CN114447296B - Positive electrode material, preparation method and application thereof, and lithium ion battery - Google Patents
Positive electrode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- CN114447296B CN114447296B CN202111652365.9A CN202111652365A CN114447296B CN 114447296 B CN114447296 B CN 114447296B CN 202111652365 A CN202111652365 A CN 202111652365A CN 114447296 B CN114447296 B CN 114447296B
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- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 171
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 104
- 239000011247 coating layer Substances 0.000 claims abstract description 81
- 239000011248 coating agent Substances 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 239000011159 matrix material Substances 0.000 claims abstract description 54
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 48
- 239000010955 niobium Substances 0.000 claims description 48
- 239000010936 titanium Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910052721 tungsten Inorganic materials 0.000 claims description 23
- 229910052758 niobium Inorganic materials 0.000 claims description 22
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical group 0.000 claims description 15
- 239000002019 doping agent Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- DUSBUJMVTRZABV-UHFFFAOYSA-M [O-2].O[Nb+4].[O-2] Chemical compound [O-2].O[Nb+4].[O-2] DUSBUJMVTRZABV-UHFFFAOYSA-M 0.000 claims description 2
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 16
- 238000007086 side reaction Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000011572 manganese Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 17
- 238000007873 sieving Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention relates to the field of lithium ion batteries, and discloses a positive electrode material, a preparation method and application thereof, and a lithium ion battery. The positive electrode material comprises a matrix and a coating layer coated on the surface of the matrix; the matrix has a composition represented by formula I: li 1+ aNixCoyMnzMkO2 formula I; -0.5.ltoreq.a.ltoreq.0.3, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, 0.ltoreq.k.ltoreq.0.06, 0< x+y+z+k.ltoreq.1, the coating having a composition represented by formula II: ti 1‑αM′αNbγ‑βM″βO2+2.5γ‑δGδ formula II; alpha is more than or equal to 0 and less than or equal to 0.5, gamma is more than or equal to 2 and less than or equal to 30, beta is more than or equal to 0 and less than or equal to 0.5, and delta is more than or equal to 0 and less than or equal to 0.4. The positive electrode material has high ion and electron conduction capability, can avoid side reaction between the positive electrode material and electrolyte, improves compatibility, and further can improve the rate capability and energy density of the lithium ion battery containing the positive electrode material.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a positive electrode material, a preparation method and application thereof, and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, small volume, good cycle performance and the like, and is widely applied to the fields of portable electric appliances, electric bicycles, unmanned aerial vehicles, new energy electric vehicles, energy storage and the like. In a lithium ion battery, the advantages and disadvantages of the positive electrode materials determine the overall performance of the battery, and the main positive electrode materials of the lithium ion battery at present are lithium cobaltate, lithium manganate, lithium iron phosphate and lithium nickel cobalt manganate.
In liquid lithium ion battery systems, organic carbonates are generally used as electrolytes to provide lithium sources and channels for lithium ion transport. However, the electrolyte is unstable in the circulation process, and is easy to generate side reaction with the electrode, so that problems of in-particle cracks, pulverization of materials, gas production and the like are caused, and the performances of the battery such as circulation, capacity, multiplying power and the like are seriously influenced. In solid state battery systems, side reactions between the electrolyte and the electrodes also exist, resulting in degradation of battery performance.
In order to solve the above problems, coating modification techniques are widely used in various cathode materials. CN110648860a discloses a preparation method of a multi-element anode material with double modification of polyaluminium and graphene, which comprises the steps of mixing polyvinylpyrrolidone, a liquid medium, graphene, polyaluminium sulfate or polyaluminium chloride mixed solution with a liquid medium solution of a ternary material, and heating by heating to obtain the anode material coated by the polyaluminium and the graphene. The method has the advantages of complex preparation, large amount of organic solvent which is not beneficial to recovery, high raw material price, difficult mass production and limited improvement on electrochemical performance.
Disclosure of Invention
The invention aims to solve the problem that the performances of circulation, capacity, multiplying power and the like of a lithium ion battery caused by side reaction between an electrolyte and a positive electrode material cannot meet requirements in the prior art, and provides a positive electrode material, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material, characterized in that the positive electrode material includes a substrate and a coating layer coated on a surface of the substrate;
the matrix has a composition represented by formula I:
Li 1+aNixCoyMnzMkO2 formula I;
Wherein in the formula I, a is more than or equal to-0.5 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.06, x+y+z+k is more than or equal to 0 and less than or equal to 1, and M is at least one element selected from Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al;
the coating layer has a composition represented by formula II:
Ti 1-αM′αNbγ-βM″βO2+2.5γ-δGδ formula II;
Wherein in the formula II, alpha is more than or equal to 0 and less than or equal to 0.5, gamma is more than or equal to 2 and less than or equal to 30, beta is more than or equal to 0 and less than or equal to 0.4, M 'is at least one element selected from Ru, zr, si, sn, cu, cr, al, mg, zn, fe, co, mn, ni and Mo, M' is at least one element selected from V, ta, bi, W and Sb, and G is at least one element selected from N, F, br, S and Cl.
The second aspect of the present invention provides a method for preparing a positive electrode material, which is characterized by comprising the steps of:
S1, firstly mixing a nickel cobalt manganese hydroxide precursor, a lithium source and an optional doping agent M to obtain a mixture I, and calcining, crushing and screening the mixture I in air or oxygen atmosphere to obtain a positive electrode material matrix;
S2, carrying out second mixing on a titanium source, a niobium source, an optional M ' source and an optional G source according to the molar ratio of n (Ti) to n (M ')ton (Nb) to n (M ') to n (G) = (1-alpha) to alpha (gamma-beta) to beta to delta to obtain a mixture II, and sintering and crushing the mixture II in an air atmosphere to obtain a coating material;
And S3, carrying out third mixing on the positive electrode material matrix and the coating material to obtain a mixture III, and carrying out heat treatment on the mixture III to obtain the positive electrode material.
The third aspect of the present invention provides a positive electrode material produced by the above-described production method.
The fourth aspect of the invention provides an application of the positive electrode material in a lithium ion battery.
A fifth aspect of the present invention provides a lithium ion battery, wherein the lithium ion battery includes the above-described positive electrode material.
Through the technical scheme, the positive electrode material, the preparation method and the application thereof and the lithium ion battery have the following beneficial effects:
(1) The positive electrode material provided by the invention comprises a substrate and a coating layer coated on the surface of the substrate, and the substrate and the coating layer have specific compositions, so that the positive electrode material has electrochemical activity of lithium ion deintercalation, and further the coating material with higher ion and electron conductivity can accelerate the diffusion of ions and electrons in the positive electrode material, thereby remarkably improving the rate capability of a lithium ion battery comprising the positive electrode material.
(2) The positive electrode material provided by the invention comprises the coating layer with specific composition, so that the interface impedance of the positive electrode material can be effectively reduced, the interface side reaction between the surface of the positive electrode material particles and the electrolyte is inhibited, and the electrochemical performance of the lithium ion battery containing the positive electrode material is obviously improved.
(3) The preparation method of the positive electrode material provided by the invention has the advantages of simple process, no pollution doping element, simple introduction mode of the coating layer, small dosage, no special requirement on heat treatment atmosphere and low production cost, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in example 1.
Fig. 2 is a scanning electron microscope image of the nickel-cobalt-manganese multi-element cathode material prepared in comparative example 1.
Fig. 3 is a Transmission Electron Microscope (TEM) image of the positive electrode material prepared in example 1.
