CN112750999A - Cathode material, preparation method thereof and lithium ion battery - Google Patents
Cathode material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN112750999A CN112750999A CN202011577803.5A CN202011577803A CN112750999A CN 112750999 A CN112750999 A CN 112750999A CN 202011577803 A CN202011577803 A CN 202011577803A CN 112750999 A CN112750999 A CN 112750999A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- positive electrode
- cathode material
- electrode material
- Prior art date
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- Granted
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 114
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 215
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 115
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 95
- 239000010941 cobalt Substances 0.000 claims abstract description 95
- 239000011572 manganese Substances 0.000 claims abstract description 88
- 239000007774 positive electrode material Substances 0.000 claims abstract description 82
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 56
- 239000002243 precursor Substances 0.000 claims description 52
- 239000013078 crystal Substances 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000002019 doping agent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000003825 pressing Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 150000002696 manganese Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011268 mixed slurry Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- -1 cobalt oxyhydroxide Chemical compound 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- IXONOEXDSRFORV-UHFFFAOYSA-N 2-aminoacetic acid;cobalt Chemical compound [Co].NCC(O)=O.NCC(O)=O IXONOEXDSRFORV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 36
- 239000010405 anode material Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005245 sintering Methods 0.000 description 18
- 238000007873 sieving Methods 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 229910052814 silicon oxide Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 10
- 239000011164 primary particle Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229940053662 nickel sulfate Drugs 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- 239000012716 precipitator Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 4
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- 239000002033 PVDF binder Substances 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 230000001351 cycling effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a positive electrode material, a preparation method thereof and a lithium ion battery. The cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate and a cobalt-containing compound coated on the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, and the cobalt-containing compound accounts for 0.5-5 mol% of cobalt element based on the total mole number of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate. The positive electrode material has the advantages of stable structure, high energy density, good rate capability, high capacity retention rate, simple preparation method and low cost.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material, a preparation method thereof and a lithium ion battery.
Background
With the increasing global energy and environmental problems, there is an urgent need for new, clean energy sources to replace traditional fossil energy sources. The power lithium ion battery is a high-energy density battery, has the advantages of zero pollution, zero emission, small size and the like, and is a trend of development and application of power batteries at home and abroad.
The positive electrode material is used as a main component of the lithium ion battery, determines the capacity and the cost of the battery, and the high-nickel multi-component material is widely concerned due to high energy density, long cycle life and high cost performance.
By reaction in Ni in CN101378126A0.5Mn0.5(OH)2Coating a layer of cobalt hydroxide on the outer layer of the substrate to obtain yNi0.5Mn0.5(OH)2]·(1-y)[Co(OH)2](y is more than or equal to 0.2 and less than or equal to 0.8) and the precursor is sintered at high temperature to obtain the coated multi-element anode material, and the method has complex process and higher requirement on automation of equipment in the synthesis process of the precursor and is not beneficial to industrial production; in the high-temperature lithiation process, due to the migration of transition metals, the anode material and a precursor are difficult to ensure to have the same gradient; and the Co content is higher, about 20-80%, and the cost is higher.
In CN109088067A, a spinel-structured nickel-manganese precursor, a layered-structured nickel-manganese precursor, a lithium source and a cobalt source are mixed and then calcined to obtain a composite cathode material, and the method needs to synthesize various precursors and is complex in process; and a cobalt source is introduced into the multi-component material by a doping method, so that the uniformity of Co dispersion is difficult to ensure.
CN106532006A and CN109713262A utilize cobalt oxide to coat the multi-element anode material, the main body is still the multi-element anode material, the Co content exceeds 10 percent, and the cost is still higher.
In order to obtain a multi-component cathode material with high energy density and low cost, the content of Co needs to be controlled. However, the current high-nickel low-cobalt material has poor structural stability, poor rate capability and poor cycle performance, and is difficult to be applied to power lithium ion batteries.
Therefore, it is important to obtain a positive electrode material with high energy density and stable structure through reasonable structural design.
Disclosure of Invention
The invention aims to solve the problems of high Co content and high cost in the anode material, complex preparation process and unstable structure of the anode material in the prior art, and provides the anode material, the preparation method thereof and the lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a high-nickel low-cobalt single-crystal cathode material, wherein the cathode material includes a high-nickel cobalt-free multi-element cathode material intermediate and a cobalt-containing compound coated on an outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, and a content of the cobalt-containing compound in terms of cobalt element is 0.5 to 5 mol% based on a total molar number of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
The second aspect of the present invention provides a preparation method of the aforementioned high-nickel low-cobalt single crystal cathode material, wherein the preparation method includes:
(1) under the protection of nitrogen, a mixed salt solution containing nickel salt and manganese salt, an optional salt solution A, an alkali solution and ammonia water are contacted in a parallel flow manner to react to obtain solid-liquid mixed slurry; washing, filter pressing and drying the solid-liquid mixed slurry to obtain a precursor;
(2) contacting the precursor, a lithium source and an optional dopant D, performing first mixing, and performing first roasting treatment to obtain a cathode material intermediate;
(3) and contacting the cathode material intermediate, the nano cobalt-containing compound and the optional coating agent E, performing second mixing, and performing second roasting treatment to obtain the high-nickel low-cobalt single crystal cathode material.
The invention provides a lithium ion battery, wherein the lithium ion battery contains the high-nickel low-cobalt single-crystal cathode material.
Through the technical scheme, the invention has the following advantages:
(1) according to the high-nickel low-cobalt single crystal cathode material provided by the invention, the Co is a nano-scale compound, so that the dosage of expensive Co is reduced as much as possible, the effect of uniform surface coating is achieved, and the cost of raw materials can be well reduced. The specific capacity of the material for the first discharge of 0.1C under 3.0-4.3V can reach more than 195 mAh/g.
(2) The high-nickel low-cobalt single crystal cathode material provided by the invention has the advantages that the surface is coated with Co element, the material structure can be stabilized, the material phase is ensured to be a uniform and stable layered structure, lithium ions can be smoothly inserted and extracted, the mobility of the Li ions can be improved by the Co coating layer on the surface, and the problem of poor multiplying power caused by low Co content is solved.
(3) The high nickel material has more residual Li due to the serious Li/Ni mixed discharge2CO3And LiOH is enriched on the surface of the material, and side reactions are easy to occur in the circulating process, so that the battery is out of service. Usually, a water washing step is needed in the production process of the high-nickel material to reduce the surface residual alkali, and the cobalt-containing compound coated by the material can react with the surface residual alkali through high-temperature calcination, so that the surface Li is effectively reduced2CO3And the content of LiOH, so that a complex water washing step can be replaced, the production cost is reduced, the damage of water washing to the material structure is eliminated, and the structural stability of the material is improved.
