CN117525386A - High-nickel positive electrode material, and preparation method and application thereof - Google Patents
High-nickel positive electrode material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117525386A CN117525386A CN202410023036.5A CN202410023036A CN117525386A CN 117525386 A CN117525386 A CN 117525386A CN 202410023036 A CN202410023036 A CN 202410023036A CN 117525386 A CN117525386 A CN 117525386A
- Authority
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- China
- Prior art keywords
- nickel
- positive electrode
- sintering
- electrode material
- cobalt
- Prior art date
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- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 336
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 173
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 218
- 239000002243 precursor Substances 0.000 claims description 156
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 138
- 238000005245 sintering Methods 0.000 claims description 136
- 239000002245 particle Substances 0.000 claims description 127
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 102
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 102
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 238000002156 mixing Methods 0.000 claims description 45
- 239000010406 cathode material Substances 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- 239000011572 manganese Substances 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 33
- 239000000654 additive Substances 0.000 claims description 31
- 230000000996 additive effect Effects 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 238000000975 co-precipitation Methods 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 24
- 239000010405 anode material Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000003756 stirring Methods 0.000 description 29
- 238000009826 distribution Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000007788 liquid Substances 0.000 description 21
- 238000000926 separation method Methods 0.000 description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 20
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 18
- 229940044175 cobalt sulfate Drugs 0.000 description 18
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 18
- 229910013716 LiNi Inorganic materials 0.000 description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- -1 nickel metals Chemical class 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
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- 229910052727 yttrium Inorganic materials 0.000 description 7
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- 239000002033 PVDF binder Substances 0.000 description 6
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910006565 Li—Co—O Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 239000002131 composite material Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
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- 239000011261 inert gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 relates to the technical field of lithium ion batteries, in particular to a high-nickel positive electrode material, a preparation method and application thereof. The general formula of the high nickel positive electrode material is Li x Ni a Co b Mn c Al d Zr e Sr f Y g B h Q i O 2 ；0.98≤x≤1.04，0.8≤a≤0.95，0.045≤b≤0.145，0.005≤c≤0.055，0≤d≤0.0187，0≤e≤0.004，0≤f≤0.003，0≤g≤0.002，0<h is equal to or more than 0.008,0 and equal to or less than i is equal to or less than 0.002, and a+b+c+d+e+f+g+h+i=1; q comprises at least one of Ti, W and Nb elements; high nickel positive electrode materialThe content of cobalt element gradually decreases from the surface to the center. The high nickel positive electrode material has low Li/Ni misce and low initial DCR.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-nickel positive electrode material, a preparation method and application thereof.
Background
With the rapid development of industries such as portable electronic products and new energy automobiles, the market demand of lithium ion batteries is rapidly increasing, and the demand of positive electrode materials is rapidly increasing. The lithium ion battery has the advantages of high specific energy, high battery voltage, wide working temperature range, light weight, small volume, long endurance time and the like, and is widely applied to the fields of electric automobiles, electronic equipment, aerospace and the like.
Wherein, ternary positive electrode material Li (Ni x Co y Mn 1-x-y )O 2 The method is widely applied to a power type lithium ion battery system due to the characteristics of high specific capacity, good safety, simple preparation process and the like.
However, the conditions for synthesizing the high nickel cathode material are severe, one of the important reasons being Ni during the firing reaction 2+ Is difficult to be completely oxidized into Ni 3+ Resulting in part of Ni 2+ And Li (lithium) + Mixed discharge is generated, a small amount of Ni 2+ Occupying Li + The electrochemical performance of the material is seriously affected, and the specific capacity is reduced, the cycle performance is deteriorated and the rate performance is reduced. In addition, the high-nickel ternary material is not easy to maintain a layered structure, so that higher Li/Ni mixed arrangement is caused, and the material is madeThe initial DCR (internal dc resistance) is high and the need for fast charging cannot be met. The lithium and nickel mixed discharge is more serious, the conductivity of the material is poor, the irreversible loss of lithium ion intercalation and deintercalation is also more serious, and the generation of particle cracks and the release amount of oxygen are accelerated, so that the lithium and nickel mixed discharge is also considered as a main reason for the performance attenuation of the ultra-high nickel layered anode material.
In the prior art, improvements have been made in order to solve this problem, usually from the calcination stage in an oxygen atmosphere. For example: increasing the concentration of oxygen and providing O 3 Extending the oxidation time or adding a pre-oxidation step. However, the effect is poor because trivalent nickel is easily decomposed at high temperature to generate divalent nickel, and long-time low-temperature sintering leads to significant increase in cost. However, as the nickel content is further increased, the problem cannot be satisfied by simply improving the calcination method.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a high nickel positive electrode material, in which the content of cobalt element gradually decreases from the surface to the center, and the Li/Ni mixed discharge of the material can be reduced, thereby reducing the initial DCR.
The second object of the present invention is to provide a method for preparing a high nickel positive electrode material, wherein cobalt hydroxide is used to coat a nickel cobalt manganese hydroxide precursor material, and Co on the surface of the precursor material can reduce Li + Diffusion rate of Ni in the first sintering process 2+ Providing sufficient time for oxidation to Ni 3+ While Ni 3+ Magnetic steel of (C) is higher than Ni 2+ Low, thus reducing Li/Ni superschange; meanwhile, co serving as a non-magnetic element can further reduce the Li/Ni super-exchange effect, and the combined effect of the Co and the non-magnetic element obviously reduces the Li/Ni mixed discharge rate.
The third object of the invention is to provide a positive plate, which improves the capacity and cycle performance of the positive plate by adopting a high nickel positive material with low initial DCR.
A fourth object of the present invention is to provide a lithium ion battery having excellent electrochemical properties.
A fifth object of the present invention is to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The invention provides a high-nickel positive electrode material, which has a chemical general formula of Li x Ni a Co b Mn c Al d Zr e Sr f Y g B h Q i O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.98 and less than or equal to 1.04,0.8, a is more than or equal to 0.95,0.045 and less than or equal to 0.95,0.045, b is more than or equal to 0.145,0.005 and less than or equal to 0.055,0, d is more than or equal to 0.0187,0 and less than or equal to e is more than or equal to 3552, f is more than or equal to 0.004,0 and less than or equal to 0.003,0 and g is more than or equal to 0.002,0<h is equal to or more than 0.008,0 is equal to or less than i is equal to or less than 0.002, and a+b+c+d+e+f+g+h+i=1; q comprises at least one of Ti, W and Nb elements;
the content of cobalt element in the particles of the high-nickel positive electrode material is gradually reduced from the surface to the center, and the depth of the region N from the surface of the particles to the center of the particles is 1 mu m 1 Wherein Co element accounts for 5-21 mol percent, and the area is from area N 1 Region N having a depth of 2 μm toward the center of the particle 2 Wherein Co element accounts for 4-12 mol percent, and the area is from area N 2 Region N having a depth of 2 μm toward the center of the particle 3 Wherein the Co element accounts for 3-11% by mole percent; and, region N 1 The molar quantity of the Co element in the high-nickel cathode material particles accounts for 40% -50% of the total molar quantity of the Co element in the high-nickel cathode material particles.
Preferably, the lithium nickel mixed discharge rate of the high nickel anode material is less than or equal to 1.2%.
Preferably, the initial direct current internal resistance of the high-nickel positive electrode material is less than or equal to 85mΩ.
Preferably, the residual alkali free lithium content of the high-nickel positive electrode material is less than or equal to 1300ppm.
Preferably, the (104) interplanar spacing of the high-nickel positive electrode material is 52 nm-58 nm.
Preferably, the median particle diameter of the high nickel cathode material is 8-12 μm.
Preferably, the specific surface area of the high nickel positive electrode material is 0.5m 2 /g~0.7m 2 /g。
The invention also provides a preparation method of the high-nickel positive electrode material, which comprises the following steps:
mixing a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material with a lithium source and performing first sintering, or mixing a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, a lithium source and an additive and performing first sintering to obtain a primary sintering material, wherein the additive comprises at least one of an additive containing Al element, an additive containing Zr element, an additive containing Sr element, an additive containing Y element or an additive containing Q, and the Q comprises at least one of Ti, W and Nb elements;
the primary sintering material is crushed and then mixed with an additive containing Co element, and secondary sintering is carried out to obtain a secondary sintering material;
and (3) washing the secondary sintering material, mixing the secondary sintering material with a surface repairing agent and an inert agent, and performing third sintering to obtain the high-nickel anode material.
Preferably, the surface remediation agent comprises boric acid;
And/or the inert agent comprises alumina.
Preferably, the temperature of the first sintering is 750-775 ℃, and the heat preservation time is 16-30 hours;
and/or the temperature of the second sintering is 670-690 ℃, and the heat preservation time is 16-24 hours;
and/or the temperature of the third sintering is 285-335 ℃, and the heat preservation time is 8-16 h.
Preferably, the first sintering, the second sintering and the third sintering are performed in an oxygen-containing atmosphere having an oxygen content of >95% by volume.
