JP2019169412A - Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery arranged by use thereof - Google Patents
Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery arranged by use thereof Download PDFInfo
- Publication number
- JP2019169412A JP2019169412A JP2018057696A JP2018057696A JP2019169412A JP 2019169412 A JP2019169412 A JP 2019169412A JP 2018057696 A JP2018057696 A JP 2018057696A JP 2018057696 A JP2018057696 A JP 2018057696A JP 2019169412 A JP2019169412 A JP 2019169412A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- nmc
- lithium ion
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 142
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000011164 primary particle Substances 0.000 claims abstract description 26
- 239000011163 secondary particle Substances 0.000 claims abstract description 25
- -1 lithium nickel manganese cobalt aluminum Chemical compound 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims description 56
- 238000007254 oxidation reaction Methods 0.000 claims description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 48
- 238000002425 crystallisation Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 239000002905 metal composite material Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 150000002642 lithium compounds Chemical class 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 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 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 87
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 57
- 239000002243 precursor Substances 0.000 description 34
- 239000012298 atmosphere Substances 0.000 description 31
- 238000010304 firing Methods 0.000 description 21
- 239000013078 crystal Substances 0.000 description 18
- 238000010899 nucleation Methods 0.000 description 16
- 230000006911 nucleation Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000009826 distribution Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- 239000011255 nonaqueous electrolyte Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000538 analytical sample Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- SGDQMWNLOSTDSU-UHFFFAOYSA-L lithium;sodium;sulfate Chemical compound [Li+].[Na+].[O-]S([O-])(=O)=O SGDQMWNLOSTDSU-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、高強度リチウムイオン二次電池用正極活物質、及び、該正極活物質を用いたリチウムイオン二次電池に関する。 The present invention relates to a positive electrode active material for a high-strength lithium ion secondary battery and a lithium ion secondary battery using the positive electrode active material.
近年、スマートフォンやタブレット、ミニノートパソコンなどの携帯用電子機器をはじめ、ハイブリット自動車や電気自動車の普及により、高いエネルギー密度を有する、小型で軽量なリチウムイオン二次電池のほか、中型・大型で高出力のリチウムイオン二次電池に関する開発ニーズが急速に拡大している。
これらのリチウムイオン二次電池は、正極及び負極のほか、セパレータや電解液などにより構成され、正極及び負極の活物質には、リチウムイオンを脱離・挿入することが可能な材料が用いられている。リチウムイオン二次電池は、現在も、研究・開発が盛んに行われているが、このうち、層状又はスピネル型のリチウム金属複合酸化物を正極材料に用いたリチウムイオン二次電池では、４Ｖ級の高い電圧が得られるため、高いエネルギー密度を有する電池として、実用化が進んでいる。
In recent years, with the spread of portable electronic devices such as smartphones, tablets, mini-notebook computers, hybrid cars and electric cars, small and light lithium-ion secondary batteries with high energy density, as well as medium and large size Development needs for high-power lithium-ion secondary batteries are expanding rapidly.
These lithium ion secondary batteries are composed of a positive electrode and a negative electrode, as well as a separator and an electrolytic solution. The active material for the positive electrode and the negative electrode is made of a material capable of desorbing and inserting lithium ions. Yes. Currently, research and development of lithium-ion secondary batteries are actively carried out. Of these, lithium-ion secondary batteries using a layered or spinel-type lithium metal composite oxide as a positive electrode material have a 4V class. As a battery having a high energy density, practical application is progressing.
これまで主に提案されている正極材料としては、合成が比較的容易なリチウムコバルト複合酸化物（ＬｉＣｏＯ２）や、コバルトより安価なニッケルを用いたリチウムニッケル複合酸化物（ＬｉＮｉＯ２）をはじめ、リチウムニッケルマンガンコバルト複合酸化物（ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２）や、マンガンを用いたリチウムマンガン複合酸化物（ＬｉＭｎ２Ｏ４）などを挙げることが出来る。
この中でも、リチウムニッケルマンガンコバルト複合酸化物（以降、リチウム、ニッケル、マンガン、コバルトを主成分とする、リチウム金属複合酸化物を「ＮＭＣ」とも称する）は、電池のサイクル特性が良く、低抵抗で高出力が得られる材料として注目されており、先述した様に、搭載スペースにある程度の制約を受ける、ハイブリッド車用電源や電気自動車用電源にも好適であり、車載用電源として重要視されている。
例えば、特許文献１では、α−ＮａＦｅＯ２型の結晶構造を有するなど、ＮＭＣにおける性状が記載されており、特許文献２では、硫酸リチウムナトリウム（ＬｉＮａＳＯ４）の形態で存在している硫酸根を水洗し、その濃度を０．１％未満としたＮＭＣが好ましいと記載されている。
特許文献３では、ＢＥＴ法で測定された時に０．１〜３ｍ２／ｇの比表面積で、レーザー回折・散乱法によるＤ５０値から決定された時に６μｍより大きな集塊物サイズで、Ｄ９０値から決定された時に１００μｍ以下の直径、及び、０．３μｍ＜Ｄｉｎｔｒａ（内部細孔径）＜Ｄ５０値／４μｍのサイズを有する内部細孔、並びに、少なくとも、０．０８ｍｌ／ｇの内部細孔容量を有するＮＭＣが好ましいと記載されている。
また、特許文献４では、リチウムイオンと他の金属イオンを、超臨界又は亜臨界状態の水中で水熱反応させることにより、少なくとも一部が単結晶構造となるＮＭＣの製造方法が記載されており、特許文献５では、最大５０時間という長時間焼成を行うことにより、高容量かつ高耐久性のＮＭＣを得る製造方法が記載されている。
更に、特許文献６では、初期充放電効率やサイクル特性の向上を目的に、ＮＭＣを圧壊した際の圧壊強度の最小値が、７０ＭＰａより大きい粒子で構成されるＮＭＣが記載されており、特許文献７では、４０〜９０℃の反応槽内へ原料溶液を連続投入しながら、ｐＨを９〜１１に保持して、ニッケルマンガンコバルト複合水酸化物（以降、ニッケル、マンガン、コバルトを主成分とする金属複合水酸化物を「ＮＭＣ前駆体」とも称する）を共沈させ、ＮＭＣ前駆体を３００〜７００℃の温度で酸化焙焼し、水洗及び乾燥工程を経てＮＭＣを得る製造方法が記載されている。
As positive electrode materials mainly proposed so far, including lithium cobalt composite oxide (LiCoO 2 ) that is relatively easy to synthesize and lithium nickel composite oxide (LiNiO 2 ) using nickel that is cheaper than cobalt, Examples thereof include lithium nickel manganese cobalt composite oxide (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) and lithium manganese composite oxide (LiMn 2 O 4 ) using manganese.
Among these, lithium nickel manganese cobalt composite oxide (hereinafter, lithium metal composite oxide mainly composed of lithium, nickel, manganese, and cobalt is also referred to as “NMC”) has good battery cycle characteristics and low resistance. It is attracting attention as a material that can provide high output, and as described above, it is suitable for power sources for hybrid vehicles and electric vehicles that are subject to some restrictions on the mounting space, and is regarded as important for in-vehicle power sources. .
For example, Patent Document 1 describes properties in NMC, such as having an α-NaFeO 2 type crystal structure, and Patent Document 2 describes a sulfate group existing in the form of lithium sodium sulfate (LiNaSO 4 ). NMC washed with water and having a concentration of less than 0.1% is described as preferable.
In Patent Document 3, the specific surface area is 0.1 to 3 m 2 / g when measured by the BET method, and the agglomerate size is larger than 6 μm when determined from the D50 value by the laser diffraction / scattering method. Having a diameter of 100 μm or less as determined and an internal pore having a size of 0.3 μm <Dintra (internal pore diameter) <D50 value / 4 μm, and an internal pore volume of at least 0.08 ml / g NMC is described as preferred.
Patent Document 4 describes a method for producing NMC in which at least a part has a single crystal structure by hydrothermal reaction of lithium ions and other metal ions in supercritical or subcritical water. Patent Document 5 describes a production method for obtaining a high-capacity and high-durability NMC by performing long-time firing for a maximum of 50 hours.
Furthermore, Patent Document 6 describes NMC composed of particles having a minimum crushing strength of 70 MPa or more when the NMC is crushed for the purpose of improving initial charge / discharge efficiency and cycle characteristics. In No. 7, while continuously feeding the raw material solution into a reaction vessel at 40 to 90 ° C., the pH is maintained at 9 to 11, and nickel manganese cobalt composite hydroxide (hereinafter, nickel, manganese and cobalt are the main components). A manufacturing method is described in which a metal composite hydroxide is co-precipitated), and the NMC precursor is oxidized and roasted at a temperature of 300 to 700 ° C., followed by washing and drying steps to obtain NMC. Yes.
一般的に、電池の高容量化のために、高エネルギー密度の正極活物質及び高密度の電極を利用するには、電極中の正極活物質の充填密度を上げることが知られている。ところが、充填密度を上げる際に、正極活物質に高い圧力が付加されるので、粒子強度が弱い場合は、二次粒子にクラックが生じて電気伝導性が低下する。また、正極活物質は、充放電により膨張・収縮を繰り返すが、一部に不可逆反応が起こって膨張する。このため、粒子強度が弱いと二次粒子が壊れ、電気伝導性が低下するほか、正極板自体が膨張することにより電池性能が低下する。
また、正極膜塗工プロセスにおいても、正極活物質に高い圧力が付加されるので、粒子強度が弱いと二次粒子が崩壊し、崩壊粒子がロールプレス時のロールに付着して、歩留まりが低下する。更には、ロールに付着しなかった崩壊粒子についても、一次粒子間におけるリチウムの導電性が途切れるために電池性能の悪化を招く。
上記の通り、電池の高容量化・高耐久性化などの電池性能の向上や、歩留まり率の低下を防ぐためには、正極活物質の粒子強度が非常に重要な因子となる。
これに対して、特許文献１〜３に記載されているＮＭＣでは、粒子強度について全く触れられておらず、容量・耐久性も十分ではない。特許文献４及び５に記載されているＮＭＣの製造方法では、どちらも多量のエネルギーを必要とし、工業的に好ましくない。また、特許文献６では、示された実施例によれば、作製された粒子の圧壊強度は７５〜８５ＭＰａ程度であり、依然として粒子強度が低いため、初期充放電効率やサイクル特性の効果が十分ではない。更に、特許文献７では、開示されているｐＨ制御値では、ＮＭＣ中に残留する硫酸塩が増加し、電池性能が低下する。しかも、ＮＭＣ前駆体を熱処理することで、ＮＭＣの粒子強度は向上するが、その効果には全く着目していない。なお、酸化焙焼後のＮＭＣ前駆体を水洗しており、硫酸塩などの不純物が低減される反面、粒界に存在する不純物が洗い流されることで、一次粒子同士の結束が弱まり、これが二次粒子の粒子強度が低下を招き、電池性能が悪化する。
この様に、特許文献１〜７に記載されているＮＭＣでは、環境対応自動車用としてのニーズに見合った正極活物質であるとは言えず、更なる高容量・高耐久性を持つ正極活物質が求められている。
本発明は、係る問題点に鑑み、放電容量や耐久性に加えて、更に安全性を改善した優れたリチウムイオン二次電池を得るために、高い粒子強度を保ちながら、一次粒子平均粒径及び二次粒子平均粒径を最適範囲内に制御しつつ、硫酸根濃度を抑制したリチウムニッケルマンガンコバルトアルミニウム複合酸化物とその製造方法を提供することを課題とする。
Generally, in order to use a high energy density positive electrode active material and a high density electrode for increasing the capacity of a battery, it is known to increase the packing density of the positive electrode active material in the electrode. However, when the packing density is increased, a high pressure is applied to the positive electrode active material. Therefore, if the particle strength is weak, the secondary particles are cracked and the electrical conductivity is lowered. In addition, the positive electrode active material repeatedly expands and contracts due to charge and discharge, but partially expands due to an irreversible reaction. For this reason, when the particle strength is weak, the secondary particles are broken and the electrical conductivity is lowered, and the positive electrode plate itself is expanded, whereby the battery performance is lowered.
Also, in the positive electrode film coating process, high pressure is applied to the positive electrode active material, so if the particle strength is weak, the secondary particles collapse, and the collapsed particles adhere to the roll during roll press, resulting in a decrease in yield. To do. Further, the collapsed particles that have not adhered to the roll also cause deterioration in battery performance because the lithium conductivity is interrupted between the primary particles.
As described above, the particle strength of the positive electrode active material is a very important factor for improving battery performance such as increasing the capacity and durability of the battery and preventing the yield rate from decreasing.
On the other hand, the NMC described in Patent Documents 1 to 3 does not mention the particle strength at all, and the capacity and durability are not sufficient. The NMC production methods described in Patent Documents 4 and 5 both require a large amount of energy and are not industrially preferable. Moreover, in patent document 6, according to the Example shown, since the crushing strength of the produced particle is about 75 to 85 MPa and the particle strength is still low, the effects of the initial charge / discharge efficiency and the cycle characteristics are not sufficient. Absent. Furthermore, in Patent Document 7, at the disclosed pH control value, sulfate remaining in NMC increases and battery performance deteriorates. Moreover, although the NMC particle strength is improved by heat-treating the NMC precursor, no attention is paid to the effect. In addition, the NMC precursor after oxidative roasting is washed with water, and impurities such as sulfate are reduced. On the other hand, the impurities present at the grain boundaries are washed away, and the binding between the primary particles is weakened. The particle strength of the particles is lowered, and the battery performance is deteriorated.
Thus, the NMC described in Patent Documents 1 to 7 cannot be said to be a positive electrode active material that meets the needs for environmentally friendly automobiles, and has a higher positive electrode active material with higher capacity and higher durability. Is required.
In view of such problems, the present invention provides a primary lithium average particle size and a high average particle size while maintaining high particle strength in order to obtain an excellent lithium ion secondary battery with improved safety in addition to discharge capacity and durability. It is an object of the present invention to provide a lithium nickel manganese cobalt aluminum composite oxide in which the sulfate group concentration is suppressed while controlling the average particle size of secondary particles within the optimum range, and a method for producing the same.
