CN115911355B - Preparation method of zirconium-doped ternary positive electrode material, ternary positive electrode material and application thereof - Google Patents
Preparation method of zirconium-doped ternary positive electrode material, ternary positive electrode material and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000002243 precursor Substances 0.000 claims abstract description 57
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 239000012266 salt solution Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride 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
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 29
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- NXBARPSOQWENKD-UHFFFAOYSA-N [Zr].[Mn].[Co].[Ni] Chemical compound [Zr].[Mn].[Co].[Ni] NXBARPSOQWENKD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium 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
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- DAYYOITXWWUZCV-UHFFFAOYSA-L cobalt(2+);sulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O DAYYOITXWWUZCV-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
根据本发明的一个方面，提供一种锆掺杂三元正极材料的制备方法，包括如下步骤：S1.按照锆掺杂三元正极材料中各元素的化学计量比，采用可溶性镍盐、可溶性钴盐以及含有M元素的可溶性盐通过第一次共沉淀反应制备第一前驱体，第一前驱体中含有镍元素、钴元素以及M元素，其中，M元素包括锰元素、铝元素中的至少一种；S2.通过第二次共沉淀反应在第一前驱体的表面沉积含锆化合物得到第二前驱体；S3.按照锆掺杂三元正极材料中各元素的化学计量比，将第二前驱体与锂源混合得到第三前驱体，并采用高温固相法对第三前驱体进行煅烧，从而制得锆掺杂三元正极材料。
According to one aspect of the present invention, a method for preparing a zirconium-doped ternary positive electrode material is provided, comprising the following steps: S1. According to the stoichiometric ratio of each element in the zirconium-doped ternary positive electrode material, a first precursor is prepared by a first coprecipitation reaction using a soluble nickel salt, a soluble cobalt salt and a soluble salt containing the M element, wherein the first precursor contains nickel element, cobalt element and M element, wherein the M element includes at least one of manganese element and aluminum element; S2. A zirconium-containing compound is deposited on the surface of the first precursor by a second coprecipitation reaction to obtain a second precursor; S3. According to the stoichiometric ratio of each element in the zirconium-doped ternary positive electrode material, the second precursor is mixed with a lithium source to obtain a third precursor, and the third precursor is calcined by a high-temperature solid phase method to obtain the zirconium-doped ternary positive electrode material.
Description
Technical Field
The invention belongs to the lithium ion battery technology, and particularly relates to a preparation method of a zirconium doped ternary positive electrode material, a ternary positive electrode material and application of the ternary positive electrode material.
Background
In recent years, nickel-rich ternary materials have received attention due to their relatively high reversible capacity. However, the nickel-rich ternary material has the problems of lithium-nickel mixed discharge, structural phase transformation, microcracking, oxygen loss and the like. These problems can lead to capacity degradation of the electrode material and thermal effects of the battery. In order to ameliorate the above problems, many effective solutions have been explored, and electrolyte optimization, surface coating and metal ion doping have proven to be viable strategies. The metal ion doping introduces ions with different valence states into a crystal lattice, such as K +、Mg2+、Ga3+、Al3+、Zr4+、Ti4+、Nb5+, and different metal ions can occupy different crystal positions, so that the structural stability of the material is improved.
Therefore, the metal ions with the radius larger than that of Ni 2+、Co3+、Mn4+ ions can be doped to occupy part of lithium positions, so that the Ni 2+ can not occupy lithium positions in the charging and discharging process, and meanwhile, the unit cell parameters and the interlayer spacing of the positive electrode material are further enlarged, and the stability of the nickel-rich ternary material is improved.
As the ionic radius of Zr 4+ is larger than that of Ni 2+、Co3+、Mn4+, zirconium is doped in the ternary positive electrode material, the distance between lithium layers can be increased, the diffusion of Li + is promoted, in addition, the free energy of a migration structure of Zr 4+ is lower than that of Ni 4+, zr 4+ is easier to migrate to the lithium layer, strong electrostatic repulsion is generated between Zr 4+ and Ni 4+ after the Zr 4+ exists in the lithium layer, migration of Ni 4+ to the lithium layer is prevented, and lithium nickel mixed discharge is reduced. Therefore, zirconium doping can be selectively carried out on the ternary positive electrode material so as to improve the stability of the ternary positive electrode material.