Preferably, the preparation method of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material specifically comprises the following steps: mixing a nickel source, a cobalt source, a manganese source, a precipitant solution and a complexing agent solution, and performing a first coprecipitation reaction to obtain a nickel cobalt manganese hydroxide precursor kernel; and mixing the nickel cobalt manganese hydroxide precursor inner core, a cobalt source, a precipitator solution and a complexing agent solution, and performing a second coprecipitation reaction to form cobalt hydroxide and coating the nickel cobalt manganese hydroxide precursor inner core, thereby obtaining the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material.
Preferably, the median particle diameter of the first coprecipitation reaction to the nickel cobalt manganese hydroxide precursor core is 9.5-10.5 μm.
Preferably, the second coprecipitation reaction is carried out until the median particle diameter of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is 9.8-10.8 mu m.
Preferably, in the process of the first coprecipitation reaction and/or the second coprecipitation reaction, the pH of the mixture is 10.5-12.
Preferably, the temperature of the mixture is 40 ℃ to 60 ℃ in the process of the first coprecipitation reaction and/or the second coprecipitation reaction.
The invention also provides a positive plate which comprises the high-nickel positive electrode material.
The invention also provides a lithium ion battery, which comprises the positive plate.
The invention further provides electric equipment, which comprises the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The high-nickel positive electrode material provided by the invention has low Li/Ni mixed discharge, and the initial DCR is obviously reduced.
(2) The high-nickel positive electrode material provided by the invention has high crystallinity and low residual alkali content.
(3) According to the preparation method of the high-nickel positive electrode material, provided by the invention, the cobalt hydroxide is adopted to coat the nickel cobalt manganese hydroxide precursor material, and the Co coating on the surface of the nickel cobalt manganese hydroxide can reduce Li + Diffusion rate of Ni in the first sintering process 2+ Providing sufficient time for oxidation to Ni 3+ ，Ni 3+ Magnetic steel of (C) is higher than Ni 2+ Low, and further reduces Li/Ni superswitch effect; meanwhile, co is used as a non-magnetic element to further reduce the Li/Ni superswitching effect, and the combined effect of the Co and the non-magnetic element obviously reduces the Li/Ni mixing rate.
(4) According to the preparation method of the high-nickel positive electrode material, disclosed by the invention, the Li-Co-O stable structure is formed by adding the additive containing Co element and performing the second sintering coating Co, so that the surface structure can be protected in the subsequent water washing process, the generation of rock salt phase NiO in the water washing process is reduced, and the polarization is reduced.
(5) According to the preparation method of the high-nickel positive electrode material, the surface repairing agent and the inert agent are coated at low temperature through third sintering, so that the surface interface structure is stabilized.
(6) According to the preparation method of the high-nickel positive electrode material, provided by the invention, the coating structure is more uniform.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a SEM sectional view of a high nickel positive electrode material and its detection points according to embodiment 1 of the present invention;
FIG. 2 is a SEM sectional view of the high nickel cathode material provided in comparative example 5 and its detection points;
fig. 3 is an SEM cross-sectional view of the high nickel cathode material provided in comparative example 6 of the present invention and its detection points.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this invention, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
In the present invention, "one or more" or "at least one" means any one, any two or more of the listed items unless specifically stated otherwise. Wherein "several" means any two or more.
In the present invention, unless specifically stated otherwise, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity or as implicitly indicating the importance or quantity of the indicated technical feature. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the first aspect, the invention provides the high-nickel positive electrode material which has the chemical formula of Li on the basis of considering that the high-nickel ternary material is not easy to maintain a layered structure and can cause higher Li/Ni mixed arrangement x Ni a Co b Mn c Al d Zr e Sr f Y g B h Q i O 2 。
By way of example, in the above chemical formula, 0.98.ltoreq.x.ltoreq.1.04 includes, but is not limited to, any one of the dot values or range values between any two of 0.98, 1.00, 1.02, 1.04.
0.8.ltoreq.a.ltoreq.0.95, including but not limited to any one of or a range of values between 0.8, 0.83, 0.85, 0.88, 0.9, 0.93, 0.95.
0.045.ltoreq.b.ltoreq.0.145, including but not limited to any one or range of point values between any two of 0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.145.
0.005 c.ltoreq.0.055 including, but not limited to, any one of the dot values or range values between any two of 0.005, 0.006, 0.007, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.055.
0.ltoreq.d.ltoreq.0.0187 including, but not limited to, point values of any one of 0, 0.001, 0.003, 0.005, 0.008, 0.01, 0.012, 0.014, 0.015, 0.016, 0.018, 0.0182, 0.0185, 0.0187 or a range value therebetween.
0.ltoreq.e.ltoreq.0.004 including, but not limited to, a dot value of any one of 0, 0.001, 0.002, 0.003, 0.004 or a range of values therebetween.
0.ltoreq.f.ltoreq.0.003, including but not limited to, a point value of any one of 0, 0.0005, 0.001, 0.0015, 0.002, 0.0022, 0.0025, 0.0028, 0.003, or a range value between any two.
0.ltoreq.g.ltoreq.0.002, including but not limited to, point values of any one of 0, 0.0001, 0.0003, 0.0005, 0.0008, 0.001, 0.0012, 0.0014, 0.0015, 0.0017, 0.0019, 0.002, or range values between any two.
0<h is less than or equal to 0.008, including but not limited to a dot value of any one of 0.001, 0.002, 0.003, 0.005, 0.006, 0.008 or a range value between any two.
0.ltoreq.i.ltoreq.0.002, including but not limited to point values of any one of 0.0001, 0.0003, 0.0005, 0.0008, 0.001, 0.0012, 0.0014, 0.0015, 0.0017, 0.0019, 0.002 or range values between any two.
The above a+b+c+d+e+f+g+h+i=1.
In the chemical general formula, the element Al has the function of improving the thermal stability and the high-temperature storage performance of the material; the element Zr has the function of maintaining the structural stability of the material in the circulating process; the element Sr has the effects of reducing the residual alkali on the surface and reducing the gas production rate; the element Y can improve the stability of the surface structure, and the element Y and the element Sr can reduce the gas production in a synergistic way; the element B can form a fast ion conductor on the surface, reduce BET (specific surface area) and repair water washing damage.
It is understood that Al, zr, sr, Y each independently is 0, that is, represents that the positive electrode material does not contain a corresponding element. In some specific embodiments, the alloy may not contain Al, zr, sr and Y elements at the same time, may contain at least one, two or three of Al, zr, sr and Y elements, and may contain four elements of Al, zr, sr and Y at the same time.
In some specific embodiments, in order to further improve the electrochemical performance of the battery prepared from the high-nickel positive electrode material and further improve the comprehensive performance of the high-nickel positive electrode material, such as thermal stability, high-temperature storage performance, low-surface residual alkali, low gas production and the like, it is preferable that the positive electrode material contains four elements, i.e., al, zr, sr and Y.
In the chemical formula, Q comprises at least one of Ti element, W element and Nb element. Wherein Ti element, W element or Nb element plays a role in stabilizing the positive electrode material.
The content of cobalt element in the particles of the high-nickel positive electrode material is gradually reduced from the surface to the center, and the surfaces of the particles are rich in cobalt element. Namely, the content of cobalt element in the particles of the high-nickel positive electrode material gradually decreases from the surface layer to the inside thereof.
The content of cobalt element in the particles of the high-nickel positive electrode material is gradually reduced from the surface to the center, and the depth of the region N from the surface of the particles to the center of the particles is 1 mu m 1 Wherein Co element accounts for 5-21 mol percent, and the area is from area N 1 Region N having a depth of 2 μm toward the center of the particle 2 Wherein Co element accounts for 4-12 mol percent, and the area is from area N 2 Region N having a depth of 2 μm toward the center of the particle 3 Wherein the Co element accounts for 3-11% by mole percent; and, region N 1 The molar quantity of the Co element in the high-nickel cathode material particles accounts for 40% -50% of the total molar quantity of the Co element in the high-nickel cathode material particles.
Wherein, the mole percentage of Co element is: the mole amount of Co element accounts for mole percent of the total mole amount of the four elements, namely Al element, mn element, co element and Ni element.
The Co element content is distributed in a continuously decreasing form from the particle surface to the particle center, and the depth area N is 1 mu m from the particle surface 1 The content of Co element accounts for 40% -50% of the total Co content.
It can be understood that the above elements can further improve the comprehensive electrochemical performance of the high nickel cathode material by integrating the content distribution of Co element.
The Co element has positive effect on maintaining the stability of the layered structure of the high-nickel positive electrode material, and the high-Li/Ni mixed discharge is easier to occur on the surface of the material, so that the high-nickel positive electrode material with rich Co on the surface and gradient Co element content is provided, even if the content of cobalt element in particles of the high-nickel positive electrode material is gradually reduced from the surface to the center, the high-nickel positive electrode material is beneficial to reducing the Li/Ni mixed discharge of the high-nickel positive electrode material, and the initial DCR (direct current internal resistance) is reduced.
