CN112103496A - High-nickel ternary cathode material and preparation method thereof - Google Patents
High-nickel ternary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-nickel ternary cathode material and a preparation method thereof, belonging to the technical field of lithium ion battery materials. The chemical general formula of the high-nickel ternary cathode material is LiNixCoyMn(1‑x‑y‑z)MzO2Sr is coated in a molten state or is not coated and enriched on the surface of the material, and the concentration is reduced from outside to inside to form gradient doping. The high-nickel ternary cathode material prepared by adopting the processes of primary sintering doping, secondary Sr coating and primary coating agent coating can be applied to a high-voltage system with the voltage of more than 4.35V, and has high capacity and good cycling stability.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a high-nickel lithium ion battery anode material and a preparation method thereof.
Background
With the development of 3C-type and power lithium ion battery markets, the demand for high-capacity lithium ion batteries is increasingly urgent. The methods for increasing the capacity of the lithium ion battery mainly comprise two methods: one is to increase the content of Ni; the other is to boost the charging voltage of the battery. The Ni content is increased, the structural stability and the safety performance of the material can be further deteriorated, and the development difficulty is high. For example, the voltage range of the high-nickel ternary cathode material NCM811 is generally 4.2-4.25V, but if higher capacity is to be achieved, the applied voltage range is increased to more than 4.35V, and the NCM811 cannot meet the requirement of the high-voltage system test of more than 4.35V. Therefore, it is urgently needed to develop a high-nickel ternary cathode material which can be suitable for a high-voltage system.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-nickel ternary cathode material and a preparation method thereof.
The solution of the invention is realized by the following steps:
a high-nickel ternary positive electrode material with chemical molecular formula LiNixCoyMn(1-x-y-z)MzO2Wherein x is more than or equal to 0.76 and less than or equal to 0.97, Y is more than or equal to 0.02 and less than or equal to 0.15, z is more than 0 and less than or equal to 0.05, x + Y + z is less than or equal to 1, M is one or more selected from Sr and Al, W, Ti, Mg, Zr, Ba, V, Mo, F, B, Y and La, Sr is enriched on the surface of the material, and the concentration is reduced from outside to inside to form gradient doping. The Sr of the high-nickel ternary material is coated on the surface of the material in a molten state or has no coating layer, and the Sr element accounts for the total metal elements through XPS analysis of the ternary material from the surface of particles to different depths in the particlesThe weight ratio, as the depth increases, shows a downward trend. The Sr element content on the surface layer of the particle is obviously higher than that in the interior of the particle.
The invention also provides a preparation method of the high-nickel ternary cathode material, which comprises the following steps:
step S1, adding Ni as high-nickel ternary precursorxCoyMn(1-x-y)(OH)2Or NixCoyMn(1-x-y)O2(x is more than or equal to 0.8 and less than or equal to 0.97, y is more than or equal to 0.02 and less than or equal to 0.15, and x + y is less than 1) is mixed with a Li source and an additive containing M, primary sintering is carried out, and then cooling, crushing and sieving are carried out to obtain a primary sintered product;
preferably, the Li source is LiOH & H2O、LiOH、Li2O or Li2CO3One or more of (a).
Preferably, the M-containing additive is Sr and one or more of oxides or hydroxides of Al, W, Ti, Mg, Zr, Ba, Y, La. The ratio of the addition amount of M to the molar content of the cathode material is a, wherein a is more than 0 and less than 0.03.
Further, the sintering is carried out in an oxygen atmosphere, and the temperature rise speed is 0.5-10 ℃/min, and more preferably 1-3 ℃/min; raising the temperature to 650-900 ℃, keeping the temperature for 8-20 h, and preferably 10-15 h.
And S2, mixing the primary sintering product obtained in the step S1 with an Sr compound, heating the uniformly mixed primary Sr coating material to 400-600 ℃ in an oxygen atmosphere, keeping the temperature constant for 0.5-6 h, heating to 600-700 ℃ at the speed of 0.5-3 ℃/min, keeping the temperature constant for 2-20 h, and obtaining a secondary sintering material. The Sr compound may be one or more of strontium hydroxide, strontium oxide, strontium carbonate, strontium sulfate, strontium chloride and strontium hydrogen phosphate: the molar content ratio of the Sr to the positive electrode material is b, wherein b is more than 0 and less than 0.03, and the more preferable addition amount of Sr is 0.05-0.5 mol% of the molar content of the positive electrode material.