Fig. 4 is an ac impedance diagram of a liquid battery assembled from the positive electrode materials of comparative example 1, and example 2.
Fig. 5 is a graph showing the rate performance of the liquid battery assembled from the positive electrode materials of comparative example 1, example 1 and example 2.
Fig. 6 is a graph of the rate performance of the liquid battery assembled from the positive electrode materials of comparative example 2 and example 3.
Fig. 7 is a charge-discharge graph at 0.1C rate of the solid-state battery assembled from the cathode materials of comparative example 2 and example 4.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a positive electrode material, which is characterized by comprising a substrate and a coating layer coated on the surface of the substrate;
the matrix has a composition represented by formula I:
Li 1+aNixCoyMnzMkO2 formula I;
Wherein in the formula I, a is more than or equal to-0.5 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.1, x+y+z+k is more than or equal to 0 and less than or equal to 1, and M is at least one element selected from Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al;
the coating layer has a composition represented by formula II:
Ti 1-αM′αNbγ-βM″βO2+2.5γ-δGδ formula II;
Wherein in the formula II, alpha is more than or equal to 0 and less than or equal to 0.5, gamma is more than or equal to 2 and less than or equal to 30, beta is more than or equal to 0 and less than or equal to 0.4, M 'is at least one element selected from Ru, zr, si, sn, cu, cr, al, mg, zn, fe, co, mn, ni and Mo, M' is at least one element selected from V, ta, bi, W and Sb, and G is at least one element selected from N, F, br, S and Cl.
In the invention, the positive electrode material comprises a matrix and a coating layer coated on the surface of the matrix, and the matrix and the coating layer have specific compositions, so that the surface of the positive electrode material has high ion and electron conduction capacity, and the rate capability of a lithium ion battery containing the positive electrode material is obviously improved.
Further, the positive electrode material comprises a coating layer with a specific composition, so that the interface impedance of the positive electrode material can be effectively reduced, the interface side reaction between the surface of the positive electrode material particles and the electrolyte is inhibited, and the electrochemical performance of a lithium ion battery containing the positive electrode material is obviously improved.
Further, in the formula I, a is more than or equal to-0.05 and less than or equal to-0.05, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0.01 and less than or equal to 0.06, k is more than or equal to 0 and less than or equal to 0+y+z+k and M is at least one element selected from Ce, co, la, cr, mo, Y, zr, W, nb and Al.
Further, in the formula II, alpha is more than or equal to 0 and less than or equal to 0.1,2 and less than or equal to 24,0 and less than or equal to beta is more than or equal to 0.1, delta is more than or equal to 0 and less than or equal to 0.2, M 'is at least one element selected from Ru, zr, cu, cr, al, mg, zn, co, mn, ni and Mo, M' is at least one element selected from V, ta, bi and W, and G is at least one element selected from N, br, S and Cl.
Further preferably, in formula II, the α includes, but is not limited to, 0.05, 0.07, 0.09, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, etc.;
the γ includes, but is not limited to, 4, 6, 7, 10, 12, 14, 16, 18, 20, 22, 26, etc.;
the beta includes, but is not limited to, 0.05, 0.07, 0.09, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, etc.;
the delta includes, but is not limited to, 0.02, 0.04, 0.05, 0.07, 0.09, 0.15, etc.
In the invention, the coating layer is compact or non-compact, specifically, as shown in a scanning electron microscope image of the positive electrode material shown in figure 1, fine coating particles are uniformly attached to the surfaces of secondary particles of the positive electrode material to form the non-compact coating layer,
In the invention, the compactness of the coating layer is characterized by adopting a scanning electron microscope method.
According to the invention, the coating layer is present in an amount of 0.05 to 0.5 wt.%, based on the total weight of the substrate.
In the invention, when the content of the coating layer in the positive electrode material meets the above range, the positive electrode material has better electrochemical performance.
Further, the coating layer is contained in an amount of 0.1 to 0.3wt% based on the total weight of the substrate.
According to the invention, the thickness of the coating layer is 2-10nm.
In the present invention, the thickness of the coating layer is measured by transmission electron microscopy.
In the present invention, when the thickness of the coating layer satisfies the above range, the positive electrode material can be made to have excellent ion-conducting ability and electron-conducting ability.
Further, the thickness of the coating layer is 3-9nm.
According to the invention, the average particle diameter D 50 of the positive electrode material is 2-30 μm.
In the present invention, the average particle diameter D 50 of the positive electrode material was measured using a malvern particle sizer.
Further, the average particle diameter D 50 of the positive electrode material is 3-20 mu m
According to the invention, the residual alkali content of the surface of the positive electrode material is less than or equal to 1 weight percent.
In the invention, the residual alkali content on the surface of the positive electrode material is measured by an acid-base titration method.
In the invention, when the residual alkali content of the surface of the positive electrode material meets the range, the positive electrode material has better electrochemical performance.
Further, the surface residual alkali amount of the positive electrode material is 0.2-1wt%.
In one specific embodiment of the invention, in the formula II, when 0< alpha is less than or equal to 0.5,2 is less than or equal to gamma is less than or equal to 30,0< beta is less than or equal to 0.5, and 0 is less than or equal to delta is less than or equal to 0.4, namely when the coating layer contains doping elements M 'and M', the forbidden band width of the coating layer is 1.5-2.9eV.
In the invention, the forbidden bandwidth is obtained by calculating the density of states theory.
In the present invention, when the forbidden bandwidth of the coating layer satisfies the above range, the surface of the positive electrode material has high electron transport ability.
Further, when the cladding layer contains doping elements M' and M ", the forbidden bandwidth of the cladding layer is 1.6-2.7eV.
In a preferred embodiment of the invention, in formula II, the electron conductivity of the coating is 10 -4S/cm-10-9 S/cm when 0< alpha > is less than or equal to 0.5,2 < gamma > is less than or equal to 30,0< beta > is less than or equal to 0.5, and 0< delta > is less than or equal to 0.4, i.e. the coating contains doping elements M 'and M'.
In the invention, the electronic conductivity is measured by a four-probe method.
In the present invention, when the electron conductivity of the coating layer satisfies the above range, the surface of the positive electrode material has a high electron transport ability.
Further, when the coating layer contains doping elements M' and M ", the electron conductivity of the coating layer is 10 -4S/cm-10-7 S/cm.
The second aspect of the present invention provides a method for preparing a positive electrode material, which is characterized by comprising the steps of:
S1, firstly mixing a nickel cobalt manganese hydroxide precursor, a lithium source and an optional doping agent M to obtain a mixture I, and calcining, crushing and screening the mixture I in air or oxygen atmosphere to obtain a positive electrode material matrix;
S2, carrying out second mixing on a titanium source, a niobium source, an optional M 'source and an optional G source according to the molar ratio of n (Ti): n (M'): n (Nb): n (M "): n (G) = (1-alpha): alpha (gamma-beta): beta: delta) to obtain a mixture II, and sintering and crushing the mixture II in an air atmosphere to obtain a coating material;
And S3, carrying out third mixing on the positive electrode material matrix and the coating material to obtain a mixture III, and carrying out heat treatment on the mixture III to obtain the positive electrode material.
According to the invention, the positive electrode material which is prepared by carrying out heat treatment on the coating material containing the titanium source, the niobium source and the like and the positive electrode material matrix and comprises the matrix and the coating layer coated on the surface of the matrix has high ion conduction capacity and high electron conduction capacity, so that the multiplying power performance of the lithium ion battery containing the positive electrode material is remarkably improved, the interface impedance of the positive electrode material can be effectively reduced by the coating layer, the interface side reaction between the surface of the positive electrode material particles and electrolyte is inhibited, and the electrochemical performance of the lithium ion battery containing the positive electrode material is remarkably improved.
