CN111564625A - Single crystal ternary positive electrode material and preparation method thereof - Google Patents
Single crystal ternary positive electrode material and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 title claims description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000013067 intermediate product Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 24
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 niobia Chemical compound 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—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
-
- 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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Abstract
The invention provides a preparation method of a single crystal ternary cathode material, which comprises the following steps: (1) mixing lithium carbonate and NixCoyMn1‑x‑y(OH)2Uniformly mixing the metal oxide and the metal oxide according to the proportion, wherein x is more than or equal to 0.65 and less than or equal to 0.7, and y is more than or equal to 0.05 and less than or equal to 0.1; (2) sintering the uniformly mixed raw materials in the step (1) at 500-935 ℃ in an oxygen-containing atmosphere to obtain an intermediate product A; (3) crushing the intermediate product A and uniformly mixing the crushed intermediate product A with a pre-coated material, wherein the pre-coated material is nano Zr (OH)4Nano ZrO 22Nano Ti (OH)4TiO 2 nanoparticles2Nano Al (OH)3And nano Al2O3At least one of; (4) and (4) sintering the uniformly mixed material obtained in the step (3) in an atmosphere containing air to obtain the single crystal ternary cathode material. The method has low cost and controllable processAnd is relatively simple; the prepared single crystal ternary cathode material has the advantages of low content of residual lithium on the surface, high capacity, good cycle performance, stable property, difficult deterioration and easy storage.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a single crystal ternary cathode material and a preparation method thereof.
Background
The conventional 523-type LiNi0.5Co0.2Mn0.3O2And 622 type LiNi0.6Co0.2Mn0.2O2And 811 type LiNi0.8Co0.1Mn0.1O2The gram capacity of 0.1C is respectively close to 173mAh g at 25 ℃ and 4.3V-1、185mAh·g-1、201mAh·g-1And the demand of the domestic market for the high specific energy battery cell is more and more urgent, and various large battery cell factories and material factories are in need of accelerating the industrialization of the high nickel material. The energy density of 523 type ternary positive electrode material cannot meet the requirement of the power market, but the current 811 type LiNi0.8Co0.1Mn0.1O2Although the energy density is high, the method has the problems of difficult processing, easy deterioration, easy gas generation and the like. And type 622 LiNi0.6Co0.2Mn0.2O2The lithium ion battery is considered to be a long-cycle and high-safety power product, but the lithium ion battery is high in cost and relatively low in capacity, so that the cost performance is low, and the low-cost trend of the whole industry at present cannot be met, and therefore a ternary cathode material with high capacity, long cycle and high safety is urgently needed to replace a 622 type ternary cathode material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a single crystal ternary cathode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a single-crystal ternary cathode material comprises the following steps:
(1) mixing lithium carbonate and NixCoyMn1-x-y(OH)2Uniformly mixing the metal oxide and the metal oxide according to the proportion, wherein x is more than or equal to 0.65 and less than or equal to 0.7, and y is more than or equal to 0.05 and less than or equal to 0.1;
(2) sintering the uniformly mixed raw materials in the step (1) at 500-935 ℃ in an oxygen-containing atmosphere to obtain an intermediate product A;
(3) crushing the intermediate product A and uniformly mixing the crushed intermediate product A with a pre-coated material, wherein the pre-coated material is nano Zr (OH)4Nano ZrO 22Nano Ti (OH)4TiO 2 nanoparticles2Nano Al (OH)3And nano Al2O3At least one of;
(4) and (4) sintering the uniformly mixed material obtained in the step (3) in an oxygen-containing atmosphere to obtain the single crystal ternary cathode material.
The method uses Ni with high content of nickel and low content of cobaltxCoyMn1-x-y(OH)2And lithium carbonate and metal oxide as raw materials, a small amount of one or more metal elements are doped by sintering to make up the defect of low cobalt of the material, the stability of the material structure is improved, the cation mixed discharge of the material is inhibited, the specific capacity and the cycling stability are improved, and then nano Zr (OH) is added by secondary sintering4Nano ZrO 22Nano Ti (OH)4TiO 2 nanoparticles2Nano Al (OH)3And nano Al2O3At least one of the three-component lithium ion battery anode material is coated on the surface layer of the material, so that the corrosion of electrolyte to the material is inhibited, the cycle performance of the single crystal ternary anode material is ensured, and the capacity is improved compared with a 622-type mainstream product in the current market; the method adopts lithium carbonate as a lithium source, has low cost, low content of residual lithium on the surface and controllable and relatively simple process; the prepared single crystal ternary cathode material has stable property, is not easy to deteriorate and is easy to store.