And S3, adding the secondary sintering material obtained in the step S2 into an ammonium carbonate solution, stirring, slowly adding a saturated strontium nitrate solution, stirring, and reacting for 1-60 min. And then carrying out suction filtration and vacuum drying on the reaction slurry, or directly carrying out vacuum drying on the reaction slurry to obtain a secondary Sr coated drying material.
Preferably, the temperature of the ammonium carbonate solution is 50-80 ℃, and the concentration is 5-15 wt%.
Further, the weight of the ammonium carbonate solution is 0.4-2.0 times of the weight of a calcined product.
Further, the weight of the strontium nitrate is calculated according to the secondary Sr coating amount, the molar weight ratio of Sr to the molar content of the positive electrode material is c, 0 & lt c & lt 0.03, a + b + c is less than or equal to 0.03, and the more preferable Sr coating amount is 0.05-0.5 mol% of the molar content of the positive electrode material.
Further, the vacuum drying temperature is 80-250 ℃, and the drying time is 1-30 h.
And S4, mixing the secondary Sr coated dry material obtained in the step S3 with a coating agent, and then sintering for three times in an oxygen atmosphere to obtain the Sr gradient doped high-nickel ternary positive electrode material.
Preferably, the coating agent contains at least one of Al, W, Ti, Mg, B, Ba, V, Mo, Co, F, P, and La. The mol ratio of the coating amount of the coating agent to the anode material is d, c is more than 0 and less than 0.02, and a + b + c + d = z is less than or equal to 0.05.
Further, during the third sintering, the temperature rising speed is 0.5-10 ℃/min, preferably 3-8 ℃/min; heating to 250-600 ℃, and keeping the temperature for 4-15 h, preferably 6-10 h.
The preparation method provided by the invention adopts the mode of secondary Sr coating and the sequentially decreasing sintering temperature of each Sr coating, thereby realizing the gradient doping of Sr. The Sr and high-nickel ternary material are easy to permeate and fuse, the higher the sintering temperature is, the more uniform the Sr is distributed in particles, and when the sintering temperature is low, the Sr is mainly enriched on the surface. In the secondary sintering material washing process, ammonium carbonate weak base substances are added to serve as a buffering agent for the alkalinity of a washing medium, so that the excessive high alkalinity of a solution caused by the dissolution of residual lithium in the washing process is prevented, and the damage to a positive electrode material is prevented. Slowly adding saturated strontium carbonate solution into a slurry system in which ammonium carbonate solution and the anode material are mixed, and uniformly depositing a layer of SrCO on the surface of the anode material3Compound to form a uniform coating of Sr element. After the drying, the mixture is dried,and the coating and sintering are carried out together with other coating agents, so that the working procedure is simplified, and the material performance is further optimized.
Through mixing and sintering the secondary Sr coated dry material and the coating agent, Sr is further enriched on the surface of the material to play a role in stabilizing the crystal result of the surface material, and the coating agent can also repair the performance of a sample, fill crystal gaps, reduce BET (BET), prevent the electrolyte from generating side reaction with the material, and further improve the cycle performance. Meanwhile, the ionic conductivity at the grain boundary is improved, so that the sample capacity is further improved.
The Sr gradient doped high-nickel ternary cathode material has an Sr-rich state on the outer surface. The Sr can effectively improve the structural stability of the ternary cathode material, and meanwhile, the Sr-rich outer layer on the surface can effectively prevent side reaction between electrolyte and the cathode material, so that the stability of the crystal structure on the surface of particles is enhanced, and the deterioration of the crystal structure of the material from outside to inside is prevented. Since Sr is mainly enriched on the surface of the material, the capacity exertion of the material is not obviously reduced, and the material can be applied to a high-voltage system with the voltage of more than 4.35V.
Compared with the prior art, the invention has the following beneficial effects:
1. the high-nickel ternary cathode material provided by the invention can be applied to a high-voltage system with the voltage of more than 4.35V, and has high capacity and good cycle stability.
2. The preparation method provided by the invention is simple in process and easy to industrialize.
Drawings
Fig. 1 is an SEM image of a high nickel ternary cathode material prepared in example 1 of the present invention.
Fig. 2 is a graph of high-temperature cycle performance of the high-nickel ternary positive electrode materials prepared in example 1 and comparative example 1 of the present invention at a voltage of 4.35V in an actual battery.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way.