本発明者らは、上記の課題を解決するべく、鋭意研究を行った。その結果、サイクル時の容量劣化要因であるＮＭＣ粒子の崩壊を防ぎ、高い耐久性を得るために、晶析工程において、ＮＭＣ主成分であるニッケル、マンガン、コバルトのほか、必須元素としてアルミニウムを加え、かつ、任意元素として元素Ｍを加えたＮＭＣ前駆体を生成させると共に、ＮＭＣ前駆体を、酸化焙焼工程で金属複合酸化物（以降、ニッケル、マンガン、コバルトを主成分とする金属複合酸化物を「ＮＭＣ中間物」とも称する）とし、金属複合酸化物であるＮＭＣ中間物を、混合工程においてリチウム化合物と混合してリチウム混合物とした後、リチウム混合物を、焼成工程で処理する際、二酸化炭素を導入して低酸素濃度で焼成することにより、粒子強度、平均粒径、硫酸根濃度が好ましいＮＭＣが得られることを見出した。これにより、高容量・高耐久性を持つＮＭＣを装備することで、サイクル特性を向上させ、高電圧下での電池の膨化を抑制出来る、リチウムイオン二次電池を製造することが可能となり、本発明を完成するに至った。
即ち、上記の知見に基づいて成された、本発明に係る第１の態様は、
一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋α（但し、０．９５＜ｖ＜１．２２、０．０１≦ｗ≦０．３５、０．０１≦ｘ≦０．５０、０．０１≦ｙ≦０．１５、０≦ｚ≦０．１０、０≦α≦０.２０であり、Ｍは、Ｗ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、Ｔｉ、Ｓｉ、Ｚｎ、Ｃｕ、Ｆｅから選ばれる１種以上の元素）で表され、主に一次粒子が凝集された二次粒子からなるリチウムニッケルマンガンコバルトアルミニウム複合酸化物の粒子強度が１００〜２３０ＭＰａであり、一次粒子平均粒径が０．１〜０．５μｍであり、二次粒子平均粒径が３〜２０μｍであり、硫酸根濃度が０．５重量％以下であることを特徴とするリチウムイオン二次電池用正極活物質である。
In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, in addition to nickel, manganese and cobalt, which are the main components of NMC, in addition to the main components of NMC, aluminum is added as an essential element to prevent the collapse of NMC particles, which is a cause of capacity degradation during cycling, and to obtain high durability In addition, an NMC precursor in which the element M is added as an optional element is generated, and the NMC precursor is converted into a metal composite oxide (hereinafter, a metal composite oxide mainly composed of nickel, manganese, and cobalt) by an oxidation roasting step. And NMC intermediate which is a metal composite oxide is mixed with a lithium compound in the mixing step to form a lithium mixture, and then, when the lithium mixture is treated in the firing step, carbon dioxide It was found that NMC with favorable particle strength, average particle diameter, and sulfate group concentration can be obtained by introducing sinter and firing at a low oxygen concentration. This makes it possible to manufacture a lithium ion secondary battery that can improve cycle characteristics and suppress expansion of the battery under high voltage by installing NMC with high capacity and durability. The invention has been completed.
That is, the first aspect according to the present invention, which is made based on the above knowledge,
Formula: Li v Ni 1-w- x-y-z Mn w Co x Al y M z O 2 + α ( where, 0.95 <v <1.22,0.01 ≦ w ≦ 0.35,0. 01 ≦ x ≦ 0.50, 0.01 ≦ y ≦ 0.15, 0 ≦ z ≦ 0.10, 0 ≦ α ≦ 0.20, and M is W, V, Mg, Mo, Nb, Ti 1 or more elements selected from Si, Zn, Cu, and Fe), and the particle strength of lithium nickel manganese cobalt aluminum composite oxide mainly composed of secondary particles in which primary particles are aggregated is 100 to 230 MPa. A lithium ion having a primary particle average particle size of 0.1 to 0.5 μm, a secondary particle average particle size of 3 to 20 μm, and a sulfate radical concentration of 0.5% by weight or less; It is a positive electrode active material for secondary batteries.
本発明に係る第２の態様は、
請求項１に記載のリチウムイオン二次電池用正極活物質が含まれた正極を備え、初期放電容量が１５５〜１７５ｍＡｈ／ｇであり、容量維持率が７５％以上であり、膨化量が１０５％以下であることを特徴とするリチウムイオン二次電池である。
本発明に係る第３の態様は、
一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋α（但し、０．９５＜ｖ＜１．２２、０．０１≦ｗ≦０．３５、０．０１≦ｘ≦０．５０、０．０１≦ｙ≦０．１５、０≦ｚ≦０．１０、０≦α≦０.２０であり、Ｍは、Ｗ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、Ｔｉ、Ｓｉ、Ｚｎ、Ｃｕ、Ｆｅから選ばれる１種以上の元素）で表され、主に一次粒子が凝集された二次粒子からなるリチウムニッケルマンガンコバルトアルミニウム複合酸化物の粒子強度が１００〜２３０ＭＰａであり、一次粒子平均粒径が０．１〜０．５μｍであり、二次粒子平均粒径が３〜２０μｍであり、硫酸根濃度が０．５重量％以下であることを特徴とするリチウムイオン二次電池用正極活物質の製造方法であって、
少なくとも、ニッケル、マンガン、コバルトを含む溶液と、アルミニウムを含む溶液と、アンモニウムイオン供給体を含む溶液と、アルカリ溶液と、任意でＭ元素を含む溶液とを、反応槽に供給し混合することにより、金属複合水酸化物を晶析させる晶析工程と、
前記晶析工程で得られた前記金属複合水酸化物を、４００〜９００℃で酸化焙焼することにより、金属複合酸化物を得る酸化焙焼工程と、
前記酸化焙焼工程で得られた前記金属複合酸化物とリチウム化合物とを混合することにより、リチウム混合物を得る混合工程と、
前記混合工程で得られた前記リチウム混合物を、酸素濃度を０．１〜２０容量％に制御して、７００〜１０００℃で焼成することにより、リチウム金属複合酸化物を得る焼成工程と、
を有することを特徴とするリチウムイオン二次電池用正極活物質の製造方法である。
A second aspect according to the present invention includes:
A positive electrode including the positive electrode active material for a lithium ion secondary battery according to claim 1 is provided, the initial discharge capacity is 155 to 175 mAh / g, the capacity retention rate is 75% or more, and the expansion amount is 105%. The lithium ion secondary battery is characterized by the following.
A third aspect according to the present invention is as follows.
Formula: Li v Ni 1-w- x-y-z Mn w Co x Al y M z O 2 + α ( where, 0.95 <v <1.22,0.01 ≦ w ≦ 0.35,0. 01 ≦ x ≦ 0.50, 0.01 ≦ y ≦ 0.15, 0 ≦ z ≦ 0.10, 0 ≦ α ≦ 0.20, and M is W, V, Mg, Mo, Nb, Ti 1 or more elements selected from Si, Zn, Cu, and Fe), and the particle strength of lithium nickel manganese cobalt aluminum composite oxide mainly composed of secondary particles in which primary particles are aggregated is 100 to 230 MPa. A lithium ion having a primary particle average particle size of 0.1 to 0.5 μm, a secondary particle average particle size of 3 to 20 μm, and a sulfate radical concentration of 0.5% by weight or less; A method for producing a positive electrode active material for a secondary battery, comprising:
By supplying and mixing at least a solution containing nickel, manganese, cobalt, a solution containing aluminum, a solution containing an ammonium ion supplier, an alkaline solution, and optionally a solution containing M element, into the reaction vessel. A crystallization step for crystallizing the metal composite hydroxide;
An oxidation roasting step of obtaining a metal composite oxide by oxidizing and baking the metal composite hydroxide obtained in the crystallization step at 400 to 900 ° C;
A mixing step of obtaining a lithium mixture by mixing the metal composite oxide obtained in the oxidation roasting step and a lithium compound;
A baking step of obtaining a lithium metal composite oxide by baking the lithium mixture obtained in the mixing step at 700 to 1000 ° C. while controlling the oxygen concentration to 0.1 to 20% by volume;
It is a manufacturing method of the positive electrode active material for lithium ion secondary batteries characterized by having.
本発明におけるリチウムイオン二次電池用正極活物質は、比較的安価で、工業的に取り扱いが容易であるほか、高容量・高耐久性を持つリチウムニッケルマンガンコバルトアルミニウム複合酸化物である。これを用いることで、従来のものよりも電池特性が遥かに優れたリチウムイオン二次電池を得られるため、その工業的価値は極めて大きい。 The positive electrode active material for a lithium ion secondary battery in the present invention is a lithium nickel manganese cobalt aluminum composite oxide that is relatively inexpensive, easy to handle industrially, and has high capacity and high durability. By using this, it is possible to obtain a lithium ion secondary battery having battery characteristics far superior to those of the conventional one, and its industrial value is extremely large.
本発明について、その一実施形態を、以下の順序の通り、詳細に説明する。
１．リチウムイオン二次電池用正極活物質
２．リチウムイオン二次電池用正極活物質の製造方法
３．リチウムイオン二次電池
本発明における、リチウムイオン二次電池用正極活物質とその製造方法は、以下の説明に限定されるものではなく、本発明の趣旨を逸脱しない限り、当業者の知識に基づいて実施形態を多様に改変することが出来る。
１．リチウムイオン二次電池用正極活物質
本発明の実施形態におけるリチウムイオン二次電池用正極活物質は、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋α（但し、０．９５＜ｖ＜１．２２、０．０１≦ｗ≦０．３５、０．０１≦ｘ≦０．５０、０．０１≦ｙ≦０．１５、０≦ｚ≦０．１０、０≦α≦０.２０であり、Ｍは、Ｗ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、Ｔｉ、Ｓｉ、Ｚｎ、Ｃｕ、Ｆｅから選ばれる１種以上の元素）で表され、主に一次粒子が凝集された二次粒子からなるリチウムニッケルマンガンコバルトアルミニウム複合酸化物の粒子強度が１００〜２３０ＭＰａであり、一次粒子平均粒径が０．１〜０．５μｍであり、二次粒子平均粒径が３〜２０μｍであり、硫酸根濃度が０．５重量％以下であることを特徴としている。
また、上記のリチウムイオン二次電池用正極活物質は、
（１）少なくとも、ニッケル、マンガン、コバルトを含む溶液と、アルミニウムを含む溶液と、アンモニウムイオン供給体を含む溶液と、アルカリ溶液と、任意でＭ元素を含む溶液とを、反応槽に供給し混合することにより、金属複合水酸化物を晶析させる晶析工程。
An embodiment of the present invention will be described in detail in the following order.
1. 1. Positive electrode active material for lithium ion secondary battery 2. Method for producing positive electrode active material for lithium ion secondary battery Lithium ion secondary battery In the present invention, the positive electrode active material for a lithium ion secondary battery and the method for producing the same are not limited to the following description, and are based on the knowledge of those skilled in the art without departing from the spirit of the present invention. The embodiments can be modified in various ways.
1. Cathode active material for a lithium ion secondary battery in an embodiment of the positive electrode active material present invention for lithium ion secondary batteries, the general formula: Li v Ni 1-w- x-y-z Mn w Co x Al y M z O 2 + α (provided that 0.95 <v <1.22, 0.01 ≦ w ≦ 0.35, 0.01 ≦ x ≦ 0.50, 0.01 ≦ y ≦ 0.15, 0 ≦ z ≦ 0. 10, 0 ≦ α ≦ 0.20, and M is represented by one or more elements selected from W, V, Mg, Mo, Nb, Ti, Si, Zn, Cu, and Fe), and is primarily primary. The particle strength of the lithium nickel manganese cobalt aluminum composite oxide comprising secondary particles in which the particles are aggregated is 100 to 230 MPa, the primary particle average particle size is 0.1 to 0.5 μm, and the secondary particle average particle size Is 3 to 20 μm, and the sulfate radical concentration is 0.5% by weight or less. It is characterized.
The positive electrode active material for a lithium ion secondary battery is
(1) At least a solution containing nickel, manganese, cobalt, a solution containing aluminum, a solution containing an ammonium ion supplier, an alkali solution, and optionally a solution containing M element are supplied to the reaction vessel and mixed. A crystallization step of crystallizing the metal composite hydroxide.
（２）晶析工程で得られた金属複合水酸化物を、４００〜９００℃で酸化焙焼することにより、金属複合酸化物を得る酸化焙焼工程。 (2) An oxidation roasting step in which the metal composite hydroxide obtained in the crystallization step is oxidized and roasted at 400 to 900 ° C. to obtain a metal composite oxide.
（３）酸化焙焼工程で得られた金属複合酸化物とリチウム化合物とを混合することにより、リチウム混合物を得る混合工程。 (3) A mixing step of obtaining a lithium mixture by mixing the metal composite oxide obtained in the oxidation roasting step and a lithium compound.
