CN111180690B - Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof - Google Patents
Modified nickel-cobalt lithium aluminate anode material and preparation method and application thereof Download PDFInfo
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- CN111180690B CN111180690B CN201911395194.9A CN201911395194A CN111180690B CN 111180690 B CN111180690 B CN 111180690B CN 201911395194 A CN201911395194 A CN 201911395194A CN 111180690 B CN111180690 B CN 111180690B
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- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical class [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000007774 positive electrode material Substances 0.000 claims abstract description 64
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 35
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 34
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 229910052788 barium Inorganic materials 0.000 claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 88
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 65
- 238000005245 sintering Methods 0.000 claims description 62
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 58
- 238000000576 coating method Methods 0.000 claims description 57
- 239000011248 coating agent Substances 0.000 claims description 56
- 239000011572 manganese Substances 0.000 claims description 53
- 239000003513 alkali Substances 0.000 claims description 52
- 239000010406 cathode material Substances 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000008139 complexing agent Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000011858 nanopowder Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- -1 aluminum compound Chemical class 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 15
- 239000011575 calcium Substances 0.000 description 32
- 239000011777 magnesium Substances 0.000 description 29
- 239000010936 titanium Substances 0.000 description 16
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 11
- 238000011160 research Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 208000028659 discharge Diseases 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a modified nickel cobalt lithium aluminate anode material and a preparation method and application thereof. The positive electrode material has a composition represented by general formula I: li1+αNixCoyAlzMdGePfO2The formula I is shown in the specification, wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, Y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04, and M is selected from at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; wherein d, e and f are not 0 at the same time. The positive electrode material has high cycle rate performance and low surface residual Li, and the battery prepared from the positive electrode material has good cycle stability, thermal stability and safety performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a modified nickel cobalt lithium aluminate anode material and a preparation method and application thereof.
Background
The lithium ion battery is a green recyclable energy source, has the advantages of high voltage, high energy density, good cycle performance, high safety, low self-discharge, no memory effect and the like, and is widely applied to the fields of 3C electronic equipment, space power supplies, portable electric tools, weaponry and the like; meanwhile, lithium ion batteries are also widely applied in the fields of energy storage equipment, electric automobiles, electric buses and the like.
In recent years, with the rapid rise and popularization of tesla electric vehicles, electric vehicles of various brands have started to partially replace fuel vehicles. The 2016-2020 planning of China proposes that the energy density of the lithium ion battery for the vehicle needs to reach 300Wh/kg, and countries such as Japan, America, Germany and the like also successively propose a series of measures such as stopping producing fuel vehicles in the year of 2025-. However, with the popularization of lithium ion batteries, the safety performance and the driving range of the lithium ion batteries have become the focus of wide attention, and how to improve the energy density of the lithium ion batteries and simultaneously improve the safety performance and the cycle performance of the lithium ion batteries becomes a key problem to be solved urgently.
At present, the ternary material which is widely used and commercialized is mainly nickel cobalt lithium manganate (Ni: Co: Mn: 3:3 or 5:2:3), the energy density of which is only about 200Wh/kg, and the requirement of new energy automobiles on high energy density cannot be met. The most direct and effective method for improving the energy density of the ternary material is to improve the content of nickel element in the material, namely to more than 80%, and nickel cobalt lithium aluminate (NCA) is the earliest high-nickel ternary material used in vehicle-mounted power batteries. The biggest characteristic of the NCA which is different from other ternary materials is that the aluminum element has the function of stabilizing the crystal structure, can improve the stability of the NCA material, but has no electrochemical activity and can reduce the specific discharge capacity of the material. In addition, the high-nickel NCA material has strong sensitivity to the environment, high surface residual Li and serious problems of gas generation and bulging in the circulation process, and how to reduce the surface residual Li and improve the circulation stability and the thermal stability of the NCA material on the premise of not influencing the specific discharge capacity of the material is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to overcome the problems of poor cycling stability and thermal stability of a high-nickel material for a battery and high surface residual Li in the prior art, and provides a doped and coated modified nickel-cobalt lithium aluminate anode material, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a modified nickel cobalt lithium aluminate cathode material, wherein the cathode material has a composition represented by general formula I:
Li1+αNixCoyAlzMdGePfO2the compound of the formula I is shown in the specification,
wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04,
m is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; wherein d, e and f are not 0 at the same time.
The second aspect of the invention provides a preparation method of a modified nickel cobalt lithium aluminate cathode material, wherein the method comprises the following steps:
(1) preparing a mixed salt solution from a nickel salt, a cobalt salt and optionally an aluminum salt; respectively preparing a compound containing a doping element M, alkali and a complexing agent into solutions; respectively introducing the mixed salt solution, the alkali liquor, the complexing agent solution and the compound solution containing the doping element M into a reaction kettle, carrying out a first reaction, and separating, washing, drying and screening the obtained slurry to obtain a precursor of the positive electrode material;
(2) mixing the positive electrode material precursor obtained in the step (1), a lithium source, a compound containing a doping element G and an optional aluminum compound, and performing first sintering on the mixed material in an oxygen atmosphere to obtain a first sintered material;
(3) carrying out first stirring and mixing on the first sintering material obtained in the step (2) and first alkali liquor Y1, adding a coating solution containing a P element and second alkali liquor Y2, carrying out coating reaction, continuing carrying out second stirring, filtering and drying to obtain a coating material;
(4) in an oxygen atmosphere, carrying out secondary sintering on the coating material obtained in the step (3) to obtain a second sintered material;
(5) sieving and removing iron from the second sintering material obtained in the step (4) to obtain a positive electrode material;
preferably, the positive electrode material has a composition represented by general formula I:
Li1+αNixCoyAlzMdGePfO2the compound of the formula I is shown in the specification,
wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04,
m is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; and d, e and f are not simultaneously 0.
The third aspect of the invention provides a modified nickel cobalt lithium aluminate cathode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the modified nickel cobalt lithium aluminate cathode material in a lithium ion battery.
Through the technical scheme, the doped and coated modified nickel-cobalt lithium aluminate cathode material and the preparation method and application thereof provided by the invention have the following beneficial technical effects:
(1) the nickel cobalt lithium aluminate anode material provided by the invention has high cycle rate performance and low surface residual Li, and the battery prepared from the nickel cobalt lithium aluminate anode material has good cycle stability, thermal stability and safety performance.