Preferably, the metal oxide is at least one of alumina, magnesia, niobia, zirconia, strontium oxide, yttrium oxide, and titanium oxide.
The inventors found through research that when at least one metal element selected from alumina, magnesia, niobia, zirconia, strontium oxide, yttrium oxide, and titanium oxide is doped by sintering, the stability of the material structure can be improved to a greater extent.
Preferably, the metal oxides are used in amounts of: metal element weight and Ni in metal oxidexCoyMn1-x-y(OH)2The weight ratio is 0.1-1.0%.
The inventor finds that the weight of the metal element in the metal oxide is equal to Ni through researchxCoyMn1-x-y(OH)2When the weight ratio is 0.1-1.0%, the stability of the material structure can be improved to a greater extent.
Preferably, the lithium carbonate and NixCoyMn1-x-y(OH)2The molar ratio of (1.03-1.15): 1.
the inventor finds out through research that lithium and Ni in lithium carbonatexCoyMn1-x-y(OH)2The molar ratio of (1.03-1.15): 1, the capacity of the prepared single crystal ternary cathode material is higher.
Preferably, the amount of the pre-coated substance is as follows: the mass ratio of the pre-coated substance to the crushed intermediate product A is 0.05-1.0%.
The inventor finds that the cycle of the prepared single crystal ternary cathode material is better when the mass ratio of the pre-coated substance to the crushed intermediate product A is 0.05-1.0%.
Preferably, in the step (1), the sintering time is not less than 19 h.
Preferably, in the step (4), the sintering time at 500-800 ℃ is 8-10 h.
Preferably, in the step (2), the volume content of oxygen in the oxygen-containing atmosphere is not less than 60%.
Preferably, in the step (2), the sintering temperature program is 500-700 ℃ for 3-5 h, 720-850 ℃ for 4-6 h, and 890-935 ℃ for 11-13 h.
Preferably, in the step (1), the particle size of the lithium carbonate is smaller than 120 meshes.
Preferably, in the step (3), the intermediate product A is pulverized to D50＝3.0～5.0μm。
The invention also provides the single crystal ternary cathode material prepared by any one of the methods.
The single crystal ternary cathode material has high capacity, good cycle performance, stable property, difficult deterioration and easy storage.
The invention has the beneficial effects that: the invention provides a single crystal ternary anode material and a preparation method thereofxCoyMn1-x-y(OH)2And lithium carbonate and metal oxide as raw materials, a small amount of one or more metal elements are doped by sintering to make up the defect of low cobalt of the material, the stability of the material structure is improved, the cation mixed discharge of the material is inhibited, the specific capacity and the cycling stability are improved, and then nano Zr (OH) is added by secondary sintering4Nano ZrO 22Nano Ti (OH)4TiO 2 nanoparticles2Nano Al (OH)3And nano Al2O3At least one of the three-component lithium ion battery anode material is coated on the surface layer of the material, so that the corrosion of electrolyte to the material is inhibited, the cycle performance of the single crystal ternary anode material is ensured, and the capacity is improved compared with a 622-type mainstream product in the current market; the method adopts lithium carbonate as a lithium source, has low cost, low content of residual lithium on the surface of the prepared single crystal ternary cathode material, controllable process and relative simplicity; the prepared single crystal ternary positive electrode material has high capacity, good cycle performance, stable property, difficult deterioration and easy storage.
Drawings
Fig. 1 is an XRD pattern of the single crystal ternary cathode material of example 1 of the present invention.
FIG. 2 is an SEM photograph of a pulverized intermediate A of example 1 of the present invention.
Fig. 3 is an SEM image of the single crystal ternary cathode material of example 1 of the present invention.
