CN114975965B - Core-shell type positive electrode material, and preparation method and application thereof - Google Patents
Core-shell type positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN114975965B CN114975965B CN202210750811.8A CN202210750811A CN114975965B CN 114975965 B CN114975965 B CN 114975965B CN 202210750811 A CN202210750811 A CN 202210750811A CN 114975965 B CN114975965 B CN 114975965B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 319
- 239000011258 core-shell material Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000010941 cobalt Substances 0.000 claims abstract description 77
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 77
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000011737 fluorine Substances 0.000 claims abstract description 70
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 70
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 41
- 239000011572 manganese Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 69
- 239000002245 particle Substances 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 29
- 239000010406 cathode material Substances 0.000 claims description 28
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 26
- 239000010405 anode material Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- -1 aluminum hexafluorophosphate Chemical compound 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910013733 LiCo Inorganic materials 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 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 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 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
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- 229910013716 LiNi Inorganic materials 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 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
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- MDKXFHZSHLHFLN-UHFFFAOYSA-N alumanylidynecobalt Chemical compound [Al].[Co] MDKXFHZSHLHFLN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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 field of lithium ion batteries, and discloses a core-shell type positive electrode material, and a preparation method and application thereof. The core of the positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, and has a composition shown in a formula I; li (Li) z Ni x Co y Mn 1‑x‑y‑w M w O 2 A formula I; the shell of the positive electrode material has a composition shown in formula II; liCo α Al 1‑α F β O 2‑β Formula II. The positive electrode material takes nickel cobalt manganese positive electrode material as a core and takes oxide containing cobalt, aluminum and fluorine as a shell, and can effectively reduce Li on the surface of the positive electrode material 2 CO 3 And the content of residual alkali such as LiOH, the mobility of the positive electrode material is improved, and the corrosion of HF generated in the battery cycle process on the surface of the positive electrode material is slowed down, so that the capacity, the rate capability and the cycle performance of the lithium ion battery containing the core-shell positive electrode material are obviously improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a core-shell type positive electrode material, and a preparation method and application thereof.
Background
In recent years, lithium ion batteries are widely favored in the fields of energy storage, power, intelligent wearing and the like due to the characteristics of high energy density, long service life, high efficiency and environmental protection. With the continuous improvement of life quality, the requirements of people on the performance of lithium batteries are also more severe. The positive electrode material is an important component of a lithium battery and plays a decisive role in the capacity and the service life of the battery.
The ternary nickel-cobalt-manganese material integrates three materials of lithium manganate, lithium cobaltate and lithium nickelateThe material has the advantages that the material is one of the most widely applied positive electrode materials at present. Due to Ni 2+ And Li (lithium) + The radius is close, and the nickel layer and the lithium layer in the nickel-cobalt-manganese ternary material are easy to mix and arrange, so that the multiplying power and the cycle performance are poor. In addition, li remaining on the surface of the positive electrode material 2 CO 3 And LiOH reacts with the electrolyte to form HF, which causes corrosion of the electrode, and hinders lithium ion transport, thereby disabling the battery.
At present, the conventional improvement modes are as follows: residual lithium on the surface of the positive electrode material can be reduced by adopting water washing (deionized water and organic solvent washing), but the water washing can lead lithium in the material to be lost, so that the cycle life of the material can be reduced; the method adopts a dry method to coat cobalt to reduce the consumption of residual alkali on the surface of the positive electrode material, but the cobalt on the surface of the material is still in a particle state and cannot be uniformly coated on the surface of particles, and the particle cobalt can increase the van der Waals force effect among particles to cause the fluidity to be poor, and the blocking phenomenon occurs in the production process of the positive electrode material, so that the production efficiency and the production rate are reduced.
Disclosure of Invention
The invention aims to overcome the defects of Li remained on the surface of the nickel-cobalt-manganese ternary positive electrode material in the prior art 2 CO 3 And LiOH and other residual alkali to cause the problem of deterioration of the multiplying power performance and the cycle performance of the positive electrode material, and provides a core-shell positive electrode material, a preparation method and application thereof, wherein the positive electrode material takes a nickel cobalt manganese positive electrode material as a core and takes an oxide containing cobalt, aluminum and fluorine as a shell, so that Li on the surface of the positive electrode material can be effectively reduced 2 CO 3 And the content of residual alkali such as LiOH, the mobility of the positive electrode material is improved, and the corrosion of HF generated in the battery cycle process on the surface of the positive electrode material is slowed down, so that the capacity, the rate capability and the cycle performance of the lithium ion battery containing the core-shell positive electrode material are obviously improved.
In order to achieve the above object, a first aspect of the present invention provides a core-shell type positive electrode material, wherein the core of the positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, and the positive electrode material has a composition shown in formula I;
Li z Ni x Co y Mn 1-x-y-w M w O 2 a formula I;
wherein x is more than or equal to 0.4 and less than 1, w is more than or equal to 0 and less than or equal to 0.1, x+y+w is more than or equal to 1, and z is more than or equal to 0.9 and less than or equal to 1.1;
m is at least one element selected from B, mg, si, co, nb, zr, Y, al, sr and W;
the shell of the positive electrode material comprises a composition having a formula II;
LiCo α Al 1-α F β O 2-β a formula II;
wherein 0< alpha <1,0< beta <0.0005.
The second aspect of the invention provides a preparation method of a core-shell type positive electrode material, which is characterized by comprising the following steps:
(1) Mixing a nickel-cobalt-manganese ternary anode material, a fluorine source, a cobalt source and an aluminum source to obtain a mixture;
(2) Sintering the mixture in an oxygen-containing atmosphere to obtain the core-shell type anode material;
preferably, the core of the positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, and has a composition shown in a formula I;
Li z Ni x Co y Mn 1-x-y-w M w O 2 a formula I;
wherein x is more than or equal to 0.4 and less than 1, w is more than or equal to 0 and less than or equal to 0.1, x+y+w is more than or equal to 1, and z is more than or equal to 0.9 and less than or equal to 1.1;
m is at least one element selected from B, mg, si, co, nb, zr, Y, al, sr and W;
the shell of the positive electrode material has a composition shown in formula II;
LiCo α Al 1-α F β O 2-β a formula II;
wherein 0< alpha <1,0< beta <0.0005.
