径はレーザ回折・散乱法により求めた。
<残存アルカリ量の測定>
LNMC試料の残存アルカリ量については、試料5g、超純水100gをビーカーに計り採りマグネチックスターラーを用いて25℃で5分間分散させた。次いで、この分散液をろ過し、そのろ液70mlを自動滴定装置(型式COMTITE-2500)にて0.1N-HClで滴定し、試料中に存在している残存アルカリ量(リチウム量を測定して炭酸リチウムに換算した値)を算出した。
<加圧密度>
試料2.25gを秤取り直径1.5cmの両軸成形器内に投入し、プレス機を用いて0.65tonf/cm2の圧力を1分間加えた状態で、圧縮物の高さを測定し、その高さから計算される圧縮物の見掛け体積と計り採った試料の質量とから、試料の加圧密度を算出した。 Table 1 shows various physical properties of the lithium nickel manganese cobalt composite oxide sample (LNMC sample) obtained above.
The average particle size, residual alkali amount and pressure density of the LNMC sample were measured as follows.
<Average particle size>
The average particle size was determined by the laser diffraction / scattering method.
<Measurement of residual alkali amount>
Regarding the residual alkalinity of the LNMC sample, 5 g of the sample and 100 g of ultrapure water were weighed in a beaker and dispersed at 25 ° C. for 5 minutes using a magnetic stirrer. Next, this dispersion is filtered, and 70 ml of the filtrate is titrated with 0.1N-HCl by an automatic titrator (model COMITE-2500), and the amount of residual alkali (lithium amount) present in the sample is measured. (Value converted to lithium carbonate) was calculated.
<Pressurization density>
2.25 g of the sample was placed in a double-screw molder with a weighing diameter of 1.5 cm, and the height of the compressed product was measured with a pressure of 0.65 tonf / cm 2 applied for 1 minute using a press machine. , The pressure density of the sample was calculated from the apparent volume of the compressed material calculated from the height and the mass of the measured sample.
<乳酸チタンキレート含有表面処理液の調製>
マツモトファインケミカル社製チタンラクテートアンモニウム塩(Ti(OH)2〔(OCH(CH3)COO-)〕2(NH4 +)2)水溶液(製品名 TC-335、pH 4.4)にアンモニア水を加えてpHを8.5になるように調整して、下記の表2に示す濃度の乳酸チタンキレート含有表面処理液を作成した。 <Preparation of surface treatment liquid>
<Preparation of surface treatment liquid containing titanium lactate chelate>
Titanium lactate ammonium salt manufactured by Matsumoto Fine Chemical Co., Ltd. (Ti (OH) 2 [(OCH (CH 3 ) COO- )] 2 (NH 4 + ) 2 ) Aqueous solution (product name TC-335, pH 4.4) with ammonia water In addition, the pH was adjusted to 8.5 to prepare a surface treatment solution containing a titanium lactate chelate having the concentrations shown in Table 2 below.
LNMC試料及び表面処理液を用い、表3に示す割合となるように秤量し、固形分濃度が25質量%のスラリーとなるように調製した。
次いで、出口の温度を120℃に設定したスプレードライヤーにスラリーの供給速度が65g/分で供給し、乳酸チタンキレートがLNMC試料の粒子表面に付着した被覆粒子を得た。
次いで、被覆粒子を800℃で5時間、加熱処理を行いLNMC試料の粒子表面にTiの酸化物が付着した改質LNMC試料(A)及びLNMC試料にTiを固溶させて含有させた改質LNMC試料(B)を得た。
なお、Tiの酸化物が付着した改質LNMC試料及びLNMC試料にTiを固溶させて含有させた改質LNMC試料であるかは、20,000倍の拡大倍率でサンプル粒子の粒子表面をSEM-EDX(日立ハイテクノロジーズ社製電界放出形走査電子顕微鏡SU-8220およびBRUKER社製エネルギー分散型X線分析装置XFlash5060FlatQUAD)でTiの元素マッピング分析を行って確認した。LNMC試料としてLNMC試料1を用いたものはSEM-EDXにより、サンプル粒子の粒子表面をTiの元素マッピング分析した結果、Tiが偏在して不均一に分布しているものであることから改質リチウムニッケルマンガンコバルト複合酸化物粒子(A)であることが確認できた。一方、LNMC試料としてLNMC試料2を用いたものはSEM-EDXにより、サンプル粒子の粒子表面をTiの元素マッピング分析した結果、Co、Ni及びMnと同様にTiが均一に分布しているものであることから改質リチウムニッケルマンガンコバルト複合酸化物粒子(B)であることが確認できた。