Furthermore, the preparation method of the positive electrode material provided by the invention has the advantages of simple process, no pollution doping element, simple introduction mode of the coating layer, small dosage, no special requirement on heat treatment atmosphere, low production cost and suitability for large-scale industrial production.
According to the present invention, in step S1, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium fluoride, lithium nitrate, and lithium acetate.
According to the invention, the dopant M is selected from compounds containing at least one element of Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al.
Further, the dopant M is selected from a compound containing at least one element of Ce, co, la, cr, mo, Y, zr, W, nb and Al.
According to the invention, the nickel cobalt manganese hydroxide precursor, the lithium source and the dopant M are used in amounts such that:
0.95≤[n(Li)]/[n(Ni)+n(Co)+n(Mn)+n(M)]≤1.05；
0≤[n(M)]/[n(Ni)+n(Co)+n(Mn)+n(M)]≤0.06。
Further, the nickel cobalt manganese hydroxide precursor, the lithium source, and the dopant M are used in amounts such that:
0.98≤[n(Li)]/[n(Ni)+n(Co)+n(Mn)+n(M)]≤1.02；
0.01≤[n(M)]/[n(Ni)+n(Co)+n(Mn)+n(M)]≤0.05。
According to the invention, the conditions of the calcination include: the calcination temperature is 600-1000 ℃ and the calcination time is 4-20h.
In the invention, the mixture I is calcined under the above conditions, so that a pure-phase positive electrode material matrix can be obtained, and the prepared positive electrode material has excellent stability and electrochemical activity.
Further, the calcining conditions include: the calcination temperature is 650-950 ℃ and the calcination time is 5-18h.
According to the present invention, in step S2, the titanium source is selected from at least one of titanium dioxide, titanium tetrachloride, titanyl sulfate, tetrabutyl titanate, and titanium isopropoxide.
According to the present invention, the niobium source is at least one selected from the group consisting of niobium pentoxide, niobium dioxide, niobium trioxide, niobium hydroxide, niobium pentachloride, niobium pentaethoxide, ammonium niobium oxalate and niobium oxalate,
According to the invention, the M' source is selected from compounds containing at least one element of Ru, zr, si, sn, cu, mo, cr, al, mg, zn, fe, co, mn and Ni.
Further, the M' source is selected from compounds containing at least one element of Ru, zr, cu, cr, al, mg, zn, co, mn, ni and Mo.
According to the invention, the M' source is selected from compounds containing at least one element of V, ta, bi, W and Sb.
Further, the M' source is selected from compounds containing at least one element of V, ta, bi and W.
According to the invention, the G source is selected from compounds containing at least one element of N, F, br, S and Cl.
Further, the G source is selected from compounds containing at least one element of N, br, S and Cl.
According to the invention, the sintering conditions include: the sintering temperature is 350-900 ℃ and the sintering time is 1-12h.
In the invention, under the above conditions, the mixture II containing the niobium source, the titanium source and the like is sintered to prepare the coating material, so that the pure phase doped surface coating layer can be obtained, and the surface of the prepared positive electrode material has excellent ion conduction capability and electron transfer capability.
Further, the sintering conditions include: the sintering temperature is 400-800 ℃ and the sintering time is 3-8h.
According to the present invention, in step S2, the second mixing is at least one of solid phase mixing, sol gel mixing and hydrothermal mixing.
In one embodiment of the present invention, the second mixing is solid phase mixing, and the specific operation steps of the second mixing are as follows:
The titanium source, niobium source, optionally M' source, optionally M "source and optionally G source are mixed with stirring at a speed of 500-900rpm, preferably 600-800rpm, for 2-6h, preferably 3-4h, to obtain said mixture II.
In the present invention, the solid phase mixing may be performed in a mixing apparatus conventional in the art, such as a high-speed mixer.
In one specific embodiment of the present invention, the second mixing is sol-gel mixing, and the specific operation steps of the sol-gel mixing are as follows:
Mixing a titanium source, a niobium source, an optional M' source and an optional G source with a solvent, adjusting the pH, stirring at 50-90 ℃, preferably 60-80 ℃ for 3-7h, preferably 3-5h to obtain a mixed solution, and drying to obtain the mixture II.
In the present invention, the solvent may be a solvent of a kind conventional in the art, for example, ethanol.
In the present invention, the adjustment of the pH can be accomplished using reagents conventional in the art, for example, citric acid to adjust the pH to 8-10.
In one specific embodiment of the present invention, the second mixing is a hydrothermal mixing, and the specific steps of the hydrothermal mixing are as follows:
Mixing a titanium source, a niobium source, an optional M' source and an optional G source with a solvent to obtain a mixture, transferring the mixture into a reaction kettle, preserving heat for 5-12h at 80-250 ℃, and performing solid-liquid separation to obtain solid-liquid which is the mixture II.
Further, in step S2, the second mixing is solid phase mixing and/or sol gel mixing.
In the present invention, the D 50 of the coating is 30-250nm, preferably 50-200nm.
According to the invention, in step S3, the coating material is used in an amount of 0.05-0.5wt% of the positive electrode material.
In the present invention, when the amount of the coating material satisfies the above range, the positive electrode material thus obtained has excellent electrochemical properties.
Further, the amount of the coating material is 0.1 to 0.3wt% of the amount of the positive electrode material.
According to the invention, the conditions of the third mixing include: the mixture is stirred and mixed for 3 to 6 hours at a rotation speed of 500 to 950 rpm.
In the present invention, the third mixing may be implemented in a mixing apparatus conventional in the art, such as a high-speed mixer.
Further, the conditions of the third mixing include: the mixture is stirred and mixed for 4 to 6 hours at the rotating speed of 600 to 850 rpm.
According to the present invention, the conditions of the heat treatment include: the heat treatment temperature is 350-900 ℃, and the heat treatment time is 1-12h.
According to the invention, under the above conditions, the mixture III containing the coating material and the positive electrode material matrix is subjected to heat treatment, so that the coating material and the positive electrode material matrix are fully and uniformly mixed, the coating material can be uniformly dispersed, and the positive electrode material prepared by the method has good electrochemical performance.
Further, the conditions of the heat treatment include: the heat treatment temperature is 400-800 ℃, and the heat treatment time is 3-8h.
In the present invention, the nickel cobalt manganese hydroxide precursor may be a precursor conventional in the art, preferably the nickel cobalt manganese hydroxide precursor is a hydroxide containing Ni, co, mn and optionally a dopant M.
In one specific embodiment of the invention, the nickel cobalt manganese hydroxide precursor is prepared according to the following steps:
(1) Preparing a mixed salt solution of nickel salt, cobalt salt, manganese salt and optionally dopant M according to a molar ratio of Ni: co: mn: m=x: y: z: k; respectively preparing a precipitator solution and a complexing agent solution;
(2) Adding the mixed salt solution, the precipitator solution and the complexing agent solution into a reaction kettle for reaction to obtain precursor slurry, and carrying out solid-liquid separation, washing, drying and screening on the precursor slurry to obtain the nickel-cobalt-manganese hydroxide precursor.
In the present invention, the nickel salt, the cobalt salt, and the manganese salt may be conventional nickel salts, cobalt salts, and manganese salts in the art. In particular, the nickel salt is selected from nickel sulphate and/or nickel chloride; the cobalt salt is selected from cobalt sulfate and/or cobalt chloride; the manganese salt is selected from manganese sulfate and/or manganese chloride.