Disclosure of Invention
In order to improve stability of a ternary positive electrode material, the invention aims to provide a preparation method of a zirconium doped ternary positive electrode material, the ternary positive electrode material and application thereof.
According to the stoichiometric ratio of each element in the zirconium-doped ternary positive electrode material, a soluble nickel salt, a soluble cobalt salt and a soluble salt containing M element are adopted to prepare a first precursor through a first coprecipitation reaction, the first precursor contains nickel element, cobalt element and M element, wherein the M element comprises at least one of manganese element and aluminum element, S2, a zirconium-containing compound is deposited on the surface of the first precursor through a second coprecipitation reaction to obtain a second precursor, and S3, the second precursor is mixed with a lithium source according to the stoichiometric ratio of each element in the zirconium-doped ternary positive electrode material to obtain a third precursor, and the third precursor is calcined through a high-temperature solid phase method, so that the zirconium-doped ternary positive electrode material is prepared.
The conventional zirconium doping method comprises the following three steps of firstly carrying out zirconium doping through ball milling after preparing a precursor, secondly carrying out zirconium doping through stirring in an ethanol solution after preparing the precursor, and thirdly carrying out coprecipitation reaction by adopting a mode of feeding nickel cobalt manganese main element and doping element zirconium simultaneously to prepare the zirconium doped ternary cathode material precursor. The applicant finds that the preparation of the precursor by ball milling only allows zirconium to be doped on the surface of the material and the zirconium to be unevenly distributed, while for the second preparation scheme, doping zirconium in an ethanol solvent consumes a large amount of ethanol, which not only increases the preparation cost, but also allows the prepared precursor to absorb moisture, which results in easier oxidation of the precursor, and for the scheme of simultaneous feeding, the nickel cobalt manganese zirconium four elements are simultaneously fed for precipitation, the arrangement of zirconium in the ternary cathode material cannot be controlled, and the structure of the prepared precursor has higher uncertainty.
In the invention, a first precursor with a certain size is formed through a first coprecipitation reaction, the formed first precursor has a sheet structure, then a zirconium-containing compound is attached to the sheet structure on the surface layer of the first precursor through a second coprecipitation reaction to obtain a second precursor, and then the zirconium element attached to the surface of the second precursor is subjected to ion solid phase migration through a high-temperature calcination solid phase reaction to finish doping of the zirconium element in the ternary positive electrode material. Compared with the existing doping method, the preparation method provided by the invention can not only effectively improve the uniform distribution of zirconium in the ternary cathode material doped by the zirconium element, but also improve the controllability of the doping amount of the zirconium element so as to improve the quality stability, the product cycle characteristics and the discharge specific capacity of the zirconium doped ternary cathode material.
Preferably, the particle size of the first precursor is 5-10 mu m, and the particle size of the zirconium-containing compound is less than or equal to 100nm. For example, the particle size of the first precursor is 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or the like, and the particle size of the zirconium-containing compound is 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, or the like.
Preferably, the zirconium-containing compound comprises at least one of zirconium dioxide, zirconium sulfate.
Preferably, in the zirconium-doped ternary cathode material, the doping amount of zirconium is 0.1-1%. For example, the doping amount of zirconium is 0.1％、0.15％、0.2％、0.25％、0.3％、0.35％、0.4％、0.2％、0.25％、0.3％、0.35％、0.4％、0.45％、0.5％、0.55％、0.6％、0.65％、0.7％、0.75％、0.8％、0.85％、0.9％、0.95％ or 1%.