In some specific embodiments, the high-nickel positive electrode material provided by the invention has lower mixing rate through the limitation of the distribution of Co element concentration. The lithium-nickel mixed discharge rate of the high-nickel positive electrode material is less than or equal to 1.2 percent; including but not limited to any one of a point value or a range value between any two of 1.2%, 1.1%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%.
It is understood that the lithium nickel miscibility refers to the ratio of lithium to nickel metals in a rechargeable battery. Specifically, the mix-rate can be described as the sum of the proportion of the weight of lithium to the total weight and the proportion of the weight of nickel to the total weight.
In some specific embodiments, the high-nickel anode material provided by the invention limits the distribution rule of Co element concentration, and effectively reduces the lithium nickel mixed discharge rate, so that the high-nickel anode material has lower initial DCR. The initial DCR of the high-nickel positive electrode material is less than or equal to 85mΩ; including but not limited to a point value of any one of 85mΩ, 80mΩ, 79mΩ, 78mΩ, 77mΩ, 76mΩ, 75mΩ, 74mΩ, 73mΩ, 72mΩ, 71mΩ, 70mΩ, 68mΩ, 65mΩ, 63mΩ, 60mΩ, or a range value therebetween.
It is understood that the initial DCR refers to the initial dc resistance of the positive electrode material.
In some specific embodiments, the high-nickel positive electrode material provided by the invention also has lower residual alkali content, and the residual alkali free lithium content of the high-nickel positive electrode material is less than or equal to 1300ppm; including but not limited to a point value of any one of 1300ppm, 1200ppm, 1100ppm, 1000ppm, 900ppm, 800ppm, 700ppm, 600ppm, 500ppm, or a range value between any two.
In some embodiments, the (104) interplanar spacing D in the XRD pattern of the high nickel positive electrode material (104) The value is 52 nm-58 nm; including but not limited to a point value of any one of 52nm, 53nm, 54nm, 55nm, 56nm, 57nm, 58nm, or a range value between any two. Therefore, the high-nickel positive electrode material prepared by the invention has high crystallinity, which is beneficial to capacity exertion and improvement of cycle stability.
In some embodiments, the median particle diameter D of the high nickel positive electrode material 50 Is 8-12 mu m; including but not limited to a dot value of any one of 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, or a range value between any two. Wherein D is 50 Refers to the particle size corresponding to the cumulative particle size distribution percentage of the positive electrode material particles reaching 50 percent.
In some embodiments, the high nickel positive electrode material has a specific surface area of 0.5m 2 /g~0.7m 2 /g, including but not limited to 0.5m 2 /g、0.55m 2 /g、0.6m 2 /g、0.65m 2 /g、0.7m 2 A point value of any one of/g or a range value between any two.
Having the median particle diameter D 50 And the high nickel anode material with specific surface area can keep moderate contact with electrolyte, so that the lithium ion conduction rate is improved and serious side reaction is avoided.
It is to be understood that the high nickel positive electrode materials provided by the present invention may be prepared by any conventional method, including, but not limited to, co-precipitation and/or solid phase methods. The cobalt element content of the high-nickel cathode material particles can also be controlled by any method commonly used in the art, for example, by controlling the concentration, flow and proportioning relationship of raw materials in the coprecipitation reaction process, or controlling the proportioning relationship of raw materials in the solid phase reaction process, step doping, multiple sintering and the like, but the method is not limited thereto.
In a second aspect, the invention provides a method for preparing a high nickel positive electrode material, comprising the following steps:
mixing a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material with a lithium source and performing first sintering, or mixing a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, a lithium source and an additive and performing first sintering to obtain a primary sintering material, wherein the additive comprises at least one of an Al element-containing additive, a Zr element-containing additive, a Sr element-containing additive, a Y element-containing additive or a Q element-containing additive, and Q comprises at least one of Ti, W and Nb elements.
The primary sintering material is crushed and then is uniformly mixed with the additive containing Co element, and secondary sintering is carried out to obtain the secondary sintering material, so that the coating is more uniform.
And (3) washing the secondary sintering material with water, uniformly mixing the secondary sintering material with a surface repairing agent and an inert agent, and performing third sintering to obtain the high-nickel anode material.
The diffusion rate of Li around Co atoms is slower than that around Ni atoms, so the invention adopts cobalt hydroxide to coat the nickel cobalt manganese hydroxide precursor material, and the Co coating on the surface of the nickel cobalt manganese hydroxide can reduce Li + Is Ni in the first sintering process 2+ Providing sufficient time for oxidation to Ni 3+ While Ni 3+ Is greater than Ni in magnetic bulk (magnetic frustration, i.e. reluctance bulk) 2+ Low, thus reducing Li/Ni superswitching. Meanwhile, co is used as a non-magnetic element, and the Li/Ni super-exchange effect can be reduced, so that the Li/Ni mixed discharge is obviously reduced under the combined action of the Co and the Ni.
Furthermore, the additive containing Co element is added and the second sintering is carried out to coat Co, so that a Li-Co-O stable structure is formed, the surface structure can be protected during subsequent water washing, the generation of rock salt phase NiO during the water washing process is reduced, the polarization is reduced, the charge-discharge capacity is further improved, and the initial DCR is reduced.
Furthermore, the surface repairing agent and the inert agent are coated at low temperature through the third sintering, so that the surface interface structure is stabilized, the circulation capacity retention rate is further improved, the circulation DCR growth rate is reduced, and the high-temperature storage capacity retention rate/recovery rate is improved.
The low Li/Ni miscibility promotes the diffusion rate of Li ions in the bulk phase and surface, thus reducing the initial DCR.
In some specific embodiments, the preparation method provided by the invention can reduce the initial DCR by more than 2%.
In addition, the preparation method of the high-nickel positive electrode material provided by the invention has the advantages of simple process and more uniform coating structure, and is suitable for large-scale mass production.
In some embodiments, the temperature of the first sintering is 750 ℃ to 775 ℃, including, but not limited to, a point value of any one of 750 ℃, 755 ℃, 760 ℃, 765 ℃, 770 ℃, 775 ℃, or a range of values between any two.
The temperature range is adopted for the first sintering, so that the crystallinity of the prepared positive electrode material is improved.
In some specific embodiments, the first sintering has a soak time of 16 h-30 h, including but not limited to a point value of any one of 16h, 17h, 18h, 19h, 20h, 22h, 24h, 25h, 28h, 30h, or a range of values therebetween.
In some specific embodiments, the temperature of the second sintering is 670 ℃ -690 ℃, including but not limited to any one of the point values or a range of values between any two of 670 ℃, 672 ℃, 674 ℃, 675 ℃, 678 ℃, 680 ℃, 690 ℃.
The second sintering adopts the temperature range, which is favorable for forming a Li-Co-O stable structure.
In some specific embodiments, the second sintering is performed for a holding time of 16 h-24 h, including but not limited to any one of 16h, 17h, 18h, 19h, 20h, 22h, 24h, or a range of values therebetween.
In some specific embodiments, the temperature of the third sintering is 285 ℃ -335 ℃, including, but not limited to, a point value of any one of 285 ℃, 290 ℃, 295 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 335 ℃, or a range value between any two.
The third sintering adopts the temperature range, and the surface repairing agent and the inert agent are coated at low temperature, so that the surface interface structure can be stabilized.
In some specific embodiments, the third sintering has a holding time of 8h to 16h, including but not limited to a point value of any one of 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, or a range value between any two.
In some embodiments, the first sintering is performed in an oxygen-containing atmosphere having an oxygen content of >95% by volume. Such as an oxygen atmosphere, or a mixed atmosphere of oxygen and an inert gas, but is not limited thereto.
In some embodiments, the second sintering is performed in an oxygen-containing atmosphere having an oxygen content of >95% by volume. Such as an oxygen atmosphere, or a mixed atmosphere of oxygen and an inert gas, but is not limited thereto.
In some embodiments, the third sintering is performed in an oxygen-containing atmosphere having an oxygen content of >95% by volume. Such as an oxygen atmosphere, or a mixed atmosphere of oxygen and an inert gas, but is not limited thereto.
In some embodiments, the surface remediation agent includes boric acid, but is not limited thereto, and other materials having the same effect can be used. The boric acid is used as a surface repairing agent, and the BET of the surface of the material is reduced by forming a surface fast ion conductor, so that the effect of repairing the washing damage is achieved, and the polarization of the material in the working process is reduced.
In some embodiments, the inert agent includes alumina, but is not limited thereto, and other materials having the same function may be used. The aluminum oxide is used as an inert agent, and reacts with hydrofluoric acid by reducing BET of the surface of the material and simultaneously used as a sacrificial agent, so that the active material is prevented from being corroded by the hydrofluoric acid directly, and the effect of stabilizing the surface structure of the material is achieved.
In some embodiments, to further enhance the function of the inert agent, it is preferred to use alpha-alumina.
