CN115394984A - Lithium cobaltate composite material, preparation method and application thereof, and lithium ion battery - Google Patents
Lithium cobaltate composite material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- CN115394984A CN115394984A CN202211053503.6A CN202211053503A CN115394984A CN 115394984 A CN115394984 A CN 115394984A CN 202211053503 A CN202211053503 A CN 202211053503A CN 115394984 A CN115394984 A CN 115394984A
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- Prior art keywords
- metal
- coating layer
- lithium cobaltate
- composite material
- doped
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 169
- 239000002131 composite material Substances 0.000 title claims abstract description 124
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims description 177
- 239000002184 metal Substances 0.000 claims description 169
- 239000011247 coating layer Substances 0.000 claims description 126
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 52
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 51
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- 229910017052 cobalt Inorganic materials 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052706 scandium Inorganic materials 0.000 claims description 9
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000010410 layer Substances 0.000 description 23
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 230000002572 peristaltic effect Effects 0.000 description 10
- 239000010405 anode material Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 6
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 6
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
-
- 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
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- 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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Abstract
The invention relates to a lithium cobaltate composite material, a preparation method and application thereof, and a lithium ion battery. The lithium cobaltate composite material has good cycle performance and high-temperature performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium cobaltate composite material, a preparation method and application thereof and a lithium ion battery.
Background
The lithium ion battery has the characteristics of high energy density, good cycle performance, no memory effect and environmental friendliness, and is widely applied to the fields of electronic products, electric vehicles, aerospace and the like.
The lithium cobaltate has the characteristics of high capacity and high compaction, and the theoretical compaction of the lithium cobaltate can reach 5.06g/cm 3 The actual compaction can reach 4.2g/cm 3 As described above, the lithium ion secondary battery is generally used as a positive electrode material for a lithium ion battery. However, the conventional lithium cobaltate material has cycle performance at high voltage and high temperatureThe performance is poor.
Therefore, the lithium cobaltate material with better cycle performance and high-temperature performance under high voltage has important significance.
Disclosure of Invention
Based on the above, the invention provides a lithium cobaltate composite material with good cycle performance and high-temperature performance, a preparation method and application thereof, and a lithium ion battery.
The technical scheme of the invention for solving the technical problems is as follows.
The lithium cobaltate composite material takes first metal-doped lithium cobaltate as a core and a coating layer as a shell, the coating layer comprises a first coating layer, a second coating layer and a third coating layer which are sequentially arranged on the surface of the core, the first coating layer comprises an oxide of a second metal, the second coating layer comprises third metal-doped lithium cobaltate, and the third coating layer comprises an oxide of a fourth metal.
In some of these embodiments, the first metal and the third metal are each independently selected from at least one of lithium, sodium, potassium, calcium, iron, copper, aluminum, zirconium, magnesium, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
In some of these embodiments, the second metal and the fourth metal are each independently selected from at least one of calcium, magnesium, aluminum, iron, copper, zirconium, tungsten, strontium, zinc, molybdenum, and cerium in the lithium cobaltate composite.
In some of the embodiments, the surface of the third coating layer in the lithium cobaltate composite material further comprises a fourth coating layer, and a composition of the fourth coating layer is selected from at least one of an oxide of the fifth metal and a fluoride of the sixth metal.
In some of these embodiments, the fifth metal and the sixth metal are each independently selected from at least one of zirconium, titanium, magnesium, aluminum, nickel, manganese, iron, copper, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
In some of the embodiments, the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the first metal in the lithium cobaltate composite material is 1 (0.001-0.3).
In some embodiments, the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the second metal in the lithium cobaltate composite material is 1 (0.001-0.2).
In some embodiments, the molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the third metal in the lithium cobaltate composite material is 1 (0.001-0.3).
In some of the embodiments, the molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the fourth metal in the lithium cobaltate composite material is 1 (0.001-0.2).
The invention provides a preparation method of a lithium cobaltate composite material, which comprises the following steps:
providing a first metal-doped cobalt carbonate seed crystal, and arranging a hydroxide coating layer of a second metal on the surface of the first metal-doped cobalt carbonate seed crystal;
arranging a third metal-doped cobalt carbonate coating on the surface of the hydroxide coating of the second metal;
after a hydroxide coating layer of a fourth metal is arranged on the surface of the cobalt carbonate coating layer doped with the third metal, calcining is carried out to prepare a cobaltosic oxide composite material;
and mixing and calcining the cobaltosic oxide composite material and a lithium source.
In some embodiments, in the method for preparing a lithium cobaltate composite material, the D50 of the first metal-doped cobalt carbonate seed crystal is 0.1 μm to 10 μm.
In some of the embodiments, in the method of preparing a lithium cobaltate composite material, the thickness of the hydroxide coating layer of the second metal is 0.01 μm to 3 μm.
In some of the embodiments, in the method for preparing a lithium cobaltate composite material, the thickness of the third metal-doped cobalt carbonate coating layer is 1 μm to 30 μm.
In some of the embodiments, in the method of preparing a lithium cobaltate composite material, the thickness of the hydroxide coating layer of the fourth metal is 0.01 μm to 3 μm.
The invention provides an application of the lithium cobaltate composite material or the lithium cobaltate composite material prepared by the preparation method in the preparation of a lithium ion battery.
The invention provides a lithium ion battery which comprises a positive electrode, a diaphragm and a negative electrode, wherein the positive electrode and the negative electrode are arranged on two sides of the diaphragm, and the material of the positive electrode comprises the lithium cobaltate composite material or the lithium cobaltate composite material prepared by the preparation method of the lithium cobaltate composite material.
