A coated ternary material with high environmental tolerance and its preparation method and application

Abstract

The present invention relates to a coated ternary material with high environmental tolerance, its preparation method, and application. The coated ternary material of the present invention comprises a core-shell structure, and the positive electrode material has high environmental tolerance, wherein: the core comprises the ternary material; the shell serves as a coating layer and comprises a zirconium phosphate; the coating layer is uniformly, continuously, completely, and has a controllable thickness and is coated on the core surface. The coated ternary material of the present invention can improve the environmental tolerance of high-nickel ternary positive electrode materials, facilitate long-term storage and use in high dew point environments, and has high practical application prospects in the field of lithium-ion batteries.

Description

Technical Field

[0001] The present invention belongs to the technical field of lithium-ion battery positive electrode materials, and in particular relates to a coated ternary material with high environmental tolerance, a preparation method thereof, and applications thereof. Background Art

[0002] High-nickel ternary cathode materials stand out among many lithium-ion battery cathode materials due to their high energy density and low cost. While the energy density gradually improves with increasing nickel content, the inherent shortcomings of high-nickel materials are also exposed. The material's stability is inversely proportional to the nickel content, and its environmental tolerance gradually deteriorates. During storage, an amorphous alkaline impurity film (such as Li2CO3, LiOH, etc.) forms on the surface of high-nickel ternary cathode materials. The composition, formation speed, and amount of surface impurities are related to the nickel content in the active cathode material and the CO2 and H2O content in the environment. The presence of this impurity film has a significant adverse effect on the capacity decay, service life, and safety of high-nickel cathode materials. Therefore, cathode materials with higher nickel content have stricter environmental requirements for preparation, use, and storage, especially extremely stringent requirements for controlling moisture in the air. This invisibly increases the cost of the material and limits its wider application range.

[0003] In order to maintain the high capacity advantage of high nickel ternary materials, while reducing battery gas production and achieving a long battery life, it is very important to control the stability of the material surface structure and improve the environmental tolerance of the material. Usually, the industry uses the water washing process to remove alkaline impurities on the surface of high nickel ternary materials. However, Li is easily generated during the water washing process. + / H + Ion exchange reaction, too strong water washing will lead to the formation of Li + Continuous reaction and dissolution cause the collapse of the material structure. In addition, if the washed material is exposed to the air again, its surface will more easily combine with H2O and CO2 to form an alkaline material layer, aggravating the cation mixing in the structure and ultimately leading to the formation of inactive NiO cubic phase, causing the performance of the material to further decline. Therefore, the water washing process does not essentially improve the material's own tolerance to the environment. Surface coating is an effective means to effectively improve the stability of the material surface and enhance the material's tolerance to the environment. For example, Stefano Passerini et al. at the Helmholtz Institute in Germany proposed a method of coating LiNi with a lithium phosphonate functionalized polyarylethersulfone organic polymer layer. 0.8 Co 0.1 Mn 0.1O2 (NCM811) particle surface, preventing the electrode material from being directly exposed to H2O and CO2, thereby reducing the reactivity of NCM811 with the ambient atmosphere and improving the environmental tolerance of the material (DOI: 10.1002 / adfm.202105343). However, the synthesis of this method is too complicated, the raw materials used are unconventional reagents, the industrial feasibility is not high, the thickness, uniformity and integrity of the coating layer are uncontrollable, and the consistency and timeliness of the environmental tolerance improvement effect of the incompletely coated material are difficult to guarantee. How to use a simple, easy and low-cost method that does not significantly affect the electrochemical performance of the ternary positive electrode material and improve the environmental tolerance of the material for a long time is a difficult problem that needs to be solved at present. Summary of the Invention

[0004] The purpose of the present invention is to provide a coated ternary material with high environmental tolerance, a preparation method and application thereof.

[0005] The present invention provides a coated ternary material, wherein the coated ternary material comprises a core-shell structure, and the positive electrode material has high environmental tolerance, wherein:

[0006] The core comprises ternary materials;

[0007] The shell acts as a coating and comprises zirconium phosphate;

[0008] The coating layer is coated on the core surface uniformly, continuously, completely and with controllable thickness.

[0009] According to an embodiment of the present invention, the ternary material is selected from high-nickel ternary materials.

[0010] Preferably, the high nickel ternary material has a layered structure.