Drawings
FIG. 1 is an SEM photograph of the precursor prepared in example 1;
FIG. 2 is an SEM image of the high-Ni cobalt-free multi-element cathode material intermediate prepared in example 1;
FIG. 3 is an SEM image of a high-nickel low-cobalt single-crystal cathode material prepared in example 1;
FIG. 4 is a graph comparing the 1.0C/1.0C @45 ℃ cycles of example 1 and comparative example 1 for 80 weeks.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, a high-nickel low-cobalt single-crystal cathode material is provided, wherein the cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate and a cobalt-containing compound coated on an outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, and a content of the cobalt-containing compound in terms of cobalt element is 0.5 to 5 mol% based on a total molar number of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
The inventors of the present invention found that: the multielement lithium ion battery anode material mainly comprises Ni/Co/Mn, has high Ni content and high material energy density, but the problems of serious lithium-nickel mixed discharge, multiple phase change, surface oxygen evolution and the like of the material can be caused by the increase of the nickel content, so that the cycle life and the safety of the material are poor. Co is used for improving the rate capability of the material and playing a role in stabilizing the structure, but Co is expensive, the content of Co is high, and the cost of the material is high. Mn can stabilize the material structure, but Mn is not good in crystallinity and has no electrochemical activity.
Further research by the inventors of the present invention shows that the structural stability of the material mainly depends on the crystal surface structure, and structural phase change occurs from the surface and is transmitted to the interior, so that the material structure can be well stabilized by means of coating. Compared with the agglomerated material, the single crystal material has a more compact and uniform structure, has better structural stability, and can improve the cycle performance and safety of the material.
In the invention, the inventor adopts the preparation method of the invention to firstly synthesize a cobalt-free precursor containing an optional dopant A, then add the optional dopant D, obtain a single-crystal cobalt-free intermediate through high-temperature sintering, then coat a compound containing a cobalt compound and an optional coating agent E on the surface, and obtain a coated high-nickel low-cobalt single-crystal anode material with uniform appearance through high-temperature sintering again.
According to the present invention, it is preferable that the cobalt-containing compound is contained in an amount of 1 to 4 mol% in terms of cobalt element, based on the total molar number n (ni) + n (mn) of nickel and manganese in the high-nickel cobalt-free multi-element positive electrode material intermediate. In the invention, the content of the cobalt-containing compound calculated by cobalt element is limited to the range, and the method has the advantages that the effect of uniformly coating the surface of the cathode material is achieved by using the least amount of Co, the structural stability of the obtained material is high, and the cost is low. And the surface residual alkali can be controlled in an optimal range.
According to the present invention, preferably, the cobalt-containing compound is selected from lithium cobaltate and/or lithium nickel cobalt manganese.
According to the invention, the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate is optionally coated with a compound containing E, wherein E is selected from one or more of Al, Nb, Mo, W, B, Si, N, P, S, F and Cl; preferably, E is selected from one or more of Al, Nb, W, B and Si.
According to the invention, the E-containing compound is selected from one or more of alumina, niobium pentoxide, tungsten oxide, boron oxide, aluminium fluoride and silicon oxide. In the present invention, the coating with the E-containing compound has an advantage of further stabilizing the material structure and preventing the corrosion of the surface of the material by the electrolyte.
According to the invention, the positive electrode material also contains optional doping elements A and/or D.
According to the present invention, the composition of the cathode material intermediate is represented by the following general formula:
Li1+a(AmDnNi1-x-yMnx)CoyEzO2；
wherein a is more than or equal to 0.1 and less than or equal to 0.3, m is more than or equal to 0 and less than or equal to 0.02, n is more than or equal to 0 and less than or equal to 0.02, x is more than 0 and less than or equal to 0.2, y is more than or equal to 0.005 and less than or equal to 0.05, and z is more than or equal to 0 and less than or; preferably, a is more than or equal to 0 and less than or equal to 0.2, m is more than or equal to 0.005 and less than or equal to 0.015, n is more than or equal to 0.005 and less than or equal to 0.015, x is more than or equal to 0.05 and less than or equal to 0.2, y is more than or equal to 0.01 and less than or equal to 0.04, and z is more than or equal to 0.005 and.
According to the invention, A is selected from one or more of V, Ta, Cr, La, Al, Ce, Er, Ho, Y, Mg, Sr, Ba, Ra, Zr and Ti; preferably, A is selected from one or more of La, Al, Ce, Er, Ho, Y, Mg, Sr, Ba, Ra, Zr and Ti; more preferably, a is selected from one or more of La, Al, Ce, Er and Ho. In the invention, doping A has the advantages of supporting the crystal lattice layers in a charged state and stabilizing the crystal lattice structure.
According to the invention, the doping amount of A is 0-2 mol%, preferably 0.5-1.5 mol% based on the total mole number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
According to the invention, D is selected from one or more of Mg, Sr, Ba, Ra, Zr, Ti, Fe, Ca, Zn and Hf; preferably, D is selected from one or more of Mg, Sr, Ba, Fe and Zn. In the invention, the doping D has the advantages of stabilizing the lattice structure, improving the cycling stability of the material, and in addition, part of elements can play a fluxing role in the sintering process. According to the invention, the doping amount of D is 0-2 mol%, preferably 0.5-1.5 mol% based on the total mole number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
According to the invention, the coating E has the advantage of delaying the erosion of the electrolyte to the material during the use of the battery.
According to the invention, the doping amount of E is 0-2 mol%, preferably 0.5-1.5 mol% based on the total mole number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
According to the inventionD of the positive electrode material502-5 μm, surface-enriched Li of the positive electrode material2CO3The content is 1000-4000ppm, the LiOH content is 500-3000 ppm; preferably, D of the positive electrode material503.5-4.5 μm, surface-enriched Li of the positive electrode material2CO3The content is 1150-3500ppm, the LiOH content is 1200-2500 ppm; more preferably, D of the positive electrode material503.8 to 4.4 μm, surface-enriched Li of the positive electrode material2CO3The content is 1150-3060ppm and the LiOH content is 1420-1810 ppm.
According to the invention, the positive electrode material has a compacted density of more than 3.5g/cm3Preferably 3.5 to 4.0g/cm3。
According to a second aspect of the present invention, there is provided a method for preparing the aforementioned high nickel and low cobalt single crystal cathode material, wherein the method comprises:
(1) under the protection of nitrogen, a mixed salt solution containing nickel salt and manganese salt, an optional salt solution A, an alkali solution and ammonia water are contacted in a parallel flow manner to react to obtain solid-liquid mixed slurry; washing, filter pressing and drying the solid-liquid mixed slurry to obtain a precursor;
(2) contacting the precursor, a lithium source and an optional dopant D, performing first mixing, and performing first roasting treatment to obtain a cathode material intermediate;
(3) and contacting the cathode material intermediate, the nano cobalt-containing compound and the optional coating agent E, performing second mixing, and performing second roasting treatment to obtain the high-nickel low-cobalt single crystal cathode material.
