CN109192956B - Lithium nickel cobalt aluminate anode material coated by lithium zirconium phosphate fast ion conductor and preparation method thereof - Google Patents
Lithium nickel cobalt aluminate anode material coated by lithium zirconium phosphate fast ion conductor and preparation method thereof Download PDFInfo
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- 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
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Abstract
The lithium zirconium phosphate fast ion conductor is coated with a nickel-cobalt lithium aluminate anode material and a preparation method thereof, the mass of the lithium zirconium phosphate fast ion conductor is 0.1-10 wt%, and the lithium zirconium phosphate fast ion conductor forms a coating layer with the thickness of 5-30 nm and is coated on the nickel-cobalt lithium aluminate; the positive electrode material is spherical particles with the particle size of 5-15 mu m. The preparation method comprises the following steps: (1) preparing a solution containing a phosphorus source and a zirconium source, adding the zirconium source solution into an organic solvent or water, adding the phosphorus source solution, stirring, adding lithium nickel cobalt aluminate, heating, stirring, reacting, slowly evaporating to dryness, and drying the obtained powder in an oven; (2) and (2) placing the powder obtained in the step (1) into a tube furnace, and performing low-temperature rapid sintering to obtain the powder. The anode material has better cycle stability and rate discharge performance; the method can effectively reduce the problem of low cycling stability of surface residual lithium and ternary materials in the conventional coating process, has low cost of the process and simple process, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a positive electrode material and a preparation method thereof, in particular to a lithium nickel cobalt aluminate positive electrode material coated with a lithium zirconium phosphate fast ion conductor and a preparation method thereof.
Background
The lithium ion battery is considered to be one of the most promising energy storage circulation systems for realizing the power battery, and has the advantages of high energy density, high working voltage, good safety performance, stability, low manufacturing cost, lower toxicity and the like. The development of lithium ion batteries is of great significance in solving the problem of energy shortage and reducing environmental pollution. The positive electrode material is a key factor for determining the electrochemical performance, safety performance and price cost of the lithium ion battery, but the current market-leading ternary positive electrode material still cannot meet the development requirements of electric automobiles, and the energy density, power density, cycling stability and the like of the ternary positive electrode material still need to be improved. The surface of the ternary cathode material is easy to generate side reaction with electrolyte so as to reduce the reversibility of the material; meanwhile, organic matters which are easy to react with electrolyte to generate poor conductivity are remained on the surface; and the ternary material is placed in the air and can react with carbon dioxide and water in the air, so that the electrochemical activity is reduced. Due to the contact of the ternary cathode material and other substances, the cycle stability and rate capability of the ternary material are reduced. Therefore, the ternary positive electrode needs to be improved, the main methods for improving the performance of the ternary positive electrode material at present comprise surface modification, surface coating, element doping and the like, and in order to reduce the side reaction of the ternary positive electrode material and other substances, the surface coating is a very simple, convenient and effective method, and the substances with better stability are coated on the surface of the ternary positive electrode material to reduce the attenuation of the electrochemical activity of the ternary positive electrode material.
Patent CN 105406069A discloses a method for coating a ternary material with lithium manganese iron phosphate, which comprises the steps of mixing ascorbic acid with lithium manganese phosphate, then drying in vacuum, and sintering at a heat preservation temperature for 6-16 h.
CN 107230771A discloses a method for coating a ternary material with vanadium phosphate, which comprises mixing vanadium salt and a phosphate reducing agent in deionized water, stirring, filtering, washing, drying, mixing with the ternary material according to a mixing ratio of 1-10: 100 in a high-speed mixer, and then sintering at 200-400 ℃ in a non-oxygen atmosphere to obtain a coated ternary coating modified material.
Patent CN 105047864A discloses a method for coating a ternary material with lithium zirconate, which comprises the steps of carrying out hydrothermal reaction on a nickel-cobalt-manganese precursor prepared by oxalate and tetrabutyl zirconate at 180 ℃ to generate a zirconium oxide coating layer, sintering at high temperature to obtain a coating substance of lithium zirconate.