The third aspect of the invention provides a core-shell type positive electrode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the core-shell type positive electrode material in a lithium ion battery.
Through the technical scheme, the core-shell type positive electrode material provided by the invention and the preparation method and application thereof have the following beneficial effects:
(1) The core-shell type positive electrode material provided by the invention takes the nickel-cobalt-manganese positive electrode material as a core and takes the oxide containing cobalt, aluminum and fluorine as a shell, so that Li on the surface of the positive electrode material can be effectively reduced 2 CO 3 And the content of residual alkali such as LiOH, etc., avoid the battery comprising this positive electrode material from being influenced by side reaction in the course of circulation, especially slow down the corrosion action of HF produced in the course of battery circulation to the surface of the positive electrode material, raise the stability of the positive electrode material, make the capacity, multiplying power performance, circulation performance of the lithium ion battery comprising this core-shell positive electrode material all promote obviously.
(2) The core-shell type positive electrode material provided by the invention has good fluidity, can effectively avoid the blocking phenomenon in the processing process, and improves the processing performance.
(3) The preparation method of the core-shell type positive electrode material provided by the invention can obtain the core-shell type positive electrode material through one-step solid phase reaction, has a simple preparation method flow, can be applied to large-scale industrial production, and particularly has extremely low fluorine consumption, thereby greatly reducing the harm to personnel and equipment in the preparation process.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the core-shell type positive electrode material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the core-shell positive electrode material prepared in example 2;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in comparative example 1;
fig. 4 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in comparative example 3.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a core-shell type positive electrode material, which is characterized in that the core of the positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, and has a composition shown in a formula I;
Li z Ni x Co y Mn 1-x-y-w M w O 2 a formula I;
wherein x is more than or equal to 0.4 and less than 1, w is more than or equal to 0 and less than or equal to 0.1, x+y+w is more than or equal to 1, and z is more than or equal to 0.9 and less than or equal to 1.1;
m is at least one element selected from B, mg, si, co, nb, zr, Y, al, sr and W;
the shell of the positive electrode material comprises a composition shown in a formula II;
LiCo α Al 1-α F β O 2-β a formula II;
wherein 0< alpha <1,0< beta <0.0005.
In the invention, in the core-shell type positive electrode material, the nickel-cobalt-manganese positive electrode material is taken as a core, and the oxide containing cobalt, aluminum and fluorine is taken as a shell, so that Li on the surface of the positive electrode material can be effectively reduced 2 CO 3 And the content of residual alkali such as LiOH, etc., avoid the battery comprising this positive electrode material from being influenced by side reaction in the course of circulation, especially slow down the corrosion action of HF produced in the course of circulation of battery to the surface of the positive electrode material, raise the stability of the positive electrode material, make the capacity, multiplying power performance and circulation performance of the lithium ion battery comprising this core-shell positive electrode material get the apparent improvement.
Further, as shown in fig. 1, in the core-shell type cathode material provided by the invention, the coating shell containing oxides of cobalt, aluminum and fluorine is continuously coated on the surface of the nickel-cobalt-manganese ternary cathode material serving as a core in a water ripple shape, and the core-shell type cathode material has the characteristics of high coating rate and small surface roughness.
In the invention, oxide containing cobalt, aluminum and fluorine is taken as a coating shell, and the cobalt and the aluminum in the coating shell can consume Li on the core surface of the nickel-cobalt-manganese ternary positive electrode material 2 CO 3 And residual alkali such as LiOH, etc., reduce the generation of HF in the battery cycle process, further, cobalt in the cladding shell can improve the ability of lithium ion migration, and then promote the electrochemical kinetics of the core-shell type positive electrode material, enhance the deintercalation performance of lithium ions, and then promote the capacity and multiplying power performance of the material; the aluminum in the coating shell can protect the surface of the anode material, and reduce or prevent side reactions; the presence of fluorine in the cladding greatly reduces the corrosive effect of HF on the material. It will be appreciated by those skilled in the art that the main component of the positive electrode material in the present invention is a compound represented by formula II, and that no other substance is contained in the positive electrode material.
In the core-shell type positive electrode material, the content of each element in the shell is determined according to the mass ratio of the element to the core.
In the present invention, li in the shell mainly comes from residual alkali existing on the surface of the positive electrode material as a core, and a small part comes from Li in the positive electrode material particles as a core, and since the content of the positive electrode material as a shell is low relative to the positive electrode material as a core, the Li element content transferred to the shell in the core and its micro level do not affect the composition of the core.
Further, in the formula I, x is more than or equal to 0.45 and less than or equal to 0.95, w is more than or equal to 0 and less than or equal to 0.05, and x+y+w is less than 1.
Further, in formula II, 0.5< α <0.9,0< β <0.0001.
According to the invention, the residual alkali content of the surface of the core-shell type positive electrode material is less than or equal to 0.3wt%.
In the invention, when the residual alkali content on the surface of the core-shell type positive electrode material meets the range, the occurrence of side reaction on the surface of the positive electrode in the battery cycle process can be obviously reduced when the core-shell type positive electrode material is used for a lithium ion battery, so that the battery cycle gas production is obviously reduced.
Further, the surface residual alkali content of the core-shell type positive electrode material is 0.1-0.2wt%.
According to the invention, the mass of fluorine element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy the ratio of 0wt% < m (fluorine element)/m (nickel-cobalt-manganese ternary positive electrode material) multiplied by 100% to less than or equal to 0.01wt%.
In the core-shell type positive electrode material, when the content of fluorine element in the shell is controlled to meet the range, the invention not only can fully play the role of fluorine, namely, reduce the residual Li on the surface of the positive electrode material 2 CO 3 And the corrosion of HF generated by the reaction of residual alkali such as LiOH and the like with electrolyte to the anode material, and simultaneously, the harm to personnel and equipment in the preparation process is greatly reduced due to the extremely low use amount of a fluorine source.
Further, the mass of fluorine element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 0.0001wt% or less m (fluorine element)/m (nickel-cobalt-manganese ternary positive electrode material) ×100% or less 0.003wt%.
According to the invention, the mass of cobalt element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy the weight percentage of 0wt% < m (cobalt element)/m (nickel-cobalt-manganese ternary positive electrode material) multiplied by 100 percent less than or equal to 5wt%.