(2) In the preparation method of the nickel cobalt lithium aluminate anode material, the Al element and the doping element can be introduced in the precursor preparation stage or the primary sintering stage, and can be adjusted according to the state of the doping element and the doping effect to be achieved, so that the flexibility is higher.
(2) According to the preparation method of the nickel-cobalt lithium aluminate anode material, the high-nickel anode material is subjected to water washing and coating processes in the low-concentration alkali liquor, the isoionic effect of the low-concentration alkali liquor can inhibit the precipitation of crystal lattice Li in the material while residual Li on the surface is washed away, the problem of lithium deficiency caused by prolonging the coating time and improving the coating uniformity during discharge treatment can be effectively solved, the process flow can be simplified, and uniform coating can be realized.
(3) In the preparation method of the nickel-cobalt lithium aluminate anode material, the first sintering material is subjected to coating reaction to obtain a coating material with a layer of uniform low nickel or no nickel on the surface, and the coating material is O2And in the atmosphere, the reaction with residual Li on the surface can be further carried out through high-temperature secondary sintering, and the formed coating layer has better Li ion transmission characteristic, so that the capacity and rate capability of the material can be remarkably improved.
(4) The raw materials used in the invention are common raw materials in the market, have rich reserves and low price, and are suitable for large-scale industrial production.
Drawings
FIG. 1 is an SEM photograph at a magnification of 10K of a sample sampled at step S5 in example 1;
FIG. 2 is an SEM photograph at a magnification of 10K of a sample sampled at step S5 in comparative example 2;
fig. 3 is a capacity-rate diagram of the positive electrode materials described in example 1 and comparative example 2;
fig. 4 is a graph of capacity versus cycle number for the positive electrode materials described in example 1 and comparative example 2;
fig. 5 is a DSC diagram of the positive electrode materials described in example 3 and comparative example 4.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a modified nickel cobalt lithium aluminate cathode material, wherein the cathode material has a composition shown in a general formula I:
Li1+αNixCoyAlzMdGePfO2the compound of the formula I is shown in the specification,
wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04,
m is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; wherein d, e and f are not 0 at the same time.
In the invention, the doping element is introduced into the traditional nickel cobalt lithium aluminate anode material, so that the provided nickel cobalt lithium aluminate anode material has a more stable interlayer structure and higher thermal stability, and the doping element can also increase the electrical conductivity and Li ion migration rate of the material and improve the cycling stability of the material in the charging and discharging process.
Further, the inventors have studied and found that when M is selected from at least one of Ca, Sr, Ba, Zr, Y, Mg, Ti and Mn, preferably at least one of Ga, Mg, Zr and Mn, the provided positive electrode material has more excellent performance.
Further, the inventors have studied and found that when the G is selected from at least one of Sr, Ba, Zr, Y, Ti, B and W, preferably at least one of Zr, Y, Ti, B and Sr, the provided positive electrode material has more excellent performance.
Further, the inventors have studied and found that when P is selected from at least one of Ni, Co, Al, Nb, W, and Mn, preferably at least one of Ni, Co, Nb, and Mn, the provided positive electrode material has more excellent properties.
According to the invention, furthermore, M and G are identical and 0. ltoreq. d + e. ltoreq.0.005.
The second aspect of the invention provides a preparation method of a modified nickel cobalt lithium aluminate cathode material, wherein the method comprises the following steps:
(1) preparing a mixed salt solution of a nickel salt, a cobalt salt and optionally an aluminium salt in a molar ratio x: y: z; respectively preparing a compound containing a doping element M, alkali and a complexing agent into solutions; respectively introducing the mixed salt solution, the alkali liquor, the complexing agent solution and the compound solution containing the doping element M into a reaction kettle, carrying out a first reaction, and separating, washing, drying and screening the obtained slurry to obtain a precursor of the positive electrode material;
(2) mixing the positive electrode material precursor obtained in the step (1), a lithium source, a compound containing a doping element G and an optional aluminum compound, and performing first sintering on the mixed material in an oxygen atmosphere to obtain a first sintered material;
(3) carrying out first stirring and mixing on the first sintering material obtained in the step (2) and first alkali liquor Y1, adding a coating solution containing a P element and second alkali liquor Y2, carrying out coating reaction, continuing carrying out second stirring, filtering and drying to obtain a coating material;
(4) in an oxygen atmosphere, carrying out secondary sintering on the coating material obtained in the step (3) to obtain a second sintered material;
(5) and (5) sieving and removing iron from the second sintering material obtained in the step (4) to obtain the anode material.
In the invention, the molar ratio of the nickel salt, the cobalt salt and the aluminum salt in the mixed salt solution is x: y: z.
In the invention, the doping element is added in the step (1) and/or the step (2), so that the stability of the bulk phase structure of the nickel-cobalt lithium aluminate anode material can be obviously improved. Meanwhile, after the first sintering material obtained in the step (2) is subjected to water washing and coating treatment, residual Li on the surface of the positive electrode material can be reduced to a certain extent, in the second sintering treatment, a coating containing a P element on the surface of the particles can react with the residual Li on the surface, the residual Li content on the surface of the particles is further reduced, and a P-rich low-Ni coating layer can be formed on the surface of the particles, so that the rate capability of the prepared positive electrode material is improved, and the battery prepared from the positive electrode material has good cycle stability and safety performance.
According to the invention, the positive electrode material has a composition represented by general formula I:
Li1+αNixCoyAlzMdGePfO2the compound of the formula I is shown in the specification,
wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04,
m is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; and d, e and f are not simultaneously 0.
Furthermore, the inventor researches and discovers that when the M is selected from at least one of Ca, Sr, Ba, Zr, Y, Mg, Ti and Mn, and preferably at least one of Ga, Mg, Zr and Mn, the nickel-cobalt lithium aluminate cathode material provided by the invention has more excellent performance.
Furthermore, the inventor researches and discovers that when the G is selected from at least one of Sr, Ba, Zr, Y, Ti, B and W, preferably at least one of Zr, Y, Ti, B and Sr, the nickel-cobalt lithium aluminate positive electrode material provided by the invention has more excellent performance.
Furthermore, the inventor researches and discovers that when the P is selected from at least one of Ni, Co, Al, Nb, W and Mn, and preferably at least one of Ni, Co, Nb and Mn, the nickel-cobalt lithium aluminate cathode material provided by the invention has more excellent performance.