Example 1:
(1) reacting lithium hydroxide with Ni0.82Co0.12Mn0.06(OH)2Uniformly mixing the precursor, zirconia, strontium oxide and yttrium oxide in a high-speed mixer according to the molar ratio of 1.04:0.988:0.005:0.002:0.0025, sintering the mixture in an oxygen atmosphere at the heating rate of 3 ℃/min to 810 ℃, keeping the temperature for 10h, reducing the temperature, crushing the material, and then vibrating and screening to obtain Li1.04Ni0.8102Co0.1186Mn0.0593Zr0.005Sr0.002Y0.005O2And (5) cooking.
(2) Mixing the primary sintered product with strontium carbonate, accounting the addition amount of the strontium carbonate according to the molar ratio of the Sr coating amount to the anode material of 0.003:0.997, placing the mixture in an oxygen atmosphere for secondary sintering, firstly heating to 450 ℃, keeping the temperature for 2 hours, then heating to 600 ℃ at the rate of 1 ℃/min, keeping the temperature for 12 hours, and cooling to obtain a secondary sintered material.
(3) Preparing an ammonium carbonate solution with the solution concentration of 7wt%, wherein the weight ratio of the ammonium carbonate solution to the secondary sintering material is 1.5:1, placing the solution in a water area with the temperature of 75 ℃ for stirring, preparing a saturated strontium nitrate solution, pouring the secondary sintering material into the solution, stirring for 1min, counting the mass of the saturated strontium nitrate solution according to the secondary Sr coating amount and the molar ratio of the saturated strontium nitrate solution to the anode material of 0.001:0.999, dropwise adding the saturated strontium nitrate solution into the slurry, and stirring for 30min after the dropwise adding is finished; so that the generated strontium carbonate is precipitated and uniformly coated on the surface of the material.
(4) After stirring, filtering the slurry to obtain a filter cake, placing the filter cake in a vacuum drying oven, and drying at 150 ℃ for 10 hours to obtain a dried material.
(5) And (3) accounting the mass of the ingredients according to the molar ratio of the boric acid to the drying material of 0.01:0.99, and carrying out secondary mixing on the boric acid and the matrix by adopting a high-speed mixer. Sintering the secondary mixture for three times in an oxygen atmosphere, setting the heating rate to be 3 ℃/min, heating to 300 ℃, keeping the temperature for 10 hours, and cooling to obtain the Sr gradient doped high-nickel material Li1.02Ni0.7989Co0.1169Mn0.0585Zr0.0049Sr0.0059Y0.0049B0.01O2And (3) a positive electrode material.
Fig. 1 is a morphology of the cathode material prepared in example 1, and it can be seen from the figure that: after Sr coating sintering and B coating, no obvious coating trace exists on the surface, which indicates that the sample is doped in the matrix after Sr coating.
Table 1 shows Sr contents at different depths of the positive electrode material prepared in example 1, which were analyzed by surface etching XPS. By etching the surface of a sample and analyzing the Sr content at different depths by adopting XPS, the Sr content shows a descending trend along with the increase of the etching depth, which indicates that Sr element is mainly enriched on the surface of the material and shows a gradient doping state.
TABLE 1 surface etch XPS analysis of Sr content at different depths
Example 2:
(1) reacting lithium hydroxide with Ni0.90Co0.05Mn0.0.05(OH)2Uniformly mixing the precursor, aluminum oxide, magnesium oxide and tungsten trioxide according to the molar ratio of 1.01:0.974:0.0075:0.01:0.001 in a high-speed mixer, sintering the mixture in an oxygen atmosphere at the temperature rising speed of 1 ℃/min to 760 ℃, keeping the temperature for 12h, reducing the temperature, crushing the material, and then vibrating and screening to obtain Li1.01Ni0.8766Co0.0487Mn0.0487Al0.015Mg0.010W0.001O2And (5) cooking.
(2) Mixing the primary sintered product with strontium oxide, accounting the addition amount of the strontium oxide according to the molar ratio of the Sr coating amount to the anode material of 0.0005:0.9995, placing the mixture in an oxygen atmosphere for secondary sintering, firstly heating to 550 ℃, keeping the temperature for 4h, then heating to 650 ℃ at the speed of 2 ℃/min, keeping the temperature for 4h, and cooling to obtain a secondary sintered material.