なお、SEM-EDXの測定条件は下記のとおりである。
加速電圧:15kV、拡大倍率:20,000倍、ワーキングディスタンス:9.5~11.5mm、測定時間:6分間
また、改質LNMC試料についても、LNMC試料と同様な方法で、残存アルカリ量を測定した。
なお、表3中の表面処理液の添加量は、該表面処理液を添加したときに、LNMC試料1m2当たりのTi原子換算のTi含有量になる計算値で、下記計算式により求めた。
k=x×(1/t)
k:LNMC試料1m2当たりのTi原子換算のTi含有量(mg)
x:LNMC試料1gに対するTi原子換算のTi含有量(mg)
t:LNMC試料のBET比表面積(m2/g) (Examples 1 to 6)
Using the LNMC sample and the surface treatment liquid, the slurry was weighed so as to have the ratio shown in Table 3, and the slurry was prepared so that the solid content concentration was 25% by mass.
Next, the slurry was supplied to a spray dryer whose outlet temperature was set to 120 ° C. at a slurry supply rate of 65 g / min to obtain coated particles in which titanium lactate chelate adhered to the particle surface of the LNMC sample.
Next, the coated particles were heat-treated at 800 ° C. for 5 hours, and the modified LNMC sample (A) in which the oxide of Ti was attached to the particle surface of the LNMC sample and the modified LNMC sample in which Ti was dissolved and contained. An LNMC sample (B) was obtained.
Whether the modified LNMC sample to which the Ti oxide is attached or the modified LNMC sample in which Ti is solid-dissolved and contained in the LNMC sample is determined by SEM on the particle surface of the sample particles at a magnification of 20,000 times. -It was confirmed by performing elemental mapping analysis of Ti with EDX (electron emission scanning electron microscope SU-8220 manufactured by Hitachi High-Technologies Co., Ltd. and energy dispersive X-ray analyzer XFlash5060 FlatQUAD manufactured by BRUKER Co., Ltd.). When LNMC sample 1 was used as the LNMC sample, the surface of the sample particles was analyzed by elemental mapping of Ti using SEM-EDX. As a result, Ti was unevenly distributed and unevenly distributed. Therefore, modified lithium was used. It was confirmed that the nickel-manganese-cobalt composite oxide particles (A) were used. On the other hand, in the case of using LNMC sample 2 as the LNMC sample, as a result of elemental mapping analysis of Ti on the particle surface of the sample particles by SEM-EDX, Ti is uniformly distributed like Co, Ni and Mn. It was confirmed that the modified lithium nickel-manganese-cobalt composite oxide particles (B) were present.
The measurement conditions for SEM-EDX are as follows.
Acceleration voltage: 15 kV, magnification: 20,000 times, working distance: 9.5 to 11.5 mm, measurement time: 6 minutes Also, for the modified LNMC sample, the residual alkali amount is determined by the same method as for the LNMC sample. It was measured.
The amount of the surface treatment liquid added in Table 3 is a calculated value that gives the Ti content in terms of Ti atoms per 1 m 2 of the LNMC sample when the surface treatment liquid is added, and was calculated by the following formula.