In the core-shell type positive electrode material, when the content of cobalt element in the shell is controlled to meet the range, li remained on the surface of the positive electrode material can be fully consumed 2 CO 3 And the content of residual alkali such as LiOH, reduce the generation of HF in the cycle process of the lithium ion battery containing the core-shell type positive electrode material, and meanwhile, the capacity of lithium ion migration can be improved, the electrochemical dynamics of the core-shell type positive electrode material is improved, the deintercalation performance of lithium ions is enhanced, and the charge-discharge capacity and the rate capability of the lithium ion battery containing the core-shell type positive electrode material are obviously improved.
Further, the mass of cobalt element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 2wt% or less m (cobalt element)/m (nickel-cobalt-manganese ternary positive electrode material) ×100% or less 3wt% based on cobalt element.
According to the invention, the mass of the aluminum element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy the weight percentage of 0wt% < m (aluminum element)/m (nickel-cobalt-manganese ternary positive electrode material) multiplied by 100 percent less than or equal to 2wt%.
In the core-shell type positive electrode material, when the content of aluminum element in the shell is controlled to meet the range, li remained on the surface of the positive electrode material can be fully consumed 2 CO 3 And simultaneously, the content of residual alkali such as LiOH and the like plays a role in protecting the surface of the core-shell type positive electrode material, reduces or prevents side reaction of the core-shell type positive electrode material in the circulation process, and further remarkably improves the charge-discharge capacity and the rate capability of the lithium ion battery containing the core-shell type positive electrode material.
Further, the mass of the aluminum element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material meet the weight percent of 0 to less than m (aluminum element)/m (nickel-cobalt-manganese ternary positive electrode material) multiplied by 100 to less than or equal to 0.3 percent;
according to the invention, the core-shell positive electrode material has a repose angle theta 1 ≤40°。
In the present invention, when the repose angle of the core-shell type positive electrode material satisfies the above range, the core-shell type positive electrode material has significantly improved fluidity.
Further, the core-shell type positive electrode material has a repose angle θ 1 ≤35°。
According to the invention, the repose angle of the nickel-cobalt-manganese ternary positive electrode material is theta 0 And θ is as follows 1 <θ 0 。
In the invention, the repose angle of the core-shell type positive electrode material is smaller than that of the nickel-cobalt-manganese positive electrode material, which shows that the fluidity of the core-shell type positive electrode material is superior to that of the nickel-cobalt-manganese ternary positive electrode material serving as a core, so that the core-shell type positive electrode material has excellent fluidity, the blocking phenomenon in the processing process can be effectively avoided, and the processing performance of the core-shell type positive electrode material is improved.
Further, θ 0 -θ 1 0.1-20 °, preferably 2-10 °, more preferably 3-6 °.
According to the invention, the specific surface area BET of the core-shell positive electrode material 1 0.4-0.6m 2 /g。
In the invention, when the specific surface area of the core-shell type positive electrode material meets the range, the core-shell type positive electrode material is fully contacted with the electrolyte, so that the rapid conduction of lithium ions is realized, and the rate capability of the lithium ion battery is remarkably improved.
Further, the core-shell type positive electrode materialSpecific surface area BET of the material 1 0.5-0.55m 2 /g。
According to the invention, the specific surface area of the nickel-cobalt-manganese ternary positive electrode material is BET 0 And BET 1 ≤BET 0 。
Further, BET 0 -BET 1 0.01-0.15m 2 Preferably 0.05-0.1m 2 /g。
In the present invention, the particle diameter D50 of the core-shell type positive electrode material is 1 to 10. Mu.m, preferably 3 to 5. Mu.m.
The second aspect of the invention provides a preparation method of a core-shell type positive electrode material, which is characterized by comprising the following steps:
(1) Mixing a nickel-cobalt-manganese ternary anode material, a fluorine source, a cobalt source and an aluminum source to obtain a mixture;
(2) And sintering the mixture in an oxygen-containing atmosphere to obtain the core-shell type anode material.
According to the invention, the core-shell type anode material of the first aspect of the invention can be obtained by mixing and sintering the nickel-cobalt-manganese ternary anode material, the fluorine source, the cobalt source and the aluminum source through one-step solid phase reaction, and the preparation method has a simple flow and can be applied to large-scale industrial production.
Further, sintering the mixture in the presence of an oxygen-containing atmosphere can ensure that the fluorine source, the cobalt source and the aluminum source form a coating shell on the surface of the nickel-cobalt-manganese ternary cathode material.
In the invention, the core of the core-shell type positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, and has a composition shown in a formula I;
Li z Ni x Co y Mn 1-x-y-w M w O 2 a formula I;
wherein x is more than or equal to 0.4 and less than 1, w is more than or equal to 0 and less than or equal to 0.1, x+y+w is more than or equal to 1, and z is more than or equal to 0.9 and less than or equal to 1.1;
m is at least one element selected from B, mg, si, co, nb, zr, Y, al, sr and W;
the shell of the positive electrode material has a composition shown in formula II;
LiCo α Al 1-α F β O 2-β a formula II;
wherein 0< alpha <1,0< beta <0.0005.
In the invention, the shell of the positive electrode material is continuously coated on the surface of the core of the positive electrode material in a water ripple shape.
Further, in the formula I, x is more than or equal to 0.45 and less than or equal to 0.95, w is more than or equal to 0 and less than or equal to 0.05, and x+y+w is less than 1.
Further, in the present invention, in formula II, 0.5< α <0.9,0< β <0.0001.
According to the invention, the median particle size of the nickel-cobalt-manganese ternary positive electrode material is 3-6 mu m.
According to the invention, the nickel-cobalt-manganese ternary positive electrode material with the median particle diameter is adopted, so that the prepared core-shell positive electrode material has proper particle diameter, and the core-shell positive electrode material has good compaction performance while being used for a lithium ion battery and has high capacity.
Further, the median particle size of the nickel-cobalt-manganese ternary positive electrode material is 3-4 mu m.
According to the invention, the fluorine source and the nickel-cobalt-manganese ternary cathode material satisfy the conditions that the fluorine source and the nickel-cobalt-manganese ternary cathode material satisfy 0wt% < m (fluorine source)/m (nickel-cobalt-manganese ternary cathode material) ×.ltoreq.0.01 wt%.