(3) Preparing an ammonium carbonate solution with the concentration of 10%, wherein the weight ratio of the ammonium carbonate solution to the secondary sintering material is 0.5:1, placing the solution in a water area with the temperature of 55 ℃, stirring to prepare a saturated strontium nitrate solution, pouring the secondary sintering material into the solution, stirring for 1min, calculating the mass of the saturated strontium nitrate solution according to the Sr coating amount and the molar ratio of the saturated strontium nitrate solution to the anode material of 0.0005:0.9995, dropwise adding the saturated strontium nitrate solution into the slurry, and stirring for 15min after the dropwise adding is completed; so that the generated strontium carbonate is precipitated and uniformly coated on the surface of the material.
(4) Directly placing the slurry in a vacuum drying oven, and drying for 24h at 100 ℃ to obtain secondary Sr-coated Li1.01Ni0.8757Co0.0487Mn0.0487Al0.015Mg0.010W0.001Sr0.001O2And (4) drying the material.
(5) The aluminum phosphate and the titanium dioxide are subjected to secondary mixing by a high-speed mixer according to the amount accounting for the mass of the ingredients, wherein the molar ratio of the aluminum phosphate to the titanium dioxide to the dry matrix is 0.006:0.004: 0.990. Sintering the secondary mixture for three times in an oxygen atmosphere, setting the heating rate to be 5 ℃/min, heating to 500 ℃, keeping the temperature for 14h, and cooling to obtain the Sr gradient doped high-nickel material Li1.01Ni0.8670Co0.0482Mn0.0482Al0.0208Mg0.0099W0.001Sr0.001Ti0.004O1.991(PO4)0.006And (3) a positive electrode material.
Example 3:
(1) reacting lithium hydroxide with Ni0.96Co0.02Mn0.02(OH)2Uniformly mixing the precursor, strontium oxide, titanium oxide and lanthanum acetate according to the molar ratio of 1.06:0.982:0.003:0.005:0.01 in a high-speed mixer, sintering the mixture in an oxygen atmosphere at the temperature rise speed of 2 ℃/min to 730 ℃, keeping the temperature for 18h, reducing the temperature, crushing the material, and then vibrating and screening to obtain Li1.06Ni0.9427Co0.0196Mn0.0196Sr0.003Ti0.005La0.01O2And (5) cooking.
(2) Mixing the primary sintered product with strontium hydroxide, accounting the addition amount of the strontium oxide according to the molar ratio of the Sr coating amount to the anode material of 0.002:0.998, placing the mixture in an oxygen atmosphere for secondary sintering, firstly heating to 600 ℃, keeping the temperature for 2 hours, then heating to 700 ℃ at the rate of 0.5 ℃/min, keeping the temperature for 8 hours, and cooling to obtain a secondary sintered material.
(3) Preparing an ammonium carbonate solution with the solution concentration of 14%, wherein the weight ratio of the ammonium carbonate solution to the secondary sintering material is 1.0:1, placing the solution in a water area with the temperature of 65 ℃ for stirring, preparing a saturated strontium nitrate solution, pouring the secondary sintering material into the solution, stirring for 1min, calculating the mass of the saturated strontium nitrate solution according to the molar ratio of Sr to the anode material of 0.004:0.996, dropwise adding the saturated strontium nitrate solution into the slurry, and stirring for 30min after the dropwise adding is finished; so that the generated strontium carbonate is precipitated and uniformly coated on the surface of the material.
(4) After stirring, filtering the slurry to obtain a filter cake, placing the filter cake in a vacuum drying oven, and drying for 6h at 200 ℃ to obtain secondary Sr-coated Li1.04Ni0.9371Co0.0195Mn0.0195Sr0.009Ti0.005La0.0099O2And (4) drying the material.
(5) Calculating the mass of the ingredients of tungsten trioxide, magnesium oxide and boric acid according to the molar ratio of the tungsten trioxide, the magnesium oxide and the boric acid to a dry matrix of 0.002:0.003:0.01:0.985, and secondarily mixing the tungsten trioxide, the magnesium oxide and the boric acid with the matrix by a high-speed mixer. Sintering the secondary mixture for three times in an oxygen atmosphere, setting the heating rate to be 7 ℃/min, heating to 350 ℃, keeping the temperature for 6h, and cooling to obtain the Sr gradient doped high-nickel material Li1.04Ni0.9230Co0.0192Mn0.0192Sr0.0088Ti0.0049La0.0098W0.002Mg0.003B0.01O2And (3) a positive electrode material.