（４）混合工程で得られたリチウム混合物を、酸素濃度を０．１〜２０容量％に制御して、７００〜１０００℃で焼成することにより、リチウム金属複合酸化物を得る焼成工程。
これらの（１）〜（４）の工程を有する製造方法により得られ、（１）〜（４）の工程の順で処理が行われる。
（１）の晶析工程において、ＮＭＣ主成分であるニッケル、マンガン、コバルトのほか、必須元素としてアルミニウムを加え、任意元素として元素Ｍを加えたＮＭＣ前駆体を生成させ、得られたＮＭＣ前駆体を、（２）の酸化焙焼工程で金属複合酸化物とし、得られたＮＭＣ中間物を、（３）の混合工程でリチウム化合物と混合してリチウム混合物とした後、得られたリチウム混合物を、（４）の焼成工程で処理する際に、二酸化炭素を導入して低酸素濃度で焼成することにより、粒子強度、平均粒径、硫酸根濃度が好ましいＮＭＣとなる。
上記の様に、高容量・高耐久性を持つＮＭＣを、正極活物質として新たに電池に装備することにより、サイクル特性を向上させ、高電圧下での電池の膨化を抑制出来るなど、従来技術よりも遥かに優れたリチウムイオン二次電池を製造することが可能となる。
＜組成＞
ニッケルは、電池容量の向上に寄与する元素である。高容量を得るために、ニッケル含有量を示す「１−ｗ−ｘ−ｙ−ｚ」の範囲は、０．３０〜０．９５であることが好ましく、０．３５〜０．８０であることがより好ましく、０．４０〜０．６０であることが特に好ましい。「１−ｗ−ｘ−ｙ−ｚ」の値が０．３０未満では、電池容量が低下し、その一方で、０．９５を超えると、電子伝導率が上昇し過ぎ、短絡などによる熱暴走が発生するために、電池の安全性が十分に確保出来なくなる恐れがある。
マンガンは、熱安定性の向上に寄与する元素である。より良い熱安定性を得るために、マンガン含有量を示す「ｗ」の範囲は、０．０１〜０．３５であることが好ましく、０．１０〜０．３０であることがより好ましく、０．１５〜０．３０であることが特に好ましい。「ｗ」の値が０．０１未満では、熱安定性の向上が見られず、その一方で、０．３５を超えると、高温での作動時にマンガン溶出量が増加し、サイクル特性が低下する問題が生じる。
コバルトは、サイクル特性の向上に寄与する元素である。正極活物質に、コバルトが適正量含まれることにより、初期放電容量を損なわず、良好なサイクル特性と、高い耐久性を備えることが可能となる。コバルト含有量を示す「ｘ」の範囲は、０．０１〜０．５０であることが好ましく、０．１０〜０．３５であることがより好ましく、０．１５〜０．３５であることが特に好ましい。「ｘ」の値が０．０１未満では、十分なサイクル特性を得られず、サイクル後の容量維持率が低下し、その一方で、０．５０を超えると、コスト面の負荷が大きくなる。
アルミニウムは、過剰となった電子伝導性を抑制し、安全性を確保するのに大きく寄与する元素である。優れた安全性を確保するために、アルミニウム含有量を示す「ｙ」の値は、０．０１〜０．1５であること好ましく、０．０５〜０．１０であることがより好ましく、０．０６〜０．０８であることが特に好ましい。「ｙ」の値が０．０１未満では、安全性の改善が見られず、その一方で、０．１５を超えると、アルミニウムが粒子内部で偏析し、リチウムイオンの伝導性を阻害して、サイクル特性が低下する問題が生じる。
更に、本発明におけるＮＭＣでは、任意で元素Ｍを含有させることが出来る。元素Ｍを、正極活物質に含有させることで、リチウムイオン二次電池の耐久性など、電池特性をより向上させることが可能となる。上記の元素Ｍには、Ｗ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、Ｔｉ、Ｓｉ、Ｚｎ、Ｃｕ、Ｆｅから選択される１種以上の元素を用いることが出来る。これらの元素Ｍの選択は、リチウムイオン二次電池の用途のほか、要求される性能などに応じて適宜選択される。任意に添加される元素Ｍ含有量を示す「ｚ」の範囲は、０〜０．１０であることが好ましく、０．０２〜０．０８であることがより好ましく、０．０４〜０．０６であることが特に好ましい。「ｚ」の値が０．１０を超えると、レドックス（Ｒｅｄｏｘ）反応の効率が低下するために、電池容量も低下する。
また、元素Ｍは、後述する様に、晶析工程において、ニッケル、マンガン、コバルト、アルミニウムと共に晶析させ、得られるＮＭＣ前駆体の粒子中に均一分散させることも出来るが、晶析工程後に、ＮＭＣ前駆体の粒子表面に被覆させてもよい。更に、混合工程の際に、ＮＭＣ中間物と共に、リチウム化合物と混合することも可能であり、これらの方法を併用してもよい。いずれの方法を用いる場合であっても、上記の一般式における組成から逸脱しない様に、含有量を調整することが必要となる。
(4) A baking step of obtaining a lithium metal composite oxide by baking the lithium mixture obtained in the mixing step at 700 to 1000 ° C. while controlling the oxygen concentration to 0.1 to 20% by volume.
It is obtained by the manufacturing method having the steps (1) to (4), and the processing is performed in the order of the steps (1) to (4).
In the crystallization process of (1), an NMC precursor obtained by adding aluminum as an essential element and adding an element M as an optional element in addition to nickel, manganese, and cobalt, which are NMC main components, and the obtained NMC precursor (2) in the oxidation roasting step of (2) to a metal composite oxide, the obtained NMC intermediate was mixed with the lithium compound in the mixing step (3) to make a lithium mixture, and then the resulting lithium mixture In the firing step (4), by introducing carbon dioxide and firing at a low oxygen concentration, the NMC having a preferred particle strength, average particle size, and sulfate group concentration is obtained.
As mentioned above, by installing NMC with high capacity and durability as a positive electrode active material in the battery, the cycle characteristics can be improved and the expansion of the battery under high voltage can be suppressed. It becomes possible to manufacture a lithium ion secondary battery that is far superior to the above.
<Composition>
Nickel is an element that contributes to an improvement in battery capacity. In order to obtain a high capacity, the range of “1-wxyz” indicating the nickel content is preferably 0.30 to 0.95, and preferably 0.35 to 0.80. Is more preferable, and 0.40 to 0.60 is particularly preferable. If the value of “1-wxyz” is less than 0.30, the battery capacity decreases. On the other hand, if it exceeds 0.95, the electron conductivity increases excessively, and thermal runaway due to a short circuit or the like occurs. As a result, battery safety may not be sufficiently secured.
Manganese is an element that contributes to the improvement of thermal stability. In order to obtain better thermal stability, the range of “w” indicating the manganese content is preferably 0.01 to 0.35, more preferably 0.10 to 0.30, and 0 It is particularly preferably 15 to 0.30. When the value of “w” is less than 0.01, thermal stability is not improved. On the other hand, when it exceeds 0.35, the manganese elution amount increases during operation at high temperature, and the cycle characteristics deteriorate. Problems arise.
Cobalt is an element that contributes to improvement of cycle characteristics. By including an appropriate amount of cobalt in the positive electrode active material, it is possible to provide good cycle characteristics and high durability without impairing the initial discharge capacity. The range of “x” indicating the cobalt content is preferably 0.01 to 0.50, more preferably 0.10 to 0.35, and 0.15 to 0.35. Particularly preferred. If the value of “x” is less than 0.01, sufficient cycle characteristics cannot be obtained, and the capacity retention rate after cycling decreases. On the other hand, if it exceeds 0.50, the cost load increases.
Aluminum is an element that greatly contributes to suppressing excess electron conductivity and ensuring safety. In order to ensure excellent safety, the value of “y” indicating the aluminum content is preferably 0.01 to 0.15, more preferably 0.05 to 0.10, and It is especially preferable that it is 06-0.08. If the value of “y” is less than 0.01, no improvement in safety is observed. On the other hand, if it exceeds 0.15, aluminum segregates inside the particles and inhibits the conductivity of lithium ions, There arises a problem that the cycle characteristics deteriorate.
Further, the NMC in the present invention can optionally contain the element M. By including the element M in the positive electrode active material, battery characteristics such as durability of the lithium ion secondary battery can be further improved. As the element M, one or more elements selected from W, V, Mg, Mo, Nb, Ti, Si, Zn, Cu, and Fe can be used. The selection of these elements M is appropriately selected according to the required performance in addition to the use of the lithium ion secondary battery. The range of “z” indicating the optionally added element M content is preferably 0 to 0.10, more preferably 0.02 to 0.08, and 0.04 to 0.06. It is particularly preferred that When the value of “z” exceeds 0.10, the efficiency of the redox reaction is reduced, so that the battery capacity is also reduced.
In addition, as described later, the element M can be crystallized together with nickel, manganese, cobalt, and aluminum in the crystallization process, and can be uniformly dispersed in the obtained NMC precursor particles. The particle surface of the NMC precursor may be coated. Further, in the mixing step, it is possible to mix with the lithium compound together with the NMC intermediate, and these methods may be used in combination. Whichever method is used, it is necessary to adjust the content so as not to depart from the composition in the above general formula.
なお、組成に関する評価方法には、特に限定は無く、例えば、酸分解−ＩＣＰ（誘導結合プラズマ）発光分光分析法などによる、化学分析手法から求めることが出来る。
＜粒子強度＞
粒子強度は、１００〜２３０ＭＰａであることが好ましく、１２０〜２００ＭＰａであることがより好ましく、１５０〜１８０ＭＰａであることが特に好ましい。粒子強度が１００ＭＰａ未満では、充放電後のＮＭＣ粒子に多くの「割れ」が発生し、容量低下や電池の膨化が起こることがあり、その一方で、２３０Ｍｐａを超えると、電池の正極膜を作成する際、充填性が悪くなり、正極膜を作製出来なくなることがある。また、充填性が悪い正極膜で、充放電サイクルを行うと、容量低下が大きくなり、サイクル特性が極端に悪くなる。
In addition, there is no limitation in particular in the evaluation method regarding a composition, For example, it can obtain | require from the chemical-analysis method by acid decomposition-ICP (inductively coupled plasma) emission spectroscopy analysis etc.
<Particle strength>
The particle strength is preferably 100 to 230 MPa, more preferably 120 to 200 MPa, and particularly preferably 150 to 180 MPa. If the particle strength is less than 100 MPa, many “cracks” may occur in the NMC particles after charge and discharge, and the capacity may decrease and the battery may expand. On the other hand, if the particle strength exceeds 230 MPa, a positive electrode film for the battery is created. In this case, the filling property may be deteriorated, and the positive electrode film may not be produced. In addition, when a charge / discharge cycle is performed with a positive electrode film having poor fillability, the capacity drop increases and the cycle characteristics become extremely poor.
なお、粒子強度に関する評価方法には、特に限定は無く、例えば、微小圧縮試験装置を用いて１粒子毎に測定を行うことにより求めることが出来る。
＜平均粒径＞
一次粒子平均粒径は、０．１〜０．５μｍであることが好ましい。これにより、電池の正極に用いた際に、高い電池容量及び高いサイクル特性を得ることが可能となる。一次粒子平均粒径が０．１μｍ未満になると、高いサイクル特性が得られないことがあり、その一方で、０．５μｍを超えると、電池容量や出力特性が低下し、十分な電池特性が得られないことがある。
また、二次粒子平均粒径は、３〜２０μｍであることが好ましく、６〜１２μｍであることがより好ましい。これにより、電池の正極に用いた際に、高い電池容量のほか、正極に対する高い充填性を両立させることが可能となる。二次粒子平均粒径が３μｍ未満になると、正極に対する高い充填性が得られないことがあり、その一方で、２０μｍを超えると、電池容量や出力特性が低下し、十分な電池特性が得られないことがある。
なお、平均粒径に関する評価方法には、特に限定は無く、例えば、レーザー回折・散乱法を用いて測定した体積基準分布などから求めることが出来る。
＜硫酸根濃度＞
硫酸根濃度は、０．５重量％以下であることが好ましく、０．３重量％以下であることがより好ましく、０．１重量％以下であることが特に好ましい。硫酸根濃度が０．５重量％を超えると、リチウムイオンの拡散を阻害して電池容量が低下すると共に、硫酸根自体は、充放電反応には殆ど寄与しないため、電池の構成において、正極材料の不可逆容量に相当する分は、負極材料を余計に電池に使用せざるを得ない。その結果、電池全体としての重量当り、若しくは体積当りの容量が小さくなり、不可逆容量として負極に余分なリチウムが蓄積されることから、安全性の面からも問題となる。
In addition, there is no limitation in particular in the evaluation method regarding particle strength, For example, it can obtain | require by measuring for every particle using a micro compression test apparatus.
<Average particle size>
The average primary particle diameter is preferably 0.1 to 0.5 μm. Thereby, when it uses for the positive electrode of a battery, it becomes possible to obtain a high battery capacity and a high cycle characteristic. When the average primary particle size is less than 0.1 μm, high cycle characteristics may not be obtained. On the other hand, when the average particle diameter exceeds 0.5 μm, battery capacity and output characteristics are reduced, and sufficient battery characteristics are obtained. It may not be possible.
The average secondary particle size is preferably 3 to 20 μm, more preferably 6 to 12 μm. Thereby, when it uses for the positive electrode of a battery, it becomes possible to make high filling property with respect to a positive electrode compatible with high battery capacity. When the average particle size of the secondary particles is less than 3 μm, high filling property to the positive electrode may not be obtained. On the other hand, when the average particle size exceeds 20 μm, the battery capacity and output characteristics are lowered, and sufficient battery characteristics are obtained. There may not be.
In addition, there is no limitation in particular in the evaluation method regarding an average particle diameter, For example, it can obtain | require from the volume reference distribution etc. which measured using the laser diffraction and the scattering method.
<Sulfate radical concentration>
The sulfate radical concentration is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and particularly preferably 0.1% by weight or less. When the sulfate group concentration exceeds 0.5% by weight, the lithium ion diffusion is inhibited and the battery capacity is reduced, and the sulfate group itself hardly contributes to the charge / discharge reaction. For the amount corresponding to the irreversible capacity, the negative electrode material must be used in the battery. As a result, the capacity per weight or volume of the battery as a whole is reduced, and excess lithium is accumulated in the negative electrode as an irreversible capacity, which is also a problem in terms of safety.