According to the invention, in step (1), the concentration of the nickel salt is 1-3mol/L, preferably 1.5-2.5 mol/L; the concentration of the manganese salt is 1-3mol/L, preferably 1.5-2.5 mol/L; the concentration of the salt solution A is 0.01-0.5mol/L, preferably 0.2-0.3 mol/L; the concentration of the alkali solution is 5-10mol/L, and preferably 7-8 mol/L.
According to the present invention, in the step (1), the doped a salt may be one or more of a-containing oxide, oxyhydroxide, hydroxide, sulfate, nitrate, carbonate and oxalate; preferably, the doped a salt may be a sulfate and/or nitrate salt containing a.
According to the invention, the molar ratio of the amounts of the mixed salt solution and the salt solution A is 1: (0-0.02), preferably 1: (0.002-0.015), more preferably 1: (0.01-0.015).
According to the present invention, the pH value of the solid-liquid mixed slurry is 11 to 13, preferably 12.0 to 12.5, more preferably 12.3 to 12.4.
According to the invention, the conditions of the reaction include: the stirring speed is 150-250rpm, the temperature range is 40-60 ℃, and the time is 6-30 h; preferably, the stirring speed is 180-220rpm, the temperature range is 52-56 ℃, and the time is 20-25 h.
According to the invention, the molar ratio of the mixed salt solution to the amounts of lithium source and dopant D is 1: (0.9-1.3): (0-0.02), preferably 1: (1.0-1.2): (0.005-0.015), more preferably 1: (1.03-1.08): (0.008-0.014).
According to the invention, in the step (1), the drying temperature is 100-130 ℃, and the drying time is 4-10 h.
According to the invention, in the step (1), the solid-liquid mixed slurry is washed and filter-pressed, wherein the washing is washed by alkali liquor for 1-4 times.
According to the invention, the filter pressing is carried out by a filter press, and the water content of the filter cake after filter pressing is less than 20%.
According to the invention, the precursor is a small-particle nickel manganese hydroxide precursor containing a dopant A, wherein D of the precursor502.0 to 6.0. mu.m, preferably 3.0 to 5.0. mu.m, more preferably 3.9 to 4.5. mu.m; the loose packed density is 0.6-1.0g/cm3Preferably 0.70 to 0.82g/cm3(ii) a The tap density is 1.2-1.6g/cm3Preferably 1.31 to 1.52g/cm3(ii) a In the form of spherical or spheroidal individual particles.
In addition, in the present invention, it is noted that:
bulk density refers to the bulk density measured when the material is free to fill the container.
Tap density refers to the density of a material under sufficient vibration of the material, i.e. the density of a vibro-compaction, in this application, the density measured at (frequency 250Hz, vibration 3000).
According to the present invention, in the step (2), the conditions of the first firing treatment include: the temperature is 600-1000 ℃ and the time is 5-20 h; preferably, the temperature is 790-900 ℃, and the time is 12-15 h; more preferably, the calcination atmosphere is oxygen.
According to the invention, the molar ratio of the mixed salt solution to the amounts of the nano cobalt-containing compound and the capping agent E is 1: (0.005-0.05): (0-0.02), preferably 1: (0.01-0.04): (0.005-0.015), more preferably 1: (0.01-0.04): (0.008-0.015).
According to the invention, the particle size of the nano cobalt-containing compound is 1-100nm, preferably 5-50nm, more preferably 30-50 nm.
According to the invention, the nano cobalt-containing compound is selected from one or more of cobalt oxide, cobalt hydroxide, cobalt oxyhydroxide, cobalt fluoride, cobaltous hydroxide, cobaltosic oxide, cobalt carbonate, cobalt sulfate, cobalt sulfide, cobalt acetate and cobalt glycinate; preferably, the nano cobalt-containing compound is selected from one or more of cobalt hydroxide, cobalt oxide, cobaltosic oxide, cobaltous hydroxide and cobalt oxyhydroxide.
According to the invention, the nano cobalt-containing compound forms a continuous coating layer on the surface of the high-nickel cathode material.
According to the invention, the dopant D is one or more of an oxide, oxyhydroxide, hydroxide, carbonate and oxalate containing D.
According to the invention, the dopant D is selected from one or more of magnesium oxide, strontium oxide, iron oxide, barium oxide and zinc oxide.
According to the invention, in the step (2), D of the intermediate of the positive electrode material50Is 2.0 to 5.0 μm, preferably 3.5 to 4.5 μm, more preferably 3.8 to 4.3 μm, and is a single crystal type particle.
According to the present invention, in the step (3), the conditions of the second firing treatment include: the temperature is 500-900 ℃ and the time is 3-15 h; preferably, the temperature is 650-780 ℃, and the time is 8-10 h; the calcination atmosphere is oxygen, air or a mixed gas, and oxygen is preferred.
According to the invention, the coating agent E is one or more of an oxide, oxyhydroxide, hydroxide, carbonate, fluoride, phosphate, sulfide, nitrate and oxalate containing E.
According to the invention, the preparation method further comprises: carrying out secondary roasting treatment on the high-nickel low-cobalt single crystal positive electrode material to enable the Co part to enter the high-nickel cobalt-free multi-element positive electrode material intermediate; preferably, the conditions of the secondary calcination treatment include: the temperature is 500-900 ℃ and the time is 3-15 h.
In the invention, the secondary high-temperature sintering can ensure that the Co part enters the high-nickel cobalt-free multi-element cathode material intermediate (Ni/Mn layer structure) to form a gradient structure, so that the stripping of a coating layer can not occur in the charge and discharge process of a battery, and the cycle retention rate of the material can be improved.
According to the invention, the elements which are difficult to disperse are doped in the precursor by doping, the elements which are beneficial to single crystallization are doped by one-time sintering, the elements which are difficult to enter crystal lattices are coated on the surface of the material, and the structure of the material is stabilized by three times of modification. And finally, the anode material is made into a single crystal product with better structural stability, and the cycling stability and the thermal stability of the anode material can be improved through the combined action of the three means. The cycle capacity retention rate of the half-cell of the anode material in 80 weeks of 1C charge and discharge reaches over 90 percent under the condition of 45 ℃.
The invention provides a lithium ion battery, wherein the lithium ion battery contains the high-nickel low-cobalt single-crystal cathode material.