[0011] Preferably, the high nickel ternary material has the following structural formula: LiNi x Co y Mn z O2wherein, x+y+z=1, x≥0.6.

[0012] Exemplarily, the high nickel ternary material is selected from LiNi 0.6 Co 0.2 Mn 0.2 O2、LiNi 0.7 Co 0.15 Mn 0.15 O2、LiNi 0.8 Co 0.1 Mn 0.1 O2、LiNi 0.83 Co 0.07 Mn 0.1 O2.

[0013] According to an embodiment of the present invention, the zirconium phosphate is selected from at least one of zirconium phosphate, zirconium pyrophosphate, zirconium metaphosphate, and lithium zirconium phosphate, and is preferably zirconium phosphate.

[0014] According to an embodiment of the present invention, the thickness of the coating layer is 1 to 200 nm, preferably 10 to 100 nm, more preferably 15 to 20 nm, for example, 18 nm, 87 nm, 90 nm, or 95 nm.

[0015] According to an embodiment of the present invention, the high environmental tolerance of the coated ternary material refers to storage in a relatively high dew point environment, for example, at 25° C. and a humidity of 50 RH%.

[0016] The present invention also provides a method for preparing the above-mentioned coated ternary material, the preparation method comprising:

[0017] 1) dissolving the core material and zirconium element in a polar solvent to obtain solution A;

[0018] 2) preparing solution B containing a phosphorus-containing precipitant;

[0019] 3) adding solution B to solution A under stirring conditions, and performing in-situ coating with controllable thickness on the surface of the core material by coordination coprecipitation of the phosphorus-containing precipitant and the zirconium salt, thereby forming an intermediate product with a coated core-shell structure;

[0020] 4) The intermediate product of step 3) is calcined to obtain the coated ternary material.

[0021] According to an embodiment of the present invention, in solution A, the polar solvent is selected from at least one of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, n-butanol, acetonitrile, and acetone, preferably ethanol.

[0022] According to an embodiment of the present invention, the core material is selected from ternary materials, the ternary materials having the definition as described above.

[0023] According to an embodiment of the present invention, in solution A, the concentration of the core material is 0.1 to 150 g / L, preferably 1 to 50 g / L, more preferably 10 to 30 g / L, for example 16.7 g / L.

[0024] According to an embodiment of the present invention, the zirconium element is derived from a zirconium salt. Preferably, the zirconium salt is selected from at least one of zirconium chloride, sulfate, nitrate, acetate, or alkoxide.

[0025] According to an embodiment of the present invention, in solution A, the concentration of the zirconium element is 0.001 to 0.1 mol / L, preferably 0.01 to 0.05 mol / L, for example, 0.02 mol / L, 0.035 mol / L, or 0.04 mol / L.

[0026] According to an embodiment of the present invention, the phosphorus-containing precipitation agent is selected from phytic acid.

[0027] According to an embodiment of the present invention, in solution B, the concentration of the phosphorus-containing precipitant is 0.0002-0.02 mol / L, preferably 0.002-0.01 mol / L, for example, 0.004 mol / L, 0.006 mol / L, or 0.008 mol / L.

[0028] According to an embodiment of the present invention, in step 3), the molar ratio of the phosphorus-containing precipitant to the zirconium element is (1-3):(3-15), preferably 1:(3-10).

[0029] According to an embodiment of the present invention, in step 3), the reaction temperature is 10-100°C, preferably 20-50°C; the reaction time is 1-48 hours, preferably 1-10 hours. Preferably, the reaction temperature is 25°C and the reaction time is 5 hours.

[0030] According to an embodiment of the present invention, in step 3), after coordination co-precipitation, the surface of the intermediate product is uniform, continuous, complete, and has a controllable thickness.

[0031] According to an embodiment of the present invention, in step 4), the calcination is carried out in an oxygen atmosphere. Preferably, the oxygen atmosphere is selected from at least one of air and oxygen, preferably oxygen.

[0032] According to an embodiment of the present invention, in step 4), the calcination temperature is 400-900°C, preferably 600-900°C; the calcination time is 1-10 hours, preferably 1-5 hours. Preferably, the calcination temperature is 700°C and the calcination time is 3 hours.

[0033] The method of the present invention also provides a positive electrode material, which comprises the above-mentioned coated ternary material.