In the present invention, when the amount of the fluorine source is controlled to satisfy the above range, the effect of fluorine can be sufficiently exhibited, that is, li remaining on the surface of the positive electrode material can be reduced 2 CO 3 And the corrosion of HF generated by the reaction of residual alkali such as LiOH and the like with electrolyte to the anode material, and simultaneously, the harm to personnel and equipment in the preparation process is greatly reduced due to the extremely low use amount of a fluorine source.
Further, the fluorine source and the nickel-cobalt-manganese ternary cathode material satisfy 0.0001wt% or less m (fluorine source)/m (nickel-cobalt-manganese ternary cathode material) × or less than 0.003wt% based on fluorine element.
According to the present invention, the fluorine source is selected from at least one of lithium fluoride, aluminum fluoride, potassium fluoride, magnesium fluoride, potassium fluoride, sodium fluoride, aluminum hexafluorophosphate, and fluorine-containing gas; preferably at least one selected from lithium fluoride, aluminum fluoride and aluminum hexafluorophosphate, more preferably lithium fluoride.
According to the invention, the cobalt source and the nickel-cobalt-manganese ternary cathode material satisfy the conditions of 0wt% < m (cobalt source)/m (nickel-cobalt-manganese ternary cathode material) ×.ltoreq.5 wt% based on cobalt element.
In the present invention, when the amount of the cobalt source is controlled to satisfy the above range, li remaining on the surface of the positive electrode material can be sufficiently consumed 2 CO 3 And the content of residual alkali such as LiOH, reduce the generation of HF in the cycle process of the lithium ion battery containing the core-shell type positive electrode material, and meanwhile, the capacity of lithium ion migration can be improved, the electrochemical dynamics of the core-shell type positive electrode material is improved, the deintercalation performance of lithium ions is enhanced, and the charge-discharge capacity and the rate capability of the lithium ion battery containing the core-shell type positive electrode material are obviously improved.
Further, the cobalt source and the nickel-cobalt-manganese ternary cathode material satisfy the conditions of 2wt% or less m (cobalt source)/m (nickel-cobalt-manganese ternary cathode material) × or less 3wt% based on cobalt element.
According to the present invention, the cobalt source is selected from at least one of cobalt hydroxide, cobalt oxyhydroxide, cobalt hydroxide, cobalt oxide, cobalt carbonate, and cobalt sulfate; preferably at least one selected from the group consisting of cobalt hydroxide, cobalt oxyhydroxide, cobalt hydroxide and cobalt oxide; cobalt hydroxide and/or cobalt oxyhydroxide are preferred.
According to the invention, the cobalt source has a median particle size of 0.1-10 μm.
According to the invention, when the median particle diameter of the cobalt source meets the range, the cobalt source can be uniformly wrapped on the surface of the nickel-cobalt-manganese ternary cathode material serving as a core, so that the prepared core-shell cathode material has high stability and fluidity, and when the core-shell cathode material is used for a lithium ion battery, the capacity, the multiplying power performance and the cycle performance of the lithium ion battery can be improved.
Further, the cobalt source has a median particle size of 0.1 to 3 μm.
According to the invention, the aluminum source and the nickel-cobalt-manganese ternary cathode material satisfy the conditions of 0wt% < m (aluminum source)/m (nickel-cobalt-manganese ternary cathode material) ×.ltoreq.2wt% based on aluminum element.
In the present invention, when the amount of the aluminum source is controlled to satisfy the above range, li remaining on the surface of the positive electrode material can be sufficiently consumed 2 CO 3 And simultaneously, the content of residual alkali such as LiOH and the like plays a role in protecting the surface of the core-shell type positive electrode material, reduces or prevents side reaction of the core-shell type positive electrode material in the circulation process, and further remarkably improves the charge-discharge capacity and the rate capability of the lithium ion battery containing the core-shell type positive electrode material.
Further, the aluminum source and the nickel-cobalt-manganese ternary cathode material satisfy the conditions that the aluminum source and the nickel-cobalt-manganese ternary cathode material satisfy 0wt% < m (aluminum source)/m (nickel-cobalt-manganese ternary cathode material) × is less than or equal to 0.3wt%.
According to the present invention, the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxyhydroxide, aluminum hydroxide, aluminum oxide, aluminum carbonate, and aluminum sulfate; preferably at least one of aluminium hydroxide, aluminium oxyhydroxide, aluminium hydroxide and aluminium oxide, preferably aluminium hydroxide and/or aluminium oxide.
According to the invention, the mixing conditions include: the mixing rotating speed is 1000-2000rpm/min; the mixing time is 5-40min.
According to the invention, the nickel-cobalt-manganese ternary positive electrode material, the fluorine source, the cobalt source and the aluminum source are mixed under the conditions, so that the materials can be fully and uniformly mixed, and adverse reduction of the performance of the finally prepared core-shell type positive electrode material due to cracks on the surface of the nickel-cobalt-manganese ternary positive electrode material caused by too high rotating speed or too long mixing time is avoided.
Further, the mixing conditions include: the mixing rotating speed is 1500-2000rpm/min; the mixing time is 20-25min.
In the present invention, the equipment used for mixing is not particularly limited as long as it can mix the nickel-cobalt-manganese ternary cathode material, the fluorine source, the cobalt source, and the aluminum source, and for example, a high-speed mixer can be used.
According to the invention, the sintering conditions include: the sintering temperature is 600-900 ℃; the sintering time is 5-15h.
In the invention, the mixture is sintered under the above conditions, so that a fluorine source, a cobalt source and an aluminum source can be ensured to form a coating shell on the surface of the nickel-cobalt-manganese ternary positive electrode material, and the core-shell type positive electrode material of the first aspect of the invention is further obtained. Specifically, if the sintering temperature is too low, a fluorine source, a cobalt source and an aluminum source cannot form a coating shell on the surface of the positive electrode material, the expected electrical performance effect cannot be achieved, and fluorine, cobalt and aluminum elements exist on the surface of the positive electrode material in the form of small particles, so that van der Waals force among the particles is increased, and the fluidity of the positive electrode material is deteriorated; if the sintering temperature is too high, the original crystal structure of the positive electrode material is promoted to be destroyed, resulting in deterioration of the electrical properties.