Preferably, the S1 is operated by taking soluble nickel salt, soluble cobalt salt and soluble salt containing M element according to the stoichiometric ratio of each element in the zirconium doped ternary positive electrode material, dissolving the soluble nickel salt, the soluble cobalt salt and the soluble salt containing M element in water to obtain a mixed metal salt solution, wherein the sum concentration of the amounts of substances of the nickel element, the cobalt element and the M element in the mixed metal salt solution is 1-3 mol/L, mixing the mixed metal salt solution, a precipitator and a complexing agent, taking the obtained mixed solution as a first mixed solution, and then reacting the first mixed solution in a nitrogen atmosphere to obtain a first precursor. For example, the total concentration of the amounts of substances of nickel element, cobalt element and M element in the mixed metal salt solution is 1mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、1.5mol/L、1.6mol/L、1.7mol/L、1.8mol/L、1.9mol/L、2mol/L、2.1mol/L、2.2mol/L、2.3mol/L、2.4mol/L、2.5mol/L、2.6mol/L、2.7mol/L、2.8mol/L、2.9mol/L or 3mol/L or the like.
Preferably, in S1, the mixed metal salt solution is a precipitant=1 to 3:1 to 2, calculated according to the volume ratio. For example, mixed metal salt solution: precipitant=1:1, mixed metal salt solution: precipitant=1:1.5, mixed metal salt solution: precipitant=1:2, mixed metal salt solution: precipitant=1.5:1, mixed metal salt solution: precipitant=1.5:2, mixed metal salt solution: precipitant=2:1, mixed metal salt solution: precipitant=2:2, mixed metal salt solution: precipitant=2.5:1, mixed metal salt solution: precipitant=2.5:1.5, mixed metal salt solution: precipitant=2.5:2, mixed metal salt solution: precipitant=3:1, mixed metal salt solution: precipitant=3:1.5, mixed metal salt solution: precipitant=3:2, or mixed metal salt solution: precipitant=3:2, etc.
Preferably, the precipitant comprises at least one of sodium hydroxide, sodium carbonate.
Preferably, the concentration of the precipitant is 1-3 mol/L. For example, the concentration of the precipitant is 1mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、1.5mol/L、1.6mol/L、1.7mol/L、1.8mol/L、1.9mol/L、2mol/L、2.1mol/L、2.2mol/L、2.3mol/L、2.4mol/L、2.5mol/L、2.6mol/L、2.7mol/L、2.8mol/L、2.9mol/L or 3mol/L or the like.
Preferably, a complexing agent is added to adjust the ph=10.5 to 11.5. For example, the complexing agent is added to adjust the pH of the first mixed solution to 10.5, 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, or the like.
Preferably, the complexing agent comprises at least one of ammonia water and ammonium oxalate.
Preferably, the concentration of the complexing agent is 3-6 mol/L. For example, the concentration of the complexing agent is 3mol/L、3.1mol/L、3.2mol/L、3.3mol/L、3.4mol/L、3.5mol/L、3.6mol/L、3.7mol/L、3.8mol/L、3.9mol/L、4mol/L、4.1mol/L、4.2mol/L、4.3mol/L、4.4mol/L、4.5mol/L、4.6mol/L、4.7mol/L、4.8mol/L、4.9mol/L、5mol/L、5.1mol/L、5.2mol/L、5.3mol/L、5.4mol/L、5.5mol/L、5.6mol/L、5.7mol/L、5.8mol/L、5.9mol/L or 6mol/L, etc.
Preferably, the soluble nickel salt comprises at least one of nickel sulfate, nickel chloride and nickel nitrate, and/or the soluble cobalt salt comprises at least one of cobalt sulfate, cobalt chloride and cobalt nitrate, and/or the soluble salt containing M element comprises at least one of sulfate, chloride and nitrate.
Preferably, there is only one non-metal anion in the mixed metal salt solution.
Preferably, in S1, the nitrogen gas is introduced in an amount of 40-80 mL/min. For example, the nitrogen gas may be introduced at 40mL/min, 45mL/min, 50mL/min, 55mL/min, 60mL/min, 65mL/min, 70mL/min, 75mL/min, 80mL/min, or the like.
Preferably, in S1, the reaction temperature of the first coprecipitation reaction is 50-55 ℃, the reaction system is allowed to stand for 4-12 hours after the completion of feeding, and the reaction temperature of the second coprecipitation reaction is 50-55 ℃, and the reaction system is allowed to stand for 2-6 hours after the completion of feeding. For example, the reaction temperature of the first coprecipitation reaction is 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, etc., the standing time of the first coprecipitation reaction is 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, etc., and the standing time of the second coprecipitation reaction is 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, etc., the reaction temperature of the second coprecipitation reaction is 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, etc.