k = xx (1 / t)
k: Ti content (mg) in terms of Ti atoms per 1 m 2 of LNMC sample
x: Ti content in terms of Ti atom per 1 g of LNMC sample (mg)
t: BET specific surface area of LNMC sample (m 2 / g)
市販のコバルト酸リチウム(LiCoO2:平均粒子径9.5μm、BET比表面積0.37m2/g)を用い、実施例1~3と同様にして、コバルト酸リチウム(LCO)試料の粒子表面にTiの酸化物が付着した改質LCO試料を得た。
また、改質LCOについても、LNMC試料と同様な方法で、残存アルカリ量を測定した。
なお、表3中の表面処理液の添加量は、該表面処理液を添加したときに、LCO試料1m2当たりのTi原子換算のTi含有量になる計算値で、下記計算式により求めた。
k’’=x’’×(1/t’’)
k’’:LCO試料1m2当たりのTi原子換算のTi含有量(mg)
x’’:LCO試料1gに対するTi原子換算のTi含有量(mg)
t’’:LCO試料のBET比表面積(m2/g) (Reference example 1)
Using commercially available lithium cobalt oxide (LiCoO 2 : average particle diameter 9.5 μm, BET specific surface area 0.37 m 2 / g) on the particle surface of the lithium cobalt oxide (LCO) sample in the same manner as in Examples 1 to 3. A modified LCO sample to which an oxide of Ti was attached was obtained.
For the modified LCO, the amount of residual alkali was measured by the same method as for the LNMC sample.
The amount of the surface treatment liquid added in Table 3 is a calculated value that gives the Ti content in terms of Ti atoms per 1 m 2 of the LCO sample when the surface treatment liquid is added, and was calculated by the following formula.
k''= x'' × (1 / t'')
k'': Ti content (mg) in terms of Ti atoms per 1 m 2 of LCO sample
x'': Ti content in terms of Ti atom per 1 g of LCO sample (mg)
t'': BET specific surface area of LCO sample (m 2 / g)
<リチウム二次電池の作製1>
実施例で得られた改質LNMC試料95質量%、黒鉛粉末2.5質量%、ポリフッ化ビニリデン2.5質量%を混合して正極剤とし、これをN-メチル-2-ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストをアルミ箔に塗布したのち乾燥、プレスして直径15mmの円盤に打ち抜いて正極板を得た。 The battery performance test was conducted as follows.
<Making a lithium secondary battery 1>
95% by mass of the modified LNMC sample, 2.5% by mass of graphite powder, and 2.5% by mass of polyvinylidene fluoride obtained in the examples were mixed to prepare a positive electrode agent, which was dispersed in N-methyl-2-pyrrolidinone. To prepare a kneaded paste. The kneaded paste was applied to an aluminum foil, dried and pressed, and punched into a disk having a diameter of 15 mm to obtain a positive electrode plate.
次いで、得られたリチウム二次電池の性能評価を行った。その結果を、表4に示す。なお、参考例1で調製した改質LCO試料、改質を行わないLNMC試料1(比較例1)及びLNMC試料2(比較例2)についても同様な方法でリチウム二次電池を作成し、同様な評価を行った。その結果を、表4に併記した。 Using this positive electrode plate, a coin-type lithium secondary battery was manufactured using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution. Of these, a metallic lithium foil was used for the negative electrode, and 1 liter of a 1: 1 mixed solution of ethylene carbonate and methyl ethyl carbonate was used as the electrolytic solution in which 61 mol of LiPF was dissolved.
Next, the performance of the obtained lithium secondary battery was evaluated. The results are shown in Table 4. For the modified LCO sample prepared in Reference Example 1, the unmodified LNMC sample 1 (Comparative Example 1), and the LNMC sample 2 (Comparative Example 2), lithium secondary batteries were prepared in the same manner. Evaluation was made. The results are also shown in Table 4.
作製したコイン型リチウム二次電池を室温で下記試験条件で作動させ、下記の電池性能を評価した。
(1)サイクル特性評価の試験条件
先ず、0.5Cにて4.3Vまで2時間かけて充電を行い、更に4.3Vで3時間電圧を保持させる定電流・定電圧充電(CCCV充電)を行った。その後、0.2Cにて2.7Vまで定電流放電(CC放電)させる充放電を行い、これらの操作を1サイクルとして20サイクル繰り返した。
(2)初回充電容量、初回放電容量(活物質重量当たり)
サイクル特性評価における1サイクル目の充電容量及び放電容量を初回充電容量、初回放電容量とした。
(3)20サイクル目放電容量(活物質重量当たり)
サイクル特性評価における20サイクル目の放電容量を20サイクル目放電容量とした。
(4)容量維持率
サイクル特性評価における1サイクル目と20サイクル目のそれぞれの放電容量(活物質重量当たり)から、下記式により容量維持率を算出した。
容量維持率(%)=(20サイクル目の放電容量/1サイクル目の放電容量)×100
(5)エネルギー密度維持率
サイクル特性評価における1サイクル目と20サイクル目のそれぞれの放電時のWh容量(活物質重量当たり)から、下記式によりエネルギー密度維持率を算出した。
エネルギー密度維持率(%)=(20サイクル目の放電Wh容量/1サイクル目の放電Wh容量)×100 <Battery performance evaluation 1>
The produced coin-type lithium secondary battery was operated at room temperature under the following test conditions, and the following battery performance was evaluated.