According to the invention, preferably, M and G are identical and 0. ltoreq. d + e. ltoreq.0.005.
According to the invention, in the step (1), the concentrations of the mixed salt solution, the compound solution containing the doping element M, the alkali solution and the complexing agent solution are respectively 0.5-5mol/L, 0.05-0.5mol/L, 1-11mol/L and 1-15 mol/L.
According to the invention, the concentrations of the mixed salt solution, the compound solution containing the doping element M, the alkali solution and the complexing agent solution are respectively 1-3mol/L, 0.1-0.3mol/L, 2-10mol/L and 2-13 mol/L.
According to the invention, the addition amount of the complexing agent solution enables the concentration of the complexing agent in the reaction system to be 8-11 g/L.
According to the invention, in the step (1), the nickel salt, the cobalt salt and the aluminum salt are at least one of sulfate, chloride, nitrate and acetate of nickel, cobalt and aluminum respectively.
According to the invention, the base is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
According to the invention, the complexing agent is at least one of salicylic acid, ammonium nitrate, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid.
According to the present invention, the compound containing the doping element M is at least one of a soluble salt containing the doping element M, an oxide nano powder, a hydroxide nano powder, an oxyhydroxide nano powder, and a sol.
According to the invention, the doping element M is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn.
In the invention, the inventor researches and discovers that after the nickel-cobalt lithium aluminate anode material is doped with the doping elements limited by the invention, the layered structure can be more complete, the cycle performance and the thermal stability of the material can be improved, the corrosion of electrolyte to the anode material in the charging and discharging process can be effectively avoided, and the cycle performance can be improved.
According to the invention, the conditions of the first reaction comprise: the reaction temperature is 30-90 ℃, and preferably 40-70 ℃; the reaction pH is 9 to 13.5, preferably 10.6 to 12.5.
According to the invention, the conditions of drying include: 100-200 ℃, preferably 120-160 ℃; the drying time is 1-10h, preferably 3-6 h.
According to the present invention, in step (1), the positive electrode material precursor has a composition represented by general formula II:
Nix1Coy1Alz1Md1(OH)2+z1formula II
Wherein x1 is more than or equal to 0.80 and less than or equal to 0.99, y1 is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0 and less than or equal to 0.06, and d is more than or equal to 0 and less than or equal to 0.005.
According to the present invention, in the step (2), the lithium source is at least one selected from the group consisting of lithium hydroxide, lithium carbonate and lithium nitrate.
According to the present invention, the compound containing the doping element G is at least one of oxide nanopowder, hydroxide nanopowder and oxyhydroxide nanopowder containing the doping element G.
Further, the doping element G is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, W and Mn.
According to the invention, in the step (2), the doping element G-containing compound is added according to the molar ratio of G (Ni + Co + Al + M + G) of 0-0.004.
According to the invention, in step (2), the aluminum compound is added in an amount such that the molar ratio of Al (Ni + Co + Al + M + G) is 0 to 0.06.
According to the invention, in the step (2), the lithium source is added in a molar ratio of Li (Ni + Co + Al + M + G) of 1.01-1.10.
According to the invention, the conditions of the first sintering comprise: the sintering temperature is 600-900 ℃, preferably 650-800 ℃; the sintering time is 6-20h, preferably 8-15 h.
According to the invention, the first sintering material has a composition represented by general formula III:
Li1+α1Nix2Coy2Alz2Md2Ge1O2formula III
Wherein alpha 1 is more than or equal to 0 and less than or equal to 0.1; x2 is more than or equal to 0.80 and less than or equal to 0.99, y2 is more than or equal to 0.01 and less than or equal to 0.20, z2 is more than or equal to 0.01 and less than or equal to 0.06, d2 is more than or equal to 0 and less than or equal to 0.005, and e1 is more than or equal to 0 and less than or equal to 0.004.
According to the invention, in step (3), the first lye Y1 is selected from NaOH and/or LiOH.
In the invention, a first alkali solution Y1 is mixed with a first sintering material, and a coating solution containing P element is added to carry out coating reaction with a second alkali solution Y2, wherein the first alkali solution Y1 replaces H2The O solution can inhibit the precipitation of Li in crystal lattices of the first sintering material to a certain extent, is beneficial to prolonging the coating time, reduces the liquid inlet speed of the second alkali solution Y2 and the coating solution, and ensures the coating uniformity.
According to the invention, the concentration of the first lye Y1 is between 0.05 and 1 mol/L.
In the invention, the inventor researches and discovers that the alkali liquor with lower concentration, in particular the alkali liquor with the concentration of 0.05-1mol/L is used as the first alkali liquor Y1, the precipitation of Li in crystal lattices can be further inhibited, and the obtained cathode material has more excellent performance.
Furthermore, the concentration of the first alkali liquor Y1 is 0.1-0.6 mol/L.
Meanwhile, through extensive research by the inventors, it is shown that when the weight ratio of the first sintering material to the first alkali solution Y1 is 6:2 to 1:5, the prepared cathode material can have higher capacity and better cycle performance.
Furthermore, the dosage ratio of the first sintering material to the first alkali liquor is 5:2-1: 3.
According to the invention, the first mixing time is between 0.1 and 8min, preferably between 0.5 and 5 min.
According to the invention, the second lye Y2 is selected from at least one of ammonia, NaOH, LiOH and KOH, more preferably NaOH and/or LiOH.
According to the invention, the concentration of the second lye Y2 is 1-10mol/L, preferably 2-8 mol/L.
According to the present invention, the coating solution containing the P element is at least one of a soluble salt, an oxide nano powder and a sol containing the P element.
According to the invention, the first sintering material is coated through wet coprecipitation, so that a coating layer containing a P element is formed on the surface of the prepared anode material, and the coating layer has ionic and electronic conductivity, so that the rate capability of the prepared anode material can be obviously improved. Meanwhile, the coating layer can obviously improve the stability of the anode material, effectively avoid the corrosion of the electrolyte to the anode material, and further enable the battery prepared from the coating layer to have good cycle stability and safety performance.
Further, the P element is at least one of Ni, Co, Al, Nb, W and Mn.
According to the invention, the concentration of the coating solution is between 0.1 and 3mol/L, preferably between 0.5 and 2 mol/L.
According to the invention, the coating solution containing the P element is added according to the molar ratio of P (Ni + Co + Al + M + G) of 0-0.04.
According to the invention, the coating reaction time is 4-60min, preferably 5-30 min.