Preferably, the zirconium-containing compound is zirconium dioxide. The zirconium dioxide has stronger Zr-O bond, so that the doping of zirconium can reduce the release of lattice oxygen in the ternary anode material.
Preferably, in S2, the zirconium-containing compound is 0.2 to 2% of the sum of the amounts of the added soluble nickel salt, soluble cobalt salt and soluble salt containing M element, calculated as the ratio of the amounts of the substances. For example, the zirconium-containing compound is 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2.0% or the like of the sum of the amounts of the soluble nickel salt, the soluble cobalt salt, and the soluble salt containing the M element added.
Preferably, in the high-temperature solid phase method related to S3, the third precursor is heated to 450-500 ℃ at a temperature rising rate of 1-10 ℃ per minute, the temperature is kept for 5-10 hours to obtain a pre-reaction product, and then the pre-reaction product is heated to 750-900 ℃ at the temperature rising rate of 1-10 ℃ per minute, and the temperature is kept for 12-24 hours to obtain the zirconium doped ternary cathode material. For example, the temperature-rising rate is 1 ℃,2 ℃,3 ℃, 4 ℃,5 ℃,6 ℃,7 ℃,9, 10, etc., heating the third precursor to 450 ℃, 455 ℃, 460 ℃, 465 ℃, 470 ℃, 475 ℃, 480 ℃, 485 ℃, 490 ℃, 495, 500, etc., the first incubation time is 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, etc., and heating the pre-reaction product to 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840, 850 ℃, 860 ℃, 870, 890, or the second incubation time is 12h、12.5h、13h、13.5h、14h、14.5h、15h、15.5h、16h、16.5h、17h、17.5h、18h、18.5h、19h、19.5h、20h、20.5h、21h、21.5h、22h、22.5h、23h、23.5h, etc.
Preferably, the lithium source comprises at least one of lithium hydroxide, lithium carbonate.
Preferably, in S3, the lithium source is a second precursor=1.03 to 1.05:1, calculated according to the mass ratio. For example, the lithium source is second precursor=1.03:1, the lithium source is second precursor=1.04:1, or the lithium source is second precursor=1.05:1, etc., calculated in terms of mass ratio.
According to one aspect of the invention, a ternary cathode material is provided, which is prepared by the preparation method of any zirconium doped ternary cathode material. The prepared ternary positive electrode material has the advantages that on one hand, the lithium-nickel mixed discharge effect is weakened, side reactions between an electrode and an electrolyte can be reduced, so that the stability of the ternary positive electrode material is improved, on the other hand, the transmission of lithium ions and charges in the electrode is accelerated, and the lithium ion diffusion coefficient of the ternary positive electrode material is improved, so that the prepared zirconium-doped ternary positive electrode material shows excellent electrochemical performance.
According to another aspect of the present invention, there is provided a ternary positive electrode comprising a current collector and a positive electrode active coating layer provided on a surface of the current collector, the positive electrode active coating layer containing the above ternary positive electrode material.
Drawings
FIG. 1 is a diagram EDS MAPPING of the ternary cathode material prepared in example 3;
FIG. 2 is an XRD pattern measured by a ternary positive electrode material, wherein AC is a comparison sample of undoped zirconium, and the doping amount of zirconium element of the ternary positive electrode material doped with zirconium is 0.1-1%;
the reference numerals indicate (a) XRD patterns of the test samples in the range of 3-90 degrees and (b) XRD patterns of the test samples in the range of 18-19 degrees.