なお、硫酸根濃度に関する評価方法には、特に限定は無く、例えば、ＮＭＣの全硫黄含有量を、燃焼赤外線吸収法や、酸分解−ＩＣＰ発光分光分析法で分析して、この全硫黄含有量を硫酸根（ＳＯ４ ２−）に換算することなどにより求めることが出来る。
２．リチウムイオン二次電池用正極活物質の製造方法
本発明におけるＮＭＣ製造方法は、以下に記載する（１）〜（４）の工程を備え、かつ、（１）〜（４）の工程の順で、処理が行われる。これらの工程を経ることにより、高い粒子強度を保ちながら、一次粒子平均粒径及び二次粒子平均粒径を最適範囲内に制御しつつ、硫酸根濃度を抑制したリチウムニッケルマンガンコバルトアルミニウム複合酸化物が得られる。
（１）晶析工程
通常、ＮＭＣ前駆体を晶析法により作製する場合には、連続晶析法が用いられる。この方法は、組成の等しいＮＭＣ前駆体を、大量に、かつ、簡便に作製出来る方法である。一般的に晶析法で得られるＮＭＣ前駆体粒子は、主に一次粒子が凝集した二次粒子で構成される。しかしながら、この連続晶析法では、得られたＮＭＣ前駆体粒子の粒度分布が、比較的幅広い正規分布となり易く、必ずしも粒径の揃った粒子にならないという問題がある。粒度分布が幅広いＮＭＣ前駆体粒子を原料として作製したＮＭＣでは、リチウムイオン二次電池を組み立てた場合、３μｍ未満の微粉が混在する恐れがあり、サイクル特性悪化の要因となり易い。また、粒度分布が不揃いになると、反応抵抗が増大し、電池出力に悪影響を及ぼす可能性がある。
従って、晶析工程では、例えば、「核生成」の段階と「粒子成長」の段階とを、明確に分離することにより、粒径の均一化を図り、粒度分布の狭いＮＭＣ前駆体を得ることが好ましい。
＜核生成段階＞
まず、水溶性のニッケル塩、マンガン塩、コバルト塩を、所定割合で水に溶解し、ニッケル、マンガン、コバルトを含む原料溶液Ａを作製する。ここで用いるニッケル塩、マンガン塩、コバルト塩は、硫酸塩であることが好ましい。続いて、水溶性のアルミニウム塩を、所定割合で水に溶解し、アルミニウムを含む原料溶液Ｂを作製する。ここで用いるアルミニウム塩は、硫酸塩よりも、アルミン酸塩であることが好ましい。次に、作製した原料溶液Ａ及びＢと、アンモニア水などのアンモニウムイオン供給体を含む溶液とを、撹拌しながら晶析反応槽へ供給し、反応槽内に反応溶液を形成しつつ、かつ、水酸化ナトリウム溶液などのアルカリ溶液を同時に供給して、反応溶液のｐＨが一定となる様に制御する。また、元素Ｍを含む溶液を、任意に原料溶液Ａ及びＢに加えてもよいが、この溶液を加えることで析出が生じる場合には、各原料溶液とは別の経路から同時に反応槽内へ供給する。そして、一定のｐＨとなる様に、アルカリ溶液の添加量を制御することにより、形成した反応溶液内で、ＮＭＣ前駆体の微小な「核」を、選択的に生成させることが可能となる。
反応溶液のｐＨ（液温２５℃基準）は、１２．０以上であることが好ましいが、より好ましくは１２．０〜１４．０となる様に制御する。これにより、反応溶液中に、ＮＭＣ前駆体の微小な「核」を選択的に生成させることが出来る。このｐＨが、１２．０未満では、「核」の成長も同時に起こってしまうために、「核」の総数が不足して粒径が粗大化し、粒度分布が幅広くなり易い。「核」の総数は、核生成におけるｐＨやアンモニウムイオン濃度、及び、供給される各原料溶液の量により制御が可能である。
反応溶液のアンモニウムイオン濃度は、３〜１５ｇ／Ｌの範囲内で、一定に保持されることが好ましい。アンモニウムイオン濃度が不安定になると、金属イオンの溶解度も変化するために、整ったＮＭＣ前駆体粒子の形成が阻害され、ゲル状の「核」が生成し易くなるので、粒度分布が幅広くなり易い。更に、アンモニウムイオン濃度が３ｇ／Ｌ未満では、錯化剤として機能せず、その一方で、１５ｇ／Ｌを超えると、ＮＭＣ前駆体粒子が緻密に形成され過ぎ、最終製品であるＮＭＣも緻密な構造となり、比表面積が低下する恐れがあるので、好ましくない。
反応溶液の温度は、３５〜６０℃に設定することが好ましい。３５℃未満では、温度が低く、供給する金属イオンの溶解度が不足し、核生成が起こり易くなり、核生成の制御が難しくなる。その一方で、６０℃を超えると、アンモニアの揮発ロスが促進されることにより、錯化剤としてのアンモニウムイオン濃度が低下し、上記と同じく、金属イオンの溶解度が不足する。
その他、核生成段階の晶析時間については、目的とするＮＭＣ前駆体粒子の平均粒径により、任意に設定することが出来る。
＜粒子成長段階＞
粒子成長段階では、反応溶液のｐＨ（液温２５℃基準）を、１０．５〜１２．０の範囲に制御し、アルカリ溶液を反応槽内へ供給し、核生成段階よりも低いｐＨとする。核生成段階の後で、ｐＨをこの範囲内に制御することにより、核生成段階で生成した「核」の成長のみを、優先的に起こさせ、新たな核生成を抑制して、ＮＭＣ前駆体粒子における粒度分布の幅を狭くすることが出来る。ｐＨが１０．５未満では、反応溶液に残存する金属イオンが増加するために、生産効率が悪化し、その一方で、１２．０を超えると、粒子成長だけでなく核生成も進行するので、粒度分布が幅広くなり易い。また、硫酸塩を原料溶液に用いる場合は、ＮＭＣ前駆体粒子に残留する硫酸根濃度が高くなるために、好ましくない。なお、反応溶液のアンモニウムイオン濃度や温度については、核生成段階と同様の範囲内で制御すればよい。
また、核生成段階の後、或いは、粒子成長段階の途中で、反応溶液の一部を反応槽の外に排出することにより、反応溶液におけるＮＭＣ前駆体粒子の濃度を高めた後、引き続き、粒子成長を行うことも可能である。これにより、ＮＭＣ前駆体粒子の粒度分布をより狭くすることができ、粒子密度も高めることが出来る。
その他、核生成段階及び粒子成長段階における、反応槽内の雰囲気を制御することで、ＮＭＣ前駆体、ひいてはＭＮＣの粒子構造を制御することが可能となる。即ち、反応槽内の酸素濃度を制御することにより、ＮＭＣ前駆体粒子を構成する、一次粒子の大きさを調整することができ、ＮＭＣ前駆体粒子の緻密性を調整することが出来る。従って、反応槽内の酸素濃度を低くして、非酸化性雰囲気とすることで、ＮＭＣ前駆体粒子の緻密性が高くなり、最終的に得られるＮＭＣも緻密性が高くなり、中実構造を有する様になる。その一方で、反応槽内の酸素濃度を高くして、酸化性雰囲気とすることで、ＮＭＣ前駆体粒子の緻密性が低くなり、最終的に得られるＮＭＣは中空構造や多孔構造を有する様になる。特に、核生成段階と粒子成長段階の初期において反応槽内を酸化性雰囲気とし、その後、非酸化性雰囲気に制御することにより、ＮＭＣ前駆体粒子の中心部の緻密性を低く、外周部の緻密性を高くすることが出来る。この様なＮＭＣ前駆体粒子から得られる正極活物質は、十分な大きさの中空部を有する中空構造となる。中空部の大きさは、酸化性雰囲気とする時間と、非酸化性雰囲気とする時間とを調整することにより、制御することが出来る。
（２）酸化焙焼工程
酸化焙焼工程は、晶析工程で得られたＮＭＣ前駆体を、酸化性雰囲気として、４００〜９００℃の温度で３〜１０時間加熱することにより、ＮＭＣ中間物を得る工程である。酸化焙焼温度の保持時間は３〜１０時間であることが好ましく、５〜７時間であることがより好ましい。３時間未満では、ＮＭＣ中間物の一次粒子平均粒径が小さくなることで、最終製品であるＮＭＣの一次粒子平均粒径が０．１μｍ以下となり、粒子強度の低下を招く。その一方で、１０時間を超えると、ＮＭＣ中間物の比表面積が２．０ｍ２/ｇ以下となり、後の焼成工程においてリチウムと遷移金属との反応性が悪化し、電池容量が低下するほか、焼成時間の延長により生産性が悪化する。
In addition, there is no limitation in particular in the evaluation method regarding a sulfate radical density | concentration, For example, the total sulfur content of NMC is analyzed by a combustion infrared absorption method or an acid decomposition-ICP emission spectrometry, and this total sulfur content Can be calculated by converting it into sulfate radical (SO 4 2− ).
2. Manufacturing method of positive electrode active material for lithium ion secondary battery The NMC manufacturing method in this invention is equipped with the process of (1)-(4) described below, and is in order of the process of (1)-(4). The process is performed. Through these steps, lithium nickel manganese cobalt aluminum composite oxide with suppressed sulfate group concentration while maintaining high particle strength and controlling primary particle average particle size and secondary particle average particle size within the optimum range Is obtained.
(1) Crystallization Step Normally, when the NMC precursor is produced by a crystallization method, a continuous crystallization method is used. In this method, NMC precursors having the same composition can be easily produced in large quantities. In general, NMC precursor particles obtained by a crystallization method are mainly composed of secondary particles in which primary particles are aggregated. However, this continuous crystallization method has a problem that the particle size distribution of the obtained NMC precursor particles tends to be a relatively wide normal distribution and does not necessarily become particles having a uniform particle size. In NMC produced using NMC precursor particles having a wide particle size distribution as raw materials, when a lithium ion secondary battery is assembled, fine powders of less than 3 μm may be mixed, which is likely to cause deterioration of cycle characteristics. In addition, when the particle size distribution is uneven, the reaction resistance increases, which may adversely affect the battery output.
Therefore, in the crystallization process, for example, the “nucleation” stage and the “particle growth” stage are clearly separated to achieve uniform particle size and obtain an NMC precursor with a narrow particle size distribution. Is preferred.
<Nucleation stage>
First, a water-soluble nickel salt, manganese salt, and cobalt salt are dissolved in water at a predetermined ratio to prepare a raw material solution A containing nickel, manganese, and cobalt. The nickel salt, manganese salt, and cobalt salt used here are preferably sulfates. Subsequently, a water-soluble aluminum salt is dissolved in water at a predetermined ratio to prepare a raw material solution B containing aluminum. The aluminum salt used here is preferably an aluminate rather than a sulfate. Next, the prepared raw material solutions A and B and a solution containing an ammonium ion supplier such as aqueous ammonia are supplied to the crystallization reaction tank with stirring, while forming the reaction solution in the reaction tank, and An alkaline solution such as a sodium hydroxide solution is supplied at the same time, and the pH of the reaction solution is controlled to be constant. Further, a solution containing the element M may be optionally added to the raw material solutions A and B. However, when precipitation occurs by adding this solution, the solution is simultaneously introduced into the reaction vessel from a route different from each raw material solution. Supply. Then, by controlling the addition amount of the alkaline solution so as to obtain a constant pH, it becomes possible to selectively generate minute “nuclei” of the NMC precursor in the formed reaction solution.
The pH of the reaction solution (based on a liquid temperature of 25 ° C.) is preferably 12.0 or more, but more preferably controlled to be 12.0 to 14.0. Thereby, the minute “nucleus” of the NMC precursor can be selectively generated in the reaction solution. If this pH is less than 12.0, the growth of “nuclei” occurs at the same time, so the total number of “nuclei” is insufficient, the particle size becomes coarse, and the particle size distribution tends to be wide. The total number of “nuclei” can be controlled by the pH and ammonium ion concentration in nucleation and the amount of each raw material solution supplied.
The ammonium ion concentration in the reaction solution is preferably kept constant within a range of 3 to 15 g / L. When the ammonium ion concentration becomes unstable, the solubility of metal ions also changes, so that formation of ordered NMC precursor particles is hindered, and gel-like “nuclei” are easily generated, so that the particle size distribution tends to be wide. . Further, when the ammonium ion concentration is less than 3 g / L, it does not function as a complexing agent. On the other hand, when it exceeds 15 g / L, NMC precursor particles are formed too densely, and the final product NMC is also dense. Since it becomes a structure and there exists a possibility that a specific surface area may fall, it is not preferable.
The temperature of the reaction solution is preferably set to 35 to 60 ° C. If it is less than 35 degreeC, temperature will be low, the solubility of the metal ion supplied will be insufficient, nucleation will occur easily, and control of nucleation will become difficult. On the other hand, when it exceeds 60 ° C., the volatilization loss of ammonia is promoted, so that the concentration of ammonium ions as a complexing agent is lowered, and the solubility of metal ions is insufficient as described above.
In addition, the crystallization time in the nucleation stage can be arbitrarily set depending on the average particle size of the target NMC precursor particles.
<Particle growth stage>
In the particle growth stage, the pH of the reaction solution (based on a liquid temperature of 25 ° C.) is controlled in the range of 10.5 to 12.0, and the alkaline solution is supplied into the reaction tank to make the pH lower than that in the nucleation stage. . By controlling the pH within this range after the nucleation step, only the growth of “nuclei” generated in the nucleation step is preferentially caused, and new nucleation is suppressed, and the NMC precursor is suppressed. The width of the particle size distribution in the particles can be narrowed. If the pH is less than 10.5, the metal ions remaining in the reaction solution increase, so the production efficiency deteriorates. On the other hand, if it exceeds 12.0, not only particle growth but also nucleation proceeds. The particle size distribution tends to be wide. Also, when sulfate is used for the raw material solution, the concentration of sulfate radical remaining in the NMC precursor particles is increased, which is not preferable. The ammonium ion concentration and temperature of the reaction solution may be controlled within the same range as in the nucleation stage.
Further, after the nucleation step or during the particle growth step, a part of the reaction solution is discharged out of the reaction vessel to increase the concentration of the NMC precursor particles in the reaction solution, and then the particles It is also possible to grow. Thereby, the particle size distribution of the NMC precursor particles can be narrowed, and the particle density can be increased.
In addition, by controlling the atmosphere in the reaction vessel in the nucleation stage and the particle growth stage, it becomes possible to control the particle structure of the NMC precursor, and thus the MNC. That is, by controlling the oxygen concentration in the reaction tank, the size of the primary particles constituting the NMC precursor particles can be adjusted, and the denseness of the NMC precursor particles can be adjusted. Therefore, by reducing the oxygen concentration in the reaction vessel and making it a non-oxidizing atmosphere, the denseness of the NMC precursor particles is increased, and the final NMC is also highly dense, resulting in a solid structure. It will have. On the other hand, by increasing the oxygen concentration in the reaction vessel to create an oxidizing atmosphere, the denseness of the NMC precursor particles is lowered, so that the finally obtained NMC has a hollow structure or a porous structure. Become. In particular, by setting the inside of the reaction vessel to an oxidizing atmosphere at the initial stage of the nucleation stage and the particle growth stage and then controlling to a non-oxidizing atmosphere, the density of the central part of the NMC precursor particles is lowered and the density of the outer peripheral part is reduced. Can increase the nature. The positive electrode active material obtained from such NMC precursor particles has a hollow structure having a sufficiently large hollow portion. The size of the hollow portion can be controlled by adjusting the time for the oxidizing atmosphere and the time for the non-oxidizing atmosphere.
(2) Oxidation roasting step In the oxidation roasting step, the NMC precursor obtained in the crystallization step is heated in an oxidizing atmosphere at a temperature of 400 to 900 ° C. for 3 to 10 hours, whereby an NMC intermediate is obtained. It is a process to obtain. The holding time of the oxidation roasting temperature is preferably 3 to 10 hours, and more preferably 5 to 7 hours. If it is less than 3 hours, the primary particle average particle diameter of the NMC intermediate becomes small, so that the primary particle average particle diameter of the final product, NMC, is 0.1 μm or less, leading to a decrease in particle strength. On the other hand, when it exceeds 10 hours, the specific surface area of the NMC intermediate is 2.0 m 2 / g or less, the reactivity between lithium and the transition metal deteriorates in the subsequent firing step, and the battery capacity decreases. Productivity deteriorates due to the extended firing time.