Disclosure of Invention
The invention aims to solve the technical problems that the defects in the prior art are overcome, and the ternary cathode material which has low residual lithium content on the coating surface, high specific capacity, excellent cycle performance and excellent stability is provided; the material has low cost, simple process and low energy consumption, and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a lithium zirconium phosphate fast ionic conductor coated lithium nickel cobalt aluminate anode material is disclosed, wherein the mass of the lithium zirconium phosphate fast ionic conductor is 0.1-10 wt%, and a coating layer with the thickness of 5-30 nm is formed on the lithium nickel cobalt aluminate by the lithium zirconium phosphate fast ionic conductor; the positive electrode material is spherical particles with the particle size of 5-15 mu m.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of a lithium zirconium phosphate fast ion conductor coated lithium nickel cobalt aluminate anode material comprises the following steps:
(1) respectively preparing salts containing phosphorus and zirconium into solutions to form a zirconium source solution and a phosphorus source solution, adding the zirconium source solution into an organic solvent or water, adding the phosphorus source solution, uniformly stirring, adding lithium nickel cobalt aluminate, heating, stirring, reacting, slowly evaporating to dryness to obtain a slurry, and drying in an oven to obtain powder;
(2) and (2) placing the powder obtained in the step (1) into a tubular furnace, and sintering in an oxidizing atmosphere to obtain the lithium nickel cobalt aluminate anode material coated by the lithium zirconium phosphate fast ion conductor.
Preferably, in the step (1), the zirconium source and the phosphorus source are prepared into a solution phase, and the solid-to-liquid ratio of the solution phase is 2-5: 100. The zirconium source and the phosphorus source in the solution phase can well form the lithium zirconium phosphate gel, if the solid zirconium source is directly added, and then the solid lithium dihydrogen phosphate is added, the solid zirconium phosphate or the solid lithium phosphate can be formed on the surface of the solid lithium dihydrogen phosphate particles added into the solution, so that the further dissolution of the lithium dihydrogen phosphate is prevented, the uniform lithium zirconium phosphate gel cannot be formed, and if the zirconium source and the phosphorus source are both prepared into the solution, the problem can be avoided.
Preferably, in the step (1), the solvent for preparing the solution is one or more of water, absolute ethyl alcohol, ethylene glycol and methanol; the molar ratio of the zirconium source to the phosphorus source is 1: 1.5-2.
Preferably, in the step (1), the mass volume ratio of the nickel cobalt lithium aluminate to the organic solvent or water is 1: 100-200; the coating effect is best.
Preferably, in the step (1), the heating and stirring temperature is 70-90 ℃ and the time is 90-150 min. The stirring temperature and the stirring time are adopted, and the obtained product has the best effect.
Preferably, in the step (1), the lithium zirconium phosphate is lithium zirconium phosphate derivative LiZr2（PO4）3、Li2ZrP2O8One or more of (a).
Preferably, in the step (1), the zirconium source is one or more of zirconium nitrate, zirconyl nitrate or zirconyl chloride; the phosphorus source is lithium dihydrogen phosphate.
Preferably, in the step (1), the evaporation temperature is 70-90 ℃, the time is 20-50 min, and the evaporation is carried out until the solid-to-liquid ratio of the slurry state is 1: 3 to 10.
Preferably, in the step (1), the organic solvent is one or more of absolute ethyl alcohol, ethylene glycol, methanol or N-methyl pyrrolidone.
Preferably, in the step (1), the mass ratio of the lithium zirconium phosphate to the lithium nickel cobalt aluminate is 0.1-10: 100.
Preferably, in the step (1), the particle size of the nickel cobalt lithium aluminate is 5-15 μm.
Preferably, in the step (1), the drying temperature is 70-90 ℃, and the drying time is 0.5-2 h.
Preferably, in the step (2), the oxidizing atmosphere refers to an ozone atmosphere, an air atmosphere or an oxygen atmosphere with a purity of 99.9% or more.
Preferably, in the step (2), the low-temperature rapid sintering is that: the temperature is increased to 400-700 ℃ at the speed of 3-5 ℃/min, the sintering is carried out for 0.5-3 h, the secondary low-temperature rapid sintering is carried out, the temperature is changed as little as possible to change the ternary crystal structure, the rapid low-temperature sintering can effectively reduce the damage of the nickel-cobalt lithium aluminate crystal lattice, and the lithium storage performance of the ternary layered structure is maintained. The heating rate is controlled mainly to control the clearance of the primary particles in the secondary particles and avoid the reduction of physical properties caused by overlarge clearance.