FIG. 4 is an SEM photograph of a pulverized intermediate A of example 2 of the present invention.
Fig. 5 is an SEM image of the single crystal ternary cathode material of example 2 of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the single crystal ternary cathode material provided by the embodiment of the invention comprises the following steps:
(1) mixing lithium carbonate and Ni0.65Co0.05Mn0.3(OH)2And metal oxide which is MgO and ZrO are put in a high-speed mixer according to the proportion and are mixed uniformly2Zirconium element weight and Ni in zirconia0.65Co0.05Mn0.3(OH)2The weight ratio of the magnesium oxide to the Ni is 0.25 percent0.65Co0.05Mn0.3(OH)2The weight ratio of the lithium carbonate to the Ni is 0.2 percent0.65Co0.05Mn0.3(OH)2In a molar ratio of Li: (Ni + Co + Mn) ═ 1.03: 1, the particle size of lithium carbonate is less than 300 meshes, and the particle size D of metal oxide50Is 100 nm;
(2) sintering the uniformly mixed raw materials in the step (1) in an oxygen-containing atmosphere to obtain an intermediate product A, wherein the sintering temperature program is 700 ℃ for 5h, 850 ℃ for 6h and 935 ℃ for 13h, oxygen is continuously introduced in the sintering process, carbon dioxide is discharged in time, and the volume content of oxygen is kept to be not lower than 60%;
(3) pulverizing the intermediate product A to D50After the grain size is 3.0-5.0 mu m, uniformly mixing the grain size and a pre-coating material, wherein the pre-coating material is nano TiO2And nano Al2O3，TiO20.05% by mass of Al with respect to the intermediate product A2O3The mass ratio of the intermediate product A to the intermediate product A is 0.2 percent;
(4) and (4) sintering the uniformly mixed material obtained in the step (3) for 8 hours at 800 ℃ in an air atmosphere to obtain the single crystal ternary cathode material.
And sieving the obtained single crystal ternary positive electrode material by a 300-mesh sieve in a dehumidification room with the humidity of less than 35%, removing iron, controlling the content of magnetic substances of the single crystal ternary positive electrode material after iron removal to be less than 50ppb, and testing the single crystal ternary positive electrode material after iron removal.
As shown in fig. 1, the crystal structure analysis of the single crystal ternary cathode material obtained in this example by X-ray diffraction (XRD) showed that the ternary cathode material LiNi0.65Co0.05Mn0.3O2The crystal structure is complete.
The intermediate product a (fig. 2) and the single crystal ternary cathode material (fig. 3) after being crushed in this example are characterized by using a Scanning Electron Microscope (SEM), and comparing fig. 2 and fig. 3, it is found that the surface of the single crystal ternary cathode material after being processed in steps (3) and (4) has a uniform coating.
The electrochemical performance of the single crystal ternary cathode material is tested by using a 18650 battery, and the capacity of 0.1C gram reaches 187 mAh.g-1The 1C gram capacity reaches 172mAh g-1And the retention rate of the 1C charge-discharge cycle for 2000 times is more than 80 percent.
Example 2
The preparation method of the single crystal ternary cathode material provided by the embodiment of the invention comprises the following steps:
(1) mixing lithium carbonate and Ni0.7Co0.1Mn0.2(OH)2And metal oxide is placed in a high-speed mixer according to the proportion and mixed evenly, wherein the metal oxide is Nb2O5And ZrO2Zirconium element weight and Ni in zirconia0.7Co0.1Mn0.2(OH)2In the niobium oxide, the weight ratio of the niobium element to Ni is 0.3 percent0.7Co0.1Mn0.2(OH)2In a weight ratio of 0.1%, the lithium carbonate and Ni0.65Co0.05Mn0.3(OH)2In a molar ratio of Li: (Ni + Co + Mn) ═ 1.05: 1, the particle size of lithium carbonate is less than 300 meshes, and the particle size D50 of the metal oxide is 100 nm;
(2) sintering the uniformly mixed raw materials in the step (1) in an oxygen-containing atmosphere to obtain an intermediate product A, wherein the sintering temperature program is 500 ℃ for 3h, 720 ℃ for 4h and 890 ℃ for 11h, oxygen is continuously introduced in the sintering process, carbon dioxide is timely discharged, and the volume content of the oxygen is kept to be not lower than 60%;
(3) pulverizing the intermediate product A to D50After the thickness is 3.0-5.0 mu m, the mixture is uniformly mixed with a pre-coated substance which is nano ZrO2And nano Al2O3，ZrO2And the intermediate product A accounts for 0.2 mass percent, and Al2O3And the mass ratio of the intermediate product A is 0.25%;
(4) and (4) sintering the uniformly mixed material obtained in the step (3) for 10 hours at 500 ℃ in an air atmosphere to obtain the single crystal ternary cathode material.