Comparative example 1:
a positive electrode material was prepared in the same manner as in example 1, except that step 2 was omitted and H was used in step 32O replaces ammonium carbonate solution and saturated strontium nitrate solution.
The other steps were identical to those of example 1, and a cathode material D1 was finally obtained: li1.02Ni0.8021Co0.1174Mn0.0587Zr0.00 5Sr0.002Y0.005B0.01O2And (3) a positive electrode material.
Comparative example 2:
a cathode material was prepared in the same manner as in example 1, except that the process of step 5 was omitted. The drying material is heated to 550 ℃ at a speed of 3 ℃/min, and is kept at the constant temperature for 6 hours and then cooled.
The other steps were identical to those of example 1, and a cathode material D2 was finally obtained: li1.02Ni0.8069Co0.1181Mn0.0590Zr0.00 5Sr0.006Y0.005O2And (3) a positive electrode material.
Comparative example 3:
a cathode material was prepared in the same manner as in example 2, except that the processes of step 2, step 3 and step 4 were not performed.
The other steps are consistent with example 2, and a cathode material D3 is finally obtained: li1.01Ni0.8678Co0.0482Mn0.0482Al0.0209Mg0.0099W0.001Ti0.004O1.991(PO4)0.006And (3) a positive electrode material.
The residual alkali content and the soluble lithium content of the intermediate products of examples and comparative examples, as well as the finished products, were measured, and the results are shown in table 2.
The specific surface areas of the positive electrode materials of example 1 and comparative examples 1 and 2 were measured, and the results are shown in table 3.
The positive electrode materials of each example and comparative example were tested for cell performance after assembly into button cells, with the results shown in table 4.
TABLE 2 residual alkali content and soluble lithium content
TABLE 3 specific surface area test results
TABLE 4 sample button cell performance data sheet
Comparative example 1 differs from example 1 in that comparative example 1 is a conventional high nickel preparation process, without Sr coating and sintering processes. From the physicochemical properties, the Sr gradient doping has small influence on the residual alkali and BET of the sample, and the example 1 and the comparative example 1 are at the same level. Through the gradient doping of Sr, the first time of the sample of the embodiment 1 is slightly reduced compared with the sample of the comparative example 1, but the rate performance is slightly improved, and the normal-temperature cycle performance is also improved. Fig. 2 shows that the two samples are subjected to 45 ℃ cycle test at 4.35V by using an actual cell, and from the test results, the cycle performance of the sample in example 1 is obviously better than that of the material in comparative example 1, which indicates that Sr is doped in a gradient manner on the surface to effectively improve the high voltage resistance of the high-nickel ternary material. Mainly because Sr is doped on the surface in a gradient manner, the Sr can play a role in stabilizing the crystal structure of the high-nickel ternary material on the surface layer. Under deep charging and discharging, the high-nickel ternary material on the surface layer still can keep a higher layered structure, so that the problems of particle pulverization and performance degradation caused by collapse of an external particle structure of the high-nickel ternary material from outside to inside are further inhibited.
The difference between comparative example 2 and example 1 is that comparative example 2 has no third sintering process, and from the physical and chemical properties, the BET of comparative example 2 is significantly higher than that of example 1, and the capacity, rate and cycle performance of the button cell of the sample are slightly worse than those of the sample of example 1. Through carrying out secondary cladding B to the sample, can restoreing to the sample performance, fill the crystal clearance, reduce BET, separation electrolyte and material take place the side reaction, further promote the cycle performance. Meanwhile, the ionic conductivity at the grain boundary is improved, so that the sample capacity is further improved. For example, other coating elements proposed in the present case are: the material is characterized by comprising Al, W, Ti, Mg, Ba, V, Mo, Co, F, P and La, wherein the elements can basically form an effective coating layer on the surface of the material, or play a role in blocking side reactions of the material and electrolyte, or improve the conduction of lithium ions of the material, or further improve the structural stability of the material, and through the coating, the electrical property of the material can be further improved.
Comparative example 3 differs from example 2 in that comparative example 3 has no Sr coating and secondary sintering process, and example 2 has a slightly lower discharge capacity than the button cell of comparative example 3, but the cycle performance is effectively improved.