According to a particularly preferred embodiment of the present invention, a method for preparing a high-nickel low-cobalt single crystal cathode material comprises:
(1) under the protection of nitrogen, a mixed salt solution containing nickel salt and manganese salt, an optional salt solution A, an alkali solution and ammonia water are contacted in a parallel flow manner to react to obtain solid-liquid mixed slurry; washing, filter pressing and drying the solid-liquid mixed slurry to obtain a precursor; wherein the concentration of the nickel salt is 1.8-2.2mol/L, the concentration of the manganese salt is 1.8-2.2mol/L, the concentration of the A salt solution is 0.2-0.3mol/L, and the concentration of the alkali solution is 7.5-8 mol/L; the doped A salt can be sulfate and/or nitrate containing A; the molar ratio of the mixed salt solution to the salt solution A is 1: (0.01-0.015); the pH value of the solid-liquid mixed slurry is 12.3-12.4; the reaction conditions include: the stirring speed is 180-220rpm, the temperature range is 52-56 ℃, and the time is 20-25 h;
(2) contacting the precursor, a lithium source and an optional dopant D, performing first mixing, and performing first roasting treatment to obtain a cathode material intermediate; the molar ratio of the mixed salt solution to the lithium source and the dopant D is 1: (1.03-1.08): (0.008-0.014); the drying temperature is 100-130 ℃, and the drying time is 4-10 h; washing and filter pressing the solid-liquid mixed slurry, wherein the washing is carried out by adopting alkali liquor for washing for 1-4 times; performing filter pressing by using a filter press, wherein the water content of the filter cake after filter pressing is less than 20%; the precursor is a small-particle nickel-manganese hydroxide precursor containing a dopant A, wherein D of the precursor503.9-4.5 μm; the loose density is 0.70-0.82g/cm3(ii) a The tap density is 1.31-1.52g/cm3(ii) a In the form of spherical or spheroidal individual particles.
(3) Contacting the cathode material intermediate, the nano cobalt-containing compound and the optional coating agent E, performing second mixing, and performing second roasting treatment to obtain a high-nickel low-cobalt single crystal cathode material; wherein the molar ratio of the mixed salt solution to the usage of the nano cobalt-containing compound and the coating agent E is 1: (0.01-0.04): (0.008-0.015); the particle size of the nano cobalt-containing compound is 30-50 nm; d of the intermediate of the positive electrode material503.8-4.3 μm; the conditions of the second roasting treatment include: the temperature is 650-780 ℃ and the time is 8-10 h.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
manufacturing the button cell:
firstly, a composite nickel-cobalt-manganese multi-element positive electrode active material for a non-aqueous electrolyte secondary battery, acetylene black and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 95: 3: 2, mixing, coating on an aluminum foil, drying, stamping and forming into a positive pole piece with the diameter of 12mm and the thickness of 120 mu m by using the pressure of 100MPa, and then putting the positive pole piece into a vacuum drying box to dry for 12 hours at the temperature of 120 ℃.
The negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film having a thickness of 25 μm; LiPF of 1mol/L is used as electrolyte6And a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in equal amounts.
Assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5ppm, and taking the cell as an unactivated cell.
The performance evaluation on the button cells made is defined as follows:
placing for 2h after manufacturing the button cell, after the open-circuit voltage is stable, charging the anode to the cut-off voltage of 4.3V at the current density of 0.1C, then charging for 30min at constant voltage, and then discharging to the cut-off voltage of 3.0V at the same current density; the same procedure was repeated 1 more time, and the battery at this time was regarded as an activated battery.
The cycle performance was tested as follows: the high-temperature capacity retention rate of the material is examined by using an activated battery and circulating 80 times at the temperature of 45 ℃ in a voltage interval of 3.0-4.3V at the current density of 1C.
The electrical property test parameters are tested by a Shenzhen Xinwei CT-3008 battery test system; li2CO3And the LiOH content was obtained by potentiometric titration.
The raw materials are all commercial products.
Example 1
This example is to illustrate a positive electrode material prepared by the method of the present invention.
(1) Taking nickel sulfate and manganese sulfate as raw materials, and mixing the raw materials according to the molar ratio of Ni: and Mn is 90: 10 are prepared into 2mol/L uniform nickel and manganese salt mixed solution and 0.2mol/L Ce2(SO4)3The solution is prepared by preparing 8mol/L NaOH solution as a precipitator and directly preparing 25 percent ammonia waterAs a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent mode, and [ n (Ni) + n (Mn)]: n (ce) ═ 1:0.01, stirring speed of 200rpm, reaction temperature of 55 ℃, pH value of 12.3, cocurrent time of 23h and aging for 20 h. Filter pressing, washing and drying at 120 ℃ for 5h to obtain D504.0 mu m nickel-manganese hydroxide precursor containing a dopant Ce, wherein the precursor is spherical or spheroidal single particle, has a loose structure and a loose packing density of 0.72g/cm3Tap density of 1.34g/cm3。
(2) Nickel manganese hydroxide precursor, lithium hydroxide, magnesium oxide in the amount of [ n (Ni) + n (Mn)]: n (Li): n (mg) ═ 1: 1.06: 0.008, uniformly mixing in a high-speed mixer, sintering at 850 deg.C for 12h in oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain cobalt-free single crystal anode material intermediate, D503.8um, primary particles are independent of each other.
(3) The positive electrode material intermediate, cobalt hydroxide having a particle size of 40nm, and silicon oxide were mixed in such a manner that [ n (Ni) + n (Mn) ]: n (Co): n (si) ═ 1: 0.03: 0.012, evenly mixing in a high mixing machine, sintering for 10 hours at 720 ℃ in the atmosphere of oxygen, naturally cooling to room temperature, crushing and sieving to obtain the coated high-nickel low-cobalt single crystal anode material.
The obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and silicon oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of the cobalt-containing compound in terms of cobalt element is n (Co) 3 mol%, and the content of the silicon oxide in terms of silicon element is n (Si) 1.2 mol%, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And D of the positive electrode material50Is 3.9um, the surface of the cathode material is enriched with Li2CO31490ppm and 1460ppm of LiOH. Wherein the composition of the cathode material is represented by the general formula Li1.06(Ce0.01Mg0.008Ni0.9Mn0.1)Co0.03Si0.012O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 210.6mAh/g, the discharge specific capacity of 1.0C is 194.7mAh/g, the multiplying power of 1.0C/0.1C is 92.5 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 94.2 percent.
In addition, fig. 1 is an SEM image of the precursor prepared in example 1; as can be seen from fig. 1: the precursor is spherical or sphere-like single particles, and the structure is loose.
Fig. 2 is an SEM image of the cathode material intermediate prepared in example 1; as can be seen from fig. 2: the intermediate is a single crystal compound with mutually independent primary particles.
FIG. 3 is an SEM image of a high-nickel low-cobalt single-crystal cathode material prepared in example 1; as can be seen from fig. 3: the material is a single crystal type compound with a surface coating layer.
Example 2
This example is to illustrate a positive electrode material prepared by the method of the present invention.