The intermediate product a (fig. 4) and the single crystal ternary cathode material (fig. 5) after being crushed in this example are characterized by using a Scanning Electron Microscope (SEM), and comparing fig. 4 and fig. 5, it is found that the surface of the single crystal ternary cathode material after being processed in steps (3) and (4) has a uniform coating.
The electrochemical performance of the single crystal ternary cathode material is tested by using 18650 batteries, and the capacity of 0.1C gram reaches 196 mAh.g-1The 1C gram capacity reaches 182mAh g-1And the retention rate of the 1C charge-discharge cycle for 2000 times is more than 82%.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a single crystal ternary cathode material is characterized by comprising the following steps:
(1) mixing lithium carbonate and NixCoyMn1-x-y(OH)2Uniformly mixing the metal oxide and the metal oxide according to the proportion, wherein x is more than or equal to 0.65 and less than or equal to 0.7, and y is more than or equal to 0.05 and less than or equal to 0.1;
(2) sintering the uniformly mixed raw materials in the step (1) at 500-935 ℃ in an oxygen-containing atmosphere to obtain an intermediate product A;
(3) crushing the intermediate product A and uniformly mixing the crushed intermediate product A with a pre-coated material, wherein the pre-coated material is nano Zr (OH)4Nano ZrO 22Nano Ti (OH)4TiO 2 nanoparticles2Nano Al (OH)3And nano Al2O3At least one of;
(4) and (4) sintering the uniformly mixed material obtained in the step (3) at 500-800 ℃ in an atmosphere containing air to obtain the single crystal ternary cathode material.
2. The method for producing a single-crystal ternary positive electrode material according to claim 1, wherein the metal oxide is at least one of aluminum oxide, magnesium oxide, niobium oxide, zirconium oxide, strontium oxide, yttrium oxide, and titanium oxide.
3. The method for preparing a single-crystal ternary cathode material according to claim 2, wherein the metal oxide is used in an amount of: metal element weight and Ni in metal oxidexCoyMn1-x-y(OH)2The weight ratio is 0.1-1.0%.
4. The method for producing a single-crystal ternary positive electrode material according to claim 1 or 3, wherein the lithium carbonate and Ni arexCoyMn1-x-y(OH)2The molar ratio of (1.03-1.15): 1.
5. the method for preparing a single crystal ternary cathode material according to claim 1, wherein the pre-coating is used in an amount of: the mass ratio of the pre-coated substance to the crushed intermediate product A is 0.05-1.0%.
6. The method for producing a single-crystal ternary cathode material according to claim 1, wherein in the step (2), the volume content of oxygen in the atmosphere containing oxygen is not less than 60%.
7. The preparation method of the single crystal ternary cathode material as claimed in claim 1, wherein in the step (2), the sintering temperature program is 500-700 ℃ for 3-5 h, 720-850 ℃ for 4-6 h, and 890-935 ℃ for 11-13 h;
in the step (4), the sintering time at 500-800 ℃ is 8-10 h.
8. The method for preparing a single crystal ternary positive electrode material according to claim 1, wherein in the step (1), the particle size of the lithium carbonate is less than 120 meshes.
9. The method for producing a single-crystal ternary positive electrode material according to claim 1, wherein in the step (3), the intermediate product a is pulverized to D50＝3.0～5.0μm。
10. A single crystal ternary positive electrode material prepared by the method of any one of claims 1 to 9.
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