Detailed Description
In order that the manner in which the above-recited embodiments of the invention are attained and can be readily understood by those skilled in the art, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
1. Preparation method
S1, preparing a 2mol/L sodium hydroxide solution, calculating according to the mass ratio, dissolving cobalt sulfate hexahydrate, manganese sulfate monohydrate and manganese sulfate monohydrate in water in a ratio of 6:2:2 to prepare a mixed metal salt solution with a concentration of 1mol/L, then starting a stirring paddle of a reaction kettle, adding the mixed metal salt solution and the 2mol/L sodium hydroxide solution into the reaction kettle, calculating according to the volume ratio, adding a proper amount of 3mol/L ammonia water into the mixed metal salt solution, adjusting the pH value to 11.5, heating to 60 ℃ under a nitrogen atmosphere, reacting for 12 hours, and then preserving heat and standing for 8 hours to obtain a first precursor, wherein the introducing amount of nitrogen is maintained at 70mL/min;
S2, adding zirconium dioxide with the grain size of 100nm (calculated according to the mass ratio, wherein the zirconium dioxide is 0.1 percent of the sum of the mass of the added nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate) into a reaction kettle, heating to 60 ℃, stirring and dispersing for 2 hours, keeping the temperature and standing for 2 hours, keeping the nitrogen gas inlet amount at 70mL/min, filtering the reaction liquid after the reaction is finished, repeatedly washing the obtained solid until the pH value of the washing liquid is=7, and then filtering again to freeze-dry the obtained solid to obtain a second precursor;
S3, mixing lithium hydroxide with the second precursor to obtain a third precursor, wherein the mass ratio of the lithium hydroxide to the second precursor is calculated to be 1.05:1, calcining the third precursor in a tube furnace in an oxygen atmosphere, heating to 480 ℃ at a temperature rising rate of 5 ℃ per min, preserving heat for 5 hours, heating to 850 ℃ at a temperature rising rate of 5 ℃ per min, preserving heat for 20 hours, and sieving the obtained powder through a 200-mesh sieve to obtain the zirconium-doped ternary anode material.
Examples 2-5 ternary cathode materials were prepared by referring to the formulation and method provided in example 1, taking the percentage of the amount of zirconium dioxide added as the mixed metal salt added in the formulation as a variable, the variables used in preparing the ternary cathode materials in examples 2-5 are shown in table 2, and the operation steps for preparing the ternary cathode materials in examples 2-5 are strictly consistent with those in example 1 except the above differences.
TABLE 1 variable for preparing ternary cathode materials of examples 1-5
Test example 1
1. Test object
The batteries were prepared and tested by using the ternary cathode materials prepared in examples 1 to 5, and the specific procedures are as follows:
And (3) mixing the ternary positive electrode material (Super P: PVDF=95:2.5:2.5) with a proper amount of NMP solvent according to a mass ratio to prepare electrode slurry, uniformly coating the electrode slurry on the surface of an aluminum foil, and drying to obtain a positive electrode plate, wherein the electrolyte is a mixed solution of ethylene carbonate and dimethyl carbonate in which 1mol/L LiPF 6 is dissolved, and the volume ratio of ethylene carbonate to dimethyl carbonate=1:1. And forming the prepared positive pole piece, negative pole piece (lithium piece) and electrolyte into a battery to be tested.
2. Test method
(1) Doping amount of zirconium SEM test is carried out by using JEOL JSM-7610F with 20kV voltage to obtain morphology of the prepared ternary positive electrode material. And observing the morphology of the ternary positive electrode material in a dark field according to EDS MAPPING data measured by JEM-200F, and observing the distribution of each element.
(2) XRD X-ray diffraction pattern of the sample was measured by Ultima IV (Rigaku, japan). And spreading the ternary positive electrode material until the ternary positive electrode material covers the sample rack, wherein the test speed is 5 degrees/min, and the test angle 2 theta is 3-90 degrees.
(3) And (3) performing cyclic charge and discharge test, namely charging the prepared battery with 3C multiplying power and 3C multiplying power in a voltage range of 2.5-4.3V at 25 ℃ and discharging the battery with 3C multiplying power, and performing full charge and discharge cyclic test, namely circulating for 400 circles, and recording the capacity retention rate and the discharge specific capacity.