In the present invention, the precipitant may be at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonium carbonate, which are conventional in the art. The complexing agent may be a complexing agent conventional in the art, such as ammonia.
In the invention, the concentration of the mixed salt is 2-10mol/L; the concentration of the precipitant solution is 5-9mol/L; the concentration of the complexing agent solution is 4-7mol/L.
In the invention, in the step (2), the flow rate of the mixed salt solution entering the reaction kettle is controlled to be 30-45L/h, the flow rate of the precipitant solution entering the reaction kettle is controlled to be 14-26L/h, and the flow rate of the complexing agent solution entering the reaction kettle is controlled to be 5-10L/h.
According to the invention, the dopant M is selected from compounds containing at least one element of Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al.
Further, the dopant M is selected from a compound containing at least one element of Ce, co, la, cr, mo, Y, zr, W, nb and Al.
According to the invention, the doping agent M is added in a stoichiometric ratio of 0.ltoreq.n (M)/[ n (Ni) +n (Co) +n (Mn) +n (M) ].ltoreq.0.06.
Further, the addition amount of M is not more than 0.01 and not more than [ n (M) ]/[ n (Ni) +n (Co) +n (Mn) +n (M) ] and not more than 0.05 according to the stoichiometric ratio.
According to the invention, the reaction conditions include: the pH value is 11.2-11.9, the reaction temperature is 50-80 ℃, and the reaction time is 20-80h.
Further, the reaction conditions include: the pH value is 11.5-11.7, the reaction temperature is 60-70 ℃, and the reaction time is 30-50h.
According to the present invention, the conditions for drying include: the drying temperature is 80-120 ℃ and the drying time is 8-12h.
Further, the drying conditions include: the drying temperature is 100-110 ℃, and the drying time is 10-11h.
The second aspect of the present invention provides a positive electrode material produced by the above-described production method.
In the invention, the positive electrode material comprises a substrate and a coating layer coated on the surface of the substrate;
the matrix has a composition represented by formula I:
Li 1+aNixCoyMnzMkO2 formula I;
Wherein in the formula I, a is more than or equal to-0.5 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.06, x+y+z+k is more than or equal to 0 and less than or equal to 1, and M is at least one element selected from Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al;
the coating layer has a composition represented by formula II:
Ti 1-αM′αNbγ-βM″βO2+2.5γ-δGδ formula II;
Wherein in the formula II, alpha is more than or equal to 0 and less than or equal to 0.5, gamma is more than or equal to 2 and less than or equal to 30, beta is more than or equal to 0 and less than or equal to 0.4, M 'is at least one element selected from Ru, zr, si, sn, cu, cr, al, mg, zn, fe, co, mn, ni and Mo, M' is at least one element selected from V, ta, bi, W and Sb, and G is at least one element selected from N, F, br, S and Cl.
Further, in the formula I, a is more than or equal to-0.05 and less than or equal to-0.05, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0.01 and less than or equal to 0.06, x+y+z is more than or equal to 0 and M is at least one element selected from Ce, co, la, cr, mo, Y, zr, W, nb and Al.
Further, in the formula II, alpha is more than or equal to 0 and less than or equal to 0.1,2 and less than or equal to 24,0 and less than or equal to beta is more than or equal to 0.1, delta is more than or equal to 0 and less than or equal to 0.2, M 'is at least one element selected from Ru, zr, cu, cr, al, mg, zn, co, mn, ni and Mo, M' is at least one element selected from V, ta, bi and W, and G is at least one element selected from N, br, S and Cl.
In the invention, the coating layer is compact or non-compact.
In the present invention, the coating layer is contained in an amount of 0.05 to 0.5wt%, preferably 0.1 to 0.3wt%, based on the total weight of the substrate.
In the present invention, the thickness of the coating layer is 2 to 10nm, preferably 3 to 9nm.
In the present invention, the average particle diameter D 50 of the positive electrode material is 2 to 30. Mu.m, preferably 3 to 20. Mu.m.
In the invention, the residual alkali content of the surface of the positive electrode material is less than or equal to 1 weight percent, preferably 0.2 to 1 weight percent.
In the present invention, when the cladding layer contains doping elements M' and M ", the forbidden bandwidth of the cladding layer is 1.5-2.9eV, preferably 1.6-2.7eV.
In the present invention, when the coating layer contains the doping elements M' and M ", the electron conductivity of the coating layer is 10 -4S/cm-10-9 S/cm, preferably 10 -4S/cm-10-7 S/cm.
The third aspect of the invention provides an application of the positive electrode material in a lithium ion battery.
A fourth aspect of the present invention provides a lithium ion battery, wherein the lithium ion battery includes the above-described positive electrode material.
In the invention, the lithium ion battery is a liquid lithium ion battery and comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode is made of the positive electrode material.
In the invention, the electrolyte is common commercial electrolyte and is an equivalent mixed solution of LiPF 6, ethylene Carbonate (EC) and diethyl carbonate (DEC) with the composition of 1 mol/L.
In the invention, the lithium ion battery is a solid lithium ion battery and comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode is made of the positive electrode material.
In the present invention, the solid electrolyte is at least one selected from the group consisting of a polymer electrolyte, an inorganic solid electrolyte, and a composite solid electrolyte.
The present invention will be described in detail by examples.
The microscopic morphology of the positive electrode material was measured by scanning electron microscopy.
The electrochemical ac impedance of the positive electrode material is measured by the electrochemical workstation.
The forbidden bandwidth of the coating layer is calculated by a state density theory.
The electron conductivity of the coating was measured using a four-probe method.
The residual alkali on the surface of the positive electrode material is measured by an acid-base titration method.
The positive electrode active materials in the following examples and comparative examples were evaluated for electrical properties according to the following methods.
Assembling the liquid button cell:
Firstly, mixing a surface modified positive electrode material for a nonaqueous electrolyte secondary battery, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 95:2.5:2.5, coating the mixture on aluminum foil, drying the mixture, punching the mixture to form a positive electrode plate with a diameter of 12mm and a thickness of 120 mu m by using a pressure of 100MPa, and then placing the positive electrode plate into a vacuum drying box for drying at 120 ℃ for 12 hours.
The anode uses a Li metal sheet with a diameter of 17mm and a thickness of 1 mm; the separator uses a polyethylene porous film with a thickness of 25 μm; as the electrolyte, 1mol/L of an equivalent mixture of LiPF 6, ethylene Carbonate (EC) and diethyl carbonate (DEC) was used.
And assembling the positive electrode plate, the diaphragm, the negative electrode plate and the electrolyte into the 2025 type button cell in an Ar gas glove box with water content and oxygen content of less than 5 ppm.
Assembling the solid-state button cell:
the preparation method of the positive plate is identical with that of the liquid button cell.
PEO, liTFSI and Li 1.3Al0.3Ti1.7(PO4)3 nano-particles as solid electrolyte are dissolved in acetonitrile according to the weight ratio of 6:3:1, and the mixture is uniformly mixed to form slurry. The slurry is coated on a polytetrafluoroethylene plate in a scraping way, and is dried for 12 hours at 60 ℃ and then peeled off to obtain the solid electrolyte membrane.
And sequentially loading the positive electrode plate, the solid electrolyte membrane and the metal lithium sheet into a battery shell to obtain the solid lithium battery.