Further, the sintering conditions include: the sintering temperature is 700-800 ℃; the sintering time is 8-12h.
In the present invention, the equipment for sintering is not particularly limited as long as the sintering of the mixture can be achieved, and may be, for example, a muffle furnace.
According to the invention, the flow rate of the oxygen-containing atmosphere is 3-8m 3 /h。
In the invention, when the flow rate of the oxygen-containing atmosphere is controlled to meet the above range, the fluorine source, the cobalt source and the aluminum source can be ensured to form the coating layer on the surface of the nickel-cobalt-manganese ternary cathode material.
Further, the flow rate of the oxygen-containing atmosphere is 5-8m 3 /h。
In the present invention, the type of the oxygen-containing atmosphere is not particularly limited, and may be, for example, air as long as oxygen is contained.
The third aspect of the invention provides a core-shell type positive electrode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the core-shell type positive electrode material in a lithium ion battery.
The present invention will be described in detail by examples. In the following examples of the present invention,
the morphology of the positive electrode material is characterized by adopting a scanning electron microscope;
the median particle diameter of the core-shell type positive electrode material and the nickel-cobalt-manganese ternary positive electrode material is measured by a Markov 3000 particle size meter;
the repose angle of the core-shell type anode material and the nickel-cobalt-manganese ternary anode material is measured according to the repose angle of the physical properties of GBT6609.24-2004, and the specific test method comprises the following steps:
in the drying room, 50g of positive electrode material is respectively added into a funnel (stainless steel screen mesh is arranged at the inlet), so that the material naturally spills on a smooth bottom plate through a funnel opening. And measuring the height of the stacked books and converting to obtain the repose angle of the material. The angle of repose (i.e., angle of repose) is used to characterize the flowability of the material, the smaller the angle of repose, the better the flowability of the positive electrode material;
the specific surface area of the core-shell type positive electrode material and the nickel-cobalt-manganese ternary positive electrode material is measured by a specific surface area micropore analyzer;
the residual alkali content of the surface of the core-shell type anode material and the nickel-cobalt-manganese ternary anode material is measured by a potentiometric titrator;
the composition of the nickel-cobalt-manganese ternary anode material and the coating shell is measured by an inductively coupled plasma spectrometer;
the battery capacity, test conditions were: the battery capacities at 0.1C and 1C were tested at a normal temperature of 25℃and a voltage of 4.4V, respectively;
cycle performance of the battery, test conditions: the charge and discharge were carried out at 1C at 45 ℃ and a test voltage of 4.5V, and the retention rate was measured by cycling for 80 weeks.
The raw materials used in the examples and comparative examples are all commercially available.
Example 1
(1) 4000g of ternary material LiNi is taken 0.58 Co 0.1 Mn 0.32 O 2 As a core structure, 140.5g of Co (OH) was taken, respectively 2 (median particle diameter of 3.5 μm) and 11.5g of Al 2 O 3 And 0.11g of LiF as an additive, placing the ternary material and the additive into a high-speed mixer, continuously mixing for 20min at a rotating speed of 2000rpm/min, taking out to obtain a mixture, and placing the mixture into a sagger. Wherein, the m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.002wt%, and m (cobalt element)/m (nickel cobaltManganese ternary positive electrode material) ×100% was 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% was 0.15wt%.
(2) Continuously sintering the mixture in a muffle furnace at 800 ℃ for 12h with air flow of 5m 3 And (h) crushing and sieving the sintered material through colloid mill to obtain a core-shell type positive electrode material A1, wherein the composition of the core-shell type positive electrode material A1 is LiNi 0.58 Co 0.1 Mn 0.32 O 2 @LiCo 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 2
A positive electrode material was prepared as in example 1, except that: in the step (2), the sintering temperature is 700 ℃, and the core-shell type positive electrode material A2 is obtained, wherein the composition of the core-shell type positive electrode material A2 is LiNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 3
A positive electrode material was prepared as in example 1, except that: in step (1), 0.12g of AlF was used 3 As an additive, m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% was 0.002wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% was 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% was 0.15wt%. Obtain a core-shell type anode material A3, the composition of which is LiNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.000033 7 O 1.9999663 。
Example 4
A positive electrode material was prepared as in example 1, except that: in the step (1), the addition amount of LiF was changed to 0.275g, and the same was true. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.005wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material A4 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.12 3 F 0.0000842 O 1.9999158 。
Example 5
A positive electrode material was prepared as in example 1, except that:
in the step (1), the addition amount of LiF was changed to 0.55g, and the same was true. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.01wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material A5 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.0001684 O 1.9998316 。
Example 6
A positive electrode material was prepared as in example 1, except that:
in step (1), co (OH) 2 The amount to be added was 281g, and the other amounts were the same. The m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.002wt%, the m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 4.46wt%, and the m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type anode material A6 is obtained and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.9343 Al 0.0657 F 0.0000337 O 1.9999663 。
Example 7
A positive electrode material was prepared as in example 1, except that:
in step (1), al 2 O 3 The amount added was the same except 115 g. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.002wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 1.5wt%. The core-shell type positive electrode material A7 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.4156 Al 0.5844 F 0.0000337 O 1.9999663 。
Example 8
A positive electrode material was prepared as in example 1, except that:
in the step (2), the sintering temperature is 850 ℃, and the other sintering temperatures are the same. The core-shell type positive electrode material A8 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 9
A positive electrode material was prepared as in example 1, except that:
in the step (2), the sintering temperature is 450 ℃, and the other sintering temperatures are the same. The core-shell type positive electrode material A9 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 10
A positive electrode material was prepared as in example 1, except that:
in the step (2), the sintering temperature is 950 ℃, and the other materials are the same. The core-shell type positive electrode material A10 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 11
A positive electrode material was prepared as in example 1, except that:
in step (1), co (OH) 2 The amount added was 421.5g, all other things being equal. The m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.002wt%, the m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 6.69wt%, and the m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material A11 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.9552 Al 0.0448 F 0.0000337 O 1.9999663 。
Example 12
According to the embodiment1, except that: in the step (1), the ternary material core structure is replaced by LiNi 0.73 Co 0.08 Mn 0.19 O 2 The same applies to the other cases, that is, m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.002wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material A12 is obtained, and comprises the following components: liNi 0.73 Co 0.08 Mn 0.19 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 13
A positive electrode material was prepared as in example 1, except that: in the step (1), the ternary material core structure is replaced by LiNi 0.92 Co 0.05 Mn 0.03 O 2 The same applies to the other cases, that is, m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.002wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material A13 is obtained, and comprises the following components: liNi 0.92 Co 0.05 Mn 0.03 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 14
A positive electrode material was prepared as in example 1, except that: in the step (1), the core is LiNi 0.92 Co 0.05 Mn 0.0 3 Zr 0.003 Y 0.001 O 2 Obtaining a core-shell type positive electrode material A14, wherein the composition of the core-shell type positive electrode material A14 is LiNi 0.92 Co 0.05 Mn 0.03 Zr 0.003 Y 0.001 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Example 15
A positive electrode material was prepared as in example 1, except that: in the step (1), the core is LiNi 0.92 Co 0.05 Mn 0.0 3 Zr 0.003 Sr 0.001 O 2 Obtaining a core-shell type positive electrode material A15, wherein the composition of the core-shell type positive electrode material A15 is LiNi 0.92 Co 0.0 5 Mn 0.03 Zr 0.003 Sr 0.001 O 2 @Li Co 0.877 Al 0.123 F 0.0000337 O 1.9999663 。
Comparative example 1
With ternary cathode material LiNi in example 1 0.58 Co 0.1 Mn 0.32 O 2 Without any treatment, as the positive electrode material D1.