According to the invention, the coating solution and the second alkaline solution Y2 are added by means of a peristaltic pump and/or a metering pump.
According to the invention, the second stirring time is between 0 and 15min, preferably between 1 and 10 min.
According to the present invention, the drying conditions include: the drying temperature is 100-200 ℃, preferably 120-160 ℃; the drying time is 1-10h, preferably 2-6 h.
According to the invention, the coating solution containing the P element is Co salt and/or Mn salt;
in the invention, the inventor researches and discovers that when the coating solution containing the P element is a Co salt and/or a Mn salt, the coating formed by the reaction with the second alkali solution Y2 has better effect on reducing surface alkaline impurities and improving electrochemical performance after secondary sintering. The surface rich in Co can improve the conductivity and rate performance of the lithium ion, and the surface rich in Mn can improve the safety of the high-nickel material.
According to the invention, the Co salt is selected from at least one of cobalt sulfate, cobalt nitrate, cobalt carbonate and cobalt fluoride.
According to the invention, the Co salt is added in an amount of Co: the molar ratio of the first sintering material is 0.001-0.03: 1.
In the present invention, in order to further improve the rate capability and stability of the positive electrode material, the inventors have studied the addition amount of the Co salt, and the study shows that when the addition amount of the Co salt is in accordance with the ratio of Co: the molar ratio of the first sintering material is 0.001-0.03:1, the obtained coating layer is in nanometer level, and the residual alkali of the sintered sample is in lower level. The inventor researches and discovers that when the coating amount is too large, lattice Li is easy to be lost; when the coating amount is too small, the effect of improving the performance is low, and therefore the coating amount must be controlled within a certain range.
According to the invention, the Mn salt is selected from at least one of manganese sulphate, manganese nitrate and manganese chloride.
According to the invention, the Mn salt is added in an amount of Mn: the molar ratio of the first sintering material is 0.001-0.02: 1.
In the present invention, in order to further improve the rate capability and stability of the cathode material, the inventors have studied the addition amount of the Co salt, and the study shows that when the addition amount of the Mn salt is in accordance with the ratio of Mn: the molar ratio of the first sintering material is 0.001-0.02:1, the obtained coating layer is more stable, and the capacity of the positive electrode material is not influenced.
According to the invention, in the step (4), the conditions of the second sintering include: the sintering temperature is 200-800 ℃, and preferably 300-700 ℃; the sintering time is 3-12h, preferably 5-10 h.
According to the invention, the method further comprises the step of carrying out heat treatment on the positive electrode precursor obtained in the step (1) before the step (2) to obtain a positive electrode material precursor II.
In the invention, the inventor researches and discovers that the cycle stability, the thermal stability and the safety performance of the prepared precursor II of the cathode material can be obviously improved after the precursor II of the cathode material obtained in the step (1) is subjected to heat treatment before the step (2), so that the battery prepared by the precursor II of the cathode material has more excellent performance.
Still further, the conditions of the heat treatment include: the heat treatment temperature is 300-700 ℃, and the heat treatment time is 2-10h, so that the obtained precursor II of the positive electrode material has improved cycle stability, heat stability and safety performance.
Preferably, the heat treatment temperature is 400-600 ℃; the heat treatment time is 3-8 h.
According to the invention, the heat treatment is carried out in an oxygen and/or air atmosphere.
According to the invention, the positive electrode material precursor II has a composition represented by a general formula IV:
Nix1Coy1Alz1Md1O1+z1/2formula IV
Wherein x1 is more than or equal to 0.80 and less than or equal to 0.99, y1 is more than or equal to 0.01 and less than or equal to 0.20, z1 is more than or equal to 0 and less than or equal to 0.06, and d1 is more than or equal to 0 and less than or equal to 0.005.
The third aspect of the invention provides a modified nickel cobalt lithium aluminate cathode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the modified nickel cobalt lithium aluminate cathode material in a lithium ion battery.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
button cells were made as follows:
firstly, mixing a composite nickel-cobalt-manganese multi-element positive electrode active substance, acetylene black and polyvinylidene fluoride (PVDF) for a non-aqueous electrolyte secondary battery according to a mass ratio of 95: 2.5%, coating the mixture on an aluminum foil, drying the mixture, performing press forming by using 100MPa pressure to form a positive electrode piece with the diameter of 12mm and the thickness of 120 mu m, and then putting the positive electrode piece into a vacuum drying box to dry for 12 hours at 120 ℃.
The negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film having a thickness of 25 μm; the electrolyte solution used was a mixture of 1mol/L of LiPF6, Ethylene Carbonate (EC) and diethyl carbonate (DEC).
Assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5ppm, and taking the cell as an unactivated cell.
The performance evaluation on the button cells made is defined as follows:
and (3) standing for 2h after the button cell is manufactured, charging to a cut-off voltage of 4.3V in a mode that the current density of the anode is 0.1C after the open-circuit voltage is stabilized, then charging for 30min at a constant voltage, then discharging to the cut-off voltage of 3.0V at the same current density, and performing 1 time again in the same mode to obtain the activated cell.
Capacity test of the battery: testing the first discharge capacity of the battery with the current density of the anode of 0.1C at 25 ℃ and the voltage interval of 3.0-4.3V, wherein the capacity of the battery is shown in Table 2;
the rate performance was tested as follows: using an activated battery, charging at a voltage interval of 3.0-4.3V at 25 ℃ and a current density of 0.1C, and discharging at current densities of 0.1C, 0.2C, 0.33C, 0.5C, 1C and 2C respectively to test the rate capability of the battery, wherein the rate capability of the battery is shown in Table 3;
the cycle performance was tested as follows: the activated battery is used, the capacity retention rate of the material is examined by cycling for 80 times at the current density of 1C at 45 ℃ and the voltage interval of 3.0-4.3V, and the cycling performance of the battery is shown in Table 2;
the following definitions are defined with respect to the evaluation of the residual alkali and thermal stability of the positive electrode material:
surface residual alkali was tested as follows: adding 5g of sample into 95ml of pure water, sealing and stirring for 5min, then carrying out solid-liquid separation, weighing the weight of the filtrate, testing the contents of lithium carbonate and lithium hydroxide through acid-base titration, and measuring the contents of residual alkali on the surface in the primary sintered material and the positive material according to the contents of lithium carbonate and lithium hydroxide in the primary sintered material and the positive material as shown in table 1;
the thermal stability was tested as follows: the thermal decomposition temperature of the cathode material is adopted to represent the thermal stability of the cathode material, the thermal decomposition temperature of the cathode material is tested by a DSC thermal analysis method, and the thermal decomposition temperature of the cathode material is shown in Table 2;
the surface topography of the material was characterized using a Scanning Electron Microscope (SEM).