Compared with the prior art, the lithium cobaltate composite material has the following beneficial effects:
according to the lithium cobaltate composite material, the first coating layer comprising the oxide of the second metal, the second coating layer comprising the oxide of the third metal and the third coating layer comprising the oxide of the fourth metal are sequentially arranged on the surface of the first metal-doped lithium cobaltate, and the layers are combined through electrostatic attraction, ionic bonds and covalent bonds, so that the lithium cobaltate composite material has high stability; the first metal-doped lithium cobaltate and the third metal-doped lithium cobaltate are main active substance components of the lithium cobaltate composite material, and the first coating layer and the third coating layer can effectively prevent the penetration of electrolyte, so that the powdering, capacity attenuation and battery gas production behavior of the lithium cobaltate composite material caused by the side reaction of the electrolyte and the lithium cobaltate are effectively prevented; meanwhile, the volume change of the lithium cobaltate composite material in the charging and discharging processes is effectively relieved, so that cracks generated by structural stress of the lithium cobaltate composite material due to the volume change are reduced, and the stability of the crystal structure of the lithium cobaltate composite material is maintained; the lithium cobaltate composite material has good cycle performance and high-temperature performance due to the synergistic effect of the layers.
When the lithium cobaltate composite material is used as the lithium ion battery anode material, the volume change of the anode material in the high-voltage cycle process can be effectively relieved, the permeation of electrolyte can be shielded, a new interface film generated by the anode material and the electrolyte can be effectively controlled, the consumption of the electrolyte can be reduced, and the gas generation of the lithium ion battery under the high voltage can be reduced, so that the cycle performance of the lithium ion battery can be effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM photograph of Al-Mg doped cobalt carbonate with a layered structure obtained in step (3) of example 1;
FIG. 2 is an SEM photograph of the five-layer lithium cobaltate composite material obtained in step (7) of example 1;
FIG. 3 is an SEM photograph of the five-layer lithium cobaltate composite material obtained in step (7) of example 2;
FIG. 4 is an SEM photograph of the five-layer lithium cobaltate composite material obtained in step (7) of example 6;
FIG. 5 is a graph showing the first charge and discharge curves of the five-layer lithium cobaltate composite material prepared in example 2;
FIG. 6 is a graph showing the first charge and discharge curves of the five-layer lithium cobaltate composite material prepared in example 3;
fig. 7 is a graph comparing the cycle capacity retention at 45 ℃ of the thin film batteries manufactured by the lithium cobaltate composite materials of example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight of each component, therefore, the proportional enlargement or reduction of the content of the related components according to the description of the embodiments of the present invention is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The invention provides a lithium cobaltate composite material, which takes a first metal-doped lithium cobaltate as a core and a coating layer as a shell, wherein the coating layer comprises a first coating layer, a second coating layer and a third coating layer which are sequentially arranged on the surface of the core, the first coating layer comprises an oxide of a second metal, the second coating layer comprises a component of a third metal-doped lithium cobaltate, and the third coating layer comprises an oxide of a fourth metal.
The method comprises the following steps of sequentially arranging a first coating layer comprising an oxide of a second metal, a second coating layer comprising an oxide of a third metal and a third coating layer comprising an oxide of a fourth metal on the surface of first metal-doped lithium cobalt oxide, wherein the layers are combined through electrostatic attraction, ionic bonds and covalent bonds, so that the lithium cobalt oxide composite material has high stability; the first metal-doped lithium cobaltate and the third metal-doped lithium cobaltate are main active substance components of the lithium cobaltate composite material, and the first coating layer and the third coating layer can effectively prevent the penetration of electrolyte, so that the powdering, capacity fading and battery gas production behavior of the lithium cobaltate composite material caused by the side reaction of the electrolyte and the lithium cobaltate are effectively prevented; meanwhile, the volume change of the lithium cobaltate composite material in the charging and discharging process is effectively relieved, so that the structural stress generated by the volume change of the lithium cobaltate composite material is reduced to generate cracks, and the stability of the crystal structure of the lithium cobaltate composite material is kept; the lithium cobaltate composite material has good cycle performance and high-temperature performance due to the synergistic effect of the layers.
When the lithium cobaltate composite material is used as the lithium ion battery anode material, the volume change of the anode material in the high-voltage cycle process can be effectively relieved, the permeation of the electrolyte can be shielded, a new interface film generated by the anode material and the electrolyte can be effectively controlled, the consumption of the electrolyte can be reduced, the gas generation of the lithium ion battery under the high voltage can be reduced, and the cycle performance of the lithium ion battery can be effectively improved.
In some examples, the first metal and the third metal in the lithium cobaltate composite are each independently selected from at least one of lithium, sodium, potassium, calcium, iron, copper, aluminum, zirconium, magnesium, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
It is understood that the first metal and the third metal may be the same or different; it is also understood that the first metal and the third metal may be each independently one metal, or may be two or more metals.
In some examples, the first metal and the third metal are each independently selected from at least one of aluminum and magnesium in the lithium cobaltate composite material.
Further, the first metal and the third metal are each selected from a mixture of aluminum and magnesium.
In some examples, the second metal and the fourth metal are each independently selected from at least one of calcium, magnesium, aluminum, iron, copper, zirconium, tungsten, strontium, zinc, molybdenum, and cerium in the lithium cobaltate composite material.
It is understood that the second metal and the fourth metal may be the same or different; it is also understood that the second metal and the fourth metal may be each independently one metal, or may be two or more metals.
In some examples, the second metal and the fourth metal are each independently selected from at least one of magnesium, aluminum, iron, and copper in the lithium cobaltate composite material.
In some examples, the lithium cobaltate composite material further includes a fourth coating layer on a surface of the third coating layer, a composition of the fourth coating layer being selected from at least one of an oxide of the fifth metal and a fluoride of the sixth metal.
In some examples, the fifth metal and the sixth metal in the lithium cobaltate composite are each independently selected from at least one of titanium, magnesium, aluminum, nickel, manganese, iron, copper, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
It is understood that the species of the fifth metal and the sixth metal may be the same or different; it is also understood that the fifth metal and the sixth metal may be one metal, or may be two or more metals, respectively.