Comparative example 2
A positive electrode material was prepared as in example 1, except that: without step (1), 4000g of ternary material LiNi is taken 0.58 Co 0.1 Mn 0.32 O 2 As a nuclear structure, the material was continuously sintered in a muffle furnace at 800℃for 12 hours with an air flow of 5m 3 And (h) crushing and sieving the sintered material through colloid mill to obtain a positive electrode material D2, wherein the positive electrode material D2 comprises the following components of LiNi 0.58 Co 0.1 Mn 0.32 O 2 。
Comparative example 3
A positive electrode material was prepared as in example 1, except that: in the step (1), liF is not added to obtain a positive electrode material D4, which comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 O 2 。
Comparative example 4
A positive electrode material was prepared as in example 1, except that: in the step (1), co (OH) is not added 2 And Al 2 O 3 Only 0.11g of LiF was added to obtain a positive electrode material D4 having the composition: liNi 0.58 Co 0.1 Mn 0.32 F 0.0000337 O 1.9999663 。
Comparative example 5
A positive electrode material was prepared as in example 1, except that:
in the step (1), the addition amount of LiF was 2.2g, and the other was the same. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.04 wt.%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23 wt.%, m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15 wt.%. The core-shell type positive electrode material D5 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.000674 O 1.999326 。
Comparative example 6
A positive electrode material was prepared as in example 1, except that:
in the step (1), the addition amount of LiF was 4.4g, and the other was the same. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.08wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material D6 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.00135 O 1.99865 。
Comparative example 7
A positive electrode material was prepared as in example 1, except that:
in the step (1), the addition amount of LiF was 5.5g, and the other was the same. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.1wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. The core-shell type positive electrode material D7 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.00168 O 1.99832 。
Comparative example 8
A positive electrode material was prepared as in example 1, except that:
in the step (1), the addition amount of LiF was 11g, and the other was the same. m (fluorine element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.2wt%, m (cobalt element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 2.23wt%, and m (aluminum element)/m (nickel cobalt manganese ternary positive electrode material) ×100% is 0.15wt%. To obtain the core-shell type anode material D8,the composition of the material is as follows: liNi 0.58 Co 0.1 Mn 0.32 O 2 @Li Co 0.877 Al 0.123 F 0.00337 O 1.99663 。
Comparative example 9
A positive electrode material was prepared as in example 1, except that: in the step (1), co (OH) is not added 2 The others are the same. The core-shell type positive electrode material D9 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @LiAl F 0.0000337 O 1.9999663 。
Comparative example 10
A positive electrode material was prepared as in example 1, except that: in the step (1), al is not added 2 O 3 The others are the same. The core-shell type positive electrode material D9 is obtained, and comprises the following components: liNi 0.58 Co 0.1 Mn 0.32 O 2 @LiCoF 0.0000337 O 1.9999663 。
TABLE 1
As can be seen from table 1, the repose angle of examples 1 to 3 is significantly reduced, while the repose angle of the aluminum-cobalt coated cathode material of comparative example 3, which does not contain fluorine element, is maximized, and it can be seen that the material prepared by the present invention can significantly enhance the fluidity of the cathode material. It can be seen from examples 4 to 5 and comparative examples 5 to 8 that the repose angle can be reduced as the amount of fluorine source added increases, and that the capacity and retention rate can be significantly deteriorated as the amount of fluorine source added increases in combination with the performance data of the lithium ion battery including the positive electrode material in table 2.
The residual alkali of examples 1-5 is far lower than that of comparative examples 1, 2 and 4 and slightly lower than that of comparative example 3, and the residual alkali amount on the surface of the positive electrode material can be effectively reduced by adopting the method of the invention. By comparing comparative examples 9 to 10, it can be seen that the lack of one of the elements of the coating shell layer reduces the total alkali amount, and the replacement thereof becomes poor.
By comparing the specific surface area data of examples 1-3 and comparative example 1, it can be seen that the specific surface area of the fluorine modified core-shell type positive electrode material prepared by the method is not greater than that of the core body of the positive electrode material; it can be seen from examples 4 to 5 and comparative examples 5 to 8 that the angle of repose can be reduced as the amount of fluorine source added increases; it can be seen from examples 8 to 10 that the specific surface area is alkali-reduced with an increase in sintering temperature.
Ternary material scanning electron microscopy images of examples 1-2, comparative example 1 and comparative example 3 are shown in FIGS. 1-4, respectively. It can be seen that in the electron microscope of comparative example 1, the particle surface was smooth without any particles or coating layers, in the electron microscope of comparative example 3, many tiny particles of cobalt and aluminum additives were present on the particle surface, the additives were present in the form of particles, and no coating layers were formed, whereas in examples 1 and 2, the additive particles on the particle surface disappeared due to the addition of a trace amount of fluorine element, instead of a layer of distinct coating, it was confirmed that the additives formed a coating layer and uniformly coated on the particle surface, and the coating rate was large, and the surface roughness of the coating shell was small. And as can be seen from fig. 1, the coating shell is continuously coated on the surface of the nickel-cobalt-manganese ternary positive electrode material serving as a core in a water ripple shape.