Example 1
S1, dissolving nickel sulfate and cobalt sulfate according to the metal molar ratio of 0.95:0.05 to obtain a mixed salt solution with the concentration of 2mol/L, dissolving magnesium nitrate into a magnesium nitrate solution with the concentration of 0.1mol/L, dissolving calcium nitrate into a calcium nitrate solution with the concentration of 0.1mol/L, dissolving sodium hydroxide into an alkali solution with the concentration of 8mol/L, and dissolving ammonia water into a complexing agent solution with the concentration of 6 mol/L.
S2, adding a mixed salt solution, a magnesium nitrate solution, a calcium nitrate solution, an alkali solution and a complexing agent solution into a reaction kettle in a co-current manner for reaction, wherein the liquid inlet flow rate of the mixed salt solution is 400mL/h, the liquid inlet flow rate of the magnesium nitrate solution and the calcium nitrate solution is 16mL/h, the reaction pH is controlled to be 11.5-11.7, the reaction temperature is 60 ℃, the concentration of ammonia in a reaction system is controlled to be 8-11g/L, when the reaction is finished, the liquid inlet is stopped, the temperature and the stirring speed of the reaction solution are kept unchanged, the reaction solution is continuously stirred for 10min, then the Mg and Ca doped nickel-cobalt hydroxide slurry is subjected to solid-liquid separation and washing, heat treatment is carried out for 5h in an oxygen atmosphere at 500 ℃, and the spherical Ni is obtained after sieving0.9462Co0.0498Mg0.0020Ca0.0020And (3) O oxide precursor.
S3, mixing lithium hydroxide and Ni0.9462Co0.0498Mg0.0020Ca0.0020Mixing an O precursor and alumina uniformly in a high-speed mixer according to the molar ratio of 1.05:0.97:0.03, roasting the mixed material in an oxygen atmosphere furnace at the temperature rise rate of 5 ℃/min to 730 ℃ for 12h, and naturally cooling to obtain Li1.05Ni0.9179Co0.0483Al0.030Mg0.0019Ca0.0019O2。
S4, preparing a coating solution: preparing cobalt sulfate and manganese sulfate solutions with the concentration of 2mol/L, preparing 8mol/L NaOH alkaline solution Y2 and 0.1mol/L NaOH alkaline solution Y1, wherein during coating, the molar ratio of Co to the first sintering material is 0.01:1, the molar ratio of Mn to the first sintering material is 0.005:1, and the molar ratio of the second alkaline solution Y2 to the total mol of the Co solution and the Mn solution is 2: 1.
S5, crushing the material obtained by primary roasting, adding the crushed material into 0.1mol/L NaOH solution Y1, keeping the mass ratio of the material to 0.1mol/L NaOH alkali liquor at 2:1, stirring for 3min, then simultaneously dripping two solutions of cobalt sulfate and manganese sulfate and 8mol/L alkali liquor Y2 by using a peristaltic pump, wherein the dripping time is 10min, after the dripping is finished, continuing to stir for 5min, then filtering, drying at 120 ℃, drying for 5h, sampling, and representing the surface appearance of the sample after the coating reaction as shown in figure 1.
And S6, carrying out secondary sintering treatment on the dried material in an oxygen atmosphere, wherein the heating rate is 3 ℃/min, the temperature is 700 ℃, and the time is 8 h. Sieving the material subjected to secondary sintering for removing iron to obtain a nickel cobalt lithium aluminate anode material A1: li1.035Ni0.9043Co0.0574Al0.0296Mn0.0049Mg0.0019Ca0.0019O2。
Example 2
A positive electrode material was prepared in the same manner as in example 1, except that: in the step S1, dissolving nickel sulfate, cobalt sulfate and aluminum sulfate according to the metal molar ratio of 0.92:0.05:0.03 to obtain a mixed salt solution with the concentration of 2mol/L, and finally obtaining spherical Ni0.9163Co0.0498Al0.0299Mg0.0020Ca0.0020And (3) O oxide precursor.
Lithium hydroxide and Ni in step S30.9163Co0.0498Al0.0299Mg0.0020Ca0.0020Mixing the O precursor uniformly in a high-speed mixer according to the molar ratio of 1.05:1 to finally obtain Li1.05Ni0.9163Co0.0498Al0.0299Mg0.0020Ca0.0020O2。
The other steps were identical to those of example 1, and a cathode material a2 was finally obtained: li1.035Ni0.9027Co0.0589Al0.029 4Mn0.0049Mg0.0020Ca0.0020O2。
Example 3
Method according to example 1Preparing a positive electrode material except that: in step S3, lithium hydroxide and Ni0.9462Co0.0498Mg0.0020Ca0.0020Mixing the O precursor, the alumina and the zirconia uniformly in a high-speed mixer according to the molar ratio of 1.05:0.969:0.03:0.001, and sintering for the first time to obtain Li1.05Ni0.9169Co0.0483Al0.030Mg0.0019Ca0.0019Zr0.001O2。
The other steps were identical to those of example 1, and a cathode material a3 was finally obtained: li1.035Ni0.9033Co0.0574Al0.0296Mg0.0019Ca0.0019Zr0.001Mn0.0049O2。
Example 4
A positive electrode material was prepared according to the method of example 1, except that: in step S2, the Mg and Ca doped nickel cobalt hydroxide slurry is dried for 5h at 120 ℃ after being subjected to solid-liquid separation and washing to obtain spherical Ni0.9462Co0.0498Mg0.0020Ca0.0020(OH)2A hydroxide precursor.
The other steps were identical to those of example 1, and a cathode material a4 was finally obtained: li1.035Ni0.9043Co0.0574Al0.029 6Mn0.0049Mg0.0019Ca0.0019O2。
Example 5
A positive electrode material was prepared according to the method of example 1, except that: in step S1, magnesium nitrate and calcium nitrate are replaced by manganese nitrate, and the concentration of the manganese nitrate solution is 0.2mol/L, and finally spherical Ni is obtained0.9462Co0.0498Mn0.0040And (3) O oxide precursor.