The performance of the button cell was evaluated as follows:
(1) And (3) multiplying power performance test: the temperature is 25 ℃, and the multiplying power performance of the material is inspected by 1 circle of circulation under the multiplying power of 0.1C, 0.2C, 0.33C, 0.5C and 1C respectively in the voltage interval of 3.0-4.3V.
(2) And (3) testing charge and discharge performance: the charge and discharge performance of the material was examined at a rate of 0.1C at a temperature of 25 ℃ in a voltage range of 3.0-4.3V.
(3) Ac impedance performance test: the ac impedance test was performed at an amplitude of 5mV in the test frequency range of 0.1Hz-100 kHz.
Preparation example 1
Nickel cobalt manganese hydroxide precursor P1
(1) Preparing 2mol/L nickel sulfate, cobalt sulfate and manganese sulfate mixed salt solution according to the molar ratio of Ni, co and Mn elements of 90:5:5. Preparing 7mol/L sodium hydroxide alkali solution; preparing 6mol/L ammonia water complexing agent solution.
(2) And continuously adding the mixed salt solution, the alkali solution and the ammonia water complexing agent solution into a stirrer in a parallel flow mode for reaction, wherein the stirring speed is 120rpm. Simultaneously controlling the liquid inlet flow of the mixed salt solution to be 40L/h, the liquid inlet flow of the alkali solution to be 20L/h, the liquid inlet flow of the complexing agent solution to be 6L/h, the pH to be 11.5, the temperature to be 60 ℃ and the reaction time to be 30h. When the reaction is completed, the obtained nickel cobalt manganese hydroxide slurry is subjected to solid-liquid separation and washing, a filter cake is dried at 100 ℃ for 10 hours and then is screened, and the product is subjected to water washing, filtering and drying to obtain a nickel cobalt manganese hydroxide precursor P1.
Preparation example 2
Nickel cobalt manganese hydroxide precursor P2
(1) Preparing 2mol/L nickel sulfate, cobalt sulfate, manganese sulfate and zirconium nitrate mixed salt solution according to the mol ratio of Ni, co, mn, zr elements of 60:20:19:1. Preparing 7mol/L sodium hydroxide alkali solution; preparing 6mol/L ammonia water complexing agent solution.
(2) And continuously adding the mixed salt solution, the alkali solution and the ammonia water complexing agent solution into a stirrer in a parallel flow mode for reaction, wherein the stirring speed is 100rpm. Meanwhile, the flow rate of the mixed salt solution is controlled to be 35L/h, the flow rate of the alkali solution is controlled to be 18L/h, the flow rate of the complexing agent solution is controlled to be 6L/h, the pH is controlled to be 11.6, the temperature is 60 ℃, and the reaction is carried out for 38h. When the reaction is completed, the obtained nickel cobalt manganese hydroxide slurry is subjected to solid-liquid separation and washing, a filter cake is dried at 100 ℃ for 10 hours and then is screened, and the product is subjected to water washing, filtering and drying to obtain a nickel cobalt manganese hydroxide precursor P2.
Example 1
S1, uniformly mixing a nickel cobalt manganese hydroxide precursor P1 and lithium hydroxide in a ratio of Li/(Ni+Co+Mn) =1.02 to obtain a mixture I, calcining the mixture I at 720 ℃ for 10 hours in an oxygen atmosphere, and crushing and sieving a product to obtain a positive electrode material matrix;
s2, carrying out second mixing on a titanium source, a niobium source, an M 'source and an M' source by adopting solid phase mixing, and specifically: according to the molar ratio of n (Ti): n (M '): n (Nb): n (M ") =0.95:0.05:1.98:0.02, titanium dioxide, zirconium oxide (M ' source), dinitrile (niobium source) and vanadium pentoxide (M ' source) are stirred and mixed for 2 hours at a rotation speed of 800rpm to obtain a mixture II, the mixture II is sintered for 8 hours at 800 ℃ in an air atmosphere, and after cooling to room temperature, the mixture is crushed and sieved to obtain a coating material, wherein D 50 of the coating material is 200nm, and the composition is Ti 0.95Zr0.05Nb1.98V0.02O7. The band gap of the coating layer was 1.9eV, and the electron conductivity was 10 -4 S/cm.
S3, stirring the coating material and the positive electrode material matrix for 4 hours at the speed of 800rpm to obtain a mixture III, wherein the dosage of the coating material is 0.1wt% based on the dosage of the positive electrode material matrix. Carrying out heat treatment on the mixture III for 5 hours at 500 ℃, after cooling to room temperature, crushing and sieving to obtain a positive electrode material A1, wherein a coating layer of the positive electrode material A1 comprises Ti 0.95Zr0.05Nb1.98V0.02O7, and the matrix comprises the following components: li 1.02Ni0.9Co0.05Mn0.05O2, the content of the coating layer was 0.1wt% based on the total weight of the matrix. D 50 of the positive electrode material A1 is 12 mu m, and the surface residual alkali amount is 0.28wt%.
Fig. 1 is an SEM image of a positive electrode material A1, and it can be seen from fig. 1 that fine coating particles are uniformly attached to the surface of secondary particles of the positive electrode material A1, thereby forming a non-dense coating layer.
Fig. 3 is a TEM image of the positive electrode material A1, and as can be seen from fig. 3, the thickness of the coating layer of the positive electrode material A1 is 8nm.
Example 2
S1, uniformly mixing a nickel cobalt manganese hydroxide precursor P1 and lithium hydroxide in a ratio of Li/(Ni+Co+Mn) =1.02 to obtain a mixture I, sintering the mixture I at 720 ℃ for 10 hours in an oxygen atmosphere, and crushing and sieving a product to obtain a positive electrode material matrix;
s2, mixing a titanium source, a niobium source, an M ' source and a G source in ethanol according to a mol ratio of n (Ti) n (M ')n (Nb) n (M ') n (G) =0.92:0.08:23.94:0.06:0.03, adding citric acid to adjust pH=9.6, stirring at 60 ℃ for 5h to obtain a mixed solution, drying in an oven at 120 ℃ for 8h to obtain a mixture II, sintering the mixture II at 800 ℃ in an air atmosphere, cooling to room temperature, and crushing and sieving to obtain a coating material, wherein D 50 of the coating material is 180nm, and the composition is Ti 0.92Mo0.08Nb23.94Bi0.06O61.97S0.03. The band gap of the coating layer was 2.2eV, and the electron conductivity was 10 -5 S/cm.
S3, stirring the coating material and the positive electrode material matrix for 6 hours at the speed of 800rpm to obtain a mixture III, wherein the dosage of the coating material is 0.2wt% based on the dosage of the positive electrode material matrix. And (3) carrying out heat treatment on the mixture III for 8 hours at 450 ℃, cooling to room temperature, and then crushing and sieving to obtain the anode material A2. The composition of the matrix of the positive electrode material A2 is as follows: li 1.02Ni0.9Co0.05Mn0.05O2, coating layer composition: ti 0.92Mo0.08Nb23.94Bi0.06O61.97S0.03, the content of the coating layer was 0.2wt% based on the total weight of the substrate. The D 50 of the positive electrode material A2 was 13 μm, and the surface residual alkali amount was 0.25wt%. The thickness of the coating layer was 5nm.