3. Experimental results and analysis
The results of the cyclic charge-discharge experiments of test example 1 are shown in table 2, wherein it can be found that, in the zirconium-doped ternary cathode materials prepared in examples 1 to 5, as the zirconium doping amount in the ternary cathode materials increases, the capacity retention rate of the battery prepared by using the zirconium-doped ternary cathode materials shows a trend of increasing and decreasing after increasing, and the capacity retention rate of the battery prepared by using the zirconium-doped ternary cathode materials prepared in example 3 is highest, so that it is demonstrated that the optimal zirconium doping amount of the ternary cathode materials provided by the invention is 0.5%, and the result of the EDS MAPPING and XRD test of the zirconium-doped ternary cathode materials prepared in example 3 are shown in fig. 1 and 2, respectively, and as for EDS MAPPING analysis (fig. 1), it can be seen that the distribution uniformity of nickel element, cobalt element, manganese element and zirconium element in the test object is relatively high, and that disappearance of 003 peak and appearance of new peak in fig. 2 (b) show that the zirconium element is successfully doped in the ternary cathode materials. From the test results, the zirconium doping amount in the ternary cathode material prepared in example 1 is lower, the zirconium doping amount in the ternary cathode material prepared in example 5 is higher, the battery capacity retention rates corresponding to the two are lower than those of the other examples, the zirconium doping amount of the ternary cathode material prepared in examples 2-4 is 0.1-1%, the capacity retention rate of the ternary cathode material is higher, and the ternary cathode material has better cycle stability.
TABLE 2 Experimental results for test example 1
| Group of | Zirconium doping amount/% | Capacity retention/400 cls | Specific discharge capacity/mAh.g -1 |
| Example 1 | 0.05 | 69.0% | 94.2 |
| Example 2 | 0.1 | 69.5% | 104.7 |
| Example 3 | 0.5 | 79.7% | 118.8 |
| Example 4 | 1 | 75.8% | 109.8 |
| Example 5 | 2 | 61.8% | 93.4 |
Example 6
This example is distinguished from example 3 by the formulation and method provided in reference to example 3 in that the stoichiometry of Ni: co: mn=8:1:1 for the preparation of the ternary cathode material used in S1, heating to 480 ℃ at a temperature ramp rate of 5 ℃ per minute in S3, holding for 5 hours, and then heating to 800 ℃ at a temperature ramp rate of 5 ℃ per minute, except for the differences described above, the operational steps of this example for the preparation of the ternary cathode material are strictly consistent with example 3.
Example 7
This example is distinguished from example 3 by the formulation and method provided in reference to example 3 in that the stoichiometry of Ni: co: mn=5:2:3 for the preparation of the ternary cathode material used in S1, and in S3 the ternary cathode material was heated to 480 ℃ at a temperature ramp rate of 5 ℃ per minute, held for 5 hours, and then heated to 900 ℃ at a temperature ramp rate of 5 ℃ per minute, except for the differences described above, the operational steps of this example for the preparation of the ternary cathode material were strictly consistent with example 3.
Example 8
This example is distinguished from example 3 in that in S1, a mixed metal salt solution having a concentration of 1mol/L is prepared from nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and aluminum sulfate anhydrate=8:1.5:0.5, and in S3, the ternary cathode material is prepared by heating to 480 ℃ at a temperature rise rate of 5 ℃ per minute, maintaining the temperature for 5 hours, and then heating to 800 ℃ at a temperature rise rate of 5 ℃ per minute, except for the above differences, the operation steps of this example for preparing the ternary cathode material are strictly consistent with those of example 3.
Test example 2
1. Test object
Batteries were prepared and tested by using the ternary cathode materials prepared in examples 6 to 8, specifically according to the method provided in test example 1.
2. Test method
The test was performed according to the method provided in test example 1.
3. Experimental results and analysis
The experimental results of the test examples are shown in Table 3. As can be seen from the result of test example 2, the preparation method of the zirconium-doped ternary cathode material provided by the invention can be used for preparing various types of nickel-rich ternary materials, and the prepared ternary cathode material has good stability.
TABLE 3 Experimental results for test example 2
| Group of | Zirconium doping amount/% | Capacity retention/400 cls | Specific discharge capacity/mAh.g -1 |
| Example 6 | 0.5 | 81.2% | 119.7 |
| Example 7 | 0.5 | 73.2% | 111.7 |
| Example 8 | 0.5 | 70.1% | 108.3 |
Comparative example 1
This comparative example a ternary cathode material was prepared with the formulation provided in reference to example 3, and was distinguished from example 3 in that this comparative example was prepared by ball milling, specifically, as follows:
According to the formula provided in example 3, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate monohydrate, zirconium dioxide and lithium hydroxide are put into a cylinder, a planetary ball mill is adopted to perform 24-hour high-energy ball milling, the ball-to-material ratio is 10:1, a grinding body adopts steel balls, the rotating speed is 400r/min, the obtained powder is subjected to high-temperature solid-phase reaction, and the calcination operation is strictly consistent with that of S3 in example 3, so that the ternary positive electrode material is prepared.