The other steps were identical to those of example 1, and a cathode material a5 was finally obtained: li1.035Ni0.9042Co0.0573Al0.0296Mn0.0089O2。
Example 6
A positive electrode material was prepared in the same manner as in example 1, except that: in step S4, 0.1mol/L LiOH solution is used as alkaline solution Y1.
The other steps were identical to those of example 1, and a cathode material a6 was finally obtained: li1.035Ni0.9043Co0.0574Al0.029 6Mn0.0049Mg0.0019Ca0.0019O2。
Example 7
A positive electrode material was prepared in the same manner as in example 5, except that: in step S3, lithium hydroxide and Ni0.9462Co0.0498Mn0.0040Uniformly mixing O, alumina and zirconia precursors in a molar ratio of 1.05:0.969:0.03:0.001 in a high-speed mixer to obtain Li1.05Ni0.9169Co0.0483Al0.030Mn0.0039Al0.003Zr0.001O2。
The other steps were identical to those of example 5, and a cathode material a7 was finally obtained: li1.035Ni0.9033Co0.0589Al0.0296Mn0.0038Zr0.0095O2。
Example 8
A positive electrode material was prepared in the same manner as in example 1, except that: in step S4, the prepared coating solution is only 2mol/L cobalt sulfate solution, the molar ratio of Co to the first sintering material is 0.015:1, the molar ratio of the second alkaline solution Y2 to the Co solution is 2:1, and in step S5, the solution added by a peristaltic pump is the cobalt sulfate solution and the second alkaline solution Y2 of 8 mol/L.
The other steps were identical to those of example 1, and a cathode material A8 was finally obtained: li1.035Ni0.9043Co0.0623Al0.0296Mg0.0019Ca0.0019O2
Comparative example 1
A positive electrode material was prepared in the same manner as in example 1, except that: in step S5, H is used2O replaces the 0.1mol/L NaOH solution Y1.
The other steps were identical to those of example 1, and a cathode material D1 was finally obtained: li1.035Ni0.9043Co0.0574Al0.029 6Mn0.0049Mg0.0019Ca0.0019O2。
Comparative example 2
A positive electrode material was prepared by the method of example 1, except that: in step S4, only 0.1mol/L NaOH lye Y1 is prepared.
In the step S5, the material obtained by primary roasting is crushed, the crushed material is added into 0.1mol/L NaOH solution Y1, the mass ratio of the material to 0.1mol/L NaOH alkali solution is kept at 2:1, after stirring for 15min, filtering and drying at 120 ℃ are carried out, the drying time is 5h, sampling is carried out, and the surface appearance of a test sample is shown in figure 2.
The other steps were identical to those of example 1, and a cathode material D2 was finally obtained: li1.05Ni0.9179Co0.0483Al0.030Mg0.0019Ca0.0019O2。
Comparative example 3
A positive electrode material was prepared according to the method of example 2, except that: in step S1, magnesium nitrate solution and calcium nitrate solution are not added, and spherical Ni is obtained0.92Co0.05Al0.03And (3) O oxide precursor. .
The other steps were identical to those of example 1, and a cathode material D3 was finally obtained: li1.035Ni0.9064Co0.0591Al0.029 6Mn0.0049O2。
Comparative example 4
A positive electrode material was prepared according to the method of example 1, except that: in step S1, magnesium nitrate solution and calcium nitrate solution are not added, and spherical Ni is obtained0.95Co0.05An O oxide precursor;
the other steps are consistent with those of the example 1, and finally the cathode material is obtained, namely the cathode material D4: li1.035Ni0.9087Co0.0577Al0.0296Mn0.0049O2。
TABLE 1
TABLE 2
TABLE 3
As can be seen from fig. 1 and 2, in example 1 and comparative example 2, after sampling in step S5, the morphology of the sample shows that the surface of the sample is uniformly coated in example 1 after coating treatment, while in comparative example 2, the surface of the sample is smooth and the primary particle boundary is clear.
As can be seen from table 2, the positive electrode material a1 provided in example 1 has higher capacity and better cycle performance than the positive electrode material D1 provided in comparative example 1, indicating that the low concentration of the first alkali solution Y1 helps to reduce lattice Li loss and prevent over-washing.
Further, example 6 using the LiOH solution as the first alkali solution Y1 provides a cathode material capable of not only preventing loss of lattice Li but also further improving the capacity and cycle performance of the cathode material.
From table 1 and fig. 3 and 4, it can be seen that the positive electrode material a1 provided in example 1 has lower contents of lithium carbonate and lithium hydroxide remaining on the surface of the positive electrode material than the positive electrode material D2 provided in comparative example 2, and the rate and cycle performance of the positive electrode material are significantly improved. This is probably because, in the preparation process of the positive electrode material a1, the coating layer is formed on the surface of the primary sintered material by coating the primary sintered material, and in the secondary sintering process, the coating layer can further react with the lithium carbonate and lithium hydroxide in the primary sintered material, thereby reducing the content of lithium carbonate and lithium hydroxide remaining on the surface of the positive electrode material. The low content of the alkaline impurities can effectively prevent the jelly problem during homogenate, reduce the difficulty of the high nickel material in the using process, and the formed active substance coating layer can improve the cycle and rate performance of the anode material.
Further, example 8, which selects a Co element alone as the P element for coating, provides a positive electrode material more excellent in rate performance, particularly, rate performance at 1C and 2C.
As can be seen from table 1 and fig. 5, the cycle performance and thermal stability of the cathode materials provided in examples 1 to 8 were improved as compared with those provided in comparative examples 3 to 4. The doping elements M and/or G are introduced into the cathode material, so that the stability of the interlayer structure of the cathode material can be improved, and the cycle performance and the thermal stability of the cathode material are further improved.
Furthermore, the cycle performance of the cathode material provided in example 7 is more excellent than that of the cathode material provided in example 5, which shows that the cycle performance of the cathode material can be further improved by simultaneously introducing the doping elements M and G compared with the case of introducing the doping element M alone.
Meanwhile, compared with example 5 in which the doping element M is manganese, when the doping element M is magnesium and calcium, the cycle performance and the thermal stability of the cathode material are more excellent, which further shows that the kind of the doping element has the same influence on the thermal stability and the cycle performance of the cathode material.
