CN113764658A - Anion-cation co-doped high-nickel single crystal ternary cathode material and preparation method and application thereof - Google Patents
Anion-cation co-doped high-nickel single crystal ternary cathode material and preparation method and application thereof Download PDFInfo
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- CN113764658A CN113764658A CN202111017272.9A CN202111017272A CN113764658A CN 113764658 A CN113764658 A CN 113764658A CN 202111017272 A CN202111017272 A CN 202111017272A CN 113764658 A CN113764658 A CN 113764658A
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- single crystal
- nickel
- cathode material
- ternary cathode
- crystal ternary
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 136
- 239000013078 crystal Substances 0.000 title claims abstract description 119
- 239000010406 cathode material Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 150000001768 cations Chemical class 0.000 claims abstract description 55
- 150000001450 anions Chemical class 0.000 claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 100
- 238000010438 heat treatment Methods 0.000 claims description 57
- 229910052593 corundum Chemical group 0.000 claims description 56
- 238000001816 cooling Methods 0.000 claims description 52
- 238000005245 sintering Methods 0.000 claims description 41
- 239000002019 doping agent Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 33
- 239000012298 atmosphere Substances 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 32
- 238000004321 preservation Methods 0.000 claims description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 30
- 239000007774 positive electrode material Substances 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 19
- 239000011669 selenium Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 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
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Chemical group 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical group O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 74
- 239000010431 corundum Substances 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 53
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- 239000012768 molten material Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 28
- 238000001291 vacuum drying Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000000498 ball milling Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 239000008247 solid mixture Substances 0.000 description 23
- 238000000967 suction filtration Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- 229910007740 Zr—F Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 5
- 229910018085 Al-F Inorganic materials 0.000 description 4
- 229910018179 Al—F Inorganic materials 0.000 description 4
- 229910019094 Mg-S Inorganic materials 0.000 description 4
- 229910019397 Mg—S Inorganic materials 0.000 description 4
- 229910004338 Ti-S Inorganic materials 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910001427 strontium ion Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
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- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
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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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-nickel single crystal ternary cathode material codoped with anions and cations, a preparation method and application thereof, wherein the molecular formula is as follows: li1+aNixCoyMnzMaO2‑bQb(ii) a Wherein: m is one or more of Mg, Sf, Al, Zr, Nb, Ta, Mo, Ti, Y, W and V; q is one or more of F, N, P, S and Se; x is more than 1, y is more than or equal to z and more than 0, x is more than or equal to 0.5, and x + y + z is 1. The element Q and the element M of the anion-cation co-doped high-nickel single crystal ternary cathode material respectively replace oxygen sitesThe point and the transition metal nickel, cobalt and manganese point can inhibit the capacity attenuation and voltage drop of the high-nickel ternary single crystal anode material in the circulating process, improve the circulating stability, thermal stability and intrinsic conductivity, and improve the rate capability, thereby effectively inhibiting the capacity attenuation and microcrack of the high-nickel ternary anode material in the circulating process.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, relates to a lithium ion battery positive electrode material and a preparation method thereof, and more particularly relates to a high-nickel single crystal ternary positive electrode material co-doped with anions and cations, and a preparation method and application thereof.
Background
With the development of society and the progress of science and technology, clean and efficient energy storage and conversion are the research hotspots in the energy field.
The lithium ion battery as a novel secondary power supply has the advantages of high specific energy, no memory effect, long cycle life, small environmental pollution and the like, and injects fresh blood for the vigorous development of an energy network. The lithium ion electric automobile is an important component in a new energy automobile family, and the high-energy-density lithium ion power battery is used as the heart of the electric automobile, so that the problem of mileage anxiety in the field of electric automobiles can be effectively solved. In recent years, the demand of lithium ion power batteries has increased explosively, and high energy density positive electrode materials have received much attention from researchers as a key part of lithium ion power batteries.