[0034] The present invention also provides the use of the above-mentioned positive electrode material in a high-energy lithium storage device, preferably in a lithium-ion battery.

[0035] Beneficial effects

[0036] The highly environmentally tolerant ternary material of the present invention effectively addresses the sensitivity of high-nickel ternary materials to CO₂ and H₂O in the environment, significantly reducing the dew point requirements during the material's preparation, storage, and use. This facilitates long-term storage and use in higher dew point environments (e.g., at 25°C and 50% humidity), alleviates the need for drying rooms for high-nickel ternary cathode materials, and reduces the cost of material preparation and use. The core-shell coated ternary material obtained by the present invention enhances its environmental tolerance through in-situ thickness-controllable coating and can be used as a cathode material for lithium-ion batteries.

[0037] The preparation method of the present invention adopts a liquid phase method, utilizes a phosphorus-containing precipitant as a phosphorus source, and realizes the slow deposition and coating of phosphorus and zirconium elements on the surface of the electrode material through coordination precipitation with zirconium elements. The preparation method of the present invention can be applied to coating various types of high-nickel ternary materials, and the coating layer on the surface thereof is uniform, continuous, complete, and the thickness is controllable. Due to the chemical stability of the coating layer itself and the continuous integrity of the coating layer, the protective effect on the material is more effective and reliable, which not only improves the environmental tolerance of the ternary material, but also has the effects of inhibiting side reactions between the ternary material and the electrolyte, reducing the interface impedance, etc. The preparation method of the present invention has mild reaction conditions and is easy to operate. The obtained coating layer is uniform and continuous, and the thickness is controllable. It is suitable for large-scale production and has high practical value in the field of lithium-ion batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The zirconium phosphate coated LiNi of Example 1 0.6 Co 0.2 Mn 0.2 Transmission electron microscope image of O2 material.

[0039] Figure 2 The zirconium phosphate coated LiNi of Example 2 0.7 Co 0.15 Mn 0.15 Transmission electron microscope image of O2 material.

[0040] Figure 3 The zirconium phosphate coated LiNi of Example 3 0.8 Co 0.1 Mn 0.1 Transmission electron microscope image of O2 material.

[0041] Figure 4 The zirconium phosphate coated LiNi of Example 4 0.83 Co 0.07 Mn 0.1 Transmission electron microscope image of O2 material.

[0042] Figure 5It is the cycle performance of the battery at a charge and discharge current of 20 mA / g.

[0043] Figure 6 CO3 on the sample surface 2- Comparison of XPS C1s peak intensity of content.

[0044] Figure 7 It is the cycle performance of the battery at a charge and discharge current of 20 mA / g. DETAILED DESCRIPTION

[0045] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0046] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0047] The present invention is further described below using zirconium phosphate coated particles of certain types of positive electrode materials as an example. The methods are similar when other materials are used as coating substrates. Depending on the specific reaction system, the amount of phytic acid, metal salt, and the above-mentioned particle material as the core is changed accordingly to achieve uniform coating of different thicknesses on different materials. However, the present invention is not limited to the following examples. Unless otherwise specified, the methods described are all conventional methods. Unless otherwise specified, the raw materials can be obtained from public commercial channels.

[0048] Example 1

[0049] Preparation of zirconium phosphate-coated LiNi 0.6 Co 0.2 Mn 0.2 O2 particles

[0050] 1) LiNi 0.6 Co 0.2 Mn 0.2 Solution A was prepared by mixing 1 g of O2 particles and 0.3 g of zirconium nitrate in 60 ml of ethanol;

[0051] 2) Disperse 0.025 ml of phytic acid in 30 ml of ethanol to prepare solution B;

[0052] 3) Solution B was added to solution A under stirring, with a molar concentration ratio of phytic acid to zirconium ions of 1:4, and the reaction was continued at room temperature of 25°C for 5 hours. After centrifugation, washing, and drying, the obtained particles were calcined at 700°C in an oxygen atmosphere for 3 hours to obtain zirconium phosphate-coated LiNi 0.6 Co 0.2 Mn 0.2O2 granular material.