Further, the fifth metal and the sixth metal are each independently selected from at least one of magnesium, aluminum, tungsten, and zirconium.
In some examples, the mole ratio of cobalt element in the first metal-doped lithium cobaltate to the first metal in the lithium cobaltate composite material is 1 (0.001-0.3).
It can be understood that the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the first metal includes but is not limited to 1.
In some examples, the mole ratio of the cobalt element in the first metal-doped lithium cobaltate to the second metal in the lithium cobaltate composite material is 1 (0.001-0.2).
It can be understood that the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the second metal includes, but is not limited to, 1.
In some examples, the molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the third metal in the lithium cobaltate composite material is 1 (0.001-0.3).
It can be understood that the molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the third metal includes but is not limited to 1.
In some examples, the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the fourth metal in the lithium cobaltate composite material is 1 (0.001-0.2).
It can be understood that the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the fourth metal includes, but is not limited to, 1.
An embodiment of the present invention provides a method for preparing a lithium cobaltate composite material, including the steps of:
providing first metal-doped lithium cobalt oxide, taking the first metal-doped lithium cobalt oxide as a core, and sequentially arranging a first coating layer, a second coating layer and a third coating layer on the surface of the core, wherein the first coating layer comprises an oxide of a second metal, the second coating layer comprises the third metal-doped lithium cobalt oxide, and the third coating layer comprises an oxide of a fourth metal.
Another embodiment of the present invention provides a specific method for preparing a lithium cobaltate composite material, including steps S10 to S40.
Step S10: providing a first metal-doped cobalt carbonate seed crystal, and arranging a hydroxide coating layer of a second metal on the surface of the first metal-doped cobalt carbonate seed crystal.
In some examples, in step S10, the first metal-doped cobalt carbonate seed, the second metal salt, and the first base are mixed and reacted to form a hydroxide coating layer of the second metal on the surface of the first metal-doped cobalt carbonate seed, resulting in a coated first metal-doped cobalt carbonate seed.
In some examples, in step S10, the second metal salt is selected from at least one of chloride, sulfate, nitrate, and acetate of the second metal.
Further, the second metal is at least one selected from the group consisting of calcium, magnesium, aluminum, iron, copper, zirconium, tungsten, strontium, zinc, molybdenum, and cerium.
It is understood that, in the second metal salt, at least one hydroxide of the second metal is a precipitate.
In some examples, in step S10, the first base is selected from at least one of ammonia, sodium hydroxide, and potassium hydroxide.
Optionally, the first base is ammonia.
In some examples, in step S10, the molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the second metal is 1 (0.001-0.2).
It can be understood that by controlling the molar ratio of the cobalt element in the first metal doped lithium cobaltate to the second metal, the thickness of the hydroxide coating layer of the second metal can be controlled.
In some examples, the coating layer of the hydroxide of the second metal has a thickness of 0.01 μm to 3 μm in step S10.
It is understood that the thickness of the hydroxide coating of the second metal includes, but is not limited to, 0.01 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.25 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm.
Alternatively, the coating layer of the hydroxide of the second metal has a thickness of 0.01 μm to 1 μm.
In some examples, in step S10, the hydroxide coating layer of the second metal is distributed in island or layer shape on the surface of the cobalt carbonate seed crystal doped with the first metal.
Optionally, the coating of the hydroxide of the second metal is layered.
In some examples, the temperature of the mixing reaction in step S10 is 20 ℃ to 70 ℃.
It is understood that the temperature of the mixing reaction includes, but is not limited to, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, and 70 deg.C.
In some examples, the pH of the mixing reaction in step S10 is 7 to 12.
It is understood that in step S10, the pH of the mixing reaction includes, but is not limited to, 7, 8, 9, 10, 12.
In some examples, in step S10, the preparation of the first metal-doped cobalt carbonate seed comprises step S11.
Step S11: and mixing and reacting the first soluble cobalt salt, the first metal salt, the first carbonate and water to prepare the first metal-doped cobalt carbonate seed crystal.
In some examples, in step S11, the first soluble cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, cobalt nitrate, and cobalt acetate.
In some examples, in step S11, the first metal salt is selected from at least one of chloride, sulfate, nitrate, and acetate of the first metal.
Further, the first metal is selected from at least one of lithium, sodium, potassium, calcium, iron, copper, aluminum, zirconium, magnesium, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
In some examples, in step S11, the first carbonate is at least one selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
It is understood that in some examples, in step S11, the molar ratio of the cobalt element in the first soluble cobalt salt to the first metal is 1 (0.001-0.3).
In some examples, in step S11, the temperature of the mixing reaction is 30 ℃ to 65 ℃, and the pH value is 7 to 10.
It is understood that, in step S11, the temperature of the mixing reaction includes, but is not limited to, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C; pH values include, but are not limited to, 7, 7.5, 8, 9, 10.
In some examples, in step S11, the temperature of the mixing reaction is 45 ℃ to 55 ℃, and the pH is 7 to 8.
In some examples, the D50 of the first metal-doped cobalt carbonate seed in step S10 is 0.1 μm to 10 μm.
It is understood that the D50 of the first metal doped cobalt carbonate seed includes, but is not limited to, 0.1 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.1 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm.
Further, the D50 of the first metal-doped cobalt carbonate seed crystal is 0.3-5 μm.
Step S20: and arranging a third metal-doped cobalt carbonate coating layer on the surface of the hydroxide coating layer of the second metal.
In some examples, in step S20, the coated first metal-doped cobalt carbonate seed obtained in step S10, the second soluble cobalt salt, the third metal salt, the second carbonate and water are mixed and reacted to generate a third metal-doped cobalt carbonate coating layer on the surface of the hydroxide coating layer of the second metal, so as to obtain the layered structure-doped cobalt carbonate.
In some examples, in step S20, the second soluble cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate, cobalt nitrate, and cobalt acetate.