Comparative example 2
This comparative example a ternary cathode material was prepared with the formulation provided in reference to example 3, and was distinguished from example 3 in that this comparative example was prepared by ball milling, specifically, as follows:
S1-S2, wherein the operation is strictly consistent with that of S1 and S2 in the embodiment 3;
s3, according to the formula provided in the S3 of the embodiment 3, mixing lithium hydroxide with a second precursor, putting the mixture into a cylinder, performing high-energy ball milling for 24 hours by adopting a planetary ball mill, wherein the ball-material ratio is 10:1, the grinding body adopts steel balls, the rotating speed is 400r/min, performing high-temperature solid-phase reaction on the obtained powder, and calcining the powder, wherein the calcining operation is strictly consistent with that of the S3 of the embodiment 3, thereby preparing the ternary positive electrode material.
Comparative example 3
This comparative example a ternary cathode material was prepared with the formulation provided in reference to example 3, differing from example 3 in that this comparative example uses an ethanol solution to prepare a ternary cathode material, specifically as follows:
s1, strictly keeping the same with the S1 operation of the embodiment 3;
S2, dissolving the first precursor prepared in the step S1 in ethanol to obtain a solution A, then adding zirconium dioxide with the particle size of 100nm (1% of the added mixed metal salt according to the mass ratio), and keeping the rest operation strictly consistent with the operation S2 of the embodiment 3 to obtain a second precursor;
s3, strictly keeping the same operation as the S3 in the embodiment 3, and preparing the ternary positive electrode material.
Comparative example 4
This comparative example a ternary cathode material was prepared with the formulation provided in reference to example 3, in contrast to example 3, which uses a co-current feed co-precipitation process to prepare the ternary cathode material, specifically as follows:
s1, according to the raw materials and the proportion provided in the embodiment 3, simultaneously adding a mixed metal salt solution, zirconium dioxide and a sodium hydroxide solution in a nitrogen atmosphere, then adding ammonia water, adjusting the pH value to 11.5, heating to 60 ℃ in the nitrogen atmosphere for reaction for 12 hours, and standing for 12 hours to obtain a precursor;
s2, according to the formula provided in the S3 of the example 3, the precursor and lithium hydroxide are mixed and then calcined, and the calcining operation is strictly consistent with the S3 operation of the example 3, so that the ternary cathode material is prepared.
Test example 3
1. Test object
Batteries were prepared and tested using the ternary cathode materials prepared in example 3 and comparative examples 1 to 4, specifically according to the method provided in test example 1.
2. Test method
Stability test the preparation methods described in example 3 and comparative examples 1 to 4 were repeated three times, the prepared ternary cathode materials were correspondingly marked as sample 1, sample 2 and sample 3, the prepared samples were respectively prepared into batteries, zirconium doping amounts, capacity retention rates and specific discharge capacities of the different samples were tested, and then variances of the measured data were respectively calculated, and the smaller variances indicated that the corresponding preparation methods were higher in repeatability.
Zirconium doping amount and cyclic charge and discharge test were tested according to the method provided in test example 1.
3. Experimental results and analysis
As shown in the data of the table 4 and the table 5, the stability experiment shows that the ternary cathode material prepared in the example 3 has higher repeatability and higher capacity retention rate, and the preparation method of the example 3 has higher repeatability and higher stability. This is because the doping process of example 3 is high in stability and zirconium element can be uniformly dispersed in the prepared ternary cathode material. However, as can be seen from the data in Table 5, the variance values of comparative examples 1 to 4 are larger, which means that the experimental repeatability of comparative examples 1 to 4 is lower, and the cyclic charge-discharge experiment shows that the experimental data of comparative examples 1 to 4 fluctuate more. This is probably because there are cases where the dispersion of the zirconium element is not uniform, and this dispersion is not controllable, thereby affecting the stability of the electrode material and the battery. In addition, the discharge specific capacity was less stable for comparative example 3, since the preparation of the ternary cathode material using ethanol caused the precursor to absorb moisture, thereby causing the precursor to be more easily oxidized. The preparation method provided in comparative example 4, however, has a large fluctuation in data of capacity retention rate and specific discharge capacity measured each time due to poor quality control, which is caused by low structural stability of the prepared ternary cathode material.