[0053] Figure 1 The zirconium phosphate coated LiNi 0.6 Co 0.2 Mn 0.2 Transmission electron microscope image of O2, from Figure 1 It can be seen that the zirconium phosphate coated LiNi 0.6 Co 0.2 Mn 0.2 The O2 particles have a core-shell structure, the coating layer is 90nm thick, and the coating layer is evenly covered on the LiNi 0.6 Co 0.2 Mn 0.2 The surface of the O2 particles. X-ray diffraction analysis shows that the material constituting the coating layer on the surface is zirconium phosphate.

[0054] Example 2

[0055] Preparation of zirconium phosphate-coated LiNi 0.7 Co 0.15 Mn 0.15 O2 particles

[0056] 1) LiNi 0.7 Co 0.15 Mn 0.15 Solution A was prepared by mixing 1 g of O2 particles and 0.2 g of zirconium chloride in 60 ml of ethanol;

[0057] 2) Disperse 0.02 ml of phytic acid in 30 ml of ethanol to prepare solution B;

[0058] 3) adding solution B to solution A with stirring, with a molar concentration ratio of phytic acid to zirconium ion of 1:5.8, and continuing the reaction at room temperature of 25° C. for 5 hours. After centrifugation, washing, and drying, intermediate product particles are obtained;

[0059] 4) The intermediate product particles obtained in step 3) were calcined at 700°C in an oxygen atmosphere for 3 hours to obtain zirconium phosphate-coated LiNi 0.7 Co 0.15 Mn 0.15 O2 granular material.

[0060] Figure 2 The zirconium phosphate coated LiNi 0.7 Co 0.15 Mn 0.15 Transmission electron microscope photo of O2 granular material, from Figure 2 It can be seen that the zirconium phosphate coated LiNi 0.7 Co 0.15 Mn 0.15The O2 particles have a core-shell structure, with a coating layer that is 95nm thick and evenly covers the surface of the lithium nickel manganese oxide particles. X-ray diffraction analysis shows that the coating is made of zirconium phosphate.

[0061] Example 3

[0062] Preparation of zirconium phosphate-coated LiNi 0.8 Co 0.1 Mn 0.1 O2 particles

[0063] 1) LiNi 0.8 Co 0.1 Mn 0.1 Solution A was prepared by mixing 1 g of O2 particles and 0.2 ml of zirconium n-propoxide in 60 ml of ethanol;

[0064] 2) Disperse 0.025 ml of phytic acid in 30 ml of ethanol to prepare solution B;

[0065] 3) adding solution B to solution A with stirring, with a molar concentration ratio of phytic acid to zirconium ion of 1:3.4, and continuing the reaction at room temperature of 25° C. for 5 hours. After centrifugation, washing, and drying, intermediate product particles are obtained;

[0066] 4) The intermediate product particles obtained in step 3) were calcined at 700°C in an oxygen atmosphere for 3 hours to obtain zirconium phosphate-coated LiNi 0.8 Co 0.1 Mn 0.1 O2 granular material.

[0067] Figure 3 The zirconium phosphate coated LiNi 0.8 Co 0.1 Mn 0.1 Transmission electron microscope photo of O2 granular material, from Figure 3 It can be seen that the zirconium phosphate coated LiNi 0.8 Co 0.1 Mn 0.1 The O2 particles are core-shell structures with a coating thickness of 87nm, and the coating is evenly coated on the LiNi 0.8 Co 0.1 Mn 0.1 The surface of the O2 particles. X-ray diffraction analysis shows that the material constituting the coating layer on the surface is zirconium phosphate.

[0068] Example 4

[0069] 1. Preparation of zirconium phosphate-coated LiNi 0.83 Co 0.07 Mn 0.1 O2 particles

[0070] 1) LiNi 0.83 Co 0.07 Mn 0.1 Solution A was prepared by mixing 1 g of O2 particles and 0.1 g of zirconium nitrate in 60 ml of ethanol;

[0071] 2) Disperse 0.01 ml of phytic acid in 30 ml of ethanol to prepare solution B;

[0072] 3) adding solution B to solution A with stirring, with a molar concentration ratio of phytic acid to zirconium ion of 1:3.3, and continuing the reaction at room temperature of 25° C. for 5 hours. After centrifugation, washing, and drying, intermediate product particles are obtained;

[0073] 4) The intermediate product particles obtained in step 3) were calcined at 700°C in an oxygen atmosphere for 3 hours to obtain zirconium phosphate-coated LiNi 0.83 Co 0.07 Mn 0.1 O2 granular material.