(1) Taking nickel sulfate and manganese sulfate as raw materials, and mixing the raw materials according to the molar ratio of Ni: and Mn is 90: 10 are prepared into 2mol/L even nickel and manganese salt mixed solution and 0.2mol/L Al2(SO4)3The solution is prepared into 8mol/L KOH solution as a precipitator, and 25% ammonia water is directly used as a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent mode, and [ n (Ni) + n (Mn)]: n (al) ═ 1: 0.015 stirring speed of 200rpm, reaction temperature of 55 ℃, pH value of 12.3, cocurrent time of 20h and aging for 20 h. Washing, filter-pressing and drying at 110 ℃ for 5.5h to obtain D504.0 mu m nickel manganese hydroxide precursor containing dopant Al, which is spherical or sphere-like single particle, loose structure and loose packing density of 0.73g/cm3Tap density of 1.35g/cm3。
(2) Nickel manganese hydroxide precursor, lithium hydroxide, strontium oxide in the amount of [ n (Ni) + n (Mn)]: n (Li): n (sr) ═ 1: 1.05: 0.012, uniformly mixing in a high-speed mixer, sintering at 800 deg.C for 12h in oxygen atmosphere, and naturally cooling to room temperatureCrushing and sieving to obtain the intermediate of the cobalt-free single crystal anode material D503.8um, primary particles are independent of each other.
(3) The positive electrode material intermediate, cobalt oxide having a particle size of 30nm, and boron oxide were mixed in such a manner that [ n (Ni) + n (Mn) ]: n (Co): n (b) ═ 1: 0.01: 0.01, uniformly mixing in a high mixing machine, sintering at 650 ℃ for 10h in an oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the coated high-nickel low-cobalt single crystal anode material.
The obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and boron oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of the cobalt-containing compound in terms of cobalt element is n (Co) 1 mol%, and the content of the boron oxide in terms of boron element is n (B) 1 mol%, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And D of the positive electrode material50Is 3.8um, the surface of the cathode material is enriched with Li2CO33060ppm and LiOH 1810 ppm. Wherein the composition of the cathode material is represented by the general formula Li1.05(Al0.015Sr0.012Ni0.9Mn0.1)Co0.01B0.01O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 211.8mAh/g, the discharge specific capacity of 1.0C is 193.1mAh/g, the multiplying power of 1.0C/0.1C is 91.2 percent, and the cycle capacity retention rate of 80 weeks under the condition of 1C/1C @45 ℃ is 93.1 percent.
Example 3
This example is to illustrate a positive electrode material prepared by the method of the present invention.
(1) Taking nickel sulfate and manganese sulfate as raw materials, and mixing the raw materials according to the molar ratio of Ni: and Mn is 90: 10 are prepared into 2mol/L uniform nickel and manganese salt mixed solution and 0.2mol/L Ho (NO)3)3And preparing a solution, namely preparing an 8mol/L NaOH solution as a precipitator and directly using 25% ammonia water as a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent flow modeIn (1), control of [ n (Ni) + n (Mn)]: n (ho) ═ 1: 0.015 stirring speed of 200rpm, reaction temperature of 56 ℃, pH value of 12.4, cocurrent time of 24 hours and aging of 20 hours. Washing, filter-pressing and drying at 120 ℃ for 6h to obtain D50Is a nickel-manganese hydroxide precursor with 3.9 mu m and a dopant Ho, the precursor is spherical or sphere-like single particles, has a loose structure and a loose packing density of 0.71g/cm3Tap density of 1.33g/cm3。
(2) Nickel manganese hydroxide precursor, lithium hydroxide, and iron oxide in the amounts of [ n (Ni) + n (Mn)]: n (Li): n (fe) ═ 1: 1.04: 0.009, mixing in a high-speed mixer, sintering at 870 deg.C for 12 hr in oxygen atmosphere, naturally cooling to room temperature, crushing, sieving to obtain cobalt-free single crystal anode material intermediate, and D503.8um, primary particles are independent of each other.
(3) The positive electrode material intermediate, cobaltosic oxide having a particle size of 50nm, and aluminum fluoride were mixed in such a manner that [ n (Ni) + n (Mn) ]: n (Co): n (al) ═ 1: 0.02: 0.01, evenly mixing in a high-speed mixer, sintering for 10 hours at 700 ℃ in the air atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the coated high-nickel low-cobalt single crystal anode material.
The obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and aluminum fluoride which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of cobalt in the cobalt-containing compound is n (Co) 2 mol%, and the content of aluminum in the aluminum fluoride is n (Al) 1 mol%, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And the positive electrode material D50Is 4.0um, the surface of the cathode material is enriched with Li2CO32440ppm and 1640ppm of LiOH. Wherein the composition of the cathode material is represented by the general formula Li1.04(Ho0.015Fe0.009Ni0.9Mn0.1)Co0.02Al0.01O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 210.5mAh/g, the discharge specific capacity of 1.0C is 193.5mAh/g, the multiplying power of 1.0C/0.1C is 91.9 percent, and the cycle capacity retention rate of 80 weeks under the condition of 1C/1C @45 ℃ is 93.5 percent.
Example 4
This example is to illustrate a positive electrode material prepared by the method of the present invention.
(1) Taking nickel sulfate and manganese sulfate as raw materials, and mixing the raw materials according to the molar ratio of Ni: mn is 80: 20 is prepared into 2mol/L uniform nickel and manganese salt mixed solution and 0.2mol/L Er2(SO4)3And preparing a solution, namely preparing an 8mol/L NaOH solution as a precipitator and directly using 25% ammonia water as a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent mode, and [ n (Ni) + n (Mn)]: n (er) ═ 1: 0.005, stirring speed 200rpm, reaction temperature maintained at 52 ℃, pH value 12.3, cocurrent time 19h, aging 20 h. Washing, filter-pressing and drying at 100 ℃ for 7h to obtain D50Is a 4.1 mu m nickel-manganese hydroxide precursor containing a dopant Er, the precursor is spherical or sphere-like single particles, has a loose structure and a loose packing density of 0.70g/cm3Tap density of 1.31g/cm3。
(2) Nickel manganese hydroxide precursor, lithium carbonate and barium oxide were mixed in accordance with [ n (Ni) + n (Mn)]: n (Li): n (ba) ═ 1: 1.05: 0.01, uniformly mixing in a high-speed mixer, sintering at 900 ℃ for 12h in the atmosphere of oxygen, naturally cooling to room temperature, crushing and sieving to obtain a cobalt-free single crystal anode material intermediate, D50Is 3.9 um. The primary particles are independent of each other.
(3) The positive electrode material intermediate, cobalt hydroxide having a particle size of 45nm, and niobium pentoxide were mixed in such a manner that [ n (Ni) + n (Mn) ]: n (Co): n (nb) ═ 1: 0.03: 0.015 percent, evenly mixing in a high mixing machine, sintering for 10 hours at 780 ℃ in air atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the coated high-nickel low-cobalt single crystal anode material.
The obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and niobium pentoxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of the cobalt-containing compound in terms of cobalt element is n (Co) 3 mol% and the content of the niobium pentoxide in terms of niobium element is n (Nb) 1.5 mol% based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And the positive electrode material D50Is 4.1um, the surface of the cathode material is enriched with Li2CO31150ppm and 1420ppm of LiOH. Wherein the composition of the cathode material is represented by the general formula Li1.05(Er0.005Ba0.01Ni0.8Mn0.2)Co0.03Nb0.015O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 200.2mAh/g, the discharge specific capacity of 1.0C is 185.6mAh/g, the rate of 1.0C/0.1C is 92.7 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 95.5 percent.
Example 5
This example is to illustrate a positive electrode material prepared by the method of the present invention.
(1) Taking nickel sulfate and manganese sulfate as raw materials, and mixing the raw materials according to the molar ratio of Ni: and Mn is 95: 5 are prepared into 2mol/L uniform nickel and manganese salt mixed solution and 0.2mol/L La (NO)3)3And preparing a solution, namely preparing an 8mol/L NaOH solution as a precipitator and directly using 25% ammonia water as a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent mode, and [ n (Ni) + n (Mn)]: n (la) 1: 0.012, stirring speed 200rpm, reaction temperature maintained at 55 ℃, pH value 12.3, parallel flow time 28h, aging for 20 h. Washing, filter-pressing and drying at 120 ℃ for 6h to obtain D50The precursor is a nickel-manganese hydroxide precursor with the particle size of 4.0 mu m, the precursor is spherical or spheroidal single particle, the structure is loose, and the apparent density is 0.71g/cm3Tap density of 1.32g/cm3。
(2) Nickel manganese hydroxide precursor, lithium hydroxide, zinc oxide according to the formula [ n (Ni) + n (Mn)]: n (Li): n (zn) ═ 1: 1.08: 0.014, mixing in a high-speed mixer, sintering at 790 deg.C for 12 hr in oxygen atmosphere, and naturally cooling to room temperatureCrushing and sieving to obtain the intermediate of the cobalt-free single crystal anode material D50Is 3.9 um. The primary particles are independent of each other.
(3) The positive electrode material intermediate, cobalt oxyhydroxide having a particle diameter of 47nm, and tungsten oxide were mixed in such a manner that [ n (Ni) + n (Mn) ]: n (Co): n (w) ═ 1: 0.04: 0.008, uniformly mixing in a high mixing machine, sintering at 650 ℃ for 10h in an oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the coated high-nickel low-cobalt single crystal anode material.
The obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and tungsten oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of the cobalt-containing compound in terms of cobalt element is n (Co) 4 mol%, and the content of the tungsten oxide in terms of tungsten element is n (W) 0.8 mol%, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And the positive electrode material D50Is 3.9um, the surface of the cathode material is enriched with Li2CO32580ppm and 1690ppm LiOH. Wherein the composition of the cathode material is represented by the general formula Li1.08(La0.012Zn0.014Ni0.95Mn0.05)Co0.04W0.08O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 216.5mAh/g, the discharge specific capacity of 1.0C is 201.8mAh/g, the multiplying power of 1.0C/0.1C is 93.2 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 91.4 percent.
Example 6
A positive electrode material was prepared in the same manner as in example 1, except that:
in step (1), [ n (Ni) + n (Mn)]: n (ce) ═ 1: 0.002; to obtain D50Nickel manganese hydroxide precursor of 4.5 μm, apparent density of 0.82g/cm3Tap density of 1.52g/cm3。
In step (2), [ n (Ni) + n (Mn)]: n (Li): n (mg) ═ 1: 0.98: 0.005; crushing and sieving to obtain a cobalt-free single crystal anode material intermediate D50Is 4.3 um.
In step (3), [ n (ni) + n (mn) ]: n (Co): n (si) ═ 1: 0.006: 0.02.
the obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and silicon oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of cobalt in the cobalt-containing compound is n (Co) 0.6 mol% and the content of silicon in the silicon oxide is n (Si) 2 mol% based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And D of the positive electrode material50Is 4.4um, the surface of the cathode material is enriched with Li2CO33950ppm and LiOH 2010 ppm. Wherein the composition of the cathode material is represented by the general formula Li0.98(Ce0.002Mg0.005Ni0.9Mn0.1)Co0.006Si0.02O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial specific discharge capacity of 0.1C of the positive electrode material is 198.2mAh/g, the specific discharge capacity of 1.0C is 180.2mAh/g, the rate of 1.0C/0.1C is 90.9 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 90.8 percent.
Example 7
A positive electrode material was prepared in the same manner as in example 1, except that:
in step (1), [ n (Ni) + n (Mn)]: n (ce) ═ 1: 0.01; to obtain D50Nickel manganese hydroxide precursor of 4.2 μm, apparent density of 0.75g/cm3Tap density of 1.38g/cm3。
In step (2), [ n (Ni) + n (Mn)]: n (Li): n (mg) ═ 1: 1.03: 0.01; crushing and sieving to obtain a cobalt-free single crystal anode material intermediate D50Is 4.0 um.
In step (3), [ n (ni) + n (mn) ]: n (Co): n (si) ═ 1: 0.048: 0.012.
the obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and silicon oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of cobalt in the cobalt-containing compound is n (Co) 4.8 mol% and the content of silicon in the silicon oxide is n (Si) 1.2 mol% based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And D of the positive electrode material50Is 3.9um, the surface of the cathode material is enriched with Li2CO31010ppm and 850ppm LiOH. Wherein the composition of the cathode material is represented by the general formula Li1.03(Ce0.01Mg0.01Ni0.9Mn0.1)Co0.048Si0.012O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 197.6mAh/g, the discharge specific capacity of 1.0C is 179.5mAh/g, the multiplying power of 1.0C/0.1C is 90.8 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 92.5 percent.
Comparative example 1
(1) Taking nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, and mixing the raw materials according to a molar ratio of Ni: co: mn is 87: 3: 10 is prepared into 2mol/L uniform mixed solution of nickel, cobalt and manganese salts, 8mol/L NaOH solution is prepared to be used as a precipitator, and 25 percent ammonia water is directly used as a complexing agent.