TABLE 4 Experimental results for test example 3
TABLE 5 calculation results for test example 3
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the zirconium doped ternary cathode material is characterized by comprising the following steps of:
S1, preparing a first precursor by adopting soluble nickel salt, soluble cobalt salt and soluble salt containing M element through a first coprecipitation reaction according to the stoichiometric ratio of each element in the zirconium-doped ternary positive electrode material, wherein the first precursor contains nickel element, cobalt element and manganese element, and the stoichiometric ratio of Ni to Mn=8 to 1 in the first precursor;
s2, depositing zirconium dioxide on the surface of the first precursor through a second coprecipitation reaction to obtain a second precursor, wherein the particle size of the zirconium dioxide is less than or equal to 100nm;
s3, mixing the second precursor with a lithium source according to the stoichiometric ratio of each element in the zirconium-doped ternary cathode material to obtain a third precursor, heating to 480 ℃ at a temperature rising rate of 5 ℃ per minute, preserving heat for 5 hours, heating to 800 ℃ at a temperature rising rate of 5 ℃ per minute, and preserving heat for 20 hours, thereby preparing the zirconium-doped ternary cathode material, wherein the doping amount of zirconium in the zirconium-doped ternary cathode material is 0.5%.
2. The method of claim 1, wherein the first precursor has a particle size of 5 to 10. Mu.m.
3. The method according to any one of claims 1 to 2, wherein the step S1 is performed by dissolving the soluble nickel salt, the soluble cobalt salt, and the soluble salt containing the M element in water according to the stoichiometric ratio of each element in the zirconium-doped ternary cathode material to obtain a mixed metal salt solution, wherein the total concentration of the amounts of the nickel element, the cobalt element, and the M element in the mixed metal salt solution is 1 to 3mol/L, mixing the mixed metal salt solution, a precipitant, and a complexing agent to obtain a mixed solution as a first mixed solution, and then reacting the first mixed solution under a nitrogen atmosphere to obtain the first precursor.
4. The method according to claim 3, wherein in S1, the mixed metal salt solution is the precipitant=1 to 3:1 to 2 in terms of volume ratio.
5. The method of claim 3, wherein the complexing agent is added in an amount such that the pH of the first mixed solution is 10.5 to 11.5.
6. A method of preparation as claimed in claim 3, wherein:
The soluble nickel salt comprises at least one of nickel sulfate, nickel chloride and nickel nitrate;
And/or the soluble cobalt salt comprises at least one of cobalt sulfate, cobalt chloride and cobalt nitrate;
and/or the soluble salt containing the M element comprises at least one of sulfate, chloride and nitrate.
7. The preparation method according to any one of claims 1 to 2, characterized in that:
in the step S1, the reaction temperature of the first coprecipitation reaction is 50-55 ℃, and after the feeding is completed, the reaction system is kept stand for 4-12 hours;
in the step S2, the reaction temperature of the second coprecipitation reaction is 50-55 ℃, and after the feeding is completed, the reaction system is kept stand for 2-6 hours.
8. The ternary cathode material is characterized by being prepared by the preparation method of the zirconium-doped ternary cathode material according to any one of claims 1-7.
9. A ternary positive electrode, which is characterized by comprising a current collector and a positive electrode active coating arranged on the surface of the current collector, wherein the positive electrode active coating contains the ternary positive electrode material as claimed in claim 8.
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| CN105633395A (en) * | 2016-01-14 | 2016-06-01 | 苏州林奈新能源有限公司 | High-nickel ternary positive electrode material of lithium ion battery and preparation method of high-nickel ternary positive electrode material |
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