In some examples, in step S20, the third metal salt is selected from at least one of chloride, sulfate, nitrate, and acetate of the third metal.
Further, the third metal is selected from at least one of lithium, sodium, potassium, calcium, iron, copper, aluminum, zirconium, magnesium, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
In some examples, in step S20, the second carbonate is at least one selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
It is understood that in some examples, the molar ratio of the cobalt element in the second soluble cobalt salt to the third metal in step S21 is 1 (0.001-0.3).
In some examples, in step S20, the temperature of the mixing reaction is 30 ℃ to 65 ℃, and the pH value is 7 to 10.
It is understood that, in step S20, the temperature of the mixing reaction includes, but is not limited to, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and 65 ℃; pH values include, but are not limited to, 7, 7.5, 8, 9, 10.
In some examples, in step S20, the temperature of the mixing reaction is 45 ℃ to 55 ℃, and the pH is 7 to 8.
In some examples, in step S20, the thickness of the third metal-doped cobalt carbonate coating layer is 1 μm to 30 μm.
It is understood that the thickness of the third metal-doped cobalt carbonate coating layer includes, but is not limited to, 1 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 20 μm, 25 μm, 30 μm.
In some examples, the D50 of the layered structure aluminum magnesium doped cobalt carbonate prepared in step S20 is 3 μm to 76 μm.
It is understood that the D50 of the third metal doped cobalt carbonate includes, but is not limited to, 3 μm, 3.1 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 8 μm, 10 μm, 12 μm, 13 μm, 14.7 μm, 15 μm, 18 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 76 μm.
Step S30: and (3) after a hydroxide coating layer of a fourth metal is arranged on the surface of the cobalt carbonate coating layer doped with the third metal, calcining is carried out, and the cobaltosic oxide composite material is prepared.
It can be understood that the cobaltosic oxide composite material takes cobaltosic oxide doped with a first metal as a core, and the surface of the core is sequentially provided with an oxide coating layer of a second metal, an oxide coating layer of a cobaltosic oxide doped with a third metal and an oxide coating layer of a fourth metal.
In some examples, in step S30, the layered structure doped cobalt carbonate obtained in step S20, a fourth metal salt, and a second base are mixed and reacted to form a hydroxide coating layer of the fourth metal on the surface of the third metal doped cobalt carbonate coating layer, so as to obtain the layered structure doped cobalt carbonate.
It can be understood that the structure of the multilayer structure doped with cobalt carbonate is: taking the cobalt carbonate seed crystal doped with the first metal as a core (the first metal exists in the form of carbonate), wherein the surface of the core is sequentially provided with a hydroxide coating layer of the second metal, a cobalt carbonate coating layer doped with the third metal and a hydroxide coating layer of the fourth metal; after the multilayer structure doped cobalt carbonate is calcined, the first metal doped cobalt carbonate seed crystal generates first metal doped cobaltosic oxide, the hydroxide coating layer of the second metal generates an oxide coating layer of the second metal, the third metal doped cobalt carbonate coating layer generates a third metal doped cobaltosic oxide coating layer, and the hydroxide coating layer of the fourth metal generates an oxide coating layer of the fourth metal.
In some examples, in step S30, the fourth metal salt is selected from at least one of chloride, sulfate, nitrate, and acetate of the third metal.
Further, the fourth metal is at least one selected from the group consisting of calcium, magnesium, aluminum, iron, copper, zirconium, tungsten, strontium, zinc, molybdenum, and cerium.
It is understood that in the fourth metal salt, the hydroxide of at least one fourth metal is a precipitate.
In some examples, in step S30, the second base is selected from at least one of ammonia, sodium hydroxide, and potassium hydroxide.
Optionally, the second base is ammonia.
In some examples, in step S30, the molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the fourth metal is 1 (0.001-0.2).
It can be understood that by controlling the molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the fourth metal, the thickness of the hydroxide coating layer of the fourth metal can be controlled.
In some examples, the coating layer of the hydroxide of the fourth metal has a thickness of 0.01 μm to 3 μm in step S30.
It is understood that the thickness of the hydroxide coating layer of the fourth metal includes, but is not limited to, 0.01 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.25 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm.
Alternatively, the thickness of the hydroxide coating layer of the fourth metal is 0.01 μm to 1 μm.
In some examples, the multilayer structure doped with cobalt carbonate has a D50 of 3 μm to 25 μm in step S30.
It is understood that the D50 of the cobalt carbonate doped multilayer structure includes, but is not limited to, 3 μm, 3.1 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 8 μm, 10 μm, 12 μm, 13 μm, 14.7 μm, 15 μm, 18 μm, 20 μm, 25 μm.
In some examples, in step S30, the hydroxide coating layer of the fourth metal is distributed in island or layer shape on the surface of the cobalt carbonate seed crystal doped with the third metal.
Optionally, the coating of the hydroxide of the fourth metal is layered.
In some examples, the temperature of the mixing reaction in step S30 is 20 ℃ to 70 ℃.
It is understood that the temperature of the mixing reaction includes, but is not limited to, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, and 70 deg.C.
In some examples, the pH of the mixing reaction in step S30 is 7 to 12.
In some examples, the temperature of the calcination in step S30 is 300 ℃ to 1000 ℃.
It is understood that, in step S30, the calcination temperature includes, but is not limited to, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, 1000 deg.C.
Step S40: and mixing and calcining the cobaltosic oxide composite material and a lithium source to obtain the four-layer lithium cobaltate composite material.
In some examples, the temperature of the calcination in step S40 is 300 ℃ to 1200 ℃.
In some examples, in step S40, the calcination is a staged calcination, which is performed at 300-600 ℃ and then at 800-1100 ℃.
It is understood that, in step S40, the temperature of the first calcination includes, but is not limited to, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, and the temperature of the second calcination includes, but is not limited to, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, 1000 deg.C, 1050 deg.C, 1100 deg.C.