Example 3
S1, uniformly mixing a nickel cobalt manganese hydroxide precursor P2 and lithium hydroxide in a ratio of Li/(Ni+Co+Mn+Zr) =1.03 to obtain a mixture I, calcining the mixture I at 720 ℃ for 10 hours in an air atmosphere, and crushing and sieving the product to obtain a positive electrode material matrix;
S2, carrying out second mixing on a titanium source, a niobium source, an M 'source and an M' source by adopting solid phase mixing, and specifically: according to the molar ratio of n (Ti): n (M '): n (Nb): n (M ") =0.9:0.1:4.94:0.06, titanium dioxide, magnesium oxide (M ' source), niobium hydroxide (niobium source) and tantalum pentoxide (M ' source) were stirred at 850rpm for 3 hours to obtain a mixture II, the mixture II was sintered at 750 ℃ for 8 hours under an air atmosphere, and after cooling to room temperature, the mixture was crushed and sieved to obtain a coating material, wherein D 50 of the coating material was 170nm, and the composition was Ti 0.9Mg0.1Nb4.94Ta0.06O14.5. The band gap of the coating layer was 2.1eV, and the electron conductivity was 10 -5 S/cm.
S3, stirring the coating material and the positive electrode material matrix for 6 hours at the rotating speed of 800rpm to obtain a mixture III, wherein the dosage of the coating material is 0.1wt% based on the dosage of the positive electrode material matrix. And (3) carrying out heat treatment on the mixture III for 8 hours at 450 ℃, cooling to room temperature, and then crushing and sieving to obtain the anode material A3. The coating layer of the positive electrode material A3 comprises: ti 0.9Mg0.1Nb4.94Ta0.06O14.5, the composition of the matrix is: li 1.03Ni0.6Co0.2Mn0.19 Zr0.01 O2, the content of the coating layer was 0.1wt% based on the total weight of the matrix. The particle size of the positive electrode material A3 was 13. Mu.m, the residual alkali content on the surface was 0.26wt%, and the thickness of the coating layer was 6nm.
Example 4
S1, uniformly mixing a nickel cobalt manganese hydroxide precursor P2 and lithium carbonate in a ratio of Li/(Ni+Co+Mn+Zr) =1.03 to obtain a mixture I, calcining the mixture I at 750 ℃ for 10 hours in an air atmosphere, and crushing and sieving the product to obtain a positive electrode material matrix.
S2, adopting solid-phase mixing to carry out second mixing on a titanium source, a niobium source, an M ' source and a G source, specifically, according to the mole ratio of n (Ti) to n (M ')ton (Nb) to n (M ') to n (G) to be 0.94:0.06:23.98:0.02:0.04, stirring and mixing titanium dioxide, aluminum oxide (M ' source), niobium pentachloride (niobium source and G source) and tungsten trioxide (M ' source) for 3 hours at the rotating speed of 750rpm to obtain a mixture II, sintering the mixture II for 8 hours at 700 ℃ under the air atmosphere, after cooling to room temperature, crushing and sieving to obtain a coating, wherein D 50 of the coating is 110nm, and the composition is as follows: ti 0.94Al0.06Nb23.98W0.02O61.96Cl0.04. The band gap of the coating layer was 2.6eV, and the electron conductivity was 10 -6 S/cm.
S3, stirring the coating material and the positive electrode material matrix for 4 hours at the speed of 800rpm to obtain a mixture III, wherein the dosage of the coating material is 0.3wt% based on the dosage of the positive electrode material matrix. Carrying out heat treatment on the mixture III for 8 hours at 500 ℃, after cooling to room temperature, crushing and sieving to obtain a positive electrode material A4, wherein a coating layer of the positive electrode material comprises Ti 0.94Al0.06Nb23.98W0.02O61.96Cl0.04, and the composition of a matrix is as follows: li 1.03Ni0.6Co0.2Mn0.19 Zr0.01 O2, the content of the coating layer was 0.3wt% based on the total weight of the matrix. The particle diameter of the positive electrode material A4 was 15. Mu.m, and the amount of residual alkali on the surface was 0.3wt%. The thickness of the coating layer was 5nm.
Example 5
A positive electrode material was prepared as in example 1, except that:
In step S2, the M 'source and the M' source are not contained. The molar ratio of n (Ti): n (Nb) =1:2, titanium dioxide and niobium pentoxide (niobium source) are stirred and mixed for 2 hours at the rotating speed of 800rpm to obtain a mixture II, the mixture II is sintered for 8 hours at 780 ℃ in air atmosphere, and after cooling to room temperature, the mixture is crushed and sieved to obtain a coating material, wherein the D 50 of the coating material is 180nm, and the composition is TiNb 2O7. The band gap of the coating layer was 2.9eV, and the electron conductivity was 10 -9 S/cm.
The positive electrode material A5 is prepared, the matrix composition is Li 1.02Ni0.90Co0.05Mn0.05O2, the coating layer is TiNb 2O7, the content of the coating layer is 0.1wt% based on the total weight of the matrix, the D 50 of the positive electrode material A7 is 11 mu m, the surface residual alkali amount is 0.25wt%, and the thickness of the coating layer is 7nm.
Example 6
A positive electrode material was prepared as in example 1, except that:
in step S1, the nickel cobalt manganese hydroxide precursor P1, lithium hydroxide, and zirconium oxide are mixed in a ratio of Li/(ni+co+mn+zr) =1.02 and M/(ni+co+mn+zr) =0.03.
The prepared positive electrode material A6 has a matrix composition of Li 1.02Ni0.9Co0.02Mn0.05Zr0.03O2, a coating layer of Ti 0.95Zr0.05Nb1.98V0.02O7, D 50 of the positive electrode material A7 of 11 mu m, residual surface alkali content of 0.20wt%, thickness of 6nm, forbidden band width of 1.9eV, and electronic conductivity of 10 -4 S/cm.
Example 7
A positive electrode material was prepared as in example 1, except that:
in the step S2, the sintering temperature is 820 ℃, the sintering time is 10 hours, and the coating material is obtained, wherein the D 50 of the coating material is 210nm.
In the step S3, the use amount of the coating material is 0.5wt% based on the use amount of the positive electrode material matrix, the heat treatment temperature is 350 ℃, and the time is 11h.
The prepared positive electrode material A7 has a matrix composition of Li 1.02Ni0.90Co0.05Mn0.05O2, a coating layer of Ti 0.95Zr0.05Nb1.98V0.02O7, D 50 of the positive electrode material A7 of 13 mu m, residual surface alkali content of 0.26wt%, coating layer thickness of 9nm, a forbidden band width of 2.8eV and electron conductivity of 10 -8 S/cm.
Example 8
A positive electrode material was prepared as in example 1, except that:
In the step S2, the sintering temperature is 1000 ℃, the sintering time is 14 hours, and the coating material is obtained, wherein the D 50 of the coating material is 300nm.
In the step S3, the use amount of the coating material is 0.8wt% based on the use amount of the positive electrode material matrix, the heat treatment temperature is 300 ℃, and the time is 15 hours.
The prepared positive electrode material A8 has a matrix composition of Li 1.02Ni0.90Co0.05Mn0.05O2, a coating layer of Ti 0.95Zr0.05Nb1.98V0.02O7, D 50 of the positive electrode material A8 of 12 mu m, residual surface alkali content of 0.31wt%, coating layer thickness of 10nm, a forbidden band width of 3eV and electronic conductivity of 10 -10 S/cm.
Comparative example 1
S1, uniformly mixing a nickel cobalt manganese hydroxide precursor P1 and lithium hydroxide in a ratio of Li/(Ni+Co+Mn) =1.02 to obtain a mixture I, calcining the mixture I at 720 ℃ for 10 hours in an oxygen atmosphere, crushing and sieving a product to obtain a positive electrode material D1, wherein the composition is as follows: li 1.02Ni0.9Co0.05Mn0.05O2, average particle diameter D 50 of 12 μm and residual surface alkali content of 0.29wt%.