酸化焙焼温度は、４００℃未満では、ＮＭＣ中間物の一次粒子平均粒径が小さくなることで、ＮＭＣの一次粒子平均粒径が０．１μｍ未満となり、粒子強度が低下する。その一方で、９００℃を超えると、ＮＭＣ中間物の比表面積が２．０ｍ２/ｇ未満となり、焼成工程においてリチウムと遷移金属との反応性が悪化して電池容量が低下し、焼成時間の延長により生産性が悪化する。
酸化焙焼雰囲気は、酸化性雰囲気とするが、酸素濃度が１８〜１００容量％であることが好ましい。即ち、大気雰囲気、かつ、酸素気流中で行なわれることが好ましい。コスト面を考慮すると、空気気流中で行なうことが特に好ましく、酸素濃度が１８容量％未満であると、酸化が十分でなく、一次粒子の異常成長を引き起こす恐れがある。
When the oxidation roasting temperature is less than 400 ° C., the primary particle average particle size of the NMC intermediate becomes small, so that the primary particle average particle size of NMC becomes less than 0.1 μm, and the particle strength decreases. On the other hand, when the temperature exceeds 900 ° C., the specific surface area of the NMC intermediate becomes less than 2.0 m 2 / g, the reactivity between lithium and the transition metal deteriorates in the firing step, the battery capacity decreases, and the firing time is reduced. Productivity deteriorates due to the extension.
The oxidizing roasting atmosphere is an oxidizing atmosphere, but the oxygen concentration is preferably 18 to 100% by volume. That is, it is preferably performed in an air atmosphere and an oxygen stream. Considering the cost, it is particularly preferable to carry out in an air stream. If the oxygen concentration is less than 18% by volume, the oxidation is not sufficient and there is a possibility of causing abnormal growth of primary particles.
酸化焙焼に用いられる加熱炉は、特に限定されるものではなく、大気雰囲気、かつ、酸素気流で使用出来るものならよいが、ガスの発生が無い電気炉が好ましく、バッチ式、或いは、連続式の加熱炉が用いられる。また、ガス置換性が良く、しかも熱交換効率や生産性も良いロータリーキルンや流動焙焼炉が工業的には特に好ましい。
（３）混合工程
混合工程は、酸化焙焼工程で得られたＮＭＣ中間物に、リチウムを除いた金属元素の原子数（Ｍｅ）の合計に対するリチウム（Ｌｉ）の原子数の比（Ｌｉ／Ｍｅ）が、０．９５〜１．２０となる様に、リチウム化合物を混合してリチウム混合物を得る工程である。Ｌｉ／Ｍｅが０．９５未満では、得られたＮＭＣを用いたリチウムイオン二次電池において、正極の反応抵抗が大きくなるために、電池の出力が低くなり、その一方で、１．２０を超えると、得られたＮＭＣの初期放電容量が低下すると共に、正極の反応抵抗も増加する。
The heating furnace used for oxidative roasting is not particularly limited as long as it can be used in an air atmosphere and an oxygen stream, but an electric furnace that does not generate gas is preferable, batch type or continuous type. The heating furnace is used. In addition, a rotary kiln and a fluidized roasting furnace that have good gas replacement properties and good heat exchange efficiency and productivity are particularly preferred industrially.
(3) Mixing step In the mixing step, the ratio of the number of lithium (Li) atoms to the total number of metal element atoms (Me) excluding lithium (Li / Me) in the NMC intermediate obtained in the oxidation roasting step (Li / Me) ) Is a step of obtaining a lithium mixture by mixing lithium compounds such that 0.95 to 1.20. When Li / Me is less than 0.95, in the lithium ion secondary battery using the obtained NMC, the reaction resistance of the positive electrode is increased, so that the output of the battery is lowered, while it exceeds 1.20. As a result, the initial discharge capacity of the obtained NMC decreases and the reaction resistance of the positive electrode also increases.
リチウム化合物は、特に限定されないが、水酸化リチウム、炭酸リチウムのいずれか、若しくは、その混合物を好適に用いることが出来る。取り扱いの容易さや、品質の安定性を考慮すれば、炭酸リチウムを用いることがより好ましい。 The lithium compound is not particularly limited, but lithium hydroxide, lithium carbonate, or a mixture thereof can be preferably used. In view of ease of handling and quality stability, it is more preferable to use lithium carbonate.
ＮＭＣ中間物とリチウム化合物は、十分に混合することが好ましい。混合操作には、一般的な混合機を用いることが出来る。例えば、シェーカーミキサーや、レーディゲミキサー、ジュリアミキサー、Ｖブレンダーなどを用いることができ、ＮＭＣ中間物粒子が破壊されない様に、リチウム化合物と十分に混合すればよい。
（４）焼成工程
焼成工程は、混合工程で得られたリチウム混合物を、二酸化炭素を流し、空気中より酸素濃度を低下させた低酸素雰囲気において、７００〜１０００℃の温度で、５〜２０時間加熱することにより、最終製品のＮＭＣを得る工程である。焼成温度が７００℃未満では、ＮＭＣ中間物と、リチウム化合物の反応が進み難く、ＮＭＣ中間物へのリチウム拡散が不足し、余剰リチウムと、未反応のＮＭＣ中間物が残るほか、結晶構造も十分に整わないので、電池容量や出力特性の低下が生じる。その一方で、焼成温度が１０００℃を超えると、ＮＭＣ粒子間で激しく焼結が起こり、焼結塊となって解砕処理による粒度調整を阻害するために、２０μｍ以上の粒子が発生し、電池の充填性が大きく悪化し、電池容量の低下が生じる。
焼成温度の保持時間は、５〜２０時間であることが好ましく、５〜１０時間であることがより好ましい。５時間未満では、ＮＭＣの生成が不十分となり、その一方で、２０時間を超えると、ＮＭＣ粒子間で激しく焼結が生じ、電池容量が低下するほか、焼成時間延長により生産性が悪化する。
It is preferable that the NMC intermediate and the lithium compound are sufficiently mixed. A general mixer can be used for the mixing operation. For example, a shaker mixer, a Laedige mixer, a Julia mixer, a V blender, or the like can be used, and it may be sufficiently mixed with a lithium compound so that the NMC intermediate particles are not destroyed.
(4) Firing step In the calcining step, the lithium mixture obtained in the mixing step is allowed to flow for 5 to 20 hours at a temperature of 700 to 1000 ° C in a low-oxygen atmosphere in which carbon dioxide is flowed and the oxygen concentration is reduced from the air. In this process, the final product NMC is obtained by heating. When the firing temperature is less than 700 ° C., the reaction between the NMC intermediate and the lithium compound is difficult to proceed, the diffusion of lithium into the NMC intermediate is insufficient, surplus lithium and unreacted NMC intermediate remain, and the crystal structure is sufficient. Battery capacity and output characteristics are reduced. On the other hand, if the firing temperature exceeds 1000 ° C., intense sintering occurs between the NMC particles, and the particles become 20 μm or more in order to inhibit the particle size adjustment by the crushing process as a sintered lump. The chargeability of the battery is greatly deteriorated, and the battery capacity is reduced.
The holding time for the firing temperature is preferably 5 to 20 hours, and more preferably 5 to 10 hours. If it is less than 5 hours, the production of NMC becomes insufficient. On the other hand, if it exceeds 20 hours, intense sintering occurs between the NMC particles, the battery capacity is reduced, and the productivity is deteriorated by extending the firing time.
焼成雰囲気は、低酸素雰囲気とするが、二酸化炭素を流し、酸素濃度を０．１〜２０容量％に制御することが好ましい。酸素濃度が２０容量％超えると、ＮＭＣの結晶性が整わず、粒子強度の向上が見られない場合がある。低酸素雰囲気で結晶を成長させることにより、結晶性が大きく改善され、通常の焼成時間において粒子強度の向上が確認出来ている。これは、酸素濃度が低いために、加熱炉内の一部で酸素欠損が発生するが、その酸素欠損部を起点として、急激に結晶性が改善され、粒子強度の向上に寄与しているものと考えられる。 The firing atmosphere is a low oxygen atmosphere, but it is preferable to flow carbon dioxide and control the oxygen concentration to 0.1 to 20% by volume. When the oxygen concentration exceeds 20% by volume, the crystallinity of NMC is not adjusted, and the particle strength may not be improved. By growing the crystal in a low oxygen atmosphere, the crystallinity is greatly improved, and the improvement of the particle strength can be confirmed in the normal firing time. This is because oxygen deficiency occurs in a part of the heating furnace due to the low oxygen concentration, but the crystallinity is drastically improved starting from the oxygen deficiency and contributes to the improvement of particle strength. it is conceivable that.
焼成に用いられる加熱炉は、特に限定されるものではなく、低酸素雰囲気で使用出来るものならよいが、ガスの発生が無い電気炉が好ましく、バッチ式、連続式の加熱炉が用いられる。 The heating furnace used for firing is not particularly limited and may be any furnace that can be used in a low oxygen atmosphere. However, an electric furnace that does not generate gas is preferable, and a batch type or continuous type heating furnace is used.
上記の焼成条件では、得られるＮＭＣ粒子の激しい焼結による、焼結塊の発生は抑制されるが、軽微な焼結が生じることがある。この様な場合は、更に、得られたＮＭＣ粒子を解砕する解砕工程を備えることが出来る。解砕方法としては、公知の手段を用いることができ、例えば、ピンミルやハンマーミルなどを使用することが出来る。なお、この際、二次粒子を破壊しない様に、解砕力を適切な範囲に調整することが好ましい。
３．リチウムイオン二次電池］
次に、本発明の実施形態により製造されるＮＭＣを正極活物質として用いた、リチウムイオン二次電池について説明する。上記のリチウムイオン二次電池（以降、「二次電池」とも称する）においては、正極、負極、セパレータ及び非水系電解液など、一般的なリチウムイオン二次電池と同様の構成部材を備える。
（１）構成部材
＜正極＞
先述したＮＭＣを正極活物質として用いて、例えば、以下の様にしてリチウムイオン二次電池用の正極を作製する。
Under the above firing conditions, generation of a sintered mass due to intense sintering of the obtained NMC particles is suppressed, but slight sintering may occur. In such a case, a crushing step of crushing the obtained NMC particles can be further provided. As a crushing method, a well-known means can be used, for example, a pin mill, a hammer mill, etc. can be used. At this time, it is preferable to adjust the crushing force to an appropriate range so as not to destroy the secondary particles.
3. Lithium ion secondary battery]
Next, a lithium ion secondary battery using NMC manufactured according to the embodiment of the present invention as a positive electrode active material will be described. The lithium ion secondary battery (hereinafter also referred to as “secondary battery”) includes the same constituent members as those of a general lithium ion secondary battery, such as a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte.
(1) Component <Positive electrode>
Using the NMC described above as a positive electrode active material, for example, a positive electrode for a lithium ion secondary battery is produced as follows.
まず、本実施形態に係るＮＭＣに、導電材及び結着剤を混合し、更に、必要に応じて活性炭や、粘度調整などの溶剤を添加し、これらを混練して正極合材ペーストを作製する。その際、正極合材ペースト中のそれぞれの混合比も、リチウムイオン二次電池の性能を決定する重要な要素となる。例えば、溶剤を除いた正極合材の固形分を、１００質量部とした場合には、一般的なリチウムイオン二次電池の正極と同様に、ＮＭＣ含有量を６０〜９５質量部、導電材含有量を１〜２０質量部、及び、結着剤含有量を１〜２０質量部とすることが出来る。特に、高容量である電池とするために、ＮＭＣ含有量が９０〜９５質量部の高充填正極を作製するのがより好ましい。 First, the NMC according to this embodiment is mixed with a conductive material and a binder, and if necessary, activated carbon or a solvent such as viscosity adjustment is added and kneaded to prepare a positive electrode mixture paste. . At that time, each mixing ratio in the positive electrode mixture paste is also an important factor for determining the performance of the lithium ion secondary battery. For example, when the solid content of the positive electrode mixture excluding the solvent is 100 parts by mass, the NMC content is 60 to 95 parts by mass and the conductive material is contained in the same manner as the positive electrode of a general lithium ion secondary battery. The amount can be 1 to 20 parts by mass, and the binder content can be 1 to 20 parts by mass. In particular, in order to obtain a battery having a high capacity, it is more preferable to produce a highly filled positive electrode having an NMC content of 90 to 95 parts by mass.
得られた正極合材ペーストを、例えば、アルミニウム箔製の集電体の表面に塗布し、乾燥して、溶剤を飛散させる。必要に応じて、電極密度を高めるべく、ロールプレスなどにより加圧することもある。この様にして、シート状の正極を作製することが出来る。シート状の正極は、目的とする電池に応じて、適当な大きさに裁断し、電池の作製に利用される。なお、正極の作製方法は、上記のものに限られることはなく、他の方法であってもよい。 The obtained positive electrode mixture paste is applied to the surface of a current collector made of, for example, an aluminum foil and dried to disperse the solvent. If necessary, pressure may be applied by a roll press or the like to increase the electrode density. In this way, a sheet-like positive electrode can be produced. The sheet-like positive electrode is cut into an appropriate size according to a target battery and used for manufacturing a battery. Note that the method for manufacturing the positive electrode is not limited to the above, and other methods may be used.
導電材には、例えば、黒鉛（天然黒鉛、人造黒鉛、膨張黒鉛など）や、アセチレンブラックやケッチェンブラックなどのカーボンブラック系材料を用いることが出来る。 As the conductive material, for example, graphite (natural graphite, artificial graphite, expanded graphite, etc.), and carbon black materials such as acetylene black and ketjen black can be used.
結着剤は、ＮＭＣ粒子を繋ぎ止める役割を果たすものであり、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）のほか、ポリテトラフルオロエチレン（ＰＴＦＥ）、フッ素ゴム、エチレンプロピレンジエンゴム、スチレンブタジエン、セルロース系樹脂、又は、ポリアクリル酸を用いることが出来る。 The binder plays a role of anchoring NMC particles. For example, in addition to polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene rubber, styrene butadiene, and cellulose resin. Alternatively, polyacrylic acid can be used.