As can be seen from tables 1 to 3, the positive electrode material a4 provided in example 4, compared to the positive electrode material a1 provided in example 1, provided in example 4, has lower reactivity during lithiation than the corresponding oxide precursor in example 1 because the precursor material has not been subjected to high-temperature heat treatment, so that the lithium carbonate and lithium hydroxide remaining on the surface of the primary sintered material in example 4 are higher in content, and the capacity of the positive electrode material is reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A modified nickel cobalt lithium aluminate positive electrode material, wherein the positive electrode material has a composition represented by formula I:
Li1+αNixCoyAlzMdGePfO2the compound of the formula I is shown in the specification,
wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04,
m is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; wherein d, e and f are not 0 at the same time;
the preparation method of the cathode material comprises the following steps:
(1) preparing a mixed salt solution from a nickel salt, a cobalt salt and optionally an aluminum salt; respectively preparing a compound containing a doping element M, alkali and a complexing agent into solutions; respectively introducing the mixed salt solution, the alkali liquor, the complexing agent solution and the compound solution containing the doping element M into a reaction kettle, carrying out a first reaction, and separating, washing, drying and screening the obtained slurry to obtain a precursor of the positive electrode material;
(2) mixing the positive electrode material precursor obtained in the step (1), a lithium source, a compound containing a doping element G and an optional aluminum compound, and performing first sintering on the mixed material in an oxygen atmosphere to obtain a first sintered material;
(3) carrying out first stirring and mixing on the first sintering material obtained in the step (2) and first alkali liquor Y1, adding a coating solution containing a P element and second alkali liquor Y2, carrying out coating reaction, continuing carrying out second stirring, filtering and drying to obtain a coating material;
(4) in an oxygen atmosphere, carrying out secondary sintering on the coating material obtained in the step (3) to obtain a second sintered material;
(5) and (5) sieving and removing iron from the second sintering material obtained in the step (4) to obtain the anode material.
2. The nickel cobalt lithium aluminate positive electrode material according to claim 1, wherein the M is selected from at least one of Ca, Sr, Ba, Zr, Y, Mg, Ti and Mn;
the G is selected from at least one of Sr, Ba, Zr, Y, Ti, B and W;
the P is at least one selected from Ni, Co, Al, Nb, W and Mn.
3. The nickel cobalt lithium aluminate cathode material of claim 2, wherein the M is selected from at least one of Ga, Mg, Zr, and Mn;
the G is selected from at least one of Zr, Y, Ti, B and Sr;
and the P is selected from at least one of Ni, Co, Nb and Mn.
4. The nickel cobalt lithium aluminate positive electrode material according to any one of claims 1 to 3, wherein M and G are the same and 0. ltoreq. d + e. ltoreq.0.005.
5. A preparation method of a modified nickel cobalt lithium aluminate cathode material comprises the following steps:
(1) preparing a mixed salt solution from a nickel salt, a cobalt salt and optionally an aluminum salt; respectively preparing a compound containing a doping element M, alkali and a complexing agent into solutions; respectively introducing the mixed salt solution, the alkali liquor, the complexing agent solution and the compound solution containing the doping element M into a reaction kettle, carrying out a first reaction, and separating, washing, drying and screening the obtained slurry to obtain a precursor of the positive electrode material;
(2) mixing the positive electrode material precursor obtained in the step (1), a lithium source, a compound containing a doping element G and an optional aluminum compound, and performing first sintering on the mixed material in an oxygen atmosphere to obtain a first sintered material;
(3) carrying out first stirring and mixing on the first sintering material obtained in the step (2) and first alkali liquor Y1, adding a coating solution containing a P element and second alkali liquor Y2, carrying out coating reaction, continuing carrying out second stirring, filtering and drying to obtain a coating material;
(4) in an oxygen atmosphere, carrying out secondary sintering on the coating material obtained in the step (3) to obtain a second sintered material;
(5) and (5) sieving and removing iron from the second sintering material obtained in the step (4) to obtain the anode material.
6. The production method according to claim 5, wherein the positive electrode material has a composition represented by general formula I:
Li1+αNixCoyAlzMdGePfO2the compound of the formula I is shown in the specification,
wherein alpha is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.80 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.20, z is more than or equal to 0.01 and less than or equal to 0.06, d is more than or equal to 0 and less than or equal to 0.005, e is more than or equal to 0 and less than or equal to 0.004, f is more than or equal to 0 and less than or equal to 0.04,
m is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn; g is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B and W; p is selected from at least one of Ni, Co, Al, Nb, W and Mn; and d, e and f are not simultaneously 0.
7. The production method according to claim 5 or 6, wherein the M is selected from at least one of Ca, Sr, Ba, Zr, Y, Mg, Ti, and Mn;
the G is selected from at least one of Sr, Ba, Zr, Y, Ti, B and W;
the P is at least one selected from Ni, Co, Al, Nb, W and Mn.
8. The production method according to claim 7, wherein the M is selected from at least one of Ga, Mg, Zr, and Mn;
the G is selected from at least one of Zr, Y, Ti, B and Sr;
and the P is selected from at least one of Ni, Co, Nb and Mn.
9. The method according to claim 6, wherein M and G are the same, and 0. ltoreq. d + e. ltoreq.0.005.
10. The production method according to claim 5 or 6, wherein in the step (1), the concentrations of the mixed salt solution, the solution of the compound containing the doping element M, the alkali solution, and the solution of the complexing agent are 0.5 to 5mol/L, 0.05 to 0.5mol/L, 1 to 11mol/L, and 1 to 15mol/L, respectively;
the addition amount of the complexing agent solution enables the concentration of the complexing agent in the reaction system to be 8-11 g/L;
in the step (1), the nickel salt, the cobalt salt and the aluminum salt are at least one of sulfate, chloride, nitrate and acetate of nickel, cobalt and aluminum respectively;
the alkali is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide;
the complexing agent is at least one of salicylic acid, ammonium nitrate, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid;
the compound containing the doping element M is at least one of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol containing the doping element M;
the conditions of the first reaction include: the reaction temperature is 30-90 ℃; the reaction pH is 9-13.5;
the drying conditions include: the drying temperature is 100-200 ℃; the drying time is 1-10 h;
in the step (1), the precursor of the positive electrode material has a composition shown in a general formula II:
Nix1Coy1Alz1Md1(OH)2+z1in the formula II, x1 is more than or equal to 0.80 and less than or equal to 0.99, y1 is more than or equal to 0.01 and less than or equal to 0.20, z1 is more than or equal to 0 and less than or equal to 0.06, and d1 is more than or equal to 0 and less than or equal to 0.005.