The high-nickel ternary cathode material has higher specific capacity (about 200mAh/g) due to higher Ni content, and is one of the most potential next-generation high-energy-density lithium ion battery cathode materials. However, it is difficult to synthesize high nickel ternary materials that meet stoichiometric composition due to thermodynamic limitations. Due to Li+And Ni2+The ionic radius of (A) is extremely close in size, resulting in partial Ni2+Easily migrate to the lithium layer to occupy the lithium site, resulting in Li+/Ni2+And (4) cation mixing and discharging. The serious lithium-nickel mixed defect can increase the internal resistance of the material, hinder the extraction of lithium ions and deteriorate the electrochemical performance. In addition, the higher the Ni content of the high-nickel ternary positive electrode is, the more serious the H2-H3 phase transformation is, the severe lattice contraction is caused, the anisotropic strain is generated on primary particles, the microcrack is generated, the electrolyte penetrates into the particles along the crack, the side reaction is continuously generated to form an insulating rock salt phase layer, and even the pulverization of an electrode material is caused, the impedance of the material is increased, and the reduction of the powder content of the electrode material is realizedLow dynamic performance. After a certain number of cycles of charge and discharge, the material structure changes due to the dissolution of Ni, Co and Mn metal elements, which causes the loss of active substances and further reduces the capacity. Therefore, the neck problems such as poor stability of high nickel ternary structure and thermal stability are urgently needed to be solved.
In the prior art, in order to solve the above problems, ion doping is generally focused on the ternary cathode material, and the doping mainly includes bulk doping and surface doping.
However, both bulk and surface doping in the prior art have certain drawbacks: the capacity of the battery is reduced due to doping of the introduced inactive substance elements, and the doped ternary positive electrode material is mostly spherical secondary particles, the doping is limited on the surfaces of the secondary particles, while the primary particles do not effectively participate in the doping process, and the cycle stability and safety of the battery under high voltage still need to be improved. Therefore, the prior art methods for doping ternary cathode materials mostly have the problems of uneven distribution of doping elements in the cathode materials, further affecting the capacity and stability thereof, and the like, and the doping substances and doping methods in the doping steps thereof still need to be improved. In addition, another scheme is that a large-particle single crystal ternary cathode material is adopted, and primary particle grain boundaries do not exist, so that microcracks caused by anisotropic strain among primary particles are inhibited, structural stability and safety are greatly improved, but large-particle single crystals simultaneously cause increase of lithium ion transmission paths and deterioration of rate performance.
Therefore, the search for a proper dopant and an effective bulk phase doping method are crucial to improve the structural stability, rate capability and safety of the high-nickel ternary single-crystal cathode material.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a high-nickel single crystal ternary cathode material co-doped with anions and cations, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an anion-cation co-doped high-nickel monocrystal ternary cathode material has a molecular formula as follows: li1+aNixCoyMnzMaO2- bQb。
Wherein:
m is one or more of Mg, Sr, Al, Zr, Nb, Ta, Mo, Ti, Y, W and V;
q is one or more of F, N, P, S and Se;
x is more than 1, y is more than or equal to z and more than 0, x is more than or equal to 0.5, and x + y + z is 1.
In the technical scheme, in the molecular formula of the high-nickel single crystal ternary cathode material, a is more than or equal to 0.001 and less than or equal to 0.05, and b is more than 0.001 and less than 0.1.
In the technical scheme, the codoped elements M and Q are uniformly distributed in the high-nickel single crystal ternary cathode material.
In the technical scheme, the high-nickel single-crystal ternary cathode material has a layered structure.
In the technical scheme, the capacity of the high-nickel single crystal ternary cathode material is more than or equal to 190mAh/g when the discharge rate is 0.1C, and the capacity retention rate is more than 85% after 150 cycles.
The invention also provides a preparation method of the anion-cation co-doped high-nickel single crystal ternary cathode material, which comprises the following steps:
uniformly mixing a precursor containing nickel, cobalt and manganese with a lithium source raw material, a cation dopant containing an element M and a fluxing agent in proportion, melting at the high temperature of 900 ℃ in an oxygen atmosphere, cooling, grinding into powder, washing and drying, uniformly mixing with an anion dopant containing an element Q in proportion, heating and sintering at the temperature of 500 ℃ and 800 ℃ in an argon atmosphere, cooling, washing and drying, and heating and sintering at the temperature of 500 ℃ and 800 ℃ in an oxygen atmosphere for a second time.
In the above technical scheme, the high temperature melting is a two-stage high temperature melting, which specifically includes: keeping the temperature at 500-700 ℃ for 5-10h and then keeping the temperature at 680-900 ℃ for 8-48 h.
Preferably, in the above technical solution, the cooling rate after the high-temperature melting is 2.5-4.5 ℃/min.
Further preferably, in the above technical solution, the temperature rise rate after the heat preservation at 500-700 ℃ is 2-3.6 ℃/min.