In the embodiment 3, the ultrahigh nickel ternary material Ni96 is prepared, and through the preparation process, the high capacity of the Ni96 high nickel ternary material is exerted, and meanwhile, the rate capability and the cycle performance do not have obvious deterioration trend, so that the method has a good application effect on improving the structural stability and the electrochemical performance of the high nickel ternary material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The high-nickel ternary cathode material is characterized in that the chemical general formula of the high-nickel ternary cathode material is LiNixCoyMn(1-x-y-z)MzO2Wherein x is more than or equal to 0.76 and less than or equal to 0.97, Y is more than or equal to 0.02 and less than or equal to 0.15, z is more than 0 and less than or equal to 0.05, x + Y + z is less than 1, and M is one or more selected from Sr and Al, W, Ti, Mg, Zr, Ba, V, Mo, F, B, Y and La; sr is coated in a molten state or is not coated and enriched on the surface of the material, and the concentration is reduced from outside to inside to form gradient doping.
2. A method of making the high nickel ternary positive electrode material of claim 1, comprising the steps of:
step S1, adding Ni as high-nickel ternary precursorxCoyMn(1-x-y)(OH)2Or NixCoyMn(1-x-y)O2Mixing with Li source and additive containing M, sintering, cooling, pulverizing, and sieving to obtain a first sintered product; wherein x is more than or equal to 0.8 and less than or equal to 0.97，0.02≤y≤0.15，x+y＜1；
Step S2, uniformly mixing the primary sintered product obtained in the step S1 with an Sr compound, heating to 400-600 ℃ in an oxygen atmosphere, keeping the temperature constant for 0.5-6 h, heating to 600-700 ℃ at the speed of 0.5-3 ℃/min, keeping the temperature constant for 2-20 h, and obtaining a secondary sintered material;
step S3, adding the secondary sintering material obtained in the step S2 into an ammonium carbonate solution, slowly adding a saturated strontium nitrate solution, and reacting for 1-60 min; then, carrying out suction filtration and vacuum drying on the reaction slurry, or directly carrying out vacuum drying on the reaction slurry to obtain a secondary Sr coated dried material;
and S4, mixing the secondary Sr coated dry material obtained in the step S3 with a coating agent, and then sintering for three times in an oxygen atmosphere to obtain the Sr gradient doped high-nickel ternary positive electrode material.
3. The method of claim 2, wherein in step S1, the Li source is LiOH-H2O、LiOH、Li2O or Li2CO3One or more of; the M-containing additive is one or more of oxides or hydroxides of Sr, Al, W, Ti, Mg, Zr, Ba, Y and La; the ratio of the addition amount of M to the molar content of the cathode material is a, wherein a is more than 0 and less than 0.03.
4. The method according to claim 2, wherein in step S1, the primary sintering is performed in an oxygen atmosphere, and the temperature rise rate is 0.5 to 10 ℃/min, more preferably 1 to 3 ℃/min; raising the temperature to 650-900 ℃, keeping the temperature for 8-20 h, and preferably 10-15 h.
5. The method according to claim 3, wherein in step S2, the Sr compound is one or more selected from the group consisting of strontium hydroxide, strontium oxide, strontium carbonate, strontium sulfate, strontium chloride and strontium hydrogen phosphate; the molar content ratio of the Sr to the positive electrode material is b, wherein b is more than 0 and less than 0.03, and the more preferable addition amount of Sr is 0.05-0.5 mol% of the molar content of the positive electrode material.
6. The method according to claim 2, wherein in step S3, the ammonium carbonate solution has a temperature of 50 to 80 ℃ and a concentration of 5 to 15 wt%; the weight of the ammonium carbonate solution is 0.4-2.0 times of that of a calcined product.
7. The method according to claim 5, wherein in step S3, the weight of the strontium nitrate is calculated according to the coating amount of Sr, the molar amount of Sr coating is in proportion to the molar content of the positive electrode material, c is 0 < c < 0.03, and a + b + c is less than or equal to 0.03.
8. The method of claim 7, wherein in step S4, the cladding agent comprises at least one of Al, W, Ti, Mg, B, Ba, V, Mo, Co, F, P, La.
9. The method according to claim 8, wherein the molar ratio of the coating amount of the coating agent to the positive electrode material is d, 0 < d < 0.02, and a + b + c + d = z ≦ 0.05.
10. The method according to claim 2, wherein the temperature rise rate of the third sintering is 0.5-10 ℃/min, the temperature is raised to 250-600 ℃, and the constant temperature is kept for 4-15 h.
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