その他、必要に応じて、ＮＭＣ、導電材及び活性炭を分散させ、結着剤を溶解する溶剤を正極合材に添加することができ、溶剤には、Ｎ−メチル−２−ピロリドンなどの有機溶剤を用いることが出来る。また、正極合材には、電気二重層容量を増加させるために、活性炭を添加することも可能である。シート状の正極を製造する際に、正極合材ペーストを圧延して伸ばすが、高容量の二次電池を製造する上で、充填性向上のために、強いロール圧としたことにより、ＮＭＣ粒子が割れ、サイクル特性が劣化することがある。しかしながら、本発明における粒子強度が１００〜２３０ＭＰａに調整されたＮＭＣを、正極活物質として使用すれば、電極作製時の正極活物質の粒子割れと充填率低下を防ぐことが出来る。また、正極活物質の粒子割れに起因して、電池が膨化することがあるが、上記のＮＭＣを正極活物質とすることにより、膨化を抑制出来る。
＜負極＞
負極には、金属リチウムやリチウム合金などを使用することが出来る。また、リチウムイオンを吸蔵・脱離可能な負極活物質に、結着剤を混合し、適当な溶剤を加えてペースト状にした負極合材を、銅などの金属箔集電体の表面に塗布し、乾燥し、必要に応じて電極密度を高めるべく、圧縮して形成したものを使用することが出来る。
In addition, if necessary, a solvent that disperses NMC, conductive material, and activated carbon and dissolves the binder can be added to the positive electrode mixture, and the solvent includes an organic solvent such as N-methyl-2-pyrrolidone. Can be used. In addition, activated carbon can be added to the positive electrode mixture in order to increase the electric double layer capacity. When manufacturing a sheet-like positive electrode, the positive electrode mixture paste is rolled and stretched, but when manufacturing a high-capacity secondary battery, a strong roll pressure is used to improve the filling property. May crack and cycle characteristics may deteriorate. However, if NMC whose particle strength is adjusted to 100 to 230 MPa in the present invention is used as the positive electrode active material, particle breakage and filling rate decrease of the positive electrode active material during electrode production can be prevented. In addition, the battery may expand due to particle cracking of the positive electrode active material, but expansion can be suppressed by using the above NMC as the positive electrode active material.
<Negative electrode>
For the negative electrode, metallic lithium, a lithium alloy, or the like can be used. In addition, a negative electrode active material that can occlude and desorb lithium ions is mixed with a binder, and an appropriate solvent is added to form a paste of the negative electrode mixture on the surface of a metal foil current collector such as copper. Then, it can be dried and used after being compressed to increase the electrode density as required.
負極活物質としては、例えば、金属リチウムやリチウム合金などのリチウムを含有する物質、リチウムイオンを吸蔵・脱離可能な天然黒鉛、人造黒鉛及びフェノール樹脂などの有機化合物の焼成体並びにコークスなどの炭素物質の粉状体を用いることが出来る。この場合、負極結着剤としては、正極と同様に、ＰＶＤＦなどの含フッ素樹脂を用いることができ、これらの活物質及び結着剤を分散させる溶剤としては、Ｎ−メチル−２−ピロリドンなどの有機溶剤を用いることが出来る。
＜セパレータ＞
セパレータは、正極と負極との間に挟み込んで配置されるものであり、正極と負極とを分離し、電解質を保持する機能を有する。この様なセパレータとしては、例えば、ポリエチレンやポリプロピレンなどの薄い膜で、微細な孔を多数有する膜を用いることが出来るが、上記の様な機能を有するものであれば、特に限定されることはない。
＜非水系電解液＞
非水系電解液は、支持塩としてのリチウム塩を有機溶媒に溶解したものである。有機溶媒としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート及びトリフルオロプロピレンカーボネートなどの環状カーボネート、ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート及びジプロピルカーボネートなどの鎖状カーボネート、更に、テトラヒドロフラン、２−メチルテトラヒドロフラン及びジメトキシエタンなどのエーテル化合物、エチルメチルスルホンやブタンスルトンなどの硫黄化合物、リン酸トリエチルやリン酸トリオクチルなどのリン化合物などから選ばれる１種を単独で、或いは、２種以上を混合して用いることが出来る。
Examples of the negative electrode active material include lithium-containing materials such as metal lithium and lithium alloys, natural graphite capable of inserting and extracting lithium ions, sintered products of organic compounds such as artificial graphite and phenol resin, and carbon such as coke. A powdery substance can be used. In this case, as the negative electrode binder, a fluorine-containing resin such as PVDF can be used as in the case of the positive electrode, and as a solvent for dispersing these active materials and the binder, N-methyl-2-pyrrolidone, etc. These organic solvents can be used.
<Separator>
The separator is disposed between the positive electrode and the negative electrode, and has a function of separating the positive electrode and the negative electrode and holding the electrolyte. As such a separator, for example, a thin film such as polyethylene or polypropylene and a film having a large number of fine holes can be used. However, the separator is not particularly limited as long as it has the above functions. Absent.
<Non-aqueous electrolyte>
The nonaqueous electrolytic solution is obtained by dissolving a lithium salt as a supporting salt in an organic solvent. Examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, and dipropyl carbonate, and tetrahydrofuran, 2-methyltetrahydrofuran. And one kind selected from ether compounds such as dimethoxyethane, sulfur compounds such as ethyl methyl sulfone and butane sultone, phosphorus compounds such as triethyl phosphate and trioctyl phosphate, or a mixture of two or more. I can do it.
支持塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＮ（ＣＦ３ＳＯ２）２、及び、それらの複合塩などを用いることが出来る。なお、非水系電解液は、ラジカル捕捉剤、界面活性剤、及び、難燃剤などを含んでいてもよい。
＜リチウムイオン二次電池＞
本発明の実施形態に係るリチウムイオン二次電池は、円筒形や積層形など、種々の形状にすることが出来る。いずれの形状を採る場合であっても、正極及び負極を、セパレータを介して積層させて電極体とし、得られた電極体に、非水系電解液を含浸させて、正極集電体と外部に通じる正極端子との間、及び、負極集電体と外部に通じる負極端子との間を、集電用リードなどを用いて接続し、電池ケースに密閉して、リチウムイオン二次電池を完成させる。
＜非水系電解質二次電池の特性）
本発明の実施形態に係る非水系電解質二次電池は、上述した様に、本実施形態に係るＮＭＣを正極活物質として用いるために、負極抵抗を低減することで、電池容量、出力特性及びサイクル特性に優れている。しかも、このリチウムイオン二次電池は、従来のＮＭＣ粒子を正極活物質として用いた二次電池と比較した場合でも、粒子強度だけでなく、熱安定性や安全性などに優れている。
As the supporting salt, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , a composite salt thereof, or the like can be used. The non-aqueous electrolyte solution may contain a radical scavenger, a surfactant, a flame retardant, and the like.
<Lithium ion secondary battery>
The lithium ion secondary battery according to the embodiment of the present invention can have various shapes such as a cylindrical shape and a stacked shape. In any case, the positive electrode and the negative electrode are laminated through a separator to form an electrode body, and the obtained electrode body is impregnated with a non-aqueous electrolyte so that the positive electrode current collector and the outside are externally provided. Connect between the positive electrode terminal that communicates with the negative electrode current collector and the negative electrode terminal that communicates with the outside using a current collector lead, etc., and seal the battery case to complete the lithium ion secondary battery. .
<Characteristics of non-aqueous electrolyte secondary battery>
As described above, the non-aqueous electrolyte secondary battery according to the embodiment of the present invention uses the NMC according to the present embodiment as a positive electrode active material, thereby reducing battery resistance, output characteristics, and cycle. Excellent characteristics. Moreover, this lithium ion secondary battery is excellent not only in particle strength but also in thermal stability and safety even when compared with a secondary battery using conventional NMC particles as a positive electrode active material.
図１は、電池特性の評価に用いたコイン電池の概略断面図である。例えば、本発明の実施形態に係るＮＭＣを正極活物質として用いて、図１に示す２０３２型コイン電池を構成した場合に、粒子強度を１００〜２３０ＭＰａに保ちながら、初期放電容量を１５５ｍＡｈ／ｇ以上、５００サイクル容量維持率を７５％以上、膨化率を１０５％以下とすることが出来る。
＜用途＞
本発明の実施形態に係る非水系電解質二次電池は、上述の様に、電池容量、出力特性及びサイクル特性に優れており、これらの特性が高いレベルで要求される小型携帯電子機器（スマートフォンやタブレット、ミニノートパソコンなど）の電源として好適に利用することが出来る。また、本発明の実施形態に係る非水系電解質二次電池は安全性にも優れており、小型化及び高出力化が可能であるばかりでなく、高価な保護回路を簡略することが可能であるために、搭載スペースに制約を受ける輸送用機器の電源としても好適に利用することが出来る。
FIG. 1 is a schematic cross-sectional view of a coin battery used for evaluation of battery characteristics. For example, when the NMC according to the embodiment of the present invention is used as the positive electrode active material and the 2032 type coin battery shown in FIG. 1 is configured, the initial discharge capacity is 155 mAh / g or more while maintaining the particle strength at 100 to 230 MPa. The 500 cycle capacity retention rate can be 75% or more and the expansion rate can be 105% or less.
<Application>
As described above, the non-aqueous electrolyte secondary battery according to the embodiment of the present invention is excellent in battery capacity, output characteristics, and cycle characteristics, and small portable electronic devices (smartphones and the like) that are required to have a high level of these characteristics. It can be suitably used as a power source for tablets, mini-notebook computers, etc. In addition, the nonaqueous electrolyte secondary battery according to the embodiment of the present invention is excellent in safety, and not only can be reduced in size and output, but also an expensive protection circuit can be simplified. Therefore, it can be suitably used as a power source for transportation equipment that is restricted by the mounting space.
本発明について、実施例を用いて具体的に説明するが、本発明の技術的範囲は、これら実施例により、何ら限定されるものではない。また、本実施例に関して、ＮＭＣ（正極活物質）、及び、リチウムイオン二次電池の製造に用いた各試薬は、全てが、和光純薬工業株式会社製の試薬特級品である。
なお、実施例（及び比較例）における評価方法は、下記の通りであり、得られた評価結果は、表１に示した。
（１）ＮＭＣ（正極活物質）
１）組成
組成は、試料１ｇを無機酸で加熱分解処理し、純水で１００ｍｌに定容することにより、分析検体液とした後、分析検体液を適宜希釈し、マルチ型ＩＣＰ発光分光分析装置であるＩＣＰＥ−９０００（株式会社島津製作所製）を用いて測定した。
２）粒子強度
粒子強度は、微小強度評価試験機ＭＣＴ−５００（株式会社島津製作所製）を用いて、１個のＮＭＣ粒子に圧子で荷重を加え、破壊された際の粒子強度を算出した。具体的には、シリコン板の上にＮＭＣ粒子を静止させ、圧子の中心部に合わせて位置を微調整し、圧子を、ＮＭＣ粒子に大きな荷重が掛からない程度に接触させて、測定を行った。測定条件は、試験力を１５０ｍＮ、負荷速度を２．０ｍＮ／秒とし、１０個の粒子の平均値を求めた。
３）平均粒径
平均粒径は、レーザー回折・散乱式の粒度分布測定装置であるマイクロトラックＭＴ３３００ＥＸ２（マイクロトラック・ベル株式会社製）を用いて測定した体積基準分布から求めた。なお、試料への超音波照射強度を調整することにより、一次粒子平均粒径と、二次粒子平均粒径との分別測定を行った。
４）硫酸根濃度
硫酸根含有量は、酸分解−ＩＣＰ発光分光分析法で全硫黄含有量を分析し、この全硫黄含有量を、硫酸根（ＳＯ４ ２−）に換算することにより求めた。なお、測定にはマルチ型ＩＣＰ発光分光分析装置である、ＩＣＰＥ−９０００（株式会社島津製作所社製）を用いた。
（２）リチウムイオン二次電池
１）初期放電容量
初期放電容量は、コイン電池又は小型角型電池を、作製してから２４時間程度放置し、開回路電圧ＯＣＶ（ｏｐｅｎ−ｃｉｒｃｕｉｔ−ｖｏｌｔａｇｅ）が安定後、正極に対する電流密度を０．１ｍＡ／ｃｍ２としてカットオフ電圧４．３Ｖまで充電し、１時間の休止後、カットオフ電圧３．０Ｖまで放電した時の容量とした。また、放電容量測定には、マルチチャンネル電圧／電流発生器Ｒ６７４１Ａ（株式会社アドバンテスト製）を用いた。
２）サイクル特性
上述した充放電試験を繰り返し、初期放電容量に対する５００回目の放電容量を測定することで、５００サイクルの容量維持率を算出した。
３）膨化量
リチウムイオン小型角型電池の膨化量を、以下の式を用いて算出した。
膨化量（％）＝（５００サイクル後の電池厚み）／（１サイクル目の電池厚み） × １００
The present invention will be specifically described with reference to examples. However, the technical scope of the present invention is not limited to these examples. Moreover, regarding this example, all of the reagents used in the manufacture of NMC (positive electrode active material) and lithium ion secondary battery are reagent special grades manufactured by Wako Pure Chemical Industries, Ltd.
In addition, the evaluation method in an Example (and comparative example) is as follows, and the obtained evaluation result was shown in Table 1.
(1) NMC (positive electrode active material)
1) The composition composition was obtained by subjecting 1 g of a sample to thermal decomposition treatment with an inorganic acid and making a constant volume of 100 ml with pure water to prepare an analytical sample solution, and then appropriately diluting the analytical sample solution to obtain a multi-type ICP emission spectroscopic analyzer. It was measured using ICPE-9000 (manufactured by Shimadzu Corporation).
2) Particle strength The particle strength was calculated by applying a load to one NMC particle with an indenter using a micro strength evaluation tester MCT-500 (manufactured by Shimadzu Corporation) and breaking the particle. Specifically, the NMC particles were stopped on the silicon plate, the position was finely adjusted in accordance with the center of the indenter, and the indenter was brought into contact with the NMC particles so that a large load was not applied to the measurement. . The measurement conditions were a test force of 150 mN and a load speed of 2.0 mN / sec, and an average value of 10 particles was obtained.
3) Average particle diameter The average particle diameter was determined from the volume reference distribution measured using Microtrac MT3300EX2 (manufactured by Microtrac Bell Co., Ltd.), which is a laser diffraction / scattering particle size distribution measuring apparatus. In addition, the fractional measurement of a primary particle average particle diameter and a secondary particle average particle diameter was performed by adjusting the ultrasonic irradiation intensity | strength to a sample.
4) Sulfate radical concentration The sulfate radical content was determined by analyzing the total sulfur content by acid decomposition-ICP emission spectrometry and converting this total sulfur content into sulfate radical (SO 4 2− ). . For measurement, ICPE-9000 (manufactured by Shimadzu Corporation), which is a multi-type ICP emission spectroscopic analyzer, was used.