In some embodiments, the preparation method of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material specifically comprises the following steps: mixing a nickel source, a cobalt source, a manganese source, a precipitator solution and a complexing agent solution, and performing a first coprecipitation reaction to obtain a nickel cobalt manganese hydroxide precursor kernel; and mixing the nickel cobalt manganese hydroxide precursor inner core, a cobalt source, a precipitator solution and a complexing agent solution, and performing a second coprecipitation reaction to form cobalt hydroxide and coating the nickel cobalt manganese hydroxide precursor inner core to obtain a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material (wherein the cobalt hydroxide is coated on the outer surface of the nickel cobalt manganese hydroxide). The cobalt hydroxide coating obtained by the method is more uniform.
In some embodiments, the first coprecipitation reaction is to a median particle diameter D of the nickel cobalt manganese hydroxide precursor core 50 Is 9.5-10.5 mu m; including but not limited to a dot value of any one of 9.5 μm, 9.6 μm, 9.8 μm, 10.0 μm, 10.2 μm, 10.5 μm, or a range value between any two.
In some embodiments, the second coprecipitation reaction is to a median particle diameter D of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material 50 9.8 μm to 10.8 μm, including but not limited to a dot value of any one of 9.8 μm, 9.9 μm, 10.0 μm, 10.2 μm, 10.4 μm, 10.5 μm, 10.6 μm, 10.8 μm, or a range value between any two.
In some embodiments, the nickel source may employ any conventional nickel ion-containing solution, such as, but not limited to, nickel sulfate solution, nickel nitrate solution, and the like.
In some embodiments, the cobalt source may employ any conventional cobalt ion-containing solution, such as, but not limited to, a cobalt sulfate solution, a cobalt nitrate solution, and the like.
In some embodiments, the manganese source may employ any conventional manganese ion-containing solution, such as, but not limited to, a manganese sulfate solution, a manganese nitrate solution, and the like.
In some embodiments, the precipitant solution includes any conventional precipitant solution, such as, but not limited to, sodium hydroxide solution.
In some embodiments, the complexing agent solution includes any conventional complexing agent solution, such as, but not limited to, an aqueous ammonia solution.
In some embodiments, the ammonia concentration in the mixture during the first and/or second coprecipitation reactions is each independently 2g/L to 10g/L, including but not limited to a point value of any one of 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, or a range value therebetween.
Wherein, the ammonia concentration refers to the mass concentration of the ammonia monohydrate in the mixed system.
In some embodiments, the pH of the mixture is controlled to be 10.5-12, including but not limited to a point value of any one of 10.5, 10.8, 11.0, 11.2, 11.5, 11.8, 12.0 or a range of values between any two, independently during the first and/or second coprecipitation reactions.
In some embodiments, the mixture is stirred at 200rpm to 300rpm during the first and/or second coprecipitation reaction, wherein the stirring speed includes, but is not limited to, a point value of any one of 200rpm, 230rpm, 250rpm, 280rpm, 300rpm, or a range value between any two.
In some embodiments, the temperature of the mixture during the first and/or second coprecipitation reactions is controlled to be, independently, 40 ℃ to 60 ℃, including, but not limited to, any one of the point values or a range of values between any two of 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃.
In some embodiments, the lithium source may be any conventional lithium-containing compound, and may be one lithium-containing compound or a mixture of multiple lithium-containing compounds. Such as, but not limited to, lithium hydroxide, lithium nitrate.
In some embodiments, the above-mentioned additive containing Al element may employ any conventional Al-containing compound, such as at least one of an oxide, hydroxide or carbonate, but is not limited thereto.
In some specific embodiments, the Zr-containing additive may be any conventional Zr-containing compound, such as at least one of an oxide, hydroxide, or carbonate, but is not limited thereto.
In some embodiments, the Sr element-containing additive includes any conventional Sr-containing compound, such as at least one of an oxide, hydroxide, or carbonate, but is not limited thereto.
In some embodiments, the Y-element-containing additive may be any conventional Y-element-containing compound, such as at least one of an oxide, hydroxide, or carbonate, but is not limited thereto.
In some embodiments, the above-described Co element-containing additives include any conventional Co element-containing compound, such as at least one of an oxide, hydroxide, or carbonate, but are not limited thereto.
The primary sintering material is crushed, which is beneficial to the subsequent cladding.
In some embodiments, the crushing is to a median particle diameter D of the material 50 9 μm to 11 μm, including but not limited to any one of a dot value or a range value between any two of 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11 μm.
Crushing to the above parameter range, which is beneficial to controlling the median diameter D of the high nickel anode material 50 And specific surface area, thereby obtaining the positive electrode material with better electrochemical performance.
In some embodiments, the crushing is performed until the particle size distribution SPAN of the material is 0.6-0.7, including but not limited to a point value of any one of 0.6, 0.62, 0.64, 0.65, 0.66, 0.68, 0.7 or a range value between any two; specific surface area (BET for short) of 0.2m 2 /g~0.3m 2 /g, including but not limited to 0.2m 2 /g、0.23m 2 /g、0.25m 2 /g、0.28m 2 /g、0.3m 2 A point value of any one of/g or a range value between any two.
The particle size distribution span= (D) 90 -D 10 )/D 50 Wherein D is 90 Refers to the particle size corresponding to the cumulative particle size distribution number reaching 90%, D 10 Refers to the particle size corresponding to the cumulative particle size distribution number reaching 10%, D 50 The particle size corresponding to the cumulative particle size distribution number reaching 50%.
In some specific embodiments, in the above water washing process, the mass ratio of the secondary sintering material to water is 0.6:1-1:1, including but not limited to any one of the point values or any range between the two values of 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1.
Wherein the temperature of the water is 0 ℃ to 8 ℃, including but not limited to any one point value or any range value between any two of 0 ℃, 1 ℃, 2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃, 7 ℃ and 8 ℃.
The water used for the above water washing is preferably deionized water.
In some embodiments, the method further comprises the step of drying the water-washed material after the water-washing. The drying may be performed by any conventional drying method, such as drying, air drying, etc., but is not limited thereto.
In some embodiments, the moisture content of the dried material is 150ppm to 500ppm, including but not limited to any one of 150ppm, 200ppm, 300ppm, 400ppm, 500ppm, or a range of values therebetween.
In some embodiments, the BET of the dried material is 0.8m 2 /g~1.5m 2 /g, including but not limited to 0.8m 2 /g、0.9m 2 /g、1.0m 2 /g、1.2m 2 /g、1.4m 2 /g、1.5m 2 A point value of any one of/g or a range value between any two.
In some embodiments, the residual free lithium content of the dried material is 600ppm to 1200ppm, including but not limited to a point value of any one of 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1100ppm, 1200ppm, or a range of values therebetween.
In some embodiments, the amounts of each raw material are calculated according to the chemical formula of the high nickel positive electrode material.
In a third aspect, the present invention provides a positive electrode sheet comprising the above high nickel positive electrode material.
In some embodiments, the positive electrode sheet includes a current collector and a positive electrode material disposed on a surface of the current collector, wherein the positive electrode material is mainly made of the above-described high nickel positive electrode material, a binder, and a conductive agent.
In some embodiments, the current collector for the positive electrode sheet may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material on a polymeric material substrate. Alternatively, the metallic material may include, but is not limited to, one or more of aluminum, aluminum alloys, nickel alloys, titanium alloys, silver, and silver alloys. Alternatively, the polymer material substrate may include, but is not limited to, one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and Polyethylene (PE).
The binder for the positive electrode sheet may be any commercially available binder for positive electrode sheets, such as polyvinylidene fluoride (PVDF), or a binder prepared by any prior art, but is not limited thereto.
As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-fluoropropene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
The conductive agent for the positive electrode sheet may be any commercially available conductive agent for lithium ion batteries, or any conductive agent prepared by the prior art, such as carbon black, graphite, etc., but is not limited thereto.
As an example, the conductive agent may include at least one of carbon black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers, wherein the carbon black includes superconducting carbon, acetylene black, or ketjen black.
As an example, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining the positive electrode plate after the procedures of drying, cold pressing and the like. Alternatively, the solvent includes, but is not limited to, N-methylpyrrolidone.
In a fourth aspect, the present invention provides a lithium ion battery, including the positive electrode sheet.
In some specific embodiments, the lithium ion battery further comprises a negative electrode plate, a separator and an electrolyte.
The negative electrode plate, the diaphragm and the electrolyte can be any commercially available negative electrode plate, diaphragm and electrolyte, or can be any negative electrode plate, diaphragm and electrolyte prepared by the prior art, and the invention is not limited to the above.
In a fifth aspect, the invention provides an electric device, which comprises the lithium ion battery.