Further, in the embodiment 2, the solid-phase reaction temperature is slightly low, additive particles still remain on the surface, after the reaction temperature is increased, the additive particles on the surface of the embodiment 1 completely disappear and form an obvious corrugated coating layer, the continuous coating matrix with water corrugations has relatively small surface roughness and high coating rate; comparative example 1 illustrates that the core surface of the positive electrode material used in the present invention is smooth, while comparative example 3 has many small particles on the surface, which are additive particles, illustrating that the small particles do not form a coating layer but are attached to the surface of the positive electrode material in a particulate state.
The excessive amounts of cobalt source in examples 6 and 11 and aluminum source in example 7 result in excessive amounts of cobalt and aluminum additives, and only a part of the additives form a coating shell during the reaction, while the other part exists in the form of additive particles, thereby increasing the specific surface area of the material; meanwhile, due to the existence of additive particles, the repose angle is increased; compared with examples 1, 6 and 11, with the increase of the addition amount of the cobalt additive, the total alkali is obviously reduced, which indicates that the cobalt additive plays a role in reducing the total alkali; as can be seen from the electrical performance data of table 2, the addition of excess aluminum and cobalt resulted in capacity fade and reduced cycle retention.
In examples 12 and 13, with the increase of the nickel content in the ternary material core structure, the capacity is obviously improved by combining the data in table 2, which shows that the capacity can be improved by increasing the nickel content; however, the nickel content is increased synchronously, so that the cycle retention rate is reduced, and the higher the nickel content is, the worse the retention rate is.
In examples 14 and 15, the ternary material core structure contains doping elements, which is beneficial to improving the electrical performance of the nickel cobalt manganese positive electrode material, and the capacity and the retention rate of the ternary positive electrode material with the core structure containing the doping elements are obviously improved in combination with the data of table 2.
Test case
The positive electrode materials prepared in examples and comparative examples were assembled into a battery, and the battery assembling method specifically comprises:
the positive electrode materials prepared in the examples and the comparative examples, conductive carbon black, polyvinylidene fluoride and N-methyl-2-pyrrolidone are mixed and ground according to the mass ratio of 95:2:3, coated on aluminum foil, and then dried, rolled and punched to prepare the electrode plate. Then, a button cell is manufactured in a glove box filled with argon, a negative electrode is a lithium sheet, a polypropylene microporous membrane is a diaphragm, and electrolyte is injected after assembly, so that the button cell of CR2032 can be obtained. The capacity and high temperature cycle performance of the button cell were tested and the results are shown in table 2.
TABLE 2
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As can be seen from the results in Table 2, the 0.1C capacity, 1C capacity and retention rate after 80 weeks of circulation of examples 1-15 are all significantly higher than those of comparative examples 1-10, so that the fluorine modified coating layer can improve the electrical properties of the material, the cobalt element is mainly used for improving the capacity and rate capability, the aluminum element is used for improving the high temperature retention rate of the material, and the existence of trace fluorine element not only promotes the fusion of cobalt and aluminum elements, but also can improve the effect of cobalt and aluminum, but also can deteriorate the electrical properties due to the addition of excessive fluorine, thereby playing a negative role, and the three elements complement each other to be unavailable; in addition, examples 9 and 10 reflect that at too high or too low a temperature, the three elements are not effectively combined, resulting in a decrease in capacity and a deterioration in cycle retention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (25)
1. The core-shell type positive electrode material is characterized in that the core of the positive electrode material is a nickel-cobalt-manganese ternary positive electrode material, and the composition is shown in a formula I;
Li z Ni x Co y Mn 1-x-y-w M w O 2 a formula I;
wherein x is more than or equal to 0.4 and less than 1, w is more than or equal to 0 and less than or equal to 0.1, x+y+w is more than or equal to 1, and z is more than or equal to 0.9 and less than or equal to 1.1;
m is at least one element selected from B, mg, si, co, nb, zr, Y, al, sr and W;
the shell of the positive electrode material has a composition shown in a formula II;
LiCo α Al 1-α F β O 2-β a formula II;
wherein 0.5< α <0.9,0< β <0.0001;
the mass of fluorine element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy the condition that the weight percentage of the fluorine element in the shell is less than 0wt% < m Fluorine element /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤0.005wt%。
2. The core-shell positive electrode material according to claim 1, wherein the shell of the positive electrode material is continuously coated on the surface of the core of the positive electrode material in a water ripple shape;
and/or, in the formula I, x is more than or equal to 0.45 and less than or equal to 0.95, w is more than or equal to 0 and less than or equal to 0.05, and x+y+w is less than 1.
3. The core-shell positive electrode material according to claim 1 or 2, wherein the surface residual alkali content of the core-shell positive electrode material is 0.3wt% or less;
and/or the mass of fluorine element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 0.0001wt% or less m Fluorine element /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤0.003wt%；
And/or the mass of cobalt element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 0wt% < m Cobalt element /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤5wt%；
And/or the mass of aluminum element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 0wt% < m Elemental aluminum /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤2wt%。
4. The core-shell positive electrode material according to claim 3, wherein the surface residual alkali content of the core-shell positive electrode material is 0.1 to 0.2wt%;
and/or, calculated by cobalt element, the mass of cobalt element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 2wt% or less Cobalt element /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤3wt%；
And/or, calculated by aluminum element, the mass of the aluminum element in the shell and the mass of the nickel-cobalt-manganese ternary positive electrode material satisfy 0wt% < m Elemental aluminum /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤0.3wt%。
5. The core-shell positive electrode material according to any one of claims 1 to 2, 4, wherein the core-shellAngle of repose θ of positive electrode material 1 ≤40°；
And/or the repose angle of the nickel-cobalt-manganese ternary positive electrode material is theta 0 And θ is as follows 1 <θ 0 。
6. The core-shell positive electrode material according to claim 5, wherein the core-shell positive electrode material has a repose angle θ 1 ≤35°；
And/or, θ 0 -θ 1 0.1-20 deg..