(1) Test conditions for cycle characteristic evaluation First, constant current / constant voltage charging (CCCV charging) is performed at 0.5C for charging to 4.3V for 2 hours, and then at 4.3V for 3 hours. gone. Then, charge / discharge was performed by constant current discharge (CC discharge) up to 2.7 V at 0.2 C, and these operations were repeated for 20 cycles as one cycle.
(2) Initial charge capacity, initial discharge capacity (per active material weight)
The charge capacity and discharge capacity of the first cycle in the cycle characteristic evaluation were defined as the initial charge capacity and the initial discharge capacity.
(3) 20th cycle discharge capacity (per active material weight)
The discharge capacity at the 20th cycle in the cycle characteristic evaluation was defined as the discharge capacity at the 20th cycle.
(4) Capacity retention rate The capacity retention rate was calculated from the discharge capacities (per active material weight) of the first cycle and the 20th cycle in the cycle characteristic evaluation by the following formula.
Capacity retention rate (%) = (discharge capacity in the 20th cycle / discharge capacity in the 1st cycle) x 100
(5) Energy density maintenance rate The energy density maintenance rate was calculated by the following formula from the Wh capacity (per active material weight) at the time of each discharge in the first cycle and the 20th cycle in the cycle characteristic evaluation.
Energy density maintenance rate (%) = (Discharge Wh capacity in the 20th cycle / Discharge Wh capacity in the 1st cycle) × 100
実施例1~6で得られた改質LNMC試料及び改質前のLNMC試料を用いて、家庭用ミキサーで十分に混合して表5に示す組成の混合物を調製し、正極活物質試料とした。また、上記LNMC試料と同様にして正極活物質試料の加圧密度を測定し、その結果を表5に併記した。 <Making a lithium secondary battery 2>
Using the modified LNMC sample obtained in Examples 1 to 6 and the LNMC sample before modification, the mixture was sufficiently mixed with a household mixer to prepare a mixture having the composition shown in Table 5 and used as a positive electrode active material sample. .. In addition, the pressurization density of the positive electrode active material sample was measured in the same manner as the above LNMC sample, and the results are also shown in Table 5.
次いで、得られたリチウム二次電池の性能評価を行った。その結果を、表6に併記した。 Using this positive electrode plate, a coin-type lithium secondary battery was manufactured using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution. Of these, a metallic lithium foil was used for the negative electrode, and 1 liter of a 1: 1 mixed solution of ethylene carbonate and methyl ethyl carbonate was used as the electrolytic solution in which 61 mol of LiPF was dissolved.
Next, the performance of the obtained lithium secondary battery was evaluated. The results are also shown in Table 6.
作製したコイン型リチウム二次電池を室温で下記試験条件で作動させ、サイクル特性評価、 初回充電容量、初回放電容量(活物質重量当たり)、初回充電容量、初回放電容量(活物質重量当たり)、容量維持率、エネルギー密度維持率を前記電池の性能評価1と同様な方法で評価した。また、更に体積当たりの放電容量も評価し、その結果を表6に示す。なお、実施例2、実施例5の改質LNMC試料を正極活物質試料とし、同様な方法で評価を行った。その結果を、表6に併記した。
(6)体積当たりの放電容量
体積当たりの放電容量は、初期放電容量と、電極密度により下記計算式から求めた。
体積当たりの放電容量(mAh/cm3)=1サイクル目の放電容量(mAh/g)×電極密度(g/cm3)×0.95(正極材中の活物質量の割合)
なお、電極密度は、測定対象試料から作製した電極の質量と厚みを測定し、ここから、集電体の厚みと質量を差し引いて、正極材の密度として算出した。また、正極材は、正極活物質試料95質量%、黒鉛粉末2.5質量%、ポリフッ化ビニリデン2.5質量%の混合物であり、電極作製時のプレス圧は線圧で0.38ton/cmとした。 <Battery performance evaluation 2>
The manufactured coin-type lithium secondary battery was operated at room temperature under the following test conditions, and cycle characteristics were evaluated, initial charge capacity, initial discharge capacity (per active material weight), initial charge capacity, initial discharge capacity (per active material weight), The capacity retention rate and the energy density retention rate were evaluated by the same method as in the performance evaluation 1 of the battery. Further, the discharge capacity per volume was also evaluated, and the results are shown in Table 6. The modified LNMC samples of Examples 2 and 5 were used as positive electrode active material samples, and evaluation was performed by the same method. The results are also shown in Table 6.