(2) Lithium-ion secondary battery 1) Initial discharge capacity The initial discharge capacity is a stable open circuit voltage OCV (open-circuit-voltage) when a coin battery or a small prismatic battery is made to stand for about 24 hours. Thereafter, the current density with respect to the positive electrode was set to 0.1 mA / cm 2 and the battery was charged to a cutoff voltage of 4.3 V, and after a pause of 1 hour, the capacity was discharged to the cutoff voltage of 3.0 V. Further, a multi-channel voltage / current generator R6741A (manufactured by Advantest Corporation) was used for the discharge capacity measurement.
2) Cycle characteristics By repeating the charge / discharge test described above and measuring the discharge capacity at the 500th time with respect to the initial discharge capacity, the capacity maintenance rate of 500 cycles was calculated.
3) Expansion amount The expansion amount of the lithium ion small prismatic battery was calculated using the following formula.
Expansion amount (%) = (battery thickness after 500 cycles) / (battery thickness at the first cycle) × 100
＜晶析工程＞
まず、６０Ｌ反応槽内に、水を半分の量まで入れ、大気雰囲気中で撹拌しながら、槽内温度を４０℃に設定し、２５重量％水酸化ナトリウム溶液と、２５重量％アンモニア水を適量加えて、槽内の液のｐＨ（液温２５℃基準）を１２．８に、アンモニウムイオン濃度を１０ｇ／Ｌに調整した。次に、硫酸ニッケル、硫酸コバルト、硫酸マンガンを溶解・混合した、２．０ｍｏｌ／Ｌ原料溶液（金属元素モル比でＮｉ：Ｃｏ：Ｍｎ＝５５：２０：２５）を、０．１３Ｌ／分で給液し、反応溶液とした。これと同時に、２５質量％水酸化ナトリウム溶液、及び、２５質量％アンモニア水を一定速度で加えて、ｐＨを１２．８（核生成ｐＨ）に制御しながら２分３０秒間晶析を行った。その後、窒素ガスを供給し、反応槽内の酸素濃度を２容量％以下まで低下させながら、ｐＨが１１．６（核成長ｐＨ）となるまで、２５質量％水酸化ナトリウム溶液の給液のみ一時停止し、ｐＨが１１．６に到達した後、２５質量％水酸化ナトリウム溶液の給液を、アルミン酸ナトリウム溶液の添加量に合わせて調整し、再開した。ｐＨを１１．６に制御したまま、４時間晶析を継続し、晶析を終了させた。晶析の終了後、生成物を水洗、濾過、乾燥させて、Ｎｉ０．５４Ｍｎ０．２４Ｃｏ０．１９Ａｌ０．０３（ＯＨ）２で表されるＮＭＣ前駆体を得た。
＜酸化焙焼工程＞
晶析工程で得られたＮＭＣ前駆体をマグネシア製の加熱容器に入れ、密閉式電気炉を用いて、大気雰囲気で、酸化焙焼温度を４００℃、酸化焙焼時間を５時間の条件で処理後、酸化焙焼物を室温となるまで冷却して、Ｎｉ０．５４Ｍｎ０．２４Ｃｏ０．１９Ａｌ０．０３Ｏで表されるＮＭＣ中間物を得た。
＜混合工程＞
酸化焙焼工程で得られたＮＭＣ中間物と、Ｌｉ／Ｍｅ＝１．０３となる様に秤量した炭酸リチウムを、シェーカーミキサー装置であるＴＵＲＢＵＬＡ−ＴｙｐｅＴ２Ｃ（ウィリー・エ・バッコーフェン（ＷＡＢ）社製）を用いて十分に混合し、リチウム混合物を得た。
＜焼成工程＞
混合工程で得られたリチウム混合物をマグネシア製の加熱容器に入れ、密閉式電気炉を用いて、炉内に二酸化炭素を０．５〜２０Ｌ／分の条件で供給し、炉内の酸素濃度を１８容量％として低酸素雰囲気に保ちながら、焼成温度を８５０℃、焼成時間を１０時間の条件で処理後、焼成物を室温となるまで冷却し、解砕を行い、Ｌｉ１．０３Ｎｉ０．５４Ｍｎ０．２４Ｃｏ０．１９Ａｌ０．０３Ｏ２で表されるＮＭＣ（正極活物質）を得た。
＜電池の作製＞
得られたＮＭＣを５２．５ｍｇ、アセチレンブラックを１５ｍｇ、ポリテトラフッ化エチレン樹脂（ＰＴＦＥ）を７．５ｍｇ、それぞれ秤量して混合し、１００ＭＰａの圧力で、厚さ１００μｍに成形し、図１に示す正極（評価用電極）（１）を作製した。更に、この正極（１）を、真空乾燥機により、１２０℃で１２時間乾燥した後、正極（１）を用いた２０３２型コイン電池を、露点が−８０℃に管理されたアルゴンガス雰囲気のグローブボックスの中で作製した。負極（２）には、厚さ１ｍｍのリチウム金属、又は、カーボンを用い、電解液には、１ｍｏｌの過塩素酸リチウム（ＬｉＣｌＯ４）を支持電解質とする、エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）の等量混合液（富山薬品工業株式会社製）を用いた。セパレータ（３）には、膜厚２５μｍのポリエチレン多孔膜を用いた。また、２０３２型コイン電池は、ガスケット（４）とウェーブワッシャー（５）を有し、正極缶（６）と負極缶（７）とで電池に組み立てた。
<Crystal crystallization process>
First, a half amount of water is placed in a 60 L reaction tank, the temperature in the tank is set to 40 ° C. while stirring in the atmosphere, and an appropriate amount of 25 wt% sodium hydroxide solution and 25 wt% aqueous ammonia is added. In addition, the pH of the liquid in the tank (liquid temperature based on 25 ° C.) was adjusted to 12.8, and the ammonium ion concentration was adjusted to 10 g / L. Next, a 2.0 mol / L raw material solution (Ni: Co: Mn = 55: 20: 25 in terms of metal element molar ratio) in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved and mixed is 0.13 L / min. The solution was supplied to obtain a reaction solution. At the same time, 25% by mass sodium hydroxide solution and 25% by mass ammonia water were added at a constant rate to perform crystallization for 2 minutes and 30 seconds while controlling the pH to 12.8 (nucleation pH). Thereafter, nitrogen gas is supplied, and while the oxygen concentration in the reaction vessel is lowered to 2% by volume or less, only the supply of the 25% by mass sodium hydroxide solution is temporarily performed until the pH becomes 11.6 (nuclear growth pH). After stopping and the pH reaching 11.6, the feeding of 25 mass% sodium hydroxide solution was adjusted according to the amount of sodium aluminate solution added and restarted. Crystallization was continued for 4 hours while controlling the pH at 11.6 to complete the crystallization. After completion of crystallization, the product was washed with water, filtered and dried to obtain an NMC precursor represented by Ni 0.54 Mn 0.24 Co 0.19 Al 0.03 (OH) 2 .
<Oxidation roasting process>
The NMC precursor obtained in the crystallization process is put into a heating vessel made of magnesia, and is processed in an air atmosphere using an air atmosphere at an oxidation roasting temperature of 400 ° C. and an oxidizing roasting time of 5 hours. Thereafter, the oxidized roasted product was cooled to room temperature to obtain an NMC intermediate represented by Ni 0.54 Mn 0.24 Co 0.19 Al 0.03 O.
<Mixing process>
The NMC intermediate obtained in the oxidation roasting step and lithium carbonate weighed so as to be Li / Me = 1.03, TURBULA-TypeT2C (manufactured by Willy et Bacofen (WAB)), which is a shaker mixer device Was mixed well to obtain a lithium mixture.
<Baking process>
The lithium mixture obtained in the mixing step is put into a heating vessel made of magnesia, and carbon dioxide is supplied into the furnace under a condition of 0.5 to 20 L / min using a sealed electric furnace, and the oxygen concentration in the furnace is adjusted. While maintaining a low oxygen atmosphere at 18% by volume, after the treatment at a firing temperature of 850 ° C. and a firing time of 10 hours, the fired product was cooled to room temperature, crushed, and Li 1.03 Ni 0. An NMC (positive electrode active material) represented by 54 Mn 0.24 Co 0.19 Al 0.03 O 2 was obtained.
<Production of battery>
The obtained NMC, 52.5 mg, acetylene black, 15 mg, and polytetrafluoroethylene resin (PTFE), 7.5 mg, were weighed and mixed, molded at a pressure of 100 MPa to a thickness of 100 μm, and the positive electrode shown in FIG. (Evaluation electrode) (1) was produced. Further, this positive electrode (1) was dried by a vacuum dryer at 120 ° C. for 12 hours, and then a 2032 type coin battery using the positive electrode (1) was placed in an argon gas atmosphere glove whose dew point was controlled at −80 ° C. Made in a box. For the negative electrode (2), lithium metal having a thickness of 1 mm or carbon is used, and for the electrolyte, 1 mol of lithium perchlorate (LiClO 4 ) is used as a supporting electrolyte, and ethylene carbonate (EC) and diethyl carbonate ( DEC) equal volume mixture (Toyama Pharmaceutical Co., Ltd.) was used. As the separator (3), a polyethylene porous film having a film thickness of 25 μm was used. The 2032 type coin battery had a gasket (4) and a wave washer (5), and was assembled into a battery with a positive electrode can (6) and a negative electrode can (7).
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を５００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 500 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を６００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 600 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を６００℃とした。
＜焼成工程＞
炉内の酸素濃度を０．２容量％とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 600 ° C.
<Baking process>
The oxygen concentration in the furnace was 0.2% by volume.
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を７００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 700 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を８００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 800 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を９００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 900 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を６００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
<Oxidation roasting process>
The oxidation roasting temperature was 600 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を６００℃とした。
＜焼成工程＞
炉内の酸素濃度を０．２容量％とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
<Oxidation roasting process>
The oxidation roasting temperature was 600 ° C.
<Baking process>
The oxygen concentration in the furnace was 0.2% by volume.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を８００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
<Oxidation roasting process>
The oxidation roasting temperature was 800 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、モリブデン、ニオブを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。また、モリブデン、ニオブは、それぞれ等量とし、その合計量がＺ値において０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を８００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, molybdenum and niobium, the general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03. Molybdenum and niobium were added in equal amounts, and the total amount was added so that the Z value was 0.03.
<Oxidation roasting process>
The oxidation roasting temperature was 800 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、バナジウム、マグネシウムを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０６となる様に添加した。また、バナジウム、マグネシウムは、それぞれ等量とし、その合計量がＺ値において０．０６となる様に添加した。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, vanadium, magnesium, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.06. Vanadium and magnesium were added in equal amounts, and the total amount was added so that the Z value was 0.06.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、チタン、珪素を、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０６となる様に添加した。また、チタン、珪素は、それぞれ等量とし、その合計量がＺ値において０．０６となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を８００℃とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, titanium, silicon, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.06. Titanium and silicon were added in equal amounts, and the total amount was added so that the Z value was 0.06.
<Oxidation roasting process>
The oxidation roasting temperature was 800 ° C.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、亜鉛、銅、鉄を、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０９となる様に添加した。また、亜鉛、銅、鉄は、それぞれ等量とし、その合計量がＺ値において０．０９となる様に添加した。
[比較例１]
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼を行わなかった。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例２]
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, zinc, copper, iron, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as a 0.09. Moreover, zinc, copper, and iron were made into equal amounts, respectively, and added so that the total amount was 0.09 in the Z value.
[Comparative Example 1]
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
Oxidation roasting was not performed.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 2]
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を３００℃とした。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例３]
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 300 ° C.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 3]
下記の条件以外は、実施例１と同様の手順を行った。
＜酸化焙焼工程＞
酸化焙焼温度を１０００℃とした。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例４]
The same procedure as in Example 1 was performed except for the following conditions.
<Oxidation roasting process>
The oxidation roasting temperature was 1000 ° C.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 4]
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼を行わなかった。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例５]
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
<Oxidation roasting process>
Oxidation roasting was not performed.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 5]
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を３００℃とした。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例６]
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
<Oxidation roasting process>
The oxidation roasting temperature was 300 ° C.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 6]
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、タングステンを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼温度を１０００℃とした。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例７]
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, tungsten, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03.
<Oxidation roasting process>
The oxidation roasting temperature was 1000 ° C.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 7]
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、モリブデン、ニオブを、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０３となる様に添加した。また、モリブデン、ニオブは、それぞれ等量とし、その合計量がＺ値において０．０３となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼を行わなかった。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
[比較例８]
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, molybdenum and niobium, the general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as 0.03. Molybdenum and niobium were added in equal amounts, and the total amount was added so that the Z value was 0.03.
<Oxidation roasting process>
Oxidation roasting was not performed.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
[Comparative Example 8]
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
元素Ｍとして、亜鉛、銅、鉄を、一般式：ＬｉｖＮｉ１−ｗ−ｘ−ｙ−ｚＭｎｗＣｏｘＡｌｙＭｚＯ２＋αのＺ値が０．０９となる様に添加した。また、亜鉛、銅、鉄は、それぞれ等量とし、その合計量がＺ値において０．０９となる様に添加した。
＜酸化焙焼工程＞
酸化焙焼を行わなかった。
＜焼成工程＞
炉内を大気雰囲気（酸素濃度が２０容量％を超えた状態）とした。
The same procedure as in Example 1 was performed except for the following conditions.
<Crystal crystallization process>
As the element M, zinc, copper, iron, general formula: Z value of Li v Ni 1-w-x -y-z Mn w Co x Al y M z O 2 + α was added as a 0.09. Moreover, zinc, copper, and iron were made into equal amounts, respectively, and added so that the total amount was 0.09 in the Z value.
<Oxidation roasting process>
Oxidation roasting was not performed.
<Baking process>
The inside of the furnace was an atmospheric atmosphere (a state where the oxygen concentration exceeded 20% by volume).