It is understood that the above-mentioned electric equipment includes any equipment, device or system using the above-mentioned lithium ion battery, and the electric equipment can be applied to the field of transportation means, the field of electronic products, the field of aerospace, the field of medical treatment, the field of energy storage, etc., but is not limited thereto.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.858 3 Co 0.065 Mn 0.05 Al 0.0117 Zr 0.004 Sr 0.002 Y 0.001 B 0.008 O 2 ：
(1) Dissolving nickel sulfate solution and manganese sulfate according to the mole ratio of Ni element to Co element to Mn element=90:5:5Adding the solution and the cobalt sulfate solution into a first reaction kettle, adding an ammonia water solution and a sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of the mixed system to be 7g/L, controlling the pH to be 11.5, controlling the stirring speed to be 250rpm, controlling the reaction temperature to be 50 ℃, and waiting for the median diameter D of precursor particles 50 When=10μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
Transferring the prepared nickel cobalt manganese hydroxide precursor inner core into a second reaction kettle, adding a cobalt sulfate solution, wherein the molar quantity of Co element is 0.5% of the molar quantity of the nickel cobalt manganese hydroxide precursor inner core, adding an ammonia water solution, controlling the ammonia concentration to be 4g/L, adding sodium hydroxide, adjusting the pH value of a mixed system to be 11.0, stirring at a rotating speed of 250rpm, reacting at 50 ℃, and keeping the median particle diameter D of precursor particles 50 When the reaction is carried out with the particle size of 10.3 μm, the reaction is stopped and solid-liquid separation is carried out, so that the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is obtained.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing in a coulter for 30min, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, the molar amount of Al element is 1.0% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.4% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.2% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and the molar amount of Y element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing first sintering of the obtained mixture in a roller kiln under an oxygen atmosphere, wherein the first sintering temperature is 755 ℃ and the heat preservation time is 28h, so as to obtain a primary sintered material.
(3) Crushing the primary sintering material obtained in the step (2) by a mechanical mill to obtain a median particle diameter D of crushed materials 50 10.12 μm, particle size distribution SPAN of 0.64, BET of 0.2616m 2 And/g. Mixing the above pulverized materials with CoO in a high-speed mixer for 20minThe molar quantity of Co element is 1% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then the obtained mixed material is subjected to second sintering in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 676 ℃, and the heat preservation time is 21.5h, so as to obtain the secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 0.85:1, the temperature of the deionized water is 4 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 (boric acid) and Al 2 O 3 Mixing for 20min in a high-speed mixer, wherein the molar quantity of B element is 0.8% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar quantity of Al element is 0.17% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing third sintering on the mixed material in a roller kiln under oxygen atmosphere, wherein the temperature of the third sintering is 330 ℃, and the heat preservation time is 10h, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 9.87 μm, particle size distribution SPAN of 0.64 and BET of 0.5504m 2 /g。
Example 2
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.85 Co 0.084 Mn 0.04 Al 0.015 Zr 0.003 Sr 0.001 Y 0.001 B 0.006 O 2 ：
(1) Adding a nickel sulfate solution, a manganese sulfate solution and a cobalt sulfate solution into a first reaction kettle according to the molar ratio of Ni element to Co element to Mn element=91:5:4, then adding an ammonia water solution and a sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of a mixed system to be 5g/L, controlling the pH to be 11, controlling the stirring rotation speed to be 200rpm, controlling the reaction temperature to be 45 ℃, and waiting for the median particle diameter D of precursor particles to be obtained 50 When=9.8 μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
The nickel cobalt manganese hydroxide precursor prepared above is preparedTransferring the inner core into a second reaction kettle, adding a cobalt sulfate solution, wherein the molar quantity of Co element is 1.4% of the molar quantity of the inner core of the nickel cobalt manganese hydroxide precursor, adding an ammonia water solution, controlling the ammonia concentration to be 3g/L, adding sodium hydroxide, adjusting the pH value of a mixed system to be 11.2, stirring at a rotating speed of 250rpm, reacting at 45 ℃, and keeping the median particle diameter D of precursor particles 50 When the reaction is carried out with the particle size of 10.5 μm, the reaction is stopped and solid-liquid separation is carried out, so that the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is obtained.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing in a coulter for 30min, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, the molar amount of Al element is 1.0% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.3% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and the molar amount of Y element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing first sintering of the obtained mixture in a roller kiln under an oxygen atmosphere, wherein the first sintering temperature is 750 ℃ and the heat preservation time is 30h, so as to obtain a primary sintered material.
(3) Crushing the primary sintering material obtained in the step (2) by a mechanical mill to obtain a median particle diameter D of crushed materials 50 10.52 μm, particle size distribution SPAN of 0.65 and BET of 0.2287m 2 And/g. Mixing the crushed material with CoO in a high-speed mixer for 20min, wherein the molar quantity of Co element is 2% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing second sintering on the obtained mixed material in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 675 ℃, and the heat preservation time is 22h, so as to obtain a secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 0.8:1, the temperature of the deionized water is 5 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 And Al 2 O 3 Mixing for 20min in a high-speed mixer, wherein the molar quantity of B element is 0.6% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar quantity of Al element is 0.5% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing third sintering on the mixed material in a roller kiln under oxygen atmosphere, wherein the temperature of the third sintering is 330 ℃, and the heat preservation time is 14h, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 9.91 μm, particle size distribution SPAN of 0.63 and BET of 0.5910m 2 /g。
Example 3
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.84 Co 0.1 Mn 0.03 Al 0.018 Zr 0.004 Sr 0.002 Y 0.001 B 0.004 Ti 0.001 O 2 ：
(1) Adding a nickel sulfate solution, a manganese sulfate solution and a cobalt sulfate solution into a first reaction kettle according to the molar ratio of Ni element to Co element to Mn element=92:5:3, then adding an ammonia water solution and a sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of a mixed system to be 7g/L, controlling the pH value to be 11.3, controlling the stirring rotation speed to be 280rpm, controlling the reaction temperature to be 52 ℃, and controlling the median particle diameter D of precursor particles to be equal to the median particle diameter D of precursor particles 50 When=9.5 μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
Transferring the prepared nickel cobalt manganese hydroxide precursor inner core into a second reaction kettle, adding a cobalt sulfate solution into the second reaction kettle, adding an ammonia water solution into 2% of the molar quantity of Co element which is the molar quantity of the nickel cobalt manganese hydroxide precursor inner core to control the ammonia concentration to be 4.5g/L, adding sodium hydroxide to adjust the pH value of a mixed system to be 11.3, stirring at a rotating speed of 250rpm, wherein the reaction temperature is 53 ℃, and keeping the median particle diameter D of precursor particles 50 When the reaction is stopped and solid-liquid separation is carried out when the particle diameter is 10.8 mu m, the cobalt hydroxide coated nickel cobalt manganese hydroxide is obtained Precursor materials.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing in a coulter for 30min, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, the molar amount of Al element is 1.0% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.4% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.2% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Y element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Ti element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing first sintering of the obtained mixture in a roller kiln under an oxygen atmosphere, wherein the first sintering temperature is 760 ℃, and the heat preservation time is 24h, so as to obtain a primary sintered material.
(3) Crushing the primary sintering material obtained in the step (2) by a mechanical mill to obtain a median particle diameter D of crushed materials 50 10.38 μm, particle size distribution SPAN of 0.64 and BET of 0.2811m 2 And/g. Mixing the crushed material with CoO in a high-speed mixer for 20min, wherein the molar quantity of Co element is 3% of the molar quantity of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing second sintering on the obtained mixed material in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 673 ℃, and the heat preservation time is 24h, so as to obtain a secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 0.7:1, the temperature of the deionized water is 3 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 And Al 2 O 3 Mixing in a high-speed mixer for 20min, wherein the molar quantity of B element is 0.4% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and the molar quantity of Al element is hydrogen and oxygenAnd (3) coating cobalt oxide with 0.8% of the molar quantity of the nickel cobalt manganese hydroxide precursor material, and then carrying out third sintering on the mixed material in a roller kiln under an oxygen atmosphere, wherein the third sintering temperature is 310 ℃, and the heat preservation time is 12 hours, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 9.85 μm, particle size distribution SPAN of 0.63, BET of 0.6303m 2 /g。
Example 4
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.828 Co 0.14 Mn 0.02 Al 0.005 Zr 0.002 Sr 0.001 Y 0.001 B 0.002 W 0.001 O 2 ：
(1) Adding a nickel sulfate solution, a manganese sulfate solution and a cobalt sulfate solution into a first reaction kettle according to the ratio of Ni element to Co element to Mn element=93:5:2, then adding an ammonia water solution and a sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of a mixed system to be 7.5g/L, controlling the pH value to be 11.7, controlling the stirring rotation speed to be 250rpm, controlling the reaction temperature to be 52 ℃, and controlling the median particle diameter D of precursor particles to be equal to the median particle diameter D of precursor particles 50 When=9.8 μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
Transferring the prepared nickel cobalt manganese hydroxide precursor inner core into a second reaction kettle, adding a cobalt sulfate solution into the second reaction kettle, adding an ammonia water solution into 2% of the molar quantity of the cobalt element which is the molar quantity of the nickel cobalt manganese hydroxide precursor inner core to control the ammonia concentration to be 3.5g/L, adding sodium hydroxide to adjust the pH value of a mixed system to be 11.0, stirring at a rotating speed of 250rpm, reacting at 48 ℃, and keeping the median particle diameter D of precursor particles at the temperature of 48 DEG C 50 When the reaction is carried out with the particle size of 10.3 μm, the reaction is stopped and solid-liquid separation is carried out, so that the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is obtained.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing for 60min in a coulter, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, and the Al elementThe molar amount of element is 0.4% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.2% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Y element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and the molar amount of W element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then the obtained mixture is subjected to first sintering in a roller kiln under an oxygen atmosphere, wherein the first sintering temperature is 770 ℃, and the heat preservation time is 16h, so as to obtain a primary sintered material.