The molecular formula of the nickel cobalt lithium aluminate is LiNi0.8Co0.15Al0.05O2。
The principle of the invention is as follows: the zirconium lithium phosphate has excellent stability and excellent lithium ion transmission performance as a solid electrolyte with an NASICON structure, and the coating of the zirconium lithium phosphate on the ternary surface can reduce the direct contact of a battery material and other harmful substances and improve the lithium ion transmission rate; according to the invention, phosphate and zircon salt are taken as matrixes, milky white gel with positive electricity is formed firstly, then ternary positive electrode material nickel cobalt lithium aluminate with negative charge is added, the negative and positive charges between small particles in a liquid phase are utilized to attract and adhere to the surface of the material, a coating layer is formed on the surface of the ternary positive electrode material by drying a solid phase solvent to dryness, finally, the obtained powder material is sintered, a zirconium lithium phosphate fast ion conductor is generated on the surface of the ternary positive electrode material, and finally, the nickel cobalt lithium aluminate positive electrode material coated by the zirconium lithium phosphate fast ion conductor is obtained. The zirconium phosphate lithium fast ion conductor is coated on the surface of the ternary material as a solid electrolyte, so that the cycling stability of the ternary material is improved while the side reaction of the anode material and the electrolyte is prevented, and the lithium ion transmission stability of the ternary material is improved as the fast ion conductor, namely the cycling stability of the material.
The invention has the following beneficial effects:
(1) in the nickel cobalt lithium aluminate anode material coated by the lithium zirconium phosphate fast ion conductor, the lithium zirconium phosphate fast ion conductor forms a coating layer with the thickness of 2-20 nm, and the anode material is spherical particles with the particle size of 5-15 mu m;
(2) the nickel cobalt lithium aluminate anode material coated by the zirconium lithium phosphate fast ionic conductor is assembled into a battery, and the first discharge gram capacity can reach 207mAh/g under 2.7-4.3V and 0.1C; the first discharge gram capacity under 1C can reach 183.2mAh/g, and after 100 cycles, the capacity retention rate can reach 84.2%; under the multiplying power of 0.5C, 1C, 2C and 5C respectively, the first discharge capacity can reach 192.3mAh/g, 183.2mAh/g, 162.9mAh/g and 146.8mAh/g respectively, which shows that the nickel cobalt lithium aluminate anode material coated by the zirconium lithium phosphate fast ion conductor has better circulation stability and high multiplying power discharge performance;
(3) according to the method, the nickel cobalt lithium aluminate is coated with the zirconium phosphate lithium firstly, and then secondary low-temperature rapid sintering is carried out, so that the residual lithium amount on the surface of the nickel cobalt lithium aluminate coated by the zirconium phosphate lithium rapid ionic conductor can be effectively reduced, the side reaction of the residual lithium and the electrolyte is reduced, and the storage performance of the nickel cobalt lithium aluminate is improved;
(4) the method has low cost and simple process, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a SEM image of a lithium nickel cobalt aluminate cathode material coated with a zirconium lithium phosphate fast ion conductor obtained in example 4 of the present invention;
FIG. 2 is a TEM image of the zirconium phosphate lithium fast ion conductor coated Ni-Co lithium aluminate anode material and uncoated obtained in example 4 of the present invention;
FIG. 3 is an XRD pattern of the lithium nickel cobalt aluminate cathode material coated with the lithium zirconium phosphate fast ion conductor obtained in example 4 of the present invention;
fig. 4 is a graph showing a comparison of the capacity cycle at 1C rate of a battery assembled according to example 4 of the present invention and an uncoated positive electrode material.
Detailed Description
The present invention will now be described in detail and specifically with reference to specific examples so as to provide a better understanding of the invention, but the following examples are not intended to limit the scope of the invention.