Fig. 2 is an SEM image of the positive electrode material D1, and as can be seen from fig. 2, the secondary particle surface of the positive electrode material D1 is rough, and the inter-particle gaps are fine.
Comparative example 2
S1, uniformly mixing a nickel cobalt manganese hydroxide precursor P2 and lithium carbonate in a ratio of Li/(Ni+Co+Mn+Zr) =1.03 to obtain a mixture I, calcining the mixture I at 750 ℃ for 10 hours in an air atmosphere, crushing and sieving a product to obtain a positive electrode material D2, wherein the composition is as follows: li 1.03Ni0.6Co0.2Mn0.19 Zr0.01 O2, average particle diameter D 50 of 13 μm and residual surface alkali content of 0.32wt%.
Comparative example 3
A positive electrode material was prepared as in example 1, except that:
In step S2, the titanium source is not contained. Specifically, according to the molar ratio of n (M '): n (Nb): n (M ") =1:1.98:0.02, zirconium oxide (M' source), dinitrile pentoxide (niobium source) and vanadium pentoxide (M″ source) are stirred and mixed for 2 hours at a rotation speed of 800rpm to obtain a mixture II, the mixture II is sintered for 8 hours at 800 ℃ in an air atmosphere, and after cooling to room temperature, the mixture is crushed and sieved to obtain a coating material, wherein D 50 of the coating material is 130nm. The band gap of the coating layer was 3.1eV, and the electron conductivity was 10 - 10 S/cm.
The positive electrode material D3 is prepared, a coating layer of the positive electrode material D3 comprises ZrNb 1.98V0.02O7, and a matrix comprises the following components: li 1.02Ni0.9Co0.05Mn0.05O2, the content of the coating layer was 0.1wt% based on the total weight of the matrix. The D 50 of the positive electrode material A1 was 18 μm, the residual alkali content on the surface was 0.4wt%, and the thickness of the coating layer was 9nm.
Comparative example 4
A positive electrode material was prepared as in example 1, except that:
In step S2, a niobium source is not contained. Specifically, according to the molar ratio of n (Ti): n (M '): n (M') = 0.95:0.05:2, titanium dioxide (titanium source), zirconium oxide (M 'source) and vanadium pentoxide (M' source) are stirred and mixed for 4 hours at the rotating speed of 760rpm to obtain a mixture II, the mixture II is sintered for 8 hours at 790 ℃ in air atmosphere, and after being cooled to room temperature, the mixture is crushed and sieved to obtain a coating material, wherein the D 50 of the coating material is 115nm. The band gap of the coating layer was 3.3eV, and the electron conductivity was 10 - 10 S/cm.
The positive electrode material D4 is prepared, wherein a coating layer of the positive electrode material D4 comprises Ti 0.95Zr0.05V2O7, and a matrix comprises the following components: li 1.02Ni0.9Co0.05Mn0.05O2, the content of the coating layer was 0.2wt% based on the total weight of the matrix. The positive electrode material D4 had a D 50 of 17. Mu.m, a residual alkali content of 0.43wt% and a coating layer thickness of 9nm.
Test example 1
The positive electrode materials prepared in examples 1 to 8 and comparative examples 1 to 4 were used as positive electrodes for assembling liquid lithium ion batteries to obtain liquid lithium ion batteries C1 to C8 and DC1 to DC4, respectively. The discharge capacities of the cells at 0.1C, 0.2C, 0.5C and 1C rates were measured in the voltage range of 3.0-4.3V, respectively, and the results are shown in table 1.
TABLE 1
Fig. 4 is an ac impedance diagram of a liquid battery made of the positive electrode material A1, the positive electrode material A2, and the positive electrode material D1, and as can be seen from fig. 4, the semicircle diameter of the high frequency portion in the positive electrode material A1 is smaller than that of the positive electrode material D1 made in comparative example 1, which indicates that the Ti 0.95Zr0.05Nb1.98V0.02O7 coating significantly reduces the interface impedance of the materials. The semicircle diameter of the high frequency part in the positive electrode material A2 was smaller than that of the positive electrode material D1 prepared in comparative example 1, which suggests that Ti 0.92Mo0.08Nb23.94Bi0.06O61.97S0.03 coating significantly reduced the interface impedance of the material.
Fig. 5 is a graph showing the rate performance of liquid lithium ion batteries C1, C2, and DC1 assembled from the positive electrode material A1 prepared in example 1, the positive electrode material A2 prepared in example 2, and the positive electrode material D1 prepared in comparative example 1. As can be seen from fig. 5, the liquid lithium ion battery DC1 has a 0.1C-rate discharge capacity of 219mAh/g, a 0.2C-rate discharge capacity of 214mAh/g, a 0.5C-rate discharge capacity of 205mAh/g, and a 1C-rate discharge capacity of 198mAh/g in the voltage range of 3.0 to 4.3V. The lithium ion battery C1 has a 0.1C rate discharge capacity of 226mAh/g, a 0.2C rate discharge capacity of 221mAh/g, a 0.5C rate discharge capacity of 211mAh/g and a 1C rate discharge capacity of 203mAh/g in a voltage range of 3.0-4.3V. The lithium ion battery C2 has a 0.1C rate discharge capacity of 225mAh/g, a 0.2C rate discharge capacity of 219mAh/g, a 0.5C rate discharge capacity of 210mAh/g and a 1C rate discharge capacity of 203mAh/g in a voltage range of 3.0-4.3V. Compared with the liquid lithium ion battery DC1, the discharge capacity is increased at each multiplying power, which shows that the multiplying power performance is improved after coating.
Fig. 6 is a graph showing the rate performance of the liquid lithium ion battery C3 and DC2 assembled from the positive electrode material A3 prepared in example 3 and the positive electrode material D2 prepared in comparative example 2, and it can be seen from fig. 6 that the liquid lithium ion battery DC2 has a 0.1C rate discharge capacity of 178mAh/g, a 0.2C rate discharge capacity of 175mAh/g, a 0.5C rate discharge capacity of 169mAh/g, and a 1C rate discharge capacity of 164mAh/g in the voltage range of 3.0 to 4.3V. The liquid lithium ion battery C3 has a 0.1C rate discharge capacity of 183mAh/g, a 0.2C rate discharge capacity of 180mAh/g, a 0.5C rate discharge capacity of 174mAh/g and a 1C rate discharge capacity of 168mAh/g in a voltage range of 3.0-4.3V. Compared with the liquid lithium ion battery DC2, the discharge capacity is increased at each multiplying power, which shows that the multiplying power performance is improved after coating.
As can be seen from table 1, the liquid lithium ion batteries assembled from the cathode materials prepared in examples 1 to 8 have higher rate performance than the liquid lithium ion batteries assembled from the cathode materials prepared in comparative examples 1 to 4.
Test example 2
The positive electrode materials prepared in example 4 and comparative example 2 were used as positive electrodes for assembling solid-state lithium ion batteries, in which PEO-Li 1.3Al0.3Ti1.7(PO4)3 was used as a composite solid-state electrolyte. And obtaining a solid-state lithium ion battery C9 and DC5. The discharge capacity of the battery at 0.1C rate was tested in the voltage range of 3.0-4.3V, and the results are shown in table 3.