(3) Crushing the primary sintering material obtained in the step (2) by a mechanical mill to obtain a median particle diameter D of crushed materials 50 9.88 μm, particle size distribution SPAN of 0.63, BET of 0.2956m 2 And/g. Mixing the crushed material and CoO in a high-speed mixer for 20min, wherein the molar quantity of Co element is 7% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing second sintering on the obtained mixed material in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 678 ℃, and the heat preservation time is 20h, so as to obtain the secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 0.6:1, the temperature of the deionized water is 2 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 And Al 2 O 3 Mixing for 20min in a high-speed mixer, wherein the molar quantity of B element is 0.2% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar quantity of Al element is 0.1% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then carrying out third sintering on the mixed material in a roller kiln under the oxygen atmosphere, wherein the temperature of the third sintering is 300 ℃, and the heat preservation time is 10h, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 9.78 μm, particle size distribution SPAN of 0.64, BET of 0.6320m 2 /g。
Example 5
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.938 5 Co 0.045 Mn 0.01 Al 0.001 Zr 0.001 Sr 0.002 Y 0.0005 B 0.001 Nb 0.001 O 2 ：
(1) Adding a nickel sulfate solution, a manganese sulfate solution and a cobalt sulfate solution into a first reaction kettle according to the molar ratio of Ni element to Co element to Mn element=96:3:1, then adding an ammonia water solution and a sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of a mixed system to be 7g/L, controlling the pH to be 11, controlling the stirring rotation speed to be 250rpm, controlling the reaction temperature to be 55 ℃, and controlling the median particle diameter D of precursor particles to be equal to the median particle diameter D of precursor particles 50 When=9.5 μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
Transferring the prepared nickel cobalt manganese hydroxide precursor inner core into a second reaction kettle, adding a cobalt sulfate solution, wherein the molar quantity of Co element is 0.5% of the molar quantity of the nickel cobalt manganese hydroxide precursor inner core, adding an ammonia water solution, controlling the ammonia concentration to be 5g/L, adding sodium hydroxide, adjusting the pH value of a mixed system to be 11.0, stirring at a rotating speed of 250rpm, reacting at a temperature of 55 ℃, and keeping the median particle diameter D of precursor particles 50 When the reaction is carried out with the particle diameter of 9.8 μm, the reaction is stopped and solid-liquid separation is carried out, so that the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is obtained.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing in a coulter for 25min, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, the molar amount of Al element is 0.05% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.2% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and the molar amount of Y element is cobalt hydroxideAnd (3) coating 0.05% of the molar quantity of the nickel cobalt manganese hydroxide precursor material, wherein the molar quantity of Nb element is 0.1% of the molar quantity of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing first sintering on the obtained mixture in a roller kiln under an oxygen atmosphere, wherein the first sintering temperature is 760 ℃, and the heat preservation time is 20 hours, so as to obtain the primary sintering material.
(3) Crushing the primary sintering material obtained in the step (2) by a mechanical mill to obtain a median particle diameter D of crushed materials 50 10.45 μm, particle size distribution SPAN of 0.64 and BET of 0.2887m 2 And/g. Mixing the crushed material with CoO in a high-speed mixer for 30min, wherein the molar quantity of Co element is 1% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing second sintering on the obtained mixed material in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 680 ℃, and the heat preservation time is 18h, so as to obtain a secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 1:1, the temperature of the deionized water is 5 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 And Al 2 O 3 Mixing for 30min in a high-speed mixer, wherein the molar quantity of B element is 0.1% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar quantity of Al element is 0.05% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing third sintering on the mixed material in a roller kiln under oxygen atmosphere, wherein the temperature of the third sintering is 290 ℃, and the heat preservation time is 8h, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 10.01 μm, particle size distribution SPAN of 0.64, BET of 0.6072m 2 /g。
Example 6
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.879 Co 0.05 Mn 0.05 Al 0.01 Zr 0.001 Sr 0.002 Y 0.001 B 0.006 Ti 0.0005 W 0.0005 O 2 ：
(1) Adding a nickel sulfate solution, a manganese sulfate solution and a cobalt sulfate solution into a first reaction kettle according to the molar ratio of Ni element to Co element to Mn element=92:3:5, then adding an ammonia water solution and a sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of a mixed system to be 7g/L, controlling the pH to be 11, controlling the stirring rotation speed to be 250rpm, controlling the reaction temperature to be 55 ℃, and controlling the median particle diameter D of precursor particles to be equal to the median particle diameter D of precursor particles 50 When=9.5 μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
Transferring the prepared nickel cobalt manganese hydroxide precursor inner core into a second reaction kettle, adding a cobalt sulfate solution, wherein the molar quantity of Co element is 1% of that of the nickel cobalt manganese hydroxide precursor inner core, adding an ammonia water solution, controlling the ammonia concentration to be 5g/L, adding sodium hydroxide, adjusting the pH value of a mixed system to be 11.0, stirring at a rotating speed of 250rpm, reacting at 55 ℃, and keeping the median particle diameter D of precursor particles at the temperature of 55 DEG C 50 When the reaction is carried out with the particle diameter of 9.9 μm, the reaction is stopped and solid-liquid separation is carried out, so that the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is obtained.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing in a coulter for 25min, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, the molar amount of Al element is 0.8% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.2% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Y element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Ti element is 0.05% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of W element is 0.05% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then feeding the resulting mixture in an oxygen atmosphere in a roller kilnAnd performing first sintering, wherein the first sintering temperature is 760 ℃, and the heat preservation time is 20 hours, so as to obtain the primary sintering material.
(3) Crushing the primary sintering material obtained in the step (2) by a mechanical mill to obtain a median particle diameter D of crushed materials 50 10.25 μm, particle size distribution SPAN of 0.64 and BET of 0.2473m 2 And/g. Mixing the crushed material with CoO in a high-speed mixer for 30min, wherein the molar quantity of Co element is 1% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing second sintering on the obtained mixed material in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 680 ℃, and the heat preservation time is 18h, so as to obtain a secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 1:1, the temperature of the deionized water is 5 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 And Al 2 O 3 Mixing for 30min in a high-speed mixer, wherein the molar quantity of B element is 0.06% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar quantity of Al element is 0.2% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then carrying out third sintering on the mixed material in a roller kiln under the oxygen atmosphere, wherein the temperature of the third sintering is 300 ℃, and the heat preservation time is 8h, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 9.96 μm, particle size distribution SPAN of 0.64 and BET of 0.5772m 2 /g。
Example 7
The preparation method of the high-nickel positive electrode material provided by the embodiment comprises the following steps of a chemical formula of LiNi 0.824 5 Co 0.12 Mn 0.03 Al 0.018 Zr 0.003 Sr 0.001 Y 0.0005 B 0.002 W 0.0007 Nb 0.0003 O 2 ：
(1) Nickel sulfate solution, manganese sulfate solution and cobalt sulfate solution were prepared in a molar ratio of Ni element to Co element to Mn element=87:10:3Adding into a first reaction kettle, adding ammonia water solution and sodium hydroxide solution into the first reaction kettle, stirring, controlling the ammonia concentration of the mixed system to 7g/L, the pH value to 11, the stirring rotation speed to 250rpm, the reaction temperature to 55 ℃, and waiting for the median particle diameter D of the precursor particles 50 When=9.5 μm, the reaction was stopped and solid-liquid separation was performed to obtain a nickel cobalt manganese hydroxide precursor core.
Transferring the prepared nickel cobalt manganese hydroxide precursor inner core into a second reaction kettle, adding a cobalt sulfate solution, wherein the molar quantity of Co element is 1% of the molar quantity of the nickel cobalt manganese hydroxide precursor inner core, adding an ammonia water solution, controlling the ammonia concentration to be 5g/L, adding sodium hydroxide, adjusting the pH value of a mixed system to be 11, stirring at a rotating speed of 250rpm, reacting at 55 ℃, and keeping the median particle diameter D of precursor particles 50 When the reaction is carried out with the particle diameter of 9.8 μm, the reaction is stopped and solid-liquid separation is carried out, so that the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is obtained.