In the technical scheme, the temperature and the heat preservation time of the primary heating sintering are respectively 500-800 ℃ and 5-10 h;
preferably, in the above technical solution, the cooling rate after the primary heating sintering is 2-4.5 ℃/min.
In the technical scheme, the temperature and the heat preservation time of the secondary heating sintering are respectively 500-800 ℃ and 5-10 h.
Preferably, in the above technical solution, the cooling rate after the secondary heating sintering is 3-5.5 ℃/min.
Further, in the above technical solution, the precursor containing nickel, cobalt and manganese is one or more of carbonate, hydroxide and acetate containing nickel, cobalt and manganese.
Further, in the above technical solution, the lithium source raw material is one or more of lithium carbonate, lithium hydroxide monohydrate, lithium hydroxide, lithium acetate, and lithium nitrate.
Further, in the above technical solution, the cation dopant containing element M is MgO, Al2O3、ZrO2、TiO2、SrO、Nb2Os、MoO3、Ta2O5、V2O5、Y2O3And WO3One or more of (a).
Further, in the above technical solution, the anion dopant containing element Q is one or more of ammonium fluoride, ammonium dihydrogen phosphate, urea, sodium hydrogen hypophosphite, thiourea, sulfur powder, and selenium powder.
Further, in the above technical solution, the flux is one or more of lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, lithium carbonate, sodium carbonate, and potassium carbonate.
Still further, in the above technical solution, the mass of the added flux is 0.1-15 times of the mass of the precursor containing nickel, cobalt and manganese.
Still further, in the above technical solution, the molar excess coefficient of the lithium source material is 1 to 10%.
In one embodiment of the invention, the preparation method of the anion and cation co-doped high nickel single crystal ternary cathode material comprises the following steps:
s1, uniformly mixing the precursor containing nickel, cobalt and manganese with a lithium source raw material, a cation dopant containing an element M and a fluxing agent in proportion to obtain a raw material mixture containing the cation dopant;
s2, placing the raw material mixture containing the cationic dopant in S1 in an oxygen atmosphere, firstly preserving heat for 5-10h at the temperature of 500-700 ℃, then raising the temperature to the temperature of 680-900 ℃ at the speed of 2-3.6 ℃/min and preserving heat for 8-48h, and then cooling to the normal temperature at the speed of 2.5-4.5 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, washing with deionized water and absolute ethyl alcohol, carrying out suction filtration, and carrying out vacuum drying to obtain cation-doped intermediate powder;
s4, uniformly mixing the intermediate powder doped with the cations in the S3 and the anion dopant containing the element Q according to a proportion, placing the mixture in an argon atmosphere, preserving heat at the temperature of 500-800 ℃, heating and sintering for 5-10h for one time, and then cooling to normal temperature at the speed of 2-4.5 ℃/min to obtain a high-nickel single crystal ternary cathode material mixture containing the codoped anions and cations;
s5, carrying out suction filtration and washing on the mixture containing the anion and cation co-doped high-nickel single crystal ternary cathode material obtained in the step S4 by using a CS2 solution to remove redundant anion dopants, washing, suction filtration and vacuum drying by using deionized water and absolute ethyl alcohol to obtain anion and cation co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the anion and cation co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark again, then placing the corundum ark in an oxygen atmosphere, preserving heat at the temperature of 500-800 ℃, carrying out secondary heating sintering for 5-10h, and then cooling to the normal temperature at the speed of 3-5.5 ℃/min to obtain the anion/cation co-doped single crystal ternary cathode material.
The invention also provides a positive pole piece, which comprises the anion-cation co-doped high-nickel single crystal ternary positive pole material.
The invention further provides a lithium ion battery, which comprises the positive pole piece.