The nickel-cobalt lithium aluminate used in the embodiment of the invention is purchased from Ningbo gold and New materials Co., Ltd, and has a particle size of 5-15 μm; the chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
(1) 0.90513g (0.002108287 mol) of zirconium nitrate pentahydrate (429.32 relative molecular mass) is weighed, dissolved by adding water and transferred into a 50ml volumetric flask, deionized water is added for constant volume, 0.32867g (0.003162431mol) of lithium dihydrogen phosphate (103.93 relative molecular mass) is weighed, dissolved by adding water and transferred into a 50ml volumetric flask, and water is added for constant volume. The ratio of zirconium to phosphorus is 2:3, (under the condition of the proportioning, 1ml of zirconium nitrate is mixed with 1ml of lithium dihydrogen phosphate to obtain the proportioning required by coating 1wt% of lithium zirconium phosphate on the ternary material, namely, 1ml of each of two solutions is mixed to obtain the required amount of 1wt% coating, 0.5ml of each of the two solutions is the required amount of 0.5wt% coating, and the rest coating amounts are analogized, so that the operation is simple and convenient after the solution is prepared, the subsequent operation only needs to take the volume of the solution as the proportioning amount, the operation is simplified, and the same is not repeated below).
(2) Taking 0.5ml of the zirconium nitrate solution in the step (1) by using a pipette, adding the zirconium nitrate solution into 10ml of water, uniformly stirring, adding 0.5ml of the lithium dihydrogen phosphate solution in the step (1), and slowly stirring (the coating amount is 0.5wt% coating).
(3) And (3) adding 0.5g of lithium nickel cobalt aluminate into the solution (2), heating, stirring and evaporating to dryness for 40min at 90 ℃, stirring to evaporate to dryness, directly transferring into a tubular furnace, heating to 650 ℃ at a heating rate of 5 ℃/min in an oxygen atmosphere, and keeping the temperature for 1h to obtain the lithium nickel cobalt aluminate anode material coated by the lithium zirconium phosphate fast ion conductor.
Example 2
(1) 0.9051g (0.002108 mol) of zirconium nitrate pentahydrate are weighed, dissolved by adding water and transferred to a 50ml volumetric flask, deionized water is added for constant volume, 0.3287g (0.00316mol) of lithium dihydrogen phosphate is weighed, dissolved by adding water and transferred to a 50ml volumetric flask, and water is added for constant volume. The molar ratio of phosphorus to zirconium is 2: 3.
(2) Taking 0.5ml of the zirconium nitrate solution in the step (1) by using a pipette, adding 75ml of alcohol, stirring uniformly, adding 0.5ml of the lithium dihydrogen phosphate solution in the step (1), and slowly stirring.
(3) And (3) adding 0.5g of lithium nickel cobalt aluminate into the solution (2), heating and stirring for 1.5h at 90 ℃ until the lithium nickel cobalt aluminate is evaporated to be dry, then directly transferring into a tubular furnace, heating to 650 ℃ at a heating rate of 5 ℃/min in an oxygen atmosphere, and keeping the temperature for 1h to obtain the lithium nickel cobalt aluminate anode material coated by the lithium zirconium phosphate fast ion conductor.
Example 3
(1) 0.9051g (0.002108 mol) of zirconium nitrate pentahydrate are weighed, dissolved by adding water and transferred to a 50ml volumetric flask, deionized water is added for constant volume, 0.3287g (0.00316mol) of lithium dihydrogen phosphate is weighed, dissolved by adding water and transferred to a 50ml volumetric flask, and water is added for constant volume. The molar ratio of phosphorus to zirconium is 2: 3.
(2) Taking 0.5ml of the zirconium nitrate solution in the step (1) by using a pipette, adding the zirconium nitrate solution into 75ml of alcohol, uniformly stirring, adding 0.5ml of the lithium dihydrogen phosphate solution in the step (1), and slowly stirring.
(3) And (3) adding 0.5g of lithium nickel cobalt aluminate into the solution (2), heating, stirring and evaporating to dryness for 1.5 hours at 90 ℃, stopping stirring when the mixed slurry becomes viscous and about 3-5 ml of the mixed slurry is obtained, slowly evaporating the solution to dryness, transferring the solution into an oven for drying, transferring the dried solution into a tubular furnace, heating the solution to 650 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, and keeping the temperature for 1 hour to obtain the lithium nickel cobalt aluminate anode material coated by the zirconium phosphate lithium fast ion conductor.
Example 4
(1) 0.9051g (0.002108 mol) of zirconium nitrate pentahydrate are weighed, dissolved by adding water and transferred to a 50ml volumetric flask, deionized water is added for constant volume, 0.3287g (0.00316mol) of lithium dihydrogen phosphate is weighed, dissolved by adding water and transferred to a 50ml volumetric flask, and water is added for constant volume. The molar ratio of phosphorus to zirconium is 2: 3.