TABLE 3 Table 3
| Battery cell | 0.1C/mAh/g |
| C9 | 182 |
| DC5 | 173 |
Fig. 7 is a charge-discharge graph of solid lithium ion batteries C9 and DC5 assembled from positive electrode material A4 and positive electrode material D3 at a 0.1C rate, and as can be seen from fig. 7, the solid lithium ion battery DC5 has a 3.0-4.3V voltage range, and the 0.1C rate discharge capacity is 173mAh/g as shown in fig. 6. The discharge capacity of the solid-state lithium ion battery C9 is 182mAh/g as shown in figure 6 in the voltage range of 3.0-4.3V, and the discharge capacity is obviously higher than that of the solid-state lithium ion battery DC5, which shows that after coating, the interface performance between the solid-state electrolyte electrode and the electrolyte is improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. The positive electrode material is characterized by comprising a matrix and a coating layer coated on the surface of the matrix;
the matrix has a composition represented by formula I:
Li 1+aNixCoyMnzMkO2 formula I;
Wherein in the formula I, a is more than or equal to-0.5 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.01 and less than or equal to 0.1, x+y+z+k is more than or equal to 0 and M is at least one element selected from Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al;
the coating layer has a composition represented by formula II:
Ti 1-αM′αNbγ-βM″βO2+2.5γ-δGδ formula II;
Wherein in the formula II, 0< alpha is less than or equal to 0.5,2 is less than or equal to gamma is less than or equal to 30,0< beta is less than or equal to 0.5,0 is less than or equal to delta is less than or equal to 0.4, M 'is at least one element selected from Ru, zr, si, sn, cu, cr, al, mg, zn, fe, co, mn, ni and Mo, M' is at least one element selected from V, ta, bi, W and Sb, and G is at least one element selected from N, F, br, S and Cl;
When the coating layer contains doping elements M 'and M', the forbidden bandwidth of the coating layer is 1.6eV-2.7eV;
When the coating layer contains doping elements M 'and M', the electron conductivity of the coating layer is 10 -4 S/cm-10-7 S/cm.
2. The positive electrode material according to claim 1, wherein, -0.5.ltoreq.a.ltoreq.0.05, 0< x.ltoreq.1, 0< y.ltoreq.1, 0< z.ltoreq.1, 0.01.ltoreq.k.ltoreq.0.06, 0< x+y+z+k.ltoreq.1, m being at least one element selected from Ce, co, la, cr, mo, Y, zr, W, nb and Al;
And/or, in the formula II, 0< alpha is not less than 0.1,2 and not more than gamma is not less than 24,0 and not less than beta is not less than 0.1,0 is not less than delta is not less than 0.2, M 'is selected from at least one element of Ru, zr, cu, cr, al, mg, zn, co, mn, ni and Mo, M' is selected from at least one element of V, ta, bi and W, and G is selected from at least one element of N, br, S and Cl.
3. The positive electrode material according to claim 1 or 2, wherein the content of the coating layer is 0.05 to 0.5wt% based on the total weight of the substrate;
and/or the thickness of the coating layer is 2-10nm;
And/or the average particle diameter D 50 of the positive electrode material is 2-30 μm;
And/or the residual alkali content of the surface of the positive electrode material is less than or equal to 1wt%.
4. A method for producing the positive electrode material according to any one of claims 1 to 3, comprising the steps of:
s1, firstly mixing a nickel cobalt manganese hydroxide precursor, a lithium source and a doping agent M to obtain a mixture I, and calcining, crushing and screening the mixture I in air or oxygen atmosphere to obtain a positive electrode material matrix;
S2, carrying out second mixing on a titanium source, a niobium source, an M ' ' source and optionally a G source according to the molar ratio of n (Ti) to n (M ')ton (Nb) to n (M ' ') to n (G) = (1-alpha) to alpha (gamma-beta) to beta to delta to obtain a mixture II, and sintering and crushing the mixture II in an air atmosphere to obtain a coating material;
S3, carrying out third mixing on the anode material matrix and the coating material to obtain a mixture III, and carrying out heat treatment on the mixture III to obtain the anode material;
The sintering conditions include: the sintering temperature is 400-800 ℃ and the sintering time is 3-8h.
5. The production method according to claim 4, wherein in step S1, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium fluoride, lithium nitrate, and lithium acetate;
and/or the dopant M is selected from compounds containing at least one element of Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al;
And/or, the conditions of the calcination include: the calcination temperature is 600-1000 ℃ and the calcination time is 4-20h.
6. The production method according to claim 4 or 5, wherein in step S2, the titanium source is selected from at least one of titanium dioxide, titanium tetrachloride, titanyl sulfate, tetrabutyl titanate, and titanium isopropoxide;
and/or the niobium source is selected from at least one of niobium pentoxide, niobium dioxide, niobium trioxide, niobium hydroxide, niobium pentachloride, niobium pentaethoxide, ammonium niobium oxalate and niobium oxalate;
And/or the M' source is selected from compounds containing at least one element of Ru, zr, si, sn, cu, mo, cr, al, mg, zn, fe, co, mn and Ni;
And/or, the M' source is selected from compounds containing at least one element of V, ta, bi, W and Sb;
and/or the G source is selected from compounds containing at least one element of N, F, br, S and Cl;
and/or the second mixing is at least one of solid phase mixing, sol gel mixing and hydrothermal mixing.
7. The method of claim 4 or 5, wherein the second mixing is solid phase mixing and/or sol gel mixing.
8. The method of claim 6, wherein the conditions of solid phase mixing comprise: stirring and mixing a titanium source, a niobium source, an M '' source and optionally a G source for 2-6 hours at a rotation speed of 500-900rpm to obtain a mixture II;
and/or, the conditions of sol-gel mixing include: mixing a titanium source, a niobium source, an M '' source and optionally a G source with a solvent, adjusting the pH, stirring at 50-90 ℃ for 3-7h to obtain a mixed solution, and drying to obtain the mixture II.
9. The production method according to claim 4 or 5, wherein in step S3, the amount of the coating material is 0.05 to 0.5wt% of the amount of the positive electrode material;
and/or, the conditions of the third mixing include: stirring and mixing for 3-6h at the rotating speed of 400-800 rpm;
And/or, the conditions of the heat treatment include: the heat treatment temperature is 350-900 ℃, and the heat treatment time is 1-12h.
10. The preparation method according to claim 4 or 5, wherein the nickel cobalt manganese hydroxide precursor is prepared by the following steps:
(1) Preparing a mixed salt solution of nickel salt, cobalt salt, manganese salt and optionally dopant M according to a molar ratio of Ni: co: mn: m=x: y: z: k; respectively preparing a precipitator solution and a complexing agent solution;
(2) Adding the mixed salt solution, the precipitator solution and the complexing agent solution into a reaction kettle for reaction to obtain precursor slurry, and carrying out solid-liquid separation, washing, drying and screening on the precursor slurry to obtain the nickel-cobalt-manganese hydroxide precursor.
11. The production method according to claim 10, wherein the dopant M is selected from a compound containing at least one element of Ga, sc, in, Y, ce, co, la, cr, mo, mn, fe, hf, zr, W, nb, sm and Al;
and/or, the reaction conditions include: the pH value is 11.2-11.9, the reaction temperature is 50-80 ℃, and the reaction time is 20-80 h;
and/or, the drying conditions include: the drying temperature is 80-120 ℃ and the drying time is 8-12h.
12. A positive electrode material produced by the production method according to any one of claims 4 to 11.
13. Use of the positive electrode material according to any one of claims 1-3 and 12 in a lithium ion battery.
14. A lithium ion battery comprising the positive electrode material of any one of claims 1-3 and 12.
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