Compared with the prior art, the invention has the following advantages:
(1) according to the anion-cation co-doped high-nickel single crystal ternary positive electrode material, the element Q replaces oxygen sites in the high-nickel single crystal ternary positive electrode material, excessive oxidation of lattice oxygen can be inhibited under high potential, lattice oxygen loss is relieved, superoxide radical generated in the lattice oxygen oxidation process can be eliminated, electrolyte decomposition caused by superoxide radical is relieved, and finally capacity attenuation and voltage drop of the high-nickel ternary single crystal positive electrode material in the circulation process are synergistically inhibited;
(2) according to the anion-cation co-doped high-nickel single crystal ternary cathode material, the element M replaces sites of transition metals of nickel, cobalt and manganese in the high-nickel single crystal ternary cathode material, so that the crystal structure can be stabilized in the charge and discharge processes, the oxygen vacancy forming energy is improved, and the generation of microcracks is inhibited, so that the cycle stability and the thermal stability are improved; in addition, the cation doping can also induce lattice defects, improve intrinsic conductivity and improve rate performance;
(3) according to the preparation method of the anion and cation co-doped high-nickel single crystal ternary cathode material, the specific cosolvent is added, so that the melting point of the raw material mixture is reduced, the sintering temperature is reduced, the sintering time is shortened, the process cost is reduced, in addition, the raw material mixture is melted to form uniform fluid, the dopant is promoted to be uniformly diffused to an anode phase, and the optimized staged heating and cooling procedures are matched, so that the anion and cation co-doped high-nickel single crystal ternary cathode material with uniformly dispersed particles and uniformly doped primary particles with the particle size of more than 0.5 mu m can be obtained;
(4) the preparation process of the anion-cation co-doped high-nickel single crystal ternary cathode material provided by the invention is simple, is easy to popularize, and is a method for effectively inhibiting capacity attenuation and microcracks of the high-nickel ternary cathode material in a circulating process.
Drawings
FIG. 1 is an SEM photograph at 6000 times magnification of an NCM sample prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of a sample of NCM prepared in example 1 of the present invention at a magnification of 13000 times;
FIG. 3 is an SEM photograph at 2300 times magnification of a Nb-Se-NCM sample prepared in example 2 of the present invention;
FIG. 4 is an SEM photograph of a sample of Nb-Se-NCM prepared in example 2 of the present invention at a magnification of 10000 times;
FIG. 5 is an X-ray diffraction pattern of the NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2;
FIG. 6 is a first charge and discharge curve of a button cell using the NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2 as a positive electrode material for a lithium ion battery to prepare a positive electrode sheet according to the present invention;
fig. 7 is a graph of mass to capacity for a button cell using the NCM sample prepared in example 1 and the Nb-Se-NCM sample prepared in example 2 as a positive electrode material for a lithium ion battery to prepare a positive electrode tab, cycled 150 times at a current density of 1C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the means used are conventional in the art unless otherwise specified.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the embodiment of the invention, the precursor containing nickel, cobalt and manganese is a commercial compound product Mn0.83Ni0.11Co0.06(HO)2(ii) a The rest of the experimental raw materials are conventional commercial products.
In the embodiments of the present invention, the equipment and instruments used are commercially available or prepared by the prior art.
Example 1
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixture into an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture;
s2, transferring the raw material mixture in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5 hours, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying for 12h at 80 ℃ to obtain intermediate powder;
and S4, transferring the intermediate powder in the S3 to a corundum ark, then placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and then cooling to the normal temperature at the speed of 3 ℃/min to obtain the high-nickel single crystal ternary cathode material NCM.
Example 2
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.000025mol Nb2O5、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing the Nb ion doping agent;
s2, transferring the raw material mixture containing the Nb ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5 hours, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Nb-doped intermediate powder;
s4, placing the Nb-doped intermediate powder in the S3 and 0.00005mol of Se powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, heating to 700 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a high-nickel single crystal ternary positive electrode material mixture containing Nb-Se co-doping;
s5, washing and suction-filtering the mixture containing the Nb-Se co-doped high-nickel single crystal ternary cathode material obtained in the step S4 for 1 time by using a CS2 solution, deionized water and absolute ethyl alcohol respectively, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Nb-Se co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the Nb-Se co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Nb-Se-NCM.
Example 3
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol ZrO2、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing the Zr ion doping agent;
s2, transferring the raw material mixture containing the Zr ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5 hours, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying for 12h at 80 ℃ to obtain Zr-doped intermediate powder;
s4, placing the Zr-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to the normal temperature at the speed of 3 ℃/min to obtain a Zr-F co-doped high-nickel single crystal ternary positive electrode material mixture;
s5, respectively washing and suction-filtering the mixture containing the Zr-F co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain intermediate powder of the Zr-F co-doped high-nickel single crystal ternary cathode material;
and S6, transferring the Zr-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Zr-F-NCM.