(2) Coating the cobalt hydroxide prepared in the step (1) with nickel cobalt manganese hydroxide precursor material, liOH and Al 2 O 3 、ZrO 2 SrO and Y 2 O 3 Mixing in a coulter for 25min, wherein the molar ratio of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material to LiOH is 1:1.03, the molar amount of Al element is 1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Zr element is 0.3% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Sr element is 0.1% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of Y element is 0.05% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar amount of W element is 0.007% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and the molar amount of Nb element is 0.003% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing first sintering on the obtained mixture in an oxygen atmosphere at 760 ℃ for 20h to obtain a primary sintered material.
(3) Crushing the primary sintering material obtained in the step (2) through a mechanical mill, Median particle diameter D of the pulverized product obtained 50 9.89 μm, particle size distribution SPAN of 0.65 and BET of 0.2315m 2 And/g. Mixing the crushed material with CoO in a high-speed mixer for 30min, wherein the molar quantity of Co element is 1% of that of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing second sintering on the obtained mixed material in a roller kiln under the oxygen atmosphere, wherein the second sintering temperature is 680 ℃, and the heat preservation time is 18h, so as to obtain a secondary sintering material.
(4) Adding the secondary sintering material obtained in the step (3) into deionized water, stirring and cleaning, wherein the mass ratio of the secondary sintering material to the deionized water is 1:1, the temperature of the deionized water is 5 ℃, and performing solid-liquid separation and drying for 5 hours after washing.
Mixing the above dried material with H 3 BO 3 And Al 2 O 3 Mixing for 30min in a high-speed mixer, wherein the molar quantity of B element is 0.2% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, the molar quantity of Al element is 0.8% of the molar quantity of cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, and then performing third sintering on the mixed material in a roller kiln under oxygen atmosphere, wherein the temperature of the third sintering is 285 ℃, and the heat preservation time is 8h, so as to obtain the high-nickel anode material. Median particle diameter D of the obtained high nickel cathode material 50 10.06 μm, particle size distribution SPAN of 0.64 and BET of 0.6183m 2 /g。
Example 8
The preparation method of the high nickel cathode material provided in this example is basically the same as that of example 1, except that Y is not added in step (2) 2 O 3 And the molar quantity of Al element is replaced by 1.1 percent of the molar quantity of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material.
The chemical general formula of the high nickel anode material prepared in the embodiment is LiNi 0.8583 Co 0.065 Mn 0.05 Al 0.0127 Zr 0.004 Sr 0.002 B 0.008 O 2 。
Example 9
The preparation method of the high-nickel positive electrode material provided in the embodiment is basically the same as that of the embodiment 1The difference is that SrO and Y are not added in the step (2) 2 O 3 And the molar quantity of Al element is replaced by 1.3 percent of the molar quantity of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material.
The chemical general formula of the high nickel anode material prepared in the embodiment is LiNi 0.8583 Co 0.065 Mn 0.05 Al 0.0147 Zr 0.00 4 B 0.008 O 2 。
Example 10
The preparation method of the high-nickel cathode material provided in this example is substantially the same as that of example 1, except that ZrO was not added in step (2) 2 SrO and Y 2 O 3 And the molar amount of Al element is replaced by 1.7 percent of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material.
The chemical general formula of the high nickel anode material prepared in the embodiment is LiNi 0.8583 Co 0.065 Mn 0.05 Al 0.0187 B 0.008 O 2 。
Example 11
The preparation method of the high nickel cathode material provided in this example is basically the same as that of example 1, except that Al is not added in step (2) 2 O 3 And in step (4), al is not added 2 O 3 。
The chemical general formula of the high nickel anode material prepared in the embodiment is LiNi 0.87 Co 0.065 Mn 0.05 Zr 0.004 Sr 0.00 2 Y 0.001 B 0.008 O 2 。
Comparative example 1
The preparation method of the high nickel cathode material provided in this comparative example is basically the same as that of example 5, except that the cobalt sulfate solution (i.e., the Co element is not coated) is not added after the nickel cobalt manganese hydroxide precursor core is obtained in step (1).
The chemical general formula of the high nickel positive electrode material prepared in the comparative example is LiNi 0.9435 Co 0.04 Mn 0.01 Al 0.001 Zr 0.001 Sr 0.002 Y 0.0005 B 0.001 Nb 0.001 O 2 (i.e., b=0.04).
Comparative example 2
The preparation method of the high nickel cathode material provided in this comparative example is substantially the same as in example 5, except that CoO is not added in step (3).
The chemical general formula of the high nickel positive electrode material prepared in the comparative example is LiNi 0.9485 Co 0.035 Mn 0.01 Al 0.001 Zr 0.001 Sr 0.002 Y 0.0005 B 0.001 Nb 0.001 O 2 (i.e., b=0.035).
Comparative example 3
The preparation method of the high nickel cathode material provided in this comparative example is substantially the same as that of example 1, except that in step (1), the molar ratio of Ni element to Co element to Mn element is replaced with 77:18:5.
The chemical general formula of the high nickel positive electrode material prepared in the comparative example is LiNi 0.73 Co 0.195 Mn 0.05 Al 0.01 Zr 0.004 Sr 0.002 Y 0.001 B 0.008 O 2 (i.e., a=0.73, b=0.195).
Comparative example 4
The preparation method of the high nickel cathode material provided in this comparative example is substantially the same as in example 1, except that H is not added in step (4) 3 BO 3 。
The chemical general formula of the high nickel positive electrode material prepared in the comparative example is LiNi 0.868 Co 0.065 Mn 0.05 Al 0.01 Zr 0.004 Sr 0.002 Y 0.001 O 2 (i.e., h=0).
Comparative example 5
The preparation method of the high nickel cathode material provided in this comparative example is basically the same as that of example 1, except that the cobalt sulfate solution (i.e., no coating of Co element) is not added after the nickel cobalt manganese hydroxide precursor core is obtained in step (1), and CoO is not added and the second sintering is not performed in step (3).
The chemical general formula of the high nickel positive electrode material prepared in the comparative example is LiNi 0.8733 Co 0.05 Mn 0.05 Al 0.0117 Zr 0.004 Sr 0.002 Y 0.001 B 0.008 O 2 。
Comparative example 6
The preparation method of the high-nickel cathode material provided in this comparative example is basically the same as that of example 1, except that the cobalt sulfate solution (i.e., the Co element is not coated) is not added after the nickel cobalt manganese hydroxide precursor core is obtained in step (1), and the molar amount of the Co element is replaced with 1.5% of the molar amount of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material in step (3).
The chemical general formula of the high nickel positive electrode material prepared in the comparative example is LiNi 0.8583 Co 0.065 Mn 0.05 Al 0.0117 Zr 0.004 Sr 0.002 Y 0.001 B 0.008 O 2 。
Experimental example 1
The high nickel cathode materials prepared in the above examples and comparative examples were respectively examined for residual alkali content (including lithium carbonate, lithium hydroxide and free lithium content), median particle diameter D 50 Specific surface area, interplanar spacing D of (104) in XRD spectrum (104) The values and Li/Ni blend ratios are shown in Table 1.
Wherein, the test method of the residual alkali content refers to GB/T41704-2022; the test method of the median particle diameter is referred to GB/T19077.1-2016; BET test method is referred to GB/T19587-2017; d (D) (104) The Li/Ni mixed discharge rate is tested by an X-ray diffractometer (instrument model is Bruce D8AA25, target material is Cu, voltage is 40kV, current is 40mA, soller is 2.5), and the test result is processed by data processing software EVAr and TOPAS.
TABLE 1
As can be seen from table 1, comparative examples 1 to 11, comparative examples 1 to 2 and comparative examples 5 to 6, by coating the precursor Co element, even the ultra-high nickel material Li/Ni did not significantly increase, indicating that the precursor coating Co element can effectively reduce the Li/Ni mixed discharge of the high nickel cathode material; by coating the second sintering Co element, even the residual alkali on the surface of the ultra-high nickel material is not obviously increased, which indicates that the second sintering Co coating reduces the residual alkali on the surface after the first sintering.
Comparison of example 1 with comparative example 3 shows that low Ni content can reduce residual alkali, BET, li/Ni miscibility, which is caused by more Co element content in low Ni.
Comparative example 1 and example 11 show Al 2 O 3 Doping can reduce the BET of the high nickel material.
Comparison of example 9 and example 10 shows that Zr doping can maintain the layered structure, reduce Li/Ni miscibility and increase BET of the high nickel material.
Comparison of examples 8 and 9 shows that the synergistic effect of Sr and Y, the removal of one of the elements, results in a reduced BET, increased Li/Ni miscibility and excessive crystallization of the high nickel material.
Comparative example 1 and comparative example 4 show that elemental B coating can reduce the BET of high nickel materials.
Experimental example two
Lithium ion batteries were fabricated using the high nickel cathode materials prepared in each example and each comparative example, respectively, and electrochemical performance tests were performed on each battery, and the test results are shown in table 2.