And under the protection of nitrogen, introducing the solution into a reaction kettle in a cocurrent mode, stirring at the rotating speed of 200rpm, keeping the reaction temperature at 55 ℃, keeping the pH value at 12.3, keeping the cocurrent time at 23h, and aging for 20 h. Washing, filter-pressing and drying at 120 ℃ for 4h to obtain D50The precursor is a nickel-cobalt-manganese hydroxide precursor with the particle size of 4.0 mu m, the precursor is spherical or spheroidal single particle, the structure is loose, and the loose packing density is 0.72g/cm3Tap density of 1.34g/cm3。
(2) Mixing nickel-cobalt-manganese hydroxide precursor and lithium hydroxide according to the formula of [ n (Ni)) + n (Co)) + n (Mn)]: n (li) ═ 1: 1.06 proportion, uniformly mixing in a high-speed mixer, sintering at 830 ℃ for 12h in an oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain a positive electrode material D50Is 3.8 um. The primary particles are independent of each other.
The positive electrode material D50Is 3.9um, the surface of the cathode material is enriched with Li2CO35410ppm and 2520ppm for LiOH. The obtained positive electrode material has a content of cobalt element n (co) of 3.1 mol% based on the total mole number n (ni) + n (mn) of nickel and manganese in the high-nickel low-cobalt multi-element positive electrode material, wherein the composition of the positive electrode material is represented by the general formula Li1.06(Ni0.87Mn0.1Co0.03)O2And (4) showing.
Under the condition of a voltage of between 3.0 and 4.3V, the first discharge specific capacity of 0.1C is 208.7h/g, the discharge specific capacity of 1.0C is 189.4/g, the multiplying power of 1.0C/0.1C is 90.8 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 86.1 percent.
Additionally, FIG. 4 is a graph comparing the cycles at 1.0C/1.0C @45 ℃ for example 1 and comparative example, as can be seen in FIG. 4: comparative example 1 has a lower energy density and poorer retention of the cycle capacity than example 1.
Comparative example 2
(1) Nickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials, and the molar ratio of Ni: co: mn is 87: 3: 10 are prepared into 2mol/L even nickel, cobalt and manganese salt mixed solution and 0.2mol/L Ce2(SO4)3And (3) solution. 8mol/L NaOH solution is prepared to be used as a precipitator, and 25% ammonia water is directly used as a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent manner, and [ n (Ni) + n (Co) + n (Mn)]N (Ce) is 1:0.01, the stirring speed is 200rpm, the reaction temperature is kept at 55 ℃, the pH value is 12.3, the cocurrent time is 23h, and the aging time is 20 h. Washing, press filtering, and oven drying at 100 deg.C for 5 hr to obtain D50The precursor is a nickel-cobalt-manganese hydroxide precursor with the particle size of 4.0 mu m, the precursor is spherical or spheroidal single particle, the structure is loose, and the loose packing density is 0.72g/cm3Tap density of 1.34g/cm3。
(2) Nickel-cobalt-manganese hydroxide precursor, lithium hydroxide, magnesium oxide according to the formula [ n (Ni) + n (Co) + n (Mn)]: n (Li): n (mg) ═ 1: 1.06: 0.01, uniformly mixing in a high-speed mixer, sintering at 760 ℃ for 12h in an oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the productNickel-cobalt-manganese single crystal positive electrode material intermediate, D503.8um, primary particles are independent of each other.
(3) Uniformly mixing the cathode material intermediate and silicon oxide according to the proportion of [ n (Ni) + n (Co)) + n (Mn)) ] to n (Si) of 1:0.01 in a high-speed mixer, sintering at 720 ℃ for 10h in an oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the cathode material.
The positive electrode material D50Is 3.9um, the surface of the cathode material is enriched with Li2CO35030ppm and LiOH 2280 ppm. The obtained positive electrode material contains n (Co) 3.1 mol% in terms of cobalt element based on the total mole number n (Ni) + n (Mn) of nickel and manganese in the nickel-cobalt-manganese single crystal positive electrode material intermediate, wherein the composition of the positive electrode material is represented by the general formula Li1.06(Ce0.01Mg0.01Ni0.87Mn0.1)Co0.03Si0.01O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 209.5mAh/g, the discharge specific capacity of 1.0C is 191.6mAh/g, the multiplying power of 1.0C/0.1C is 91.5 percent, and the cycle capacity retention rate of 80 weeks under the condition of 1C/1C @45 ℃ is 88.1 percent.
Comparative example 3
A positive electrode material was prepared in the same manner as in example 1, except that:
in step (1), [ n (Ni) + n (Mn)]: n (ce) ═ 1: 0.03; to obtain D50Nickel manganese hydroxide precursor of 4.6 μm, apparent density of 0.79g/cm3Tap density of 1.41g/cm3。
In step (2), [ n (Ni) + n (Mn)]: n (Li): n (mg) ═ 1: 0.8: 0.04; crushing and sieving to obtain a cobalt-free single crystal anode material intermediate D50Is 4.3 um.
In step (3), [ n (ni) + n (mn) ]: n (Co): n (si) ═ 1: 0.07: 0.05.
the obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and silicon oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of the cobalt-containing compound in terms of cobalt element is n (Co) 7 mol%, and the content of the silicon oxide in terms of silicon element is n (Si) 5 mol%, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And D of the positive electrode material50Is 4.1um, the surface of the cathode material is enriched with Li2CO3720ppm and 420ppm of LiOH. The obtained positive electrode material has a content of n (Co) 7 mol% in terms of cobalt element and a content of n (Si) 5 mol% in terms of silicon element, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-positive electrode material intermediate, wherein the positive electrode material has a composition represented by the general formula Li0.8(Ce0.03Mg0.04Ni0.9Mn0.1)Co0.07Si0.05O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 202.1mAh/g, the discharge specific capacity of 1.0C is 182.1mAh/g, the multiplying power of 1.0C/0.1C is 90.1 percent, and the cycle capacity retention rate of 80 weeks at the temperature of 1C/1C @45 ℃ is 92.1 percent.
Comparative example 4
A positive electrode material was prepared in the same manner as in example 1, except that:
in step (1), [ n (Ni) + n (Mn)]: n (ce) ═ 1: 0.002; to obtain D50Nickel manganese hydroxide precursor of 4.2 μm, apparent density of 0.72g/cm3Tap density of 1.39g/cm3。
In step (2), [ n (Ni) + n (Mn)]: n (Li): n (mg) ═ 1: 1.05: 0.004; crushing and sieving to obtain a cobalt-free single crystal anode material intermediate D50Is 4.1 um.
In step (3), [ n (ni) + n (mn) ]: n (Co): n (si) ═ 1: 0.001: 0.001.
the obtained cathode material comprises a high-nickel cobalt-free multi-element cathode material intermediate, and a cobalt-containing compound and silicon oxide which coat the outer surface of the high-nickel cobalt-free multi-element cathode material intermediate, wherein the content of the cobalt-containing compound in terms of cobalt element is n (Co) 0.1 mol%, and the content of the silicon oxide in terms of silicon element is n (Si) 0.1 mol%, based on the total molar number n (Ni) + n (Mn) of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
And D of the positive electrode material50Is 4.0um, the surface of the cathode material is enriched with Li2CO34720ppm and 2130ppm of LiOH. Wherein the composition of the cathode material is represented by the general formula Li1.05(Ce0.02Mg0.004Ni0.9Mn0.1)Co0.001Si0.001O2And (4) showing.