In some examples, the step S40 further includes adding a seventh metal compound during the mixing and calcining.
It is understood that the seventh metal compound includes, but is not limited to, an oxide of the seventh metal, a fluoride of the seventh metal, and a salt of the seventh metal.
In some examples, in step S40, the seventh metal compound is selected from at least one of zirconia, titania, alumina, tungsten oxide, magnesia, iron oxide, and copper oxide.
In some examples, in step S40, the molar ratio of the cobalt element of the cobaltosic oxide composite material, the lithium element of the lithium source and the metal element of the seventh metal oxide is 1 (1-1.2) to 0.001-0.3.
It is understood that the molar amount of the lithium element of the lithium source includes, but is not limited to, 1 unit, 1.1 units, 1.2 units, with the molar amount of the cobalt element of the cobaltosic oxide composite material being 1 unit; the molar amount of the metal element of the seventh metal oxide includes, but is not limited to, 0.001 unit, 0.005 unit, 0.01 unit, 0.015 unit, 0.02 unit, 0.025 unit, 0.05 unit, 0.1 unit, 0.2 unit, 0.3 unit.
In some examples, the method for preparing the lithium cobaltate composite material further includes step S50.
Step S50: and (4) mixing and calcining the four layers of lithium cobaltate composite materials obtained in the step (S40) and a coating agent to obtain five layers of lithium cobaltate composite materials, wherein the coating agent is at least one selected from oxides of fifth metals and fluorides of sixth metals.
In some examples, in step S50, the fifth metal and the sixth metal are each independently selected from at least one of zirconium, titanium, magnesium, aluminum, nickel, manganese, iron, copper, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
In some examples, in step S50, the molar ratio of the cobalt element in the lithium cobaltate composite material with four layers to the metal ion in the coating agent is 1 (0.001-0.3).
In some examples, the temperature of the calcination in step S50 is 200 ℃ to 1000 ℃.
It is understood that, in step S50, the temperature of the calcination includes, but is not limited to, 200 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C, 950 deg.C, 1000 deg.C.
Alternatively, the temperature of calcination is from 300 ℃ to 600 ℃.
It is understood that the lithium cobaltate composite material can be prepared by the preparation method of the lithium cobaltate composite material.
An embodiment of the invention provides an application of the lithium cobaltate composite material or the lithium cobaltate composite material prepared by the preparation method in preparation of a lithium ion battery.
Further, an embodiment of the present invention provides an application of the lithium cobaltate composite material or the lithium cobaltate composite material prepared by the preparation method of the lithium cobaltate composite material in preparation of a lithium ion battery positive electrode material. The invention also provides a lithium ion battery positive electrode material, which comprises the lithium cobaltate composite material or the lithium cobaltate composite material prepared by the preparation method of the lithium cobaltate composite material.
The lithium cobaltate composite material is used for preparing the lithium ion battery anode material, and can endow the lithium ion battery anode material with better cycle performance and high-temperature performance.
In some embodiments, the lithium ion battery positive electrode material may be the lithium cobaltate composite material, i.e., the lithium ion battery positive electrode material is directly prepared from the lithium cobaltate composite material. In other embodiments, the lithium ion battery positive electrode material may include other materials in addition to the lithium cobaltate composite material described above.
The lithium ion battery comprises a positive electrode, a diaphragm and a negative electrode, wherein the positive electrode and the negative electrode are arranged on two sides of the diaphragm, and the material of the positive electrode comprises the lithium cobaltate composite material or the lithium cobaltate composite material prepared by the preparation method of the lithium cobaltate composite material.
An embodiment of the present invention provides an application of the lithium ion battery in an electronic device, an electric tool, an electric vehicle, or a power storage system. Another embodiment of the present invention provides an electronic device, an electric tool, an electric vehicle, or an electric power storage system including the lithium ion battery described above.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Hereinafter, the lithium cobaltate composite material, the preparation method and the application thereof, and the lithium ion battery according to the present invention are exemplified, and it is understood that the lithium cobaltate composite material, the preparation method and the application thereof, and the lithium ion battery according to the present invention are not limited to the following examples.
In the examples below, the surface topography was carried out on a scanning electron microscope SEM of model JSM-6510, JEOL, and EV018, zeiss, germany, and D50 was carried out on a Mark Mastersizer 2000 laser particle sizer, united kingdom.