(2) Taking 1ml of the zirconium nitrate solution in the step (1) by using a pipette, adding the zirconium nitrate solution into 75ml of alcohol, uniformly stirring, adding 1ml of the lithium dihydrogen phosphate solution in the step (1), and slowly stirring.
(3) And (3) adding 0.5g of lithium nickel cobalt aluminate into the solution (2), heating, stirring and evaporating to dryness for 1.5 hours at the temperature of 90 ℃, stopping stirring when the mixed slurry becomes viscous and about 3-5 ml of the mixed slurry is obtained, slowly evaporating the solution to dryness, transferring the solution into an oven for drying, transferring the dried solution into a tubular furnace, heating to 650 ℃ at the temperature rise rate of 5 ℃/min under the oxygen atmosphere, and preserving the heat for 1 hour to obtain the lithium nickel cobalt aluminate anode material coated by the zirconium phosphate lithium fast ion conductor.
SEM as shown in example 4 is shown in FIG. 1
Example 5
(1) 0.9051g (0.002108 mol) of zirconium nitrate pentahydrate are weighed, dissolved by adding water and transferred to a 50ml volumetric flask, deionized water is added for constant volume, 0.3287g (0.00316mol) of lithium dihydrogen phosphate is weighed, dissolved by adding water and transferred to a 50ml volumetric flask, and water is added for constant volume. The molar ratio of phosphorus to zirconium is 2: 3.
(2) And (3) taking 5ml of the zirconium nitrate solution in the step (1) by using a pipette, adding the zirconium nitrate solution into 100ml of alcohol, uniformly stirring, adding 5ml of the lithium dihydrogen phosphate solution in the step (1), and slowly stirring.
(3) And (3) adding 0.5g of lithium nickel cobalt aluminate into the solution (2), heating, stirring and evaporating to dryness for 1.5 hours at the temperature of 90 ℃, stopping stirring when the mixed slurry becomes viscous and about 3-5 ml of the mixed slurry is obtained, slowly evaporating the solution to dryness, transferring the solution into an oven for drying, transferring the dried solution into a tubular furnace, heating to 650 ℃ at the temperature rise rate of 5 ℃/min under the oxygen atmosphere, and preserving the heat for 1 hour to obtain the lithium nickel cobalt aluminate anode material coated by the zirconium phosphate lithium fast ion conductor.
Comparative example 1
Comparative example 1 differs from example 4 only in that: except for uncoated lithium nickel cobalt aluminate, i.e. the uncoated lithium nickel cobalt aluminate cathode material in step (2). Steps (1), (2) and (3) were not conducted, and the treatment was conducted as a comparative example.
Assembling the battery: 0.08g of the resulting lithium nickel cobalt aluminate positive electrode material was weighed, 0.01g of acetylene black as a conductive agent and 0.01g of PVDF (Poly (vinylidene fluoride)) were addedVinylidene fluoride) as adhesive, mixing uniformly, coating on aluminum foil to obtain positive plate, placing metal lithium plate as negative electrode in vacuum glove box, Celgard 2300 as diaphragm, 1mol/L LiPF6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
Through detection of the uncoated ternary cathode material, the initial discharge specific capacity of the assembled battery is 204.9mAh/g within the voltage range of 2.7-4.3V and under the multiplying power of 0.1C. Through detection, the capacity retention rate of the assembled battery in a cycle of one hundred cycles is 40.6% in a voltage range of 2.7-4.3V after 300 cycles. The first discharge capacity is 195.1mAh/g, 181.6mAh/g, 158.3mAh/g and 135.2mAh/g respectively under the multiplying power of 0.5C, 1C, 2C and 5C respectively.