(6) Discharge capacity per volume The discharge capacity per volume was calculated from the following formula based on the initial discharge capacity and the electrode density.
Discharge capacity per volume (mAh / cm 3 ) = Discharge capacity (mAh / g) in the first cycle x Electrode density (g / cm 3 ) x 0.95 (Ratio of active material amount in positive electrode material)
The electrode density was calculated as the density of the positive electrode material by measuring the mass and thickness of the electrode prepared from the sample to be measured and subtracting the thickness and mass of the current collector from this. The positive electrode material is a mixture of 95% by mass of the positive electrode active material sample, 2.5% by mass of graphite powder, and 2.5% by mass of polyvinylidene fluoride, and the press pressure at the time of electrode production is 0.38 ton / cm in linear pressure. And said.
Claims (10)
- 下記一般式(1):
LixNiyMnzCotMpO1+x (1)
(式中、Mは、Mg、Al、Ti、Zr、Cu、Fe、Sr、Ca、V、Mo、Bi、Nb、Si、Zn、Ga、Ge、Sn、Ba、W、Na及びKから選ばれる1種又は2種以上の金属元素を示す。xは0.98≦x≦1.20、yは0.30≦y<1.00、zは0<z≦0.50、tは0<t≦0.50、pは0≦p≦0.05を示し、y+z+t+p=1.00である。)
で表されるリチウムニッケルマンガンコバルト複合酸化物粒子を、チタンキレート化合物を含む表面処理液に接触させて、該リチウムニッケルマンガンコバルト複合酸化物粒子の粒子表面にチタンキレート化合物が付着した被覆粒子を得、次いで、該被覆粒子を加熱処理することにより、改質リチウムニッケルマンガンコバルト複合酸化物粒子を得る改質工程を有し、
前記チタンキレート化合物が、下記一般式(2):
Ti(R1)mLn (2)
(式中、R1は、アルコキシ基、水酸基、ハロゲン原子、アミノ基又はホスフィン類を示し、複数存在する場合、同一であってもよく、異なっていてもよい。Lはヒドロキシカルボン酸に由来する基を表し、複数存在する場合、同一であってもよく、異なっていてもよい。mは0以上3以下の数を示し、nは1以上3以下の数を示し、m+nは3~6である。)
で表されるチタンキレート又はそのアンモニウム塩であること、
を特徴とする改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The following general formula (1):
Li x Ny Mn z Cot M p O 1 + x (1)
(In the formula, M is selected from Mg, Al, Ti, Zr, Cu, Fe, Sr, Ca, V, Mo, Bi, Nb, Si, Zn, Ga, Ge, Sn, Ba, W, Na and K. 1 or more kinds of metal elements are shown. X is 0.98 ≦ x ≦ 1.20, y is 0.30 ≦ y <1.00, z is 0 <z ≦ 0.50, and t is 0. <t≤0.50, p indicates 0≤p≤0.05, and y + z + t + p = 1.00.)
The lithium nickel manganese cobalt composite oxide particles represented by (1) are brought into contact with a surface treatment liquid containing a titanium chelate compound to obtain coated particles having the titanium chelate compound adhered to the particle surface of the lithium nickel manganese cobalt composite oxide particles. Then, the coated particles are heat-treated to obtain modified lithium nickel-manganese cobalt composite oxide particles.