Example 1
(1) Adding 2mol/L cobalt sulfate, 0.01mol/L aluminum sulfate and 0.01mol/L magnesium sulfate aqueous solution into a reaction kettle of 2mol/L ammonium bicarbonate aqueous solution in a cocurrent manner through a peristaltic pump, stirring at 1000rpm, keeping the temperature at 40 ℃, reacting for 4 hours, standing and aging for 1 hour at the constant temperature of 30 ℃, filtering supernatant in the reaction kettle, and reserving a precipitate product on a bottom filter screen in the reaction kettle to obtain an aluminum-magnesium doped cobalt carbonate seed crystal with the D50 of 3.1 mu m;
(2) Adding 1mol/L sodium hydroxide aqueous solution into the reaction kettle which is reserved with the precipitation product in the step (1), adjusting the pH value of the solution to 12 by using deionized water, stirring at 1500rpm, keeping the temperature at 40 ℃, adding 0.01mol/L aluminum sulfate in a concurrent flow manner through a peristaltic pump, reacting for 0.5h, keeping the reaction kettle at 30 ℃ and standing and aging for 1h, filtering supernatant in the reaction kettle, reserving the precipitation product on a bottom filter screen in the reaction kettle, and preparing aluminum-magnesium doped cobalt carbonate crystal seeds with the D50 of 3.4 mu m and the surface of which is coated with an aluminum hydroxide coating layer;
(3) Adding 2mol/L cobalt sulfate aqueous solution and 1mol/L ammonium bicarbonate aqueous solution into the reaction kettle which is reserved with the precipitation product in the step (2), adopting 2mol/L ammonia water to adjust the pH value to 7.2, stirring at 1000rpm, keeping the temperature at 40 ℃, adding 0.01mol/L aluminum sulfate aqueous solution and 0.01mol/L magnesium sulfate aqueous solution in a concurrent flow manner through a peristaltic pump, reacting for 4 hours, keeping the reaction kettle at 30 ℃ and standing and aging for 1 hour, filtering supernatant in the reaction kettle, reserving the precipitation product on a bottom filter screen in the reaction kettle, and preparing the aluminum-magnesium doped cobalt carbonate with the layered structure, wherein D50 of the aluminum-magnesium doped cobalt carbonate is 14.7 mu m, and an SEM picture of the cobalt doped cobalt carbonate is shown in figure 1;
(4) Adding 1mol/L sodium hydroxide aqueous solution into the reaction kettle which is reserved with the precipitation product in the step (3), adjusting the pH value of the solution to 12 by using deionized water, stirring at 1500rpm, keeping the temperature at 40 ℃, adding 0.01mol/L magnesium sulfate in a concurrent flow manner through a peristaltic pump, reacting for 0.5h, keeping the reaction kettle at 30 ℃ and standing and aging for 1h, filtering supernatant in the reaction kettle, reserving the precipitation product on a bottom filter screen in the reaction kettle, and preparing the multilayer structure aluminum-magnesium doped cobalt carbonate with the D50 of 15.1 mu m;
(5) Placing the multilayer structure aluminum-magnesium-doped cobaltous carbonate obtained in the step (4) into a muffle furnace for calcining, wherein the temperature rise rate of the muffle furnace is 5 ℃/min, the temperature rises to 550 ℃ at 25 ℃, and the multilayer structure aluminum-magnesium-doped cobaltosic oxide is prepared;
(6) Uniformly mixing the multilayer-structure aluminum-magnesium-doped cobaltosic oxide obtained in the step (5) with lithium carbonate, zirconium oxide and titanium dioxide according to the stoichiometric ratio of metal elements of 1.1;
(7) Uniformly mixing the four layers of lithium cobaltate composite material obtained in the step (6) with aluminum oxide and tungsten oxide according to the stoichiometric ratio of metal elements of 1.005, placing the mixture in a muffle furnace for calcining, wherein the heating rate of the muffle furnace is 5 ℃/min, the temperature of the muffle furnace is increased to 550 ℃ at 25 ℃, and the constant temperature is kept for 5 hours, so as to prepare the five-layer lithium cobaltate composite material with the D50 of 15.27 mu m, and the SEM picture of the five-layer lithium cobaltate composite material is shown in FIG. 2; the lithium cobaltate composite material with five layers takes aluminum magnesium doped lithium cobaltate as a core, and the surface of the core is sequentially provided with an aluminum oxide coating layer (a first coating layer), an aluminum magnesium doped lithium cobaltate coating layer (a second coating layer), a magnesium oxide coating layer (a third coating layer), and an aluminum oxide and tungsten oxide uniformly dispersed coating layer (a fourth coating layer).
Example 2
Basically the same as in example 1, except that:
(1) Adding 3mol/L cobalt sulfate and 0.02mol/L aluminum sulfate aqueous solution into a reaction kettle of 2mol/L ammonium bicarbonate aqueous solution in a cocurrent manner through a peristaltic pump;
(2) Adding 0.03mol/L aluminum sulfate and 0.01mol/L magnesium sulfate aqueous solution in a concurrent flow manner through a peristaltic pump;
(3) Reacting for 10h;
(4) Adding 0.01mol/L copper sulfate in parallel flow through a peristaltic pump;
the SEM image of the five-layered lithium cobalt oxide composite material prepared in example 2 is shown in fig. 3.
Example 3
Basically the same as example 1, except that:
(1) Adding 3mol/L cobalt sulfate, 0.02mol/L aluminum sulfate and 0.01mol/L magnesium sulfate aqueous solution into a reaction kettle containing 2mol/L ammonium bicarbonate aqueous solution in a concurrent flow manner through a peristaltic pump, stirring at the speed of 1000rpm, keeping the temperature at 42 ℃, and reacting for 5 hours;
(2) Adding 0.01mol/L aluminum sulfate and 0.01mol/L copper sulfate in a concurrent flow manner through a peristaltic pump;
(4) Adding 0.01mol/L ferric sulfate in parallel flow through a peristaltic pump;
example 4
Basically the same as in example 1, except that:
(6) Uniformly mixing the multilayer structure aluminum-magnesium-doped cobaltosic oxide obtained in the step (5), lithium hydroxide monohydrate, aluminum oxide and titanium dioxide according to the stoichiometric ratio of metal elements of 1.05;
(7) And (3) uniformly mixing the four layers of lithium cobaltate composite material obtained in the step (6) with aluminum oxide and magnesium oxide according to the stoichiometric ratio of metal elements of 1.
Example 5
Basically the same as in example 1, except that:
(6) Uniformly mixing the multilayer structure aluminum-magnesium-doped cobaltosic oxide obtained in the step (5) with lithium hydroxide monohydrate, tungsten oxide and magnesium oxide according to the stoichiometric ratio of metal elements of 1.13;
(7) And (3) uniformly mixing the four layers of lithium cobaltate composite material obtained in the step (6) with zirconia and alumina according to the stoichiometric ratio of metal elements of 1.
Example 6
Basically the same as example 1, except that:
(6) Uniformly mixing the multilayer structure aluminum-magnesium-doped cobaltosic oxide obtained in the step (5) with lithium carbonate, ferric oxide and copper oxide according to the stoichiometric ratio of metal elements of 1.10;
(7) Uniformly mixing the four layers of lithium cobaltate composite material obtained in the step (6) with alumina and zirconia according to the stoichiometric ratio of metal elements of 1;
the SEM image of the lithium cobaltate composite material of five layers prepared in example 6 is shown in fig. 4.