Example 4
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol SrO、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing the Sr ion dopant;
s2, transferring the raw material mixture containing the Sr ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Sr-doped intermediate powder;
s4, placing the Sr-doped intermediate powder in the S3 and 0.00005mol of ammonium dihydrogen phosphate into an agate ball milling tank, mixing for 2h in a dry environment to obtain a solid mixture, then placing the solid mixture into an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6h, and then cooling to the normal temperature at the speed of 3 ℃/min to obtain a Sr-P co-doped high-nickel single crystal ternary positive electrode material mixture;
s5, respectively washing and suction-filtering the mixture containing the Sr-P co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Sr-P co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the Sr-P co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Sr-P-NCM.
Example 5
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol MgO、0.0702molLiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixture into an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing Mg ion dopant;
s2, transferring the raw material mixture containing the Mg ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Mg-doped intermediate powder;
s4, placing the Mg-doped intermediate powder in the S3 and 0.00005mol of sulfur powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to the normal temperature at the speed of 3 ℃/min to obtain a Mg-S co-doped high-nickel single crystal ternary cathode material mixture;
s5, washing and suction-filtering the mixture containing the Mg-S co-doped high-nickel single crystal ternary cathode material obtained in the step S4 for 1 time by using a CS2 solution, deionized water and absolute ethyl alcohol respectively, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Mg-S co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the Mg-S co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Mg-S-NCM.
Example 6
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.000025mol Ta2O5、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing a Ta ion dopant;
s2, transferring the raw material mixture containing the Ta ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Ta-doped intermediate powder;
s4, placing the Ta-doped intermediate powder in the S3 and 0.000025mol of urea in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a Ta-N co-doped high-nickel single crystal ternary positive electrode material mixture;
s5, washing and suction-filtering the mixture containing the Ta-N co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time respectively, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Ta-N co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the intermediate powder of the Ta-N co-doped high-nickel single crystal ternary cathode material in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Ta-N-NCM.
Example 7
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.000025mol Al2O3、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing an Al ion dopant;
s2, transferring the raw material mixture containing the Al ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5 hours, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Al-doped intermediate powder;
s4, placing the Al-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a high-nickel single crystal ternary cathode material mixture containing Al-F co-doping;
s5, respectively washing and suction-filtering the mixture containing the Al-F co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain intermediate powder of the Al-F co-doped high-nickel single crystal ternary cathode material;
and S6, transferring the Al-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Al-F-NCM.
Example 8
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.000025mol Y2O3、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing a Y ion doping agent;
s2, transferring the raw material mixture containing the Y ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Y-doped intermediate powder;
s4, placing the Y-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a Y-F co-doped high-nickel single crystal ternary positive electrode material mixture;
s5, washing and suction-filtering the mixture containing the Y-F co-doped high-nickel single crystal ternary cathode material obtained in the step S4 for 1 time by using a CS2 solution, deionized water and absolute ethyl alcohol respectively, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Y-F co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the intermediate powder of the Y-F co-doped high-nickel single crystal ternary positive electrode material in the S5 to a corundum ark again, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary positive electrode material Y-F-NCM.
Example 9
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol WO3、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing a W ion doping agent;
s2, transferring the raw material mixture containing the W ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain W-doped intermediate powder;
s4, placing the W-doped intermediate powder in the S3 and 0.00005mol of Se powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a W-Se co-doped high-nickel single crystal ternary cathode material mixture;
s5, washing and suction-filtering the mixture containing the W-Se co-doped high-nickel single crystal ternary cathode material obtained in the step S4 for 1 time by using a CS2 solution, deionized water and absolute ethyl alcohol respectively, and finally placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain W-Se co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the W-Se co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material W-Se-NCM.
Example 10
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol TiO2、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing a Ti ion doping agent;
s2, transferring the raw material mixture containing the Ti ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Ti-doped intermediate powder;
s4, placing the Ti-doped intermediate powder in the S3 and 0.00005mol of sulfur powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a Ti-S co-doped high-nickel single crystal ternary cathode material mixture;
s5, respectively washing and suction-filtering the mixture containing the Ti-S co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Ti-S co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the intermediate powder of the Ti-S co-doped high-nickel single crystal ternary cathode material in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Ti-S-NCM.