The nickel cobalt lithium aluminate anode material coated by the zirconium lithium phosphate fast ion conductor is assembled into a battery, and the first discharge gram capacity can reach 207mAh/g under the conditions of 2.7-4.3V and 0.1C; the first discharge gram capacity under 1C can reach 183.2mAh/g, and after 100 cycles, the capacity retention rate can reach 84.2%; the capacity retention rate after 280 cycles is 63.5%; under the multiplying power of 0.5C, 1C, 2C and 5C respectively, the first discharge capacity can reach 192.3mAh/g, 183.2mAh/g, 162.9mAh/g and 146.8mAh/g respectively,
in conclusion, the method can effectively coat the zirconium phosphate lithium fast ion conductor on the nickel cobalt lithium aluminate, effectively improves the cycle retention rate and the high-rate discharge performance of the material compared with the nickel cobalt lithium aluminate which is not coated with the zirconium phosphate lithium fast ion conductor, and initially coats the zirconium phosphate lithium type solid electrolyte on the surface of the ternary material, and has the advantages of simple step process, short flow, easy operation and suitability for large-scale industrial production.
Claims (5)
1. The preparation method of the lithium zirconium phosphate fast ion conductor coated nickel cobalt lithium aluminate anode material is characterized by comprising the following steps of: the method comprises the following steps:
(1) respectively preparing salts containing phosphorus and zirconium into solutions to form a zirconium source solution and a phosphorus source solution, adding the zirconium source solution into an organic solvent or water, uniformly stirring, adding the phosphorus source solution, and slowly stirring to form a mixed solution; adding nickel cobalt lithium aluminate, heating, stirring, reacting, slowly evaporating to dryness to obtain slurry, and oven drying to obtain powder;
(2) placing the powder obtained in the step (1) in a tubular furnace, and sintering in an oxidizing atmosphere to obtain a lithium nickel cobalt aluminate anode material coated by a lithium zirconium phosphate fast ion conductor;
in the step (1), the solvent for preparing the solution is one or more of water, absolute ethyl alcohol, glycol and methanol; the molar ratio of the zirconium source to the phosphorus source is 1: 1.5-2;
in the step (1), the zirconium source is one or more of zirconium nitrate, zirconyl nitrate or zirconyl chloride; the phosphorus source is lithium dihydrogen phosphate; the organic solvent is one or more of absolute ethyl alcohol, ethylene glycol, methanol or N-methyl pyrrolidone;
in the step (2), the sintering temperature of the tube furnace is 500-1100 ℃, and the heating rate is 3-5 ℃/min; the sintering time is 0.5-3 h;
in the nickel cobalt lithium aluminate anode material coated by the zirconium lithium phosphate fast ion conductor, the chemical formula of the zirconium lithium phosphate is LiZr2（PO4）3(ii) a The mass of the zirconium phosphate lithium fast ion conductor is 0.1-10 wt%, and the coating layer with the thickness of 5-30 nm formed by the zirconium phosphate lithium fast ion conductor is coated on the nickel-cobalt lithium aluminate; the positive electrode material is spherical particles with the particle size of 5-15 mu m.
2. The method for preparing the lithium zirconium phosphate fast ion conductor coated lithium nickel cobalt aluminate anode material according to claim 1, is characterized in that: in the step (1), the mass volume ratio of the nickel cobalt lithium aluminate to the organic solvent or water is 1: 100-200.
3. The method for preparing the lithium nickel cobalt aluminate anode material coated with the lithium zirconium phosphate fast ion conductor according to claim 1 or 2, wherein the method comprises the following steps: in the step (1), the heating and stirring temperature is 70-90 ℃, and the time is 90-150 min; the slow evaporation temperature is 70-90 ℃, and the time is 20-50 min; the drying temperature is 70-90 ℃, and the drying time is 1-2 h.
4. The method for preparing the lithium nickel cobalt aluminate anode material coated with the lithium zirconium phosphate fast ion conductor according to claim 1 or 2, wherein the method comprises the following steps: in the step (2), the oxidizing atmosphere refers to an ozone atmosphere, an air atmosphere or an oxygen atmosphere with the purity of more than or equal to 99.9%; the mass ratio of the lithium zirconium phosphate to the lithium nickel cobalt aluminate is 0.1-10: 100.
5. The method for preparing the lithium zirconium phosphate fast ion conductor coated lithium nickel cobalt aluminate anode material according to claim 3, is characterized in that: in the step (2), the oxidizing atmosphere refers to an ozone atmosphere, an air atmosphere or an oxygen atmosphere with the purity of more than or equal to 99.9%; the mass ratio of the lithium zirconium phosphate to the lithium nickel cobalt aluminate is 0.1-10: 100.
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