Comparative example 1
Basically the same as example 1, except that the step (2) is omitted, namely, the finally obtained lithium cobaltate composite material uses the aluminum magnesium doped lithium cobaltate as the core, and the surface of the core is sequentially provided with an aluminum magnesium doped lithium cobaltate coating layer (second coating layer), a magnesium oxide coating layer (third coating layer), and an aluminum oxide and tungsten oxide mixed coating layer (fourth coating layer).
Comparative example 2
The same as example 1, except that the step (4) is omitted, that is, the finally obtained lithium cobaltate composite material uses the aluminum-magnesium doped lithium cobaltate as the core, and the surface of the core is sequentially provided with an aluminum oxide coating layer (first coating layer), an aluminum-magnesium doped lithium cobaltate coating layer (second coating layer), and an aluminum oxide and tungsten oxide mixed coating layer (fourth coating layer).
Comparative example 3
The difference from example 1 is that steps (2) and (4) are omitted, that is, the finally obtained lithium cobaltate composite material uses the aluminum magnesium doped lithium cobaltate as a core, and the surface of the core is provided with an aluminum magnesium doped lithium cobaltate coating layer (second coating layer) and an aluminum oxide and tungsten oxide mixed coating layer (fourth coating layer) in this order.
Button cell test
Assembling a CR2032 button cell in a German Braun (Mbraun, unilab) glove box, filling 99.9% high-purity argon, and adopting a Shenzhenjian crystal MSK-110 small-sized hydraulic button cell packaging machine;
mixing the lithium cobaltate composite material prepared in each embodiment and each comparative example, a conductive agent Super P and a binder PVDF (HSV 900), adding a proper amount of N-methylpyrrolidone serving as a solvent, and stirring for 15 hours by using a magnetic stirrer in a glove box under the protection of argon to obtain positive electrode slurry; uniformly coating the positive electrode slurry (coating machine is an MSK-AFA-III automatic coating dryer of Shenzhen Kejing Zhi science and technology Limited company, coating gap is 25 μm, speed is 5 cm/min), vacuum drying for 12 hours at 120 ℃ on a smooth copper foil with the thickness of 9 μm and the purity of 99.8% produced by Meixian Jinxiang copper foil Limited company, and then punching into an electrode slice with the diameter of about 16mm by a Shenzhen Kejing MSK-T06 button cell punching machine to be used as a positive electrode; the negative electrode is a lithium sheet with the purity of 99.99 percent and the diameter of 15.8mm, the diaphragm is an American ENTEK LP16 PE diaphragm with the thickness of 16 mu m, the electrolyte is DMC: EMC with the mass ratio of 60 6 Electrical performance tests were performed on a CT2001A tester of wuhan blue electronics ltd, and the gram capacity and the first coulombic efficiency are shown in table 1; the first charge and discharge curve chart of example 2 is shown in fig. 5, and the first charge and discharge curve chart of example 3 is shown in fig. 6.
Thin film battery testing
The anode material is prepared from a lithium cobaltate composite material: conductive agent: binder (mass ratio 96; the cathode material comprises the following components: conductive agent: the binder (mass ratio 96.
Wherein, the curve of the capacity retention rate of the thin film battery prepared by the lithium cobaltate composite material of some examples and comparative examples at 45 ℃ by 0.7C charge/1C discharge and 0.7C charge/0.2C discharge every 25 circles is shown in figure 7, the abscissa is the number of cycles, and the ordinate is the capacity retention rate; as can be seen from fig. 7, examples 1 and 4 to 6 have higher capacity retention rates when cycled at high temperatures than comparative example 3, and comparative example 3, which does not include the first and third coating layers, has significantly reduced high-temperature cycle capacity retention rates.
Pouch cell testing
The positive electrode material is prepared from a lithium cobaltate composite material: conductive agent: binder (mass ratio 96; the cathode material comprises graphite: conductive agent: binder (mass ratio 96; the soft package battery is fully charged to 4.5V, the soft package battery is placed in a 60 ℃ thermostat at 100 percent for 7 days, then the average thickness of the soft package battery core is tested by a micrometer, and the change rate of the storage thickness of the soft package battery at 60 ℃ is calculated, and the result is shown in table 1.
TABLE 1
Compared with a comparative example, the lithium cobaltate composite material prepared in the embodiment has good cycle performance and high-temperature performance, and gram capacity and first coulombic efficiency are maintained; whereas comparative example 1 lacks the first coating layer, comparative example 2 does not contain the third coating layer, and comparative example 3 does not contain the first coating layer and the third coating layer, the high-temperature performance of the prepared lithium cobaltate composite material is significantly reduced, and the cycle performance is reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. The lithium cobaltate composite material is characterized in that a first metal-doped lithium cobaltate is taken as a core, a coating layer is taken as a shell, the coating layer comprises a first coating layer, a second coating layer and a third coating layer which are sequentially arranged on the surface of the core, the first coating layer comprises an oxide of a second metal, the second coating layer comprises a component of a third metal-doped lithium cobaltate, and the third coating layer comprises an oxide of a fourth metal.
2. The lithium cobaltate composite material of claim 1, wherein the first metal and the third metal are each independently selected from at least one of lithium, sodium, potassium, calcium, iron, copper, aluminum, zirconium, magnesium, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
3. The lithium cobaltate composite material of claim 1, wherein the second metal and the fourth metal are each independently selected from at least one of calcium, magnesium, aluminum, iron, copper, zirconium, tungsten, strontium, zinc, molybdenum, and cerium.
4. The lithium cobaltate composite material according to any one of claims 1 to 3, wherein a surface of the third coating layer further comprises a fourth coating layer, and a composition of the fourth coating layer is at least one selected from an oxide of a fifth metal and a fluoride of a sixth metal.