11. The preparation method according to claim 10, wherein the concentrations of the mixed salt solution, the compound solution containing the doping element M, the alkali solution, and the complexing agent solution are 1 to 3mol/L, 0.1 to 0.3mol/L, 2 to 10mol/L, and 2 to 13mol/L, respectively;
the doping element M is at least one of Ca, Sr, Ba, Zr, Y, Ce, Mg, Ti and Mn;
the conditions of the first reaction include: the reaction temperature is 40-70 ℃; the reaction pH is 10.6-12.5;
the drying conditions include: the drying temperature is 120-160 ℃; the drying time is 3-6 h.
12. The production method according to claim 5 or 6, wherein, in step (2), the lithium source is at least one selected from the group consisting of lithium hydroxide, lithium carbonate, and lithium nitrate;
the compound containing the doping element G is at least one of oxide nano powder, hydroxide nano powder and oxyhydroxide nano powder containing the doping element G;
in the step (2), the compound containing the doping element G is added according to the molar ratio of G (Ni + Co + Al + M + G) of 0-0.004;
in the step (2), the adding amount of the aluminum compound is 0-0.06 of the molar ratio of Al (Ni + Co + Al + M + G);
in the step (2), the addition amount of the lithium source is added according to the molar ratio of Li (Ni + Co + Al + M + G) of 1.01-1.10;
the conditions of the first sintering include: the sintering temperature is 600-900 ℃; the sintering time is 6-20 h;
the first sintering material has a composition represented by general formula III:
Li1+α1Nix2Coy2Alz2Md2Ge1O2formula III, wherein alpha 1 is more than or equal to 0 and less than or equal to 0.1; x2 is more than or equal to 0.80 and less than or equal to 0.99, y2 is more than or equal to 0.01 and less than or equal to 0.20, z2 is more than or equal to 0.01 and less than or equal to 0.06, d2 is more than or equal to 0 and less than or equal to 0.005, and e1 is more than or equal to 0 and less than or equal to 0.004.
13. The production method according to claim 12, wherein the doping element G is at least one of Ca, Sr, Ba, Zr, Y, La, Ce, Mg, Ti, B, and W;
the conditions of the first sintering include: the sintering temperature is 650-800 ℃; the sintering time is 8-15 h.
14. The preparation method according to claim 5 or 6, wherein in step (3), the first lye Y1 is selected from NaOH and/or LiOH;
the concentration of the first alkali liquor Y1 is 0.05-1 mol/L;
the weight ratio of the first sintering material to the first alkali liquor Y1 is 6:2-1: 5;
the first stirring and mixing time is 0.5-5 min;
the second alkali liquor Y2 is at least one selected from ammonia water, NaOH, LiOH and KOH;
the concentration of the second alkali liquor Y2 is 1-10 mol/L;
the coating solution containing the P element is at least one of soluble salt, oxide nano powder and sol containing the P element;
the concentration of the coating solution is 0.1-3 mol/L;
the adding amount of the coating solution containing the P element is added according to the molar ratio of P (Ni + Co + Al + M + G) of 0-0.04;
the coating reaction time is 4-60 min;
the coating solution and the second alkaline solution Y2 are added in a peristaltic pump and/or a metering pump;
the second stirring time is 0-15 min;
the drying conditions include: the drying temperature is 100-200 ℃; the drying time is 1-10 h.
15. The preparation method of claim 14, wherein the concentration of the first lye Y1 is 0.1-0.6 mol/L;
the weight ratio of the first sintering material to the first alkali liquor Y1 is 5:2-1: 3;
the first stirring and mixing time is 0.5-5 min;
the second alkali solution Y2 is NaOH and/or LiOH;
the concentration of the second alkali liquor Y2 is 2-8 mol/L;
the P element is at least one of Ni, Co, Al, Nb, W and Mn;
the concentration of the coating solution is 0.5-2 mol/L;
the coating reaction time is 5-30 min;
the second stirring time is 1-10 min;
the drying conditions include: the drying temperature is 120-160 ℃; the drying time is 2-6 h.
16. The production method according to claim 14, wherein the coating solution containing the P element is a Co salt and/or a Mn salt.
17. The production method according to claim 16, wherein the Co salt is selected from at least one of cobalt sulfate, cobalt nitrate, cobalt carbonate, and cobalt fluoride;
the Mn salt is selected from at least one of manganese sulfate, manganese nitrate and manganese chloride.
18. The production method according to claim 16 or 17, wherein the Co salt is added in an amount of Co: adding the first sintering material in a molar ratio of 0.001-0.03: 1;
the addition amount of the Mn salt is as follows: the molar ratio of the first sintering material is 0.001-0.02: 1.
19. The production method according to claim 5 or 6, wherein in step (4), the conditions of the second sintering include: the sintering temperature is 200-800 ℃; the sintering time is 3-12 h.
20. The production method according to claim 19, wherein in step (4), the conditions of the second sintering include: the sintering temperature is 300-700 ℃; the sintering time is 5-10 h.
21. The production method according to claim 5 or 6, wherein the method further comprises, before the step (2), subjecting the positive electrode precursor obtained in the step (1) to a heat treatment to obtain a positive electrode material precursor II.
22. The production method according to claim 21, wherein the conditions of the heat treatment include: the heat treatment temperature is 300-700 ℃; the heat treatment time is 2-10 h;
the heat treatment is carried out in an oxygen and/or air atmosphere;
the positive electrode material precursor II has a composition shown in a general formula IV:
Nix1Coy1Alz1Md1O1+z1/2the formula IV, wherein x1 is more than or equal to 0.80 and less than or equal to 0.99, y1 is more than or equal to 0.01 and less than or equal to 0.20, z1 is more than or equal to 0 and less than or equal to 0.06, and d1 is more than or equal to 0 and less than or equal to 0.005.
23. The production method according to claim 22, wherein the conditions of the heat treatment include: the heat treatment temperature is 400-600 ℃; the heat treatment time is 3-8 h.
24. A modified lithium nickel cobalt aluminate positive electrode material obtained by the production method according to any one of claims 5 to 23.
25. Use of a modified lithium nickel cobalt aluminate positive electrode material according to any one of claims 1 to 4 and 24 in a lithium ion battery.
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