The titanium chelate compound has the following general formula (2):
Ti (R 1 ) m L n (2)
(In the formula, R 1 represents an alkoxy group, a hydroxyl group, a halogen atom, an amino group or phosphines, and when a plurality of them are present, they may be the same or different. L is derived from hydroxycarboxylic acid. When there are a plurality of groups, they may be the same or different. M indicates a number of 0 or more and 3 or less, n indicates a number of 1 or more and 3 or less, and m + n is 3 to 6. be.)
Being a titanium chelate represented by or an ammonium salt thereof,
A method for producing modified lithium nickel-manganese-cobalt composite oxide particles. - 前記加熱処理の温度が、400~1000℃であることを特徴とする請求項1記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The method for producing modified lithium nickel-manganese-cobalt composite oxide particles according to claim 1, wherein the heat treatment temperature is 400 to 1000 ° C.
- 前記一般式(2)中のLが、1価のカルボン酸であることを特徴とする請求項1又は2記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The method for producing modified lithium nickel-manganese-cobalt composite oxide particles according to claim 1 or 2, wherein L in the general formula (2) is a monovalent carboxylic acid.
- 前記一般式(2)中のLが、乳酸であることを特徴とする請求項1又は2記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The method for producing modified lithium nickel manganese cobalt composite oxide particles according to claim 1 or 2, wherein L in the general formula (2) is lactic acid.
- 前記表面処理液のpHが7以上であることを特徴とする請求項1~4いずれか1項記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The method for producing modified lithium nickel manganese cobalt composite oxide particles according to any one of claims 1 to 4, wherein the surface treatment liquid has a pH of 7 or more.
- 前記被覆粒子における前記チタンキレート化合物の付着量が、前記一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子1m2当たり、Ti原子換算で0.1~150mgであることを特徴とする請求項1~5いずれか1項記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The amount of the titanium chelate compound adhered to the coated particles is 0.1 to 150 mg in terms of Ti atoms per 1 m 2 of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1). The method for producing a modified lithium nickel manganese cobalt composite oxide particle according to any one of claims 1 to 5.
- 前記一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子中の残存アルカリ量が、1.2質量%以下であることを特徴とする請求項1~6いずれか1項記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The amendment according to any one of claims 1 to 6, wherein the amount of residual alkali in the lithium nickel-manganese-cobalt composite oxide particles represented by the general formula (1) is 1.2% by mass or less. Quality Lithium Nickel Manganese Cobalt A method for producing composite oxide particles.
- 前記改質リチウムニッケルマンガンコバルト複合酸化物粒子中の残存アルカリ量が、1.2質量%以下であることを特徴とする請求項1~7いずれか1項記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 The modified lithium nickel manganese cobalt composite oxidation according to any one of claims 1 to 7, wherein the residual alkali content in the modified lithium nickel manganese cobalt composite oxide particles is 1.2% by mass or less. A method for producing particles.
- 前記改質工程において、
前記一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子1m2当たりのTi含有量が、Ti原子換算で0.1~150mgとなる添加量で、前記表面改質液を、前記一般式(1)で表されるリチウムニッケルマンガンコバルト複合酸化物粒子に添加して混合し、全量乾燥させること、
を特徴とする請求項1~8いずれか1項記載の改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法。 In the reforming step
The surface modification liquid was added to the surface modifier with an addition amount such that the Ti content per 1 m 2 of the lithium nickel manganese cobalt composite oxide particles represented by the general formula (1) was 0.1 to 150 mg in terms of Ti atoms. Add to lithium nickel manganese cobalt composite oxide particles represented by the general formula (1), mix, and dry the whole amount.
The method for producing modified lithium nickel-manganese-cobalt composite oxide particles according to any one of claims 1 to 8. - 請求項1~9のいずれか1項記載の製造方法により得られる平均粒子径が7.5~30.0μmの大きい粒子と、請求項1~9のいずれか1項記載の製造方法により得られる平均粒子径が0.5~7.5μmの小さい粒子とを混合する工程を含む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。
Large particles having an average particle diameter of 7.5 to 30.0 μm obtained by the production method according to any one of claims 1 to 9 and the production method according to any one of claims 1 to 9 can be obtained. A method for producing a positive electrode active material for a lithium secondary battery, which comprises a step of mixing small particles having an average particle diameter of 0.5 to 7.5 μm.
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