5. The lithium cobaltate composite material of claim 4, wherein the fifth metal and the sixth metal are each independently selected from at least one of zirconium, titanium, magnesium, aluminum, nickel, manganese, iron, copper, indium, antimony, bismuth, barium, tungsten, palladium, strontium, cerium, niobium, scandium, gallium, silver, vanadium, zinc, germanium, and molybdenum.
6. The lithium cobaltate composite material according to any one of claims 1 to 3 and 5, wherein the lithium cobaltate composite material satisfies at least one of the following conditions (1) to (4):
(1) The molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the first metal is 1 (0.001-0.3);
(2) The molar ratio of the cobalt element in the first metal-doped lithium cobaltate to the second metal is 1 (0.001-0.2);
(3) The molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the third metal is 1 (0.001-0.3);
(4) The molar ratio of the cobalt element in the third metal-doped lithium cobaltate to the fourth metal is 1 (0.001-0.2).
7. The preparation method of the lithium cobaltate composite material is characterized by comprising the following steps of:
providing a first metal-doped cobalt carbonate seed crystal, and arranging a hydroxide coating layer of a second metal on the surface of the first metal-doped cobalt carbonate seed crystal;
arranging a third metal-doped cobalt carbonate coating layer on the surface of the hydroxide coating layer of the second metal;
after a hydroxide coating layer of a fourth metal is arranged on the surface of the cobalt carbonate coating layer doped with the third metal, calcining is carried out to prepare a cobaltosic oxide composite material;
and mixing and calcining the cobaltosic oxide composite material and a lithium source.
8. The method of producing a lithium cobaltate composite material according to claim 7, wherein at least one of the following conditions (1) to (4) is satisfied:
(1) The D50 of the first metal-doped cobalt carbonate seed crystal is 0.1-10 mu m;
(2) The thickness of the hydroxide coating layer of the second metal is 0.01-3 mu m;
(3) The thickness of the third metal-doped cobalt carbonate coating layer is 1-30 mu m;
(4) The thickness of the hydroxide coating layer of the fourth metal is 0.01-3 mu m.
9. Use of a lithium cobaltate composite material according to any one of claims 1 to 6 or a lithium cobaltate composite material prepared by the method according to any one of claims 7 to 8 for the preparation of a lithium ion battery.
10. A lithium ion battery, which is characterized by comprising a positive electrode, a diaphragm and a negative electrode, wherein the positive electrode and the negative electrode are arranged on two sides of the diaphragm, and the material of the positive electrode comprises the lithium cobaltate composite material according to any one of claims 1 to 6 or the lithium cobaltate composite material prepared by the preparation method of any one of claims 7 to 8.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996831A (en) * | 2014-05-16 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery positive pole active material |
| CN104241627A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Lithium cobaltate for positive electrode of lithium ion battery and preparation method of lithium cobaltate for positive electrode of lithium ion battery |
| CN105938917A (en) * | 2016-07-01 | 2016-09-14 | 深圳市振华新材料股份有限公司 | Lithium ion secondary cell lithium cobaltate cathode material, manufacture method and application thereof |
| CN106797049A (en) * | 2014-10-02 | 2017-05-31 | 株式会社Lg 化学 | Cathode active material for lithium secondary battery, its preparation method and the lithium secondary battery comprising it |
| CN109256531A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院宁波材料技术与工程研究所 | Doping cobalt acid lithium and its preparation method and application with compound coating layer |
| CN109314238A (en) * | 2016-12-21 | 2019-02-05 | 株式会社Lg化学 | Metal-doped high voltage positive electrode active materials |
| CN111081987A (en) * | 2018-10-18 | 2020-04-28 | 湖南杉杉能源科技股份有限公司 | Lithium cobaltate cathode material of lithium ion battery with voltage of more than 4.45V and preparation method thereof |
| WO2021223635A1 (en) * | 2020-05-08 | 2021-11-11 | 北京当升材料科技股份有限公司 | Lithium cobaltate positive electrode material, preparation method therefor and use thereof |
| CN114220976A (en) * | 2021-09-29 | 2022-03-22 | 惠州锂威新能源科技有限公司 | Lithium cobaltate material and preparation method thereof, positive plate and lithium ion battery |
-
2022
- 2022-08-31 CN CN202211053503.6A patent/CN115394984A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996831A (en) * | 2014-05-16 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery positive pole active material |
| CN104241627A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Lithium cobaltate for positive electrode of lithium ion battery and preparation method of lithium cobaltate for positive electrode of lithium ion battery |
| CN106797049A (en) * | 2014-10-02 | 2017-05-31 | 株式会社Lg 化学 | Cathode active material for lithium secondary battery, its preparation method and the lithium secondary battery comprising it |
| CN105938917A (en) * | 2016-07-01 | 2016-09-14 | 深圳市振华新材料股份有限公司 | Lithium ion secondary cell lithium cobaltate cathode material, manufacture method and application thereof |
| CN109314238A (en) * | 2016-12-21 | 2019-02-05 | 株式会社Lg化学 | Metal-doped high voltage positive electrode active materials |
| CN109256531A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院宁波材料技术与工程研究所 | Doping cobalt acid lithium and its preparation method and application with compound coating layer |
| CN111081987A (en) * | 2018-10-18 | 2020-04-28 | 湖南杉杉能源科技股份有限公司 | Lithium cobaltate cathode material of lithium ion battery with voltage of more than 4.45V and preparation method thereof |
| WO2021223635A1 (en) * | 2020-05-08 | 2021-11-11 | 北京当升材料科技股份有限公司 | Lithium cobaltate positive electrode material, preparation method therefor and use thereof |
| CN114220976A (en) * | 2021-09-29 | 2022-03-22 | 惠州锂威新能源科技有限公司 | Lithium cobaltate material and preparation method thereof, positive plate and lithium ion battery |
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