Comparative example 1
The invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.000025mol Nb2O5、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing the Nb ion doping agent;
s2, transferring the raw material mixture containing the Nb cation dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 9 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Nb-doped intermediate powder;
s4, placing the Nb-doped intermediate powder in the S3 and 0.00005mol of Se powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, heating to 700 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and then cooling to normal temperature at the speed of 3 ℃/min to obtain a high-nickel single crystal ternary positive electrode material mixture containing Nb-Se co-doping;
s5, washing and suction-filtering the mixture containing the Nb-Se co-doped high-nickel single crystal ternary cathode material obtained in the step S4 for 1 time by using a CS2 solution, deionized water and absolute ethyl alcohol respectively, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Nb-Se co-doped high-nickel single crystal ternary cathode material intermediate powder;
and S6, transferring the Nb-Se co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Nb-Se-NCM.
Comparative example 2
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol ZrO2、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing the Zr ion doping agent;
s2, transferring the raw material mixture containing the Zr ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5 hours, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying for 12h at 80 ℃ to obtain Zr-doped intermediate powder;
s4, placing the Zr-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, heating to 420 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and then cooling to normal temperature at the speed of 6 ℃/min to obtain a Zr-F co-doped high-nickel single crystal ternary positive electrode material mixture;
s5, respectively washing and suction-filtering the mixture containing the Zr-F co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain intermediate powder of the Zr-F co-doped high-nickel single crystal ternary cathode material;
and S6, transferring the Zr-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 700 ℃ at a speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at a speed of 3 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Zr-F-NCM.
Comparative example 3
The embodiment of the invention provides a preparation method of a high-nickel single crystal ternary cathode material co-doped with anions and cations, which specifically comprises the following steps:
s1, adding 0.02mol of Mn0.83Ni0.11Co0.06(HO)2、0.00005mol SrO、0.0702mol LiOH·H2O、0.0966mol LiNO3Putting 0.0132mol of LiCl and the mixed solution in an agate ball milling tank, and mixing for 2 hours in a dry environment to obtain a raw material mixture containing the Sr ion dopant;
s2, transferring the raw material mixture containing the Sr ion dopant in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, firstly heating to 500 ℃ at a speed of 3 ℃/min, then preserving heat for 5h, then heating to 800 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and then cooling to normal temperature at a speed of 3 ℃/min to obtain a solid molten material;
s3, grinding the solid molten material in the S2 into powder, stirring the powder with deionized water for 30min, then respectively carrying out suction filtration and washing on the powder for 3 times with the deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying at 80 ℃ for 12h to obtain Sr-doped intermediate powder;
s4, placing the Sr-doped intermediate powder in the S3 and 0.00005mol of ammonium dihydrogen phosphate into an agate ball milling tank, mixing for 2h in a dry environment to obtain a solid mixture, then placing the solid mixture into an argon atmosphere, carrying out heat preservation sintering at 700 ℃ for 6h, and then cooling to the normal temperature at the speed of 3 ℃/min to obtain the Sr-P co-doped high-nickel single crystal ternary positive electrode material mixture.
And S5, washing and suction-filtering the mixture containing the Sr-P co-doped high-nickel single crystal ternary cathode material obtained in the step S4 with a CS2 solution, deionized water and absolute ethyl alcohol for 1 time respectively, and finally, placing the mixture at 80 ℃ for vacuum drying for 12 hours to obtain Sr-P co-doped high-nickel single crystal ternary cathode material intermediate powder.
And S6, transferring the Sr-P co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 to a corundum ark, placing the corundum ark in an oxygen atmosphere, heating to 420 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 6 hours, and cooling to normal temperature at the speed of 6 ℃/min to obtain the anion and cation co-doped high-nickel single crystal ternary cathode material Sr-P-NCM.
The NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2 were characterized.
FIGS. 1 and 2 are SEM photographs at 6000 times and 13000 times, respectively, of NCM samples prepared in example 1 of the present invention; FIGS. 3 and 4 are SEM photographs of samples of Nb-Se-NCM prepared in example 2 of the present invention at magnification of 2300 times and 10000 times, respectively.
As can be seen from FIGS. 1-4, the prepared samples are all composed of primary micrometer particles and have a size of about 1 μm; in addition, comparing fig. 1-4, it can be seen that the microstructure of the doped Nb-Se-NCM high nickel single crystal ternary cathode material sample prepared in example 2 is not significantly changed compared to the NCM sample prepared in example 1.
FIG. 5 shows X-ray diffraction patterns of the NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2.