7. The core-shell positive electrode material according to claim 6, wherein θ 0 -θ 1 Is 5-10 deg..
8. The core-shell positive electrode material according to claim 3, wherein the core-shell positive electrode material has a repose angle θ 1 ≤40°；
And/or the repose angle of the nickel-cobalt-manganese ternary positive electrode material is theta 0 And θ is as follows 1 <θ 0 。
9. The core-shell positive electrode material according to claim 8, wherein the core-shell positive electrode material has a repose angle θ 1 ≤35°；
And/or, θ 0 -θ 1 0.1-20 deg..
10. The core-shell positive electrode material according to claim 9, wherein θ 0 -θ 1 Is 5-10 deg..
11. The core-shell positive electrode material according to any one of claims 1 to 2, 4, 6 to 10, wherein the specific surface area BET of the core-shell positive electrode material 1 Is 0.4-0.6. 0.6m 2 /g；
And/or the specific surface area of the nickel-cobalt-manganese ternary positive electrode material is BET 0 And BET 1 ≤BET 0 。
12. According to the weightsThe core-shell positive electrode material according to claim 11, wherein the specific surface area BET of the core-shell positive electrode material 1 Is 0.5-0.55. 0.55m 2 /g；
And/or BET 0 - BET 1 0.01-0.15m 2 /g。
13. The core-shell positive electrode material according to claim 12, wherein BET 0 - BET 1 0.05-0.1m 2 /g。
14. The core-shell positive electrode material according to claim 3, wherein the specific surface area BET of the core-shell positive electrode material 1 Is 0.4-0.6. 0.6m 2 /g；
And/or the specific surface area of the nickel-cobalt-manganese ternary positive electrode material is BET 0 And BET 1 ≤BET 0 。
15. The core-shell positive electrode material according to claim 14, wherein the specific surface area BET of the core-shell positive electrode material 1 Is 0.5-0.55. 0.55m 2 /g；
And/or BET 0 - BET 1 0.01-0.15m 2 /g。
16. The core-shell positive electrode material according to claim 15, wherein BET 0 - BET 1 0.05-0.1m 2 /g。
17. The core-shell positive electrode material according to claim 5, wherein the specific surface area BET of the core-shell positive electrode material 1 Is 0.4-0.6. 0.6m 2 /g；
And/or the specific surface area of the nickel-cobalt-manganese ternary positive electrode material is BET 0 And BET 1 ≤BET 0 。
18. The core-shell positive electrode material according to claim 17, wherein the specific surface area BET of the core-shell positive electrode material 1 Is 0.5-0.55. 0.55m 2 /g；
And/or BET 0 - BET 1 0.01-0.15m 2 /g。
19. The core-shell positive electrode material of claim 18 wherein BET 0 - BET 1 0.05-0.1m 2 /g。
20. A method for preparing the core-shell type positive electrode material according to any one of claims 1 to 19, comprising the steps of:
(1) Mixing a nickel-cobalt-manganese ternary anode material, a fluorine source, a cobalt source and an aluminum source to obtain a mixture;
(2) And sintering the mixture in an oxygen-containing atmosphere to obtain the core-shell type anode material.
21. The preparation method of claim 20, wherein the median particle diameter of the nickel-cobalt-manganese ternary cathode material is 3-6 μm;
and/or the dosage of the cobalt source and the dosage of the nickel-cobalt-manganese ternary positive electrode material calculated by cobalt element satisfy 0 weight percent < m Cobalt source /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤5wt%；
And/or the aluminum source and the nickel-cobalt-manganese ternary positive electrode material are used in an amount of 0wt% < m calculated by aluminum element Aluminum source /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤2wt%；
And/or the fluorine source is selected from at least one of lithium fluoride, aluminum fluoride, potassium fluoride, magnesium fluoride, sodium fluoride, aluminum hexafluorophosphate and fluorine-containing gas;
and/or the cobalt source is selected from at least one of cobalt hydroxide, cobalt oxyhydroxide, cobaltous hydroxide, cobalt oxide, cobalt carbonate and cobalt sulfate;
and/or the cobalt source has a median particle size of 0.1-10 μm;
and/or the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxyhydroxide, aluminum hydroxide, aluminum oxide, aluminum carbonate, and aluminum sulfate.
22. The production method according to claim 21, wherein the amount of the fluorine source and the amount of the nickel-cobalt-manganese ternary cathode material in terms of fluorine element satisfy 0.0001 wt.% or less m Fluorine source /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤0.003wt%；
And/or the dosage of the cobalt source and the dosage of the nickel-cobalt-manganese ternary positive electrode material are 2wt% or less in terms of cobalt element Cobalt source /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤3wt%；
And/or the aluminum source and the nickel-cobalt-manganese ternary positive electrode material are used in an amount of 0wt% < m calculated by aluminum element Aluminum source /m Nickel-cobalt-manganese ternary positive electrode material ×100%≤0.3wt%；
And/or the fluorine source is selected from at least one of lithium fluoride, aluminum fluoride and aluminum hexafluorophosphate;
and/or the cobalt source is selected from at least one of cobalt hydroxide, cobalt oxyhydroxide, cobaltous hydroxide and cobalt oxide;
and/or the cobalt source has a median particle size of 0.1-3 μm;
and/or the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxyhydroxide, aluminum hydroxide, and aluminum oxide.
23. The method of any one of claims 20-22, wherein the mixing conditions include: the mixing rotating speed is 1000-2000rpm/min, and the mixing time is 5-40 min;
and/or, the sintering conditions include: the sintering temperature is 600-900 ℃ and the sintering time is 5-15 h;
and/or the flow rate of the oxygen-containing atmosphere is 3-8m 3 /h。
24. The method of preparation of claim 23, wherein the mixing conditions comprise: the mixing rotating speed is 1500-2000rpm/min, and the mixing time is 20-25 min;
and/or, the sintering conditions include: the sintering temperature is 700-800 ℃ and the sintering time is 8-12 h;
and/or the flow rate of the oxygen-containing atmosphere is 5-8m 3 /h。
25. Use of the core-shell positive electrode material according to any one of claims 1 to 19 in a lithium ion battery.
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