The preparation method of the lithium ion battery comprises the following steps: the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) in the examples or the comparative examples are weighed according to the mass ratio of 94:3:3, uniformly mixed, added with NMP and stirred for 2 hours to form sticky slurry, uniformly coated on an aluminum foil, and then baked in vacuum at 80 ℃, tabletted and cut into positive electrode plates with the diameter of 14 mm. Pure lithium sheet with diameter of 16mm is used as a negative electrode sheet, and LiPF with mol/L of 1 is used 6 And (3) using the mixed solution of DEC/EC (volume ratio of 1:1) as electrolyte, using a polypropylene microporous membrane (Celgard) as a diaphragm, and assembling the battery in a glove box filled with argon.
The test method of 0.2C discharge capacity refers to GB/T31467.1-2015,1C, the test method of 300-cycle performance refers to GB/T31484-2015, and the test method of initial DCR refers to GB/T31467.1-2015.
TABLE 2
As can be seen from table 2, comparative examples 1 to 7 show that the 0.2C discharge capacity is significantly improved with the increase of Ni content, but the 300-cycle retention rate at 1C is reduced and the initial DCR is increased.
Comparative examples 5 and 1 to 2, and examples 1 and 5 to 6, show that removal of the Co element coating deteriorates electrochemical performance.
Comparison of example 1 with comparative example 3 shows that lower Ni content improves cycle performance and reduces initial DCR.
Comparison of example 1 and example 11 shows that Al doping can improve the cycling performance of the high nickel positive electrode material.
Comparing example 1 with examples 8-10 shows that Zr, sr, Y doping can improve the electrochemical performance of the high nickel cathode material.
Comparison of example 1 and comparative example 4 shows that B coating can significantly improve the cycle retention of the high nickel positive electrode material.
Experimental example III
The high nickel cathode material prepared in example 1 was analyzed for the content of main elements (Ni, co, mn, and Al), and the results are shown in table 3. Wherein, the SEM cross-section of the high nickel cathode material of example 1 and its detection point are shown in fig. 1.
The high nickel cathode material prepared in comparative example 5 was subjected to main element content analysis, and the results are shown in table 4. Among them, the SEM cross-sectional view of the high nickel cathode material of comparative example 5 and its detection point are shown in fig. 2.
The high nickel cathode material prepared in comparative example 6 was subjected to main element content analysis, and the results are shown in table 5. Among them, the SEM cross-sectional view of the high nickel cathode material of comparative example 6 and its detection point are shown in fig. 3.
The testing method of the element content refers to GB/T25189-2010. After the mass percentages of the elements obtained by the test are converted into mole ratios, the mole percentage content of the Al element, the Mn element, the Co element and the Ni element in the total mole amount of the four elements is calculated respectively.
"spectrogram X" in tables 3 to 5 is a detection point reference numeral, and X is a reference numeral.
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
Among them, the specific distribution of the cobalt element content on the particle surface of the high nickel cathode material prepared in each of the above examples and comparative examples is shown in table 6. The mole percentages of Co elements in table 6 refer to: the mole amount of Co element is the percentage of the total mole amount of four elements of Al element, mn element, co element and Ni element.
TABLE 6
As can be seen from tables 3 to 6, the high nickel positive electrode material particles prepared in example 1 gradually decreased in cobalt element content from the surface to the center. While the high nickel cathode material particles prepared in comparative example 5 did not gradually decrease the cobalt element content from the surface to the center. The high nickel cathode material particles prepared in comparative example 6 were gradually decreased in cobalt element content from the surface to the center, but were weak in gradient change of Co element content, and at the same time, region N in comparative example 6 1 The content of Co element in the alloy is low in comparative example 1. Comparative examples 1 to 11 show that too high a content of Co element is detrimental to the electric properties.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (19)
1. A high-nickel positive electrode material is characterized in that the chemical general formula of the high-nickel positive electrode material is Li x Ni a Co b Mn c Al d Zr e Sr f Y g B h Q i O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.98 and less than or equal to 1.04,0.8, a is more than or equal to 0.95,0.045 and less than or equal to 0.95,0.045, b is more than or equal to 0.145,0.005 and less than or equal to 0.055,0, d is more than or equal to 0.0187,0 and less than or equal to e is more than or equal to 3552, f is more than or equal to 0.004,0 and less than or equal to 0.003,0 and g is more than or equal to 0.002,0<h is equal to or more than 0.008,0 is equal to or less than i is equal to or less than 0.002, and a+b+c+d+e+f+g+h+i=1; q comprises at least one of Ti, W and Nb elements;
The content of cobalt element in the particles of the high-nickel positive electrode material is gradually reduced from the surface to the center, and the depth of the region N from the surface of the particles to the center of the particles is 1 mu m 1 Wherein Co element accounts for 5-21 mol percent, and the area is from area N 1 Region N having a depth of 2 μm toward the center of the particle 2 Wherein Co element accounts for 4-12 mol percent, and the area is from area N 2 Region N having a depth of 2 μm toward the center of the particle 3 Wherein the Co element accounts for 3-11% by mole percent; and, region N 1 The molar quantity of the Co element in the high-nickel cathode material particles accounts for 40% -50% of the total molar quantity of the Co element in the high-nickel cathode material particles.
2. The high-nickel positive electrode material according to claim 1, wherein the lithium-nickel mixed discharge rate of the high-nickel positive electrode material is less than or equal to 1.2%.
3. The high nickel positive electrode material according to claim 1, wherein the initial direct current internal resistance of the high nickel positive electrode material is not more than 85mΩ.
4. The high nickel positive electrode material according to claim 1, wherein the residual alkali free lithium content of the high nickel positive electrode material is not more than 1300ppm.
5. The high nickel positive electrode material according to claim 1, wherein the (104) interplanar spacing of the high nickel positive electrode material is 52nm to 58nm.
6. The high nickel positive electrode material according to claim 1, wherein the high nickel positive electrode material has a median particle diameter of 8 μm to 12 μm.
7. The high nickel positive electrode material according to claim 1, wherein the high nickel positive electrode material has a specific surface area of 0.5m 2 /g~0.7m 2 /g。
8. A method for producing the high nickel positive electrode material according to any one of claims 1 to 7, comprising the steps of:
mixing a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material with a lithium source and performing first sintering, or mixing a cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material, a lithium source and an additive and performing first sintering to obtain a primary sintering material, wherein the additive comprises at least one of an additive containing Al element, an additive containing Zr element, an additive containing Sr element, an additive containing Y element or an additive containing Q, and the Q comprises at least one of Ti, W and Nb elements;
the primary sintering material is crushed and then mixed with an additive containing Co element, and secondary sintering is carried out to obtain a secondary sintering material;
and (3) washing the secondary sintering material, mixing the secondary sintering material with a surface repairing agent and an inert agent, and performing third sintering to obtain the high-nickel anode material.
9. The method of producing a high nickel positive electrode material according to claim 8, wherein the surface-repairing agent comprises boric acid;
And/or the inert agent comprises alumina.
10. The method for preparing a high nickel anode material according to claim 8, wherein the temperature of the first sintering is 750-775 ℃ and the heat preservation time is 16-30 h;
and/or the temperature of the second sintering is 670-690 ℃, and the heat preservation time is 16-24 hours;
and/or the temperature of the third sintering is 285-335 ℃, and the heat preservation time is 8-16 h.
11. The method for producing a high nickel positive electrode material according to claim 8, wherein the first sintering, the second sintering, and the third sintering are performed in an oxygen-containing atmosphere having an oxygen content of >95% by volume.
12. The method for preparing a high nickel positive electrode material according to claim 8, wherein the method for preparing the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material specifically comprises: mixing a nickel source, a cobalt source, a manganese source, a precipitant solution and a complexing agent solution, and performing a first coprecipitation reaction to obtain a nickel cobalt manganese hydroxide precursor kernel; and mixing the nickel cobalt manganese hydroxide precursor inner core, a cobalt source, a precipitator solution and a complexing agent solution, and performing a second coprecipitation reaction to form cobalt hydroxide and coating the nickel cobalt manganese hydroxide precursor inner core, thereby obtaining the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material.
13. The method for preparing a high nickel positive electrode material according to claim 12, wherein the median particle diameter of the first coprecipitation reaction to the nickel cobalt manganese hydroxide precursor core is 9.5 μm to 10.5 μm.
14. The method of claim 12, wherein the second coprecipitation reaction is carried out until the median particle size of the cobalt hydroxide coated nickel cobalt manganese hydroxide precursor material is 9.8 μm to 10.8 μm.
15. The method for preparing a high nickel anode material according to claim 12, wherein the pH of the mixed material is 10.5-12 during the first coprecipitation reaction and/or the second coprecipitation reaction.
16. The method for preparing a high nickel anode material according to claim 12, wherein the temperature of the mixture is 40 ℃ to 60 ℃ in the process of the first coprecipitation reaction and/or the second coprecipitation reaction.
17. A positive electrode sheet comprising the high nickel positive electrode material according to any one of claims 1 to 7.
18. A lithium ion battery comprising the positive electrode sheet of claim 17.
19. A powered device comprising the lithium-ion battery of claim 18.
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