[0074] Figure 4 The zirconium phosphate coated LiNi 0.83 Co 0.07 Mn 0.1 Transmission electron microscope photo of O2 granular material, from Figure 4 It can be seen that the zirconium phosphate coated LiNi 0.83 Co 0.07 Mn 0.1 The O2 particles have a core-shell structure, the coating layer is 18 nm thick, and the coating layer is evenly covered on the LiNi 0.83 Co 0.07 Mn 0.1 The surface of the O2 particles. X-ray diffraction analysis shows that the material constituting the coating layer on the surface is zirconium phosphate.

[0075] Example 5

[0076] 1. Preparation of zirconium phosphate-coated LiNi 0.83 Co 0.07 Mn 0.1 O2 electrode

[0077] The zirconium phosphate-coated LiNi prepared in Example 4 was 0.83 Co 0.07 Mn 0.1 0.18g of O2 particles were mixed with 0.01g of acetylene black, a conductive additive, 0.2g of a binder (PVDF with a mass concentration of 5%), and a small amount of solvent NMP. After slurrying, coating (aluminum sheet as current collector), and drying, zirconium phosphate-coated LiNi was obtained. 0.83 Co 0.07 Mn0.1 O2 electrode.

[0078] 2. Assemble the battery

[0079] The zirconium phosphate-coated LiNi 0.83 Co 0.07 Mn 0.1 The O2 electrode is used as the positive electrode and metallic lithium is used as the negative electrode to assemble into battery 5. The separator is polypropylene, and the electrolyte is a carbonate electrolyte with a concentration of 1M, in which the solvent is DMC:DEC:EC=1:1:1 (W / W / W), and the solute is LiPF6.

[0080] Example 6

[0081] Take the uncoated LiNi of Example 4 0.83 Co 0.07 Mn 0.1 O2 particles, zirconium phosphate coated LiNi 0.83 Co 0.07 Mn 0.1 The O2 granular materials were stored in air at a constant temperature of 25°C and a constant humidity of 50 RH% for 2 months and recorded as uncoated samples and coated samples.

[0082] The uncoated sample and the coated sample were prepared as described in Example 5 to prepare assembled batteries, which were designated as Battery 6-1 and Battery 6-2.

[0083] Comparative Example 1

[0084] Comparative battery 1 was assembled, the difference being that the positive electrode material was LiNi 0.83 Co 0.07 Mn 0.1 O2 particles, and the rest refer to Example 5.

[0085] Test Example 1

[0086] (1) Test the sample and get the following results: Figure 6 The surface CO3 of the sample shown 2- XPS C1s peak intensity comparison chart of content. Figure 6 It can be seen that after two months of storage, the coated sample, i.e., LiNi coated with zirconium phosphate, 0.83 Co 0.07 Mn 0.1 O2 granular material, its CO3 2- The signal peak of the uncoated sample also did not change significantly; while for the uncoated sample, the surface CO3 2- This shows that the zirconium phosphate coating can effectively block H2O and CO2 in the air, effectively improving the environmental tolerance of the material.

[0087] Test Example 2

[0088] Battery Test

[0089] Battery 5, Battery 6-1, Battery 6-2, and Comparative Battery 1-3 were subjected to constant current charge and discharge tests using a charge and discharge instrument at a charge and discharge current of 20 mA / g, a test voltage range of 3 to 4.3 V, and a test temperature of 25°C. The battery specific capacity and charge and discharge current were calculated based on the actual mass of the electrode material.

[0090] (1) Battery 5 and Comparative Battery 1

[0091] Figure 5 The figure shows the cycle performance of battery 5 and comparison battery 1 at a charge and discharge current of 20 mA / g. After 100 cycles, the battery prepared with the coated sample has a discharge capacity of 174 mAh / g, while the battery prepared with the uncoated sample has a discharge capacity of 156 mAh / g.

[0092] (2) Batteries 6-1 and 6-2

[0093] Figure 7 The figure shows the cycle performance of batteries 6-1 and 6-2 at a charge and discharge current of 20 mA / g. After 100 cycles, the capacity of the battery prepared with the coated sample decreased slightly compared to the capacity before placement, with a capacity of 158 mAh / g. The battery prepared with the uncoated sample had a more obvious decrease in both initial capacity and capacity after cycling, with a capacity of only 101 mAh / g after cycling.