As can be seen from FIG. 5, the prepared samples are all layered structures, and the corresponding space group is R-3 m; in addition, the peak intensity ratios of diffraction peaks (003)/(104) are all greater than 1.2, which proves that Li/Ni misclassification is weak; it is noteworthy that the peak intensity ratio of (003)/(104) after doping with Nb and Se elements increases, indicating that the degree of miscarrying of Li/Ni decreases; furthermore, both pairs of cleavage peaks (006)/(102) and (108)/(110) are clearly split, demonstrating that a good lamellar structure is obtained.
The samples prepared in examples 1-10 and comparative examples 1-2 are respectively used as the positive electrode material of the lithium ion battery to prepare the positive electrode piece, and the specific process is as follows:
(1) uniformly mixing the prepared powdery positive electrode material with acetylene black (a conductive agent) and polyvinylidene fluoride (PVDF, a binder) according to the mass ratio of 8: 1, dropwise adding a proper amount of N-methyl pyrrolidone (NMP) serving as a dispersing agent, and grinding into slurry; then, uniformly coating the slurry on an aluminum foil, carrying out vacuum drying at 120 ℃ for 12h, and transferring the aluminum foil into an argon atmosphere glove box for later use;
(2) assembling a half cell in an argon atmosphere glove box, taking metal lithium as a counter electrode and LiPF6Ethylene carbonate (EC: DMC: DEC: 1 in volume ratio) was used as an electrolyte, and a CR2016 type coin cell was assembled and charged in a constant current charge-discharge mode.
FIG. 6 is a first charge-discharge curve of a button cell using the NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2 as a positive electrode material of a lithium ion battery to prepare a positive electrode plate; as can be seen from FIG. 6, the first-pass discharge capacities were 199.4mAh/g (NCM) and 196.3(Nb-Se-NCM) mAh/g, respectively, and the corresponding coulombic efficiencies were 88.9% (NCM) and 89.5% (Nb-Se-NCM), respectively.
TABLE 1 first-turn discharge capacity and coulombic efficiency measured after preparation of positive electrode sheet for each sample prepared in TABLE 1
Table 1 shows the results of the first-turn discharge capacity and coulombic efficiency of the button cell using the samples prepared in the examples and comparative examples of the present invention as the positive electrode material of the lithium ion battery to prepare the positive electrode sheet.
The results of fig. 6 and table 1 show that the first coulombic efficiency of the button cell using the sample prepared after the co-doping of the anions and the cations as the positive electrode material of the lithium ion battery to prepare the positive electrode plate is significantly improved, which indicates that the irreversible capacity loss of the high nickel single crystal ternary positive electrode material co-doped with the anions and the cations in the charging process is significantly inhibited.
FIG. 7 is a graph of mass to capacity for a button cell having a positive electrode tab made using the NCM sample made in example 1 and the Nb-Se-NCM sample made in example 2 as a lithium ion battery positive electrode material for 150 cycles at a current density of 1C; as can be seen from FIG. 7, the retention after 150 cycles at a current density of 1C was 87.6% (Nb-Se-NCM) and 41.2% (NCM), respectively.
Table 2 shows the retention rate of each sample after 150 cycles of preparing the positive electrode sheet
Table 2 shows the results of the retention rate after 150 cycles of the button cell using the samples prepared in the examples and comparative examples as the positive electrode material of the lithium ion battery to prepare the positive electrode plate.
The results of fig. 7 and table 2 show that the sample prepared by co-doping the anions and cations can effectively inhibit the capacity attenuation of the button cell in the cycle process when used as the positive electrode material of the lithium ion battery.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the 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. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A negative and positive ion co-doped high-nickel monocrystal ternary positive electrode material, which is characterized in that,
the molecular formula is as follows: li1+aNixCoyMnzMaＯ2-bQb；
Wherein:
m is one or more of Mg, Sr, Al, Zr, Nb, Ta, Mo, Ti, Y, W and V;
q is one or more of F, N, P, S and Se;
x is more than 1, y is more than or equal to z and more than 0, x is more than or equal to 0.5, and x + y + z is 1.
2. The anion and cation co-doped high-nickel single crystal ternary cathode material according to claim 1,
in the molecular formula of the high-nickel single crystal ternary cathode material, a is more than or equal to 0.001 and less than or equal to 0.05, and b is more than 0.001 and less than 0.1;
and/or co-doping elements M and Q are uniformly distributed in the high-nickel single crystal ternary cathode material.