In addition, under the condition of a voltage of between 3.0 and 4.3V, the initial discharge specific capacity of 0.1C of the positive electrode material is 209.4mAh/g, the discharge specific capacity of 1.0C is 191.8mAh/g, the multiplying power of 1.0C/0.1C is 91.6 percent, and the cycle capacity retention rate of 80 weeks under the condition of 1C/1C @45 ℃ is 88.6 percent.
From the results of the examples and comparative examples, it can be seen that:
(1) examples 1 to 5 adopt conditions within the preferable range of the present invention, and as a result, the prepared positive electrode material has high energy density, good rate capability, and high capacity retention rate.
(2) Examples 6 to 7 did not employ conditions within the preferable range of the present invention, and as a result, the performance of the prepared positive electrode material was slightly inferior to that of examples 1 to 5, but better than that of comparative examples 1 to 4.
(3) Comparative examples 1 to 2 did not adopt the preparation method of the present invention, and as a result, the performance of the obtained positive electrode material was inferior.
(4) Comparative examples 3 to 4 although the preparation method of the present invention was employed, the conditions therein were not defined by the present invention, and as a result, the performance of the obtained positive electrode material was inferior.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The high-nickel low-cobalt single-crystal positive electrode material is characterized by comprising a high-nickel cobalt-free multi-element positive electrode material intermediate and a cobalt-containing compound coated on the outer surface of the high-nickel cobalt-free multi-element positive electrode material intermediate, wherein the cobalt-containing compound accounts for 0.5-5 mol% of cobalt element based on the total molar number of nickel and manganese in the high-nickel cobalt-free multi-element positive electrode material intermediate.
2. The positive electrode material according to claim 1, wherein the cobalt-containing compound is contained in an amount of 1 to 4 mol% in terms of cobalt element, based on the total number of moles of nickel and manganese in the high-nickel cobalt-free multi-positive electrode material intermediate;
preferably, the cobalt-containing compound is selected from lithium cobaltate and/or lithium nickel cobalt manganese.
3. The cathode material of claim 1, wherein the outer surface of the high nickel cobalt-free multi-component cathode material intermediate is further optionally coated with a compound comprising E, wherein E is selected from one or more of Al, Nb, Mo, W, B, Si, N, P, S, F, and Cl;
preferably, the content of the E-containing compound in terms of the E element is 0 to 2 mol%, more preferably 0.5 to 1.5 mol%, based on the total molar number of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
4. The positive electrode material according to any one of claims 1 to 3, wherein the positive electrode material further contains an optional doping element A and/or D;
wherein the composition of the cathode material is represented by the general formula Li1+a(AmDnNi1-x-yMnx)CoyEzO2It is shown that,
wherein a is more than or equal to 0.1 and less than or equal to 0.3, m is more than or equal to 0 and less than or equal to 0.02, n is more than or equal to 0 and less than or equal to 0.02, x is more than 0 and less than or equal to 0.2, y is more than or equal to 0.005 and less than or equal to 0.05, and z is more than or equal to 0 and less than or;
wherein A is selected from one or more of V, Ta, Cr, La, Al, Ce, Er, Ho, Y, Mg, Sr, Ba, Ra, Zr and Ti;
wherein D is selected from one or more of Mg, Sr, Ba, Ra, Zr, Ti, Fe, Ca, Zn and Hf;
preferably, the doping amount of the A is 0-2 mol% based on the total mole number of the nickel and the manganese in the high-nickel cobalt-free multi-element cathode material intermediate;
preferably, the doping amount of E is 0-2 mol% based on the total molar number of nickel and manganese in the high-nickel cobalt-free multi-element cathode material intermediate.
5. The positive electrode material according to any one of claims 1 to 3, wherein D of the positive electrode material502-5 μm, surface-enriched Li of the positive electrode material2CO3The content is 1000-4000ppm, the LiOH content is 500-3000 ppm;
preferably, D of the positive electrode material503.5-4.5 μm, surface-enriched Li of the positive electrode material2CO3The content is 1150-3500ppm and the LiOH content is 1200-2500 ppm.
6. A preparation method of the high-nickel low-cobalt single crystal cathode material as claimed in any one of claims 1 to 5, characterized in that the preparation method comprises the following steps:
(1) under the protection of nitrogen, a mixed salt solution containing nickel salt and manganese salt, an optional salt solution A, an alkali solution and ammonia water are contacted in a parallel flow manner to react to obtain solid-liquid mixed slurry; washing, filter pressing and drying the solid-liquid mixed slurry to obtain a precursor;
(2) contacting the precursor, a lithium source and an optional dopant D, performing first mixing, and performing first roasting treatment to obtain a cathode material intermediate;
(3) and contacting the cathode material intermediate, the nano cobalt-containing compound and the optional coating agent E, performing second mixing, and performing second roasting treatment to obtain the high-nickel low-cobalt single crystal cathode material.
7. The method according to claim 6, wherein, in the step (1), the concentration of the nickel salt is 1 to 3mol/L, the concentration of the manganese salt is 1 to 3mol/L, the concentration of the A salt solution is 0.01 to 0.5mol/L, and the concentration of the alkali solution is 5 to 10 mol/L;
preferably, the molar ratio of the mixed salt solution to the salt solution A is 1: (0-0.02);
preferably, the pH value of the solid-liquid mixed slurry is 11-13;
preferably, the conditions of the reaction include: the stirring speed is 150-250rpm, the temperature range is 40-60 ℃, and the time is 6-30 h.
8. The method of claim 6, wherein the molar ratio of the mixed salt solution to the amount of the lithium source and the dopant D is 1: (0.9-1.3): (0-0.02);
preferably, in the step (2), the conditions of the first firing treatment include: the temperature is 600 ℃ and 1000 ℃, and the time is 5-20 h.
9. The method of claim 6, wherein the molar ratio of the mixed salt solution to the amount of the nanocobalt compound and the capping agent E is 1: (0.005-0.05): (0-0.02);
preferably, the particle size of the nanometer cobalt-containing compound is 1-100 nm;
preferably, the nano cobalt-containing compound is selected from one or more of cobalt oxide, cobalt hydroxide, cobalt oxyhydroxide, cobalt fluoride, cobaltous hydroxide, cobaltosic oxide, cobalt carbonate, cobalt sulfate, cobalt sulfide, cobalt acetate and cobalt glycinate;
preferably, in the step (3), the conditions of the second firing treatment include: the temperature is 500-900 ℃ and the time is 3-15 h.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the high-nickel low-cobalt single crystal cathode material of any one of claims 1 to 5.
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