[0094] The exemplary embodiments of the present invention have been described above. However, the present invention is not limited to the aforementioned embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a coated ternary material, characterized in that: The preparation method comprises: 1) dissolving a core material and a zirconium salt in a polar solvent to obtain a solution A; the core material is selected from a high nickel ternary material, the high nickel ternary material has a layered structure, and the high nickel ternary material has the following structural formula: LiNi x Co y Mn z O2 where x+y+z=1, x≥0.6; 2) preparing a solution B containing a phosphorus-containing precipitant; the phosphorus-containing precipitant is selected from phytic acid; 3) adding solution B to solution A under stirring, and performing in-situ coating of the core material surface with controllable thickness by coordination coprecipitation of the phosphorus-containing precipitant and the zirconium salt to form an intermediate product with a coated core-shell structure; the reaction temperature is 20-50° C.; and the molar ratio of the phosphorus-containing precipitant to the zirconium salt is 1-3:3-15; 4) calcining the intermediate product of step 3) to obtain the coated ternary material; The coated ternary material comprises a core-shell structure, and the positive electrode material has high environmental tolerance, wherein: the core comprises a high-nickel ternary material; the shell serves as a coating layer and comprises zirconium phosphate; the coating layer is uniformly, continuously, completely, and has a controllable thickness and is coated on the core surface.

2. The preparation method according to claim 1, characterized in that In solution A, the polar solvent is at least one selected from water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, n-butanol, acetonitrile, and acetone; In solution A, the concentration of the core material is 0.1 to 150 g / L; The zirconium salt is selected from at least one of zirconium chloride, sulfate, nitrate, acetate or alkoxide; In solution A, the concentration of the zirconium salt is 0.001 to 0.1 mol / L.

3. The preparation method according to claim 1, characterized in that In solution B, the concentration of the phosphorus-containing precipitant is 0.0002-0.02 mol / L.

4. The preparation method according to claim 1, characterized in that In solution A, the concentration of the core material is 1 to 50 g / L; the concentration of the zirconium salt is 0.01 to 0.05 mol / L; In solution B, the concentration of the phosphorus-containing precipitant is 0.002 to 0.01 mol / L; In step 3), the molar ratio of the phosphorus-containing precipitant to the zirconium salt is 1:(3-10).

5. The preparation method according to claim 1, characterized in that In step 3), the reaction time is 1 to 48 hours; In the step 3), after the coordination co-precipitation, the surface of the intermediate product is uniform, continuous, complete, and has a controllable thickness.

6. The preparation method according to claim 1, characterized in that In step 3), the reaction time is 1 to 10 hours.

7. The preparation method according to claim 1, characterized in that In step 3), the reaction temperature is 25° C. and the reaction time is 5 h.

8. The preparation method according to claim 1, characterized in that In step 4), the calcination is carried out in an oxygen atmosphere; the oxygen atmosphere is selected from at least one of air and oxygen; In step 4), the calcination temperature is 400-900° C. and the calcination time is 1-10 hours.

9. The preparation method according to claim 1, characterized in that In step 4), the calcination temperature is 600-900° C. and the calcination time is 1-5 hours.

10. The preparation method according to claim 1, characterized in that The calcination temperature is 700°C and the calcination time is 3h.

11. The preparation method according to claim 1, characterized in that The high nickel ternary material is selected from LiNi 0.6 Co 0.2 Mn 0.2 O2、LiNi 0.7 Co 0.15 Mn 0.15 O2、LiNi 0.8 Co 0.1 Mn 0.1 O2、LiNi 0.83 Co 0.07 Mn 0.1 O2; The zirconium-containing phosphate is selected from at least one of zirconium phosphate, zirconium pyrophosphate, zirconium metaphosphate, and lithium zirconium phosphate; The coating layer has a thickness of 1 to 200 nm; The high environmental tolerance of the coated ternary material refers to storage under conditions of 25° C. and 50 RH%.

12. The preparation method according to claim 1, characterized in that The thickness of the coating layer is 10 to 100 nm.

13. The preparation method according to claim 1, characterized in that The thickness of the coating layer is 15 to 20 nm.

14. Use of the positive electrode material obtained by the preparation method according to any one of claims 1 to 13 in a high-energy lithium storage device.

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