3. The anion and cation co-doped high nickel single crystal ternary cathode material according to claim 1 or 2,
the high-nickel single crystal ternary positive electrode material has a layered structure;
and/or the capacity of the high-nickel single crystal ternary cathode material is more than or equal to 190mAh/g when the discharge rate is 0.1C, and the capacity retention rate is more than 85% after 150 cycles.
4. The method for preparing the anion and cation co-doped high nickel single crystal ternary cathode material according to any one of claims 1 to 3,
the method comprises the following steps: uniformly mixing a precursor containing nickel, cobalt and manganese with a lithium source raw material, a cation dopant containing an element M and a fluxing agent in proportion, melting at the high temperature of 900 ℃ in an oxygen atmosphere, cooling, grinding into powder, washing and drying, uniformly mixing with an anion dopant containing an element Q in proportion, heating and sintering at the temperature of 500 ℃ and 800 ℃ in an argon atmosphere, cooling, washing and drying, and heating and sintering at the temperature of 500 ℃ and 800 ℃ in an oxygen atmosphere for a second time.
5. The method for preparing the anion and cation co-doped high-nickel single crystal ternary cathode material according to claim 4,
the high-temperature melting is two-stage high-temperature melting, and specifically comprises the following steps: keeping the temperature at 500-700 ℃ for 5-10h and then keeping the temperature at 680-900 ℃ for 8-48 h;
preferably, the cooling speed after the high-temperature melting is 2.5-4.5 ℃/min;
further preferably, the temperature rise rate after the heat preservation at 500-700 ℃ is 2-3.6 ℃/min.
6. The method for preparing the anion and cation co-doped high-nickel single crystal ternary cathode material according to claim 4,
the temperature and the heat preservation time of the primary heating sintering are respectively 500-800 ℃ and 5-10 h;
preferably, the cooling speed after the primary heating sintering is 2-4.5 ℃/min;
and/or the presence of a gas in the gas,
the temperature and the heat preservation time of the secondary heating sintering are respectively 500-800 ℃ and 5-10 h;
preferably, the cooling speed after the secondary heating sintering is 3-5.5 ℃/min.
7. The method for preparing the anion and cation co-doped high-nickel single crystal ternary cathode material according to any one of claims 4 to 6,
the precursor containing nickel, cobalt and manganese is one or more of carbonate, hydroxide and acetate containing nickel, cobalt and manganese;
and/or the lithium source raw material is one or more of lithium carbonate, lithium hydroxide monohydrate, lithium hydroxide, lithium acetate and lithium nitrate;
and/or the cation dopant containing the element M is MgO and Al2Ｏ3、ZrＯ2、TiＯ2、SrO、Nb2Ｏ5、MoＯ3、Ta2Ｏ5、V2Ｏ5、Y2O3And WO3One or more of;
and/or the anion dopant containing the element Q is one or more of ammonium fluoride, lithium fluoride, ammonium dihydrogen phosphate, urea, sodium hypophosphite, thiourea, sulfur powder and selenium powder;
and/or the fluxing agent is one or more of lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, lithium carbonate, sodium carbonate and potassium carbonate.
8. The method for preparing the anion and cation co-doped high-nickel single crystal ternary cathode material according to claim 7,
the adding mass of the fluxing agent is 0.1-15 times of that of the precursor containing nickel, cobalt and manganese;
and/or the molar excess coefficient of the lithium source raw material is 1-10%.
9. A positive electrode plate is characterized in that,
the positive pole piece comprises the anion-cation co-doped high-nickel single crystal ternary positive pole material as claimed in any one of claims 1 to 3.
10. A lithium ion battery is characterized in that,
the lithium ion battery comprises the positive electrode sheet of claim 9.
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| CN114620775A (en) * | 2022-03-15 | 2022-06-14 | 北京理工大学 | Double-anion co-doped lithium-rich manganese-based composite material, preparation method and application |
| CN114620777A (en) * | 2022-03-25 | 2022-06-14 | 宁波容百新能源科技股份有限公司 | Ultrahigh nickel ternary precursor and preparation method thereof |
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| CN114843458A (en) * | 2022-04-07 | 2022-08-02 | 青岛乾运高科新材料股份有限公司 | High-nickel single crystal cobalt-free anode material and preparation method thereof |
| CN114843458B (en) * | 2022-04-07 | 2023-11-07 | 青岛乾运高科新材料股份有限公司 | High-nickel monocrystal cobalt-free positive electrode material and preparation method thereof |
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