［総合評価］
上記の表１から分かる様に、実施例１〜１５のＮＭＣは、製造工程において、酸化焙焼温度や焼成雰囲気などの条件が、全て好ましい範囲であったために、粒子強度をはじめ、一次粒子平均粒径や二次粒子平均粒径、硫酸根濃度が、揃って良好な値を示していた。この結果は、放電容量や耐久性に加えて、更に安全性を改善した優れたリチウムイオン二次電池を得るために、最適なリチウムイオン二次電池用正極活物質が開発されたことを物語っている。故に、実施例１〜１５のＮＭＣを用いて、リチウムイオン二次電池を作製し、その特性について評価したところ、初期放電容量が１５５ｍＡｈ／ｇ以上、サイクル特性での容量維持率が７５％以上、膨化率が１０５％以下と、こちらも非常に良好な値を示していた。
これに対して、比較例１〜８のＮＭＣは、製造工程において、酸化焙焼工程を経ていなかったり、酸化焙焼温度などが好ましい条件では無かったりしたことから、粒子強度のほか、一次粒子平均粒径や二次粒子平均粒径、及び、硫酸根濃度、これらのいずれかが十分な値とならなかった。しかも、比較例１〜８のＮＭＣを用いて、リチウムイオン二次電池を作製し、その特性について評価したところ、こちらは、初期放電容量、サイクル特性での容量維持率、膨化率、これら全てが実施例と比べて遥かに劣っていた。
[Comprehensive evaluation]
As can be seen from Table 1 above, the NMCs of Examples 1 to 15 had the primary particle average, including the particle strength, since the conditions such as the oxidation roasting temperature and the firing atmosphere were all in the preferred range in the production process. The particle size, secondary particle average particle size, and sulfate group concentration all showed good values. This result tells us that an optimal cathode active material for lithium ion secondary batteries was developed in order to obtain excellent lithium ion secondary batteries with improved safety in addition to discharge capacity and durability. Yes. Therefore, using the NMC of Examples 1 to 15, lithium ion secondary batteries were produced and evaluated for the characteristics. The initial discharge capacity was 155 mAh / g or more, the capacity retention rate in the cycle characteristics was 75% or more, The expansion rate was 105% or less, which also showed a very good value.
On the other hand, the NMCs of Comparative Examples 1 to 8 were not subjected to the oxidative roasting step in the manufacturing process, or the oxidative roasting temperature was not a preferable condition. None of the average particle size, the secondary particle average particle size, and the sulfate radical concentration was sufficient. Moreover, when the NMC of Comparative Examples 1 to 8 was used to produce lithium ion secondary batteries and their characteristics were evaluated, this is the initial discharge capacity, capacity retention rate in cycle characteristics, expansion rate, all of which are It was far inferior to the examples.
１ 正極（評価用電極）
２ 負極（リチウム金属、又は、カーボン）
３ セパレータ
４ ガスケット
５ ウェーブワッシャー
６ 正極缶
７ 負極缶
1 Positive electrode (Evaluation electrode)
2 Negative electrode (lithium metal or carbon)
3 Separator 4 Gasket 5 Wave washer 6 Positive electrode can 7 Negative electrode can
Claims (3)
少なくとも、ニッケル、マンガン、コバルトを含む溶液と、アルミニウムを含む溶液と、アンモニウムイオン供給体を含む溶液と、アルカリ溶液と、任意でＭ元素を含む溶液とを、反応槽に供給し混合することにより、金属複合水酸化物を晶析させる晶析工程と、
前記晶析工程で得られた前記金属複合水酸化物を、４００〜９００℃で酸化焙焼することにより、金属複合酸化物を得る酸化焙焼工程と、
前記酸化焙焼工程で得られた前記金属複合酸化物とリチウム化合物とを混合することにより、リチウム混合物を得る混合工程と、
前記混合工程で得られた前記リチウム混合物を、酸素濃度を０．１〜２０容量％に制御して、７００〜１０００℃で焼成することにより、リチウム金属複合酸化物を得る焼成工程と、
を有することを特徴とするリチウムイオン二次電池用正極活物質の製造方法。
Formula: Li v Ni 1-w- x-y-z Mn w Co x Al y M z O 2 + α ( where, 0.95 <v <1.22,0.01 ≦ w ≦ 0.35,0. 01 ≦ x ≦ 0.50, 0.01 ≦ y ≦ 0.15, 0 ≦ z ≦ 0.10, 0 ≦ α ≦ 0.20, and M is W, V, Mg, Mo, Nb, Ti 1 or more elements selected from Si, Zn, Cu, and Fe), and the particle strength of lithium nickel manganese cobalt aluminum composite oxide mainly composed of secondary particles in which primary particles are aggregated is 100 to 230 MPa. A lithium ion having a primary particle average particle size of 0.1 to 0.5 μm, a secondary particle average particle size of 3 to 20 μm, and a sulfate radical concentration of 0.5% by weight or less; A method for producing a positive electrode active material for a secondary battery, comprising:
By supplying and mixing at least a solution containing nickel, manganese, cobalt, a solution containing aluminum, a solution containing an ammonium ion supplier, an alkaline solution, and optionally a solution containing M element, into the reaction vessel. A crystallization step for crystallizing the metal composite hydroxide;
An oxidation roasting step of obtaining a metal composite oxide by oxidizing and baking the metal composite hydroxide obtained in the crystallization step at 400 to 900 ° C;
A mixing step of obtaining a lithium mixture by mixing the metal composite oxide obtained in the oxidation roasting step and a lithium compound;
A baking step of obtaining a lithium metal composite oxide by baking the lithium mixture obtained in the mixing step at 700 to 1000 ° C. while controlling the oxygen concentration to 0.1 to 20% by volume;
The manufacturing method of the positive electrode active material for lithium ion secondary batteries characterized by having.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018057696A JP7185838B2 (en) | 2018-03-26 | 2018-03-26 | Method for producing positive electrode active material for high-strength lithium-ion secondary battery |
| JP2022158293A JP2022177291A (en) | 2018-03-26 | 2022-09-30 | Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery employing the positive electrode active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018057696A JP7185838B2 (en) | 2018-03-26 | 2018-03-26 | Method for producing positive electrode active material for high-strength lithium-ion secondary battery |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022158293A Division JP2022177291A (en) | 2018-03-26 | 2022-09-30 | Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery employing the positive electrode active material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019169412A true JP2019169412A (en) | 2019-10-03 |
| JP7185838B2 JP7185838B2 (en) | 2022-12-08 |
Family
ID=68108467
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018057696A Active JP7185838B2 (en) | 2018-03-26 | 2018-03-26 | Method for producing positive electrode active material for high-strength lithium-ion secondary battery |
| JP2022158293A Pending JP2022177291A (en) | 2018-03-26 | 2022-09-30 | Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery employing the positive electrode active material |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022158293A Pending JP2022177291A (en) | 2018-03-26 | 2022-09-30 | Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery employing the positive electrode active material |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP7185838B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116655006A (en) * | 2023-08-02 | 2023-08-29 | 宜宾光原锂电材料有限公司 | Nickel-cobalt binary precursor, preparation method thereof, positive electrode material, positive electrode and battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005141983A (en) * | 2003-11-05 | 2005-06-02 | Mitsubishi Chemicals Corp | Layered lithium nickel base composite oxide powder for positive electrode material of lithium secondary battery, its manufacturing method, positive electrode for lithium secondary battery, and lithium secondary battery |
| WO2010106768A1 (en) * | 2009-03-18 | 2010-09-23 | パナソニック株式会社 | Positive electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using same, and method for producing same |
| WO2011121902A1 (en) * | 2010-03-31 | 2011-10-06 | パナソニック株式会社 | Negative electrode for a lithium-ion secondary battery, and lithium-ion secondary battery containing said negative electrode |
| JP2012230898A (en) * | 2011-04-14 | 2012-11-22 | Toda Kogyo Corp | Li-Ni COMPLEX OXIDE PARTICLE POWDER, METHOD FOR MANUFACTURING THE SAME, AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY |
| JP2012252844A (en) * | 2011-06-01 | 2012-12-20 | Sumitomo Metal Mining Co Ltd | Transition metal complex hydroxide suitable for precursor of positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same, positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same, and nonaqueous electrolyte secondary battery comprising the positive electrode active material |
| JP2013147416A (en) * | 2011-12-20 | 2013-08-01 | Sumitomo Metal Mining Co Ltd | Nickel compound hydroxide and method for producing the same, positive pole active substance for nonaqueous electrolyte secondary cell and method for producing the same, and nonaqueous electrolyte secondary cell |
| JP2014112496A (en) * | 2012-12-05 | 2014-06-19 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| WO2016017783A1 (en) * | 2014-07-31 | 2016-02-04 | 住友金属鉱山株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery, and method for producing same |
| JP6256956B1 (en) * | 2016-12-14 | 2018-01-10 | 住友化学株式会社 | Lithium metal composite oxide powder, positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery |
-
2018
- 2018-03-26 JP JP2018057696A patent/JP7185838B2/en active Active
-
2022
- 2022-09-30 JP JP2022158293A patent/JP2022177291A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005141983A (en) * | 2003-11-05 | 2005-06-02 | Mitsubishi Chemicals Corp | Layered lithium nickel base composite oxide powder for positive electrode material of lithium secondary battery, its manufacturing method, positive electrode for lithium secondary battery, and lithium secondary battery |
| WO2010106768A1 (en) * | 2009-03-18 | 2010-09-23 | パナソニック株式会社 | Positive electrode for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using same, and method for producing same |
| WO2011121902A1 (en) * | 2010-03-31 | 2011-10-06 | パナソニック株式会社 | Negative electrode for a lithium-ion secondary battery, and lithium-ion secondary battery containing said negative electrode |
| JP2012230898A (en) * | 2011-04-14 | 2012-11-22 | Toda Kogyo Corp | Li-Ni COMPLEX OXIDE PARTICLE POWDER, METHOD FOR MANUFACTURING THE SAME, AND NONAQUEOUS ELECTROLYTE SECONDARY BATTERY |
| JP2012252844A (en) * | 2011-06-01 | 2012-12-20 | Sumitomo Metal Mining Co Ltd | Transition metal complex hydroxide suitable for precursor of positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same, positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same, and nonaqueous electrolyte secondary battery comprising the positive electrode active material |
| JP2013147416A (en) * | 2011-12-20 | 2013-08-01 | Sumitomo Metal Mining Co Ltd | Nickel compound hydroxide and method for producing the same, positive pole active substance for nonaqueous electrolyte secondary cell and method for producing the same, and nonaqueous electrolyte secondary cell |
| JP2014112496A (en) * | 2012-12-05 | 2014-06-19 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| WO2016017783A1 (en) * | 2014-07-31 | 2016-02-04 | 住友金属鉱山株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery, and method for producing same |
| JP6256956B1 (en) * | 2016-12-14 | 2018-01-10 | 住友化学株式会社 | Lithium metal composite oxide powder, positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116655006A (en) * | 2023-08-02 | 2023-08-29 | 宜宾光原锂电材料有限公司 | Nickel-cobalt binary precursor, preparation method thereof, positive electrode material, positive electrode and battery |
| CN116655006B (en) * | 2023-08-02 | 2023-11-07 | 宜宾光原锂电材料有限公司 | Nickel-cobalt binary precursor, preparation method thereof, positive electrode material, positive electrode and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022177291A (en) | 2022-11-30 |
| JP7185838B2 (en) | 2022-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10038189B2 (en) | Transition metal composite hydroxide capable of serving as precursor of positive electrode active material for nonaqueous electrolyte secondary batteries | |
| JP6582824B2 (en) | Nickel-manganese-containing composite hydroxide and method for producing the same | |
| CN107615531B (en) | Transition metal-containing composite hydroxide and method for producing same, nonaqueous electrolyte secondary battery and positive electrode active material for same, and method for producing same | |
| CN107531510B (en) | Aluminum-coated nickel-cobalt-containing composite hydroxide and method for producing same, nonaqueous electrolyte secondary battery, positive electrode active material, and method for producing same | |
| JP4915488B1 (en) | Nickel-manganese composite hydroxide particles and production method thereof, positive electrode active material for non-aqueous electrolyte secondary battery, production method thereof, and non-aqueous electrolyte secondary battery | |
| JP4894969B1 (en) | Nickel-manganese composite hydroxide particles and production method thereof, positive electrode active material for non-aqueous electrolyte secondary battery and production method thereof, and non-aqueous electrolyte secondary battery | |
| JP5638232B2 (en) | Non-aqueous electrolyte secondary battery positive electrode active material nickel cobalt manganese composite hydroxide particles and production method thereof, non-aqueous electrolyte secondary battery positive electrode active material and production method thereof, and non-aqueous electrolyte secondary battery | |
| WO2014051089A1 (en) | Nickel-cobalt compound hydroxide and method and device for producing same, positive electrode active substance for nonaqueous electrolyte secondary cell and method for producing same, and nonaqueous electrolyte secondary cell | |
| WO2016017783A1 (en) | Positive electrode active material for non-aqueous electrolyte secondary battery, and method for producing same | |
| JP2013147416A (en) | Nickel compound hydroxide and method for producing the same, positive pole active substance for nonaqueous electrolyte secondary cell and method for producing the same, and nonaqueous electrolyte secondary cell | |
| JP2014129188A (en) | Nickel composite hydroxide and production method thereof, cathode active material and production method thereof, and nonaqueous electrolyte secondary battery | |
| JP7260249B2 (en) | TRANSITION METAL CONTAINING COMPOSITE HYDROXIDE PARTICLES AND MANUFACTURING METHOD THEREFOR, POSITIVE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY AND MANUFACTURING METHOD THEREOF, AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY | |
| JP7047251B2 (en) | Manufacturing method of positive electrode active material for non-aqueous electrolyte secondary battery | |
| CN107078292B (en) | Positive electrode active material for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery | |
| JP2018060759A (en) | Method for manufacturing nickel cobalt manganese-containing composite hydroxide, positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing the same, and nonaqueous electrolyte secondary battery arranged by use of positive electrode active material hereof | |
| JP2015140292A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery | |
| JP7114876B2 (en) | Transition metal composite hydroxide particles and manufacturing method thereof, positive electrode active material for lithium ion secondary battery and manufacturing method thereof, and lithium ion secondary battery | |
| JP2022177291A (en) | Positive electrode active material for high-strength lithium ion secondary battery, and lithium ion secondary battery employing the positive electrode active material | |
| JP7273260B2 (en) | Positive electrode active material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery | |
| JP2019212365A (en) | Positive electrode active material for lithium ion secondary battery and manufacturing method thereof, and lithium ion secondary battery using the same | |
| JP2022046655A (en) | Cathode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the cathode active material | |
| CN111033831B (en) | Positive electrode active material for nonaqueous electrolyte secondary battery, method for producing same, and nonaqueous electrolyte secondary battery using same | |
| JP6862786B2 (en) | Method for Producing Transition Metal-Containing Composite Hydroxide and Method for Producing Positive Electrode Active Material for Non-Aqueous Electrolyte Secondary Battery | |
| WO2023228957A1 (en) | Positive electrode active material for lithium-ion secondary battery and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180425 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210315 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220207 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220411 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20220411 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20220701 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220930 |
|
| C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20220930 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20221007 |
|
| C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20221011 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20221028 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221110 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7185838 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |