CN114940519A - Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material - Google Patents
Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material, which comprises the steps of mixing a high-nickel ternary precursor with a lithium source, a fluxing agent and a doping agent, and then carrying out primary sintering in a sintering atmosphere to obtain a monocrystal ternary cathode material substrate, wherein the primary sintering comprises the steps of firstly heating to a first sintering temperature and preserving heat for a certain time, and then heating to a second sintering temperature and preserving heat for a certain time; crushing, screening, washing, filtering and drying the obtained single crystal ternary cathode material substrate to obtain a dried product; and carrying out secondary sintering on the dried product to obtain a secondary sintered product, mixing the secondary sintered product with a coating agent, and carrying out tertiary sintering to obtain the single crystal nickel cobalt lithium manganate ternary cathode material. The invention can reduce sintering temperature, reduce sintering energy consumption, reduce lithium-nickel mixed discharge under conventional high-temperature sintering, and improve the electrochemical performance of the material, and is beneficial to preparing the high-nickel single crystal ternary cathode material with good dispersibility, high tap density, high capacity and high first efficiency.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery ternary cathode materials, and relates to a preparation method of a high-nickel single-crystal nickel cobalt lithium manganate ternary cathode material.
Background
The lithium ion battery has the advantages of high working voltage, light weight, large energy density, long cycle life and the like, and is widely applied to the fields of electric automobiles, digital cameras, mobile phones, notebook computers and the like. The anode material is used as a core material in the lithium ion battery, so that the energy density and the cost of the battery are determined to a great extent, and the performance of the anode material directly influences the performance of the lithium ion battery.
The ternary positive electrode material is the positive electrode material of the power battery with the largest market share at present, and has become one of the mainstream choices in the power battery industry. At present, the high nickel content, high voltage content, low cobalt content, high power content, high safety and high cycle number become the technological development trend of ternary cathode material products. The conventional ternary cathode material of secondary particle aggregates is composed of a plurality of primary particles, and in the circulation process, the whole secondary ball is easy to crack and break due to continuous shrinkage and expansion of the particle volume, so that the electrochemical environment of the battery is changed violently, the cycle life is shortened, and the battery performance is also deteriorated. The single crystal ternary cathode material can obtain more excellent cycle stability, structural stability and high temperature resistance, thereby having better safety performance.
At present, the method for preparing the single crystal NCM ternary cathode material is a polycrystalline precursor prepared by sintering a coprecipitation method at a higher temperature, and the method has the advantages of high sintering temperature, long heat preservation time and higher energy consumptionThe prepared single crystal material has wider particle size distribution, the serious agglomeration is easy to occur among primary particles, the dispersity is poorer, the tap density is lower, and the electrochemical performance of the single crystal material is poorer because the lithium-nickel mixed arrangement is serious under high-temperature sintering; in another method, flux is used for assisting sintering, but most of the single crystal-like materials prepared by the prior art are single crystal-like materials, and a small amount of aggregates in the single crystal-like materials can crack, pulverize and the like at a later stage like secondary particles of a conventional positive electrode material, so that the cycle performance of the materials is finally poor, and the electrochemical performance is poor. Therefore, the appearance and the dispersibility of the material still need to be improved, and the material also has the problems of certain lithium-nickel mixed arrangement and low crystallinity. In addition, the adopted fluxing agents are NaF and Li 2 SO 4 、Al 2 O 3 、 Na 2 SO 4 、B 2 O 3 NaCl, MgO, etc., are liable to introduce uncontrolled impurity elements or to cause excessive doping of other elements, and these fluxes are not conducive to subsequent removal.
Disclosure of Invention
The invention aims to provide a preparation method of a high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material, which solves the problems of high sintering temperature, high energy consumption or uncontrollable impurity introduction in the existing preparation of monocrystal NCM ternary cathode materials, poor appearance dispersibility, low tap density, poor capacity and first effect and the like of the prepared monocrystal materials.
The technical scheme adopted by the invention is that the preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material comprises the following specific operation steps:
step 1: mixing a high-nickel ternary precursor with a lithium source, a doping agent and a fluxing agent, then sintering in an oxygen atmosphere, firstly heating to a first sintering temperature of 200-600 ℃, sintering for 2-24 hours, then heating to a second sintering temperature of 400-900 ℃, sintering for 2-24 hours, cooling at a cooling rate of 0.5-10 ℃/min after sintering is finished, and crushing after a product is discharged to obtain a single crystal NCM substrate;
step 2: taking the single crystal NCM substrate obtained in the step 1, adding deionized water for washing, stirring for 5-60 min, performing suction filtration, drying and sieving;
and step 3: carrying out secondary sintering on the material dried in the step 2 in the air or oxygen atmosphere, wherein the sintering temperature is 200-800 ℃, the sintering time is 1-24 h, cooling along with the furnace after sintering is finished, and sieving the product after the product is discharged from the furnace to obtain a single crystal NCM anode material;
and 4, step 4: and (3) mixing the single-crystal NCM positive electrode material obtained in the step (3) with a coating agent, sintering for three times in the air or oxygen atmosphere, wherein the sintering temperature is 100-600 ℃, the sintering time is 2-15 h, cooling along with the furnace after sintering is finished, and sieving after the product is discharged from the furnace to obtain the single-crystal NCM product.
The present invention is also characterized in that,
the lithium source in step 1 is lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxide or lithium acetate.
And (2) the molar ratio of the lithium ions in the lithium source in the step (1) to the high-nickel ternary precursor is 0.8-1.3.
The mass ratio of the dopant to the precursor in the step 1 is 100-5000 ppm; the fluxing agent is LiBr, NaBr, KBr or LiNO 3 One or more of the above; the proportion of the fluxing agent in the total of the lithium source and the fluxing agent is 0.1-80 wt%.
In the step 1, the heating rate of the temperature rise to the first sintering temperature and the second sintering temperature rise is 0.5-10 ℃/min.
In the step 1, the metal element in the doping agent is one or more of Mg, Zr, W, Ti, Y, Sr, Al, Mo and V.
In the step 2, the mass ratio of the deionized water to the anode material is 1: 1-5: 1.
In step 4, the coating agent is Al 2 O 3 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 One or more of them.
The invention has the beneficial effects that:
the preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material comprises the steps of firstly promoting a fluxing agent and a lithium source to form an eutectic at a specific lower temperature through sectional heat preservation in one burning process, so that lithium ions can be diffused at the relatively lower temperature, and effectively promoting the lithium ions to be fully diffused by preserving heat at the specific temperature for a period of time, thereby promoting the uniform generation and growth of monocrystal particles. Then further promoting the growth of the single crystal particles at a higher temperature to form a final product, wherein the XRD result shows that the product has high crystallinity and shows a complete crystal lattice structure. The sintering system shows that the invention can also effectively reduce the sintering energy consumption and lighten the mixed discharge of lithium and nickel under the conventional high-temperature sintering, thereby improving the electrochemical performance of the material.
The bromide fluxing agent or the combination of the fluxing agents containing the bromide has higher solubility at normal temperature, is beneficial to removing residual fluxing agents by subsequent washing, can not only avoid introducing impurity elements, but also reduce washing water, ensures the performance of single crystal materials, and simultaneously reduces the consumption of the washing water and the subsequent wastewater treatment cost; meanwhile, the anion in the fluxing agent has larger ion radius, and can not be embedded into the layered structure of the single crystal material to introduce impurities, and the adsorption of the anion on the surfaces of different single crystal particles can generate electrostatic repulsion action on the single crystal particles, so that the dispersibility of the single crystal material can be improved, the prepared high-nickel single crystal ternary cathode material has good dispersibility, and few aggregates exist as seen in a control sample electron microscope, so that the material has higher tap density, and finally, the battery has higher volumetric specific energy. In addition, the appearance of the single crystal can be influenced by ions in the fluxing agent, and the specific adsorption on different crystal faces of the single crystal is realized by controlling the combination of the fluxing agent, so that the single crystal NCM cathode material with different appearances, such as an octahedron shape, can be obtained. In addition, the invention can also achieve the purpose of controlling the particle size by changing the combination and the dosage of the fluxing agent.
Drawings
FIG. 1 is an SEM image of a single crystal NCM produced in example 1 of the present invention.
FIG. 2 is a SEM photograph of single crystal NCM produced in example 1 of the present invention at magnification.
FIG. 3 is an XRD pattern of single crystal NCM prepared in example 1 of the present invention.
FIG. 4 is an SEM image of a single crystal NCM produced in example 2 of the present invention.
FIG. 5 is an SEM image of a single crystal NCM produced in example 3 of the present invention.
FIG. 6 is an SEM image of a single crystal NCM prepared in comparative example 1 of the present invention.
FIG. 7 is an SEM image of a single crystal NCM prepared by comparative example 2 of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided with reference to the drawings, and the present embodiment is implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the protection scope of the present invention is not limited to the following embodiments.
The preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material specifically comprises the following steps:
(1) mixing a high-nickel ternary precursor with a lithium source, a fluxing agent and a doping agent according to a certain proportion, sintering the mixture at a lower temperature according to a certain heating rate and a certain heat preservation time in an oxygen atmosphere, then heating and sintering according to a certain heat preservation time, cooling to a tapping temperature according to a certain cooling rate after sintering is finished, and crushing a ternary cathode material obtained by final sintering;
(2) stirring and washing the crushed product for a certain time by using deionized water with a certain mass ratio to remove residual fluxing agent, and performing suction filtration, drying and sieving after washing;
(3) performing secondary sintering on the product obtained in the step (2) in an oxygen atmosphere according to a certain temperature and heat preservation time system, crushing and sieving the product to obtain a single-crystal high-nickel ternary cathode material;
(4) and (4) sintering the single crystal anode material obtained in the step (3) and a coating agent for the third time under an oxygen atmosphere according to a certain temperature and heat preservation time system, and then crushing and sieving the single crystal anode material to obtain the final product, namely the high-nickel single crystal ternary anode material.
Wherein, in the step (1), the high-nickel ternary precursor is Ni x Co y Mn 1-x-y (OH) 2 ，x＞0.6， y＞0，1-x-y＞0。
Preferably, in the step (1), the sintering atmosphere is air or oxygen, the first heat preservation temperature is 200-600 ℃, the sintering time is 2-24 hours, the second heat preservation temperature is 400-900 ℃, and the sintering time is 2-24 hours; the heating rate is 0.5-10 ℃/min, and the cooling rate is 0.5-10 ℃/min; the lithium source is lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxide or lithium acetate, and the metal element in the doping agent is one or more of Mg, Zr, W, Ti, Y, Sr, Al, Mo and V; the molar ratio of the lithium source to the precursor is 0.8-1.3, and the mass ratio of the dopant to the precursor is 100-5000 ppm; the fluxing agent is LiBr, NaBr, KBr or LiNO 3 One or more of them, the fluxing agent accounts for 0.1-80 wt% of the total of the lithium source and the fluxing agent.
Preferably, in the step (2), the mass ratio of the deionized water to the positive electrode material is 1: 1-5: 1, and the washing time is 5-60 min.
Preferably, in the step (3), the sintering atmosphere is air or oxygen, the sintering temperature is 200-800 ℃, and the sintering time is 1-24 hours.
Preferably, in the step (4), the sintering atmosphere is air or oxygen, the sintering temperature is 100-600 ℃, the sintering time is 2-15 h, and the coating agent is Al 2 O 3 、H 3 PO 4 、Li 3 PO 4 、 H 3 BO 3 、C、B 2 O 3 、ZrO 2 One or more of them.
According to the invention, the sintering temperature is reduced by the bromide fluxing agent, and the problem of lithium-nickel mixed discharge generated by high-temperature sintering of the single crystal material is reduced by combining a specific segmented heat-preservation one-time sintering system; the dispersibility of the single crystal material is improved through an electrostatic repulsion effect generated by the adsorption of anions in the fluxing agent on the surfaces of the single crystal particles, and the appearance and the particle size of the single crystal material are controlled by regulating and controlling the combination and the using amount of the fluxing agent. Finally, the dispersibility and tap density of the single crystal high nickel ternary cathode material can be improved, and the electrochemical performance of the material is improved.
Example 1:
the preparation method of the high-nickel single crystal type nickel cobalt lithium manganate ternary positive electrode material comprises the following steps of:
(1) a certain amount of precursor Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 Mixing with a lithium source (lithium hydroxide), zirconium dioxide and LiBr + KBr (molar ratio of 9:1), wherein the molar ratio of lithium ions in the lithium source to a precursor is 1.3:1, the mass ratio of a doping agent zirconium dioxide to the precursor is 5000ppm, and the molar ratio of a fluxing agent LiBr + KBr in the lithium source and a cosolvent is 80 wt%; then sintering in an oxygen atmosphere, heating to 600 ℃ at the speed of 10 ℃/min, wherein the sintering time is 24h, heating to 900 ℃ at the speed of 10 ℃/min, wherein the sintering time is 24h, cooling at the speed of 10 ℃/min after sintering, and crushing after discharging the product to obtain a single crystal NCM cathode material preliminarily;
(2) taking a primary sintered single crystal NCM positive electrode material, adding deionized water with the mass ratio of 5:1 for washing, stirring for 60min, performing suction filtration after washing, drying and sieving;
(3) carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 24 hours, cooling along with a furnace after sintering is finished, and sieving a product after the product is discharged from the furnace to obtain a single crystal NCM cathode material;
(4) mixing single crystal NCM cathode material with 5000ppm of H 3 BO 3 And (3) sintering for three times in an oxygen atmosphere after mixing, wherein the sintering temperature is 600 ℃, the sintering time is 15h, cooling along with a furnace after sintering is finished, and sieving after the product is discharged to obtain a single crystal NCM product (shown in figures 1-3).
Example 2:
the preparation method of the high-nickel single crystal type nickel cobalt lithium manganate ternary positive electrode material comprises the following steps of:
(1) the precursor Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 Mixing with a lithium source (lithium hydroxide), tungsten trioxide and NaBr, wherein the molar ratio of lithium ions in the lithium source to a precursor is 1.06:1, the mass ratio of a doping agent tungsten trioxide to the precursor is 2000ppm, and a fluxing agent LiBr +KBr (molar ratio 1:1) was 15 wt% based on the total of the lithium source and the co-solvent. Then sintering in an oxygen atmosphere, heating to a first sintering temperature of 480 ℃ at a speed of 4 ℃/min, wherein the sintering time is 16h, heating to a second sintering temperature of 750 ℃ at a speed of 4 ℃/min, wherein the sintering time is 12h, cooling with the furnace at a speed of 3 ℃/min after sintering is finished, and crushing a product after the product is taken out of the furnace to obtain a single crystal NCM anode material;
(2) taking a certain amount of primary sintered single crystal NCM cathode material, adding deionized water with the mass ratio of 3:1 for washing, washing and stirring for 40min, performing suction filtration, drying and sieving after the washing;
(3) carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 650 ℃, the sintering time is 8 hours, cooling along with the furnace after sintering is finished, and sieving the product after the product is discharged from the furnace to obtain a single crystal NCM cathode material;
(4) mixing single crystal NCM anode material with 300ppm Al 2 O 3 And (3) sintering for three times in an oxygen atmosphere after mixing, wherein the sintering temperature is 300 ℃, the sintering time is 6h, cooling along with the furnace after sintering is finished, and sieving the product after the product is discharged to obtain a single crystal NCM product (as shown in figure 4).
Example 3:
the preparation method of the high-nickel single crystal type nickel cobalt lithium manganate ternary positive electrode material comprises the following steps of:
(1) a certain amount of precursor Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 With lithium sources (lithium carbonate), magnesium oxide, LiNO 3 + NaBr mixture with lithium ion to precursor molar ratio of 0.8 to 1, dopant magnesia in 100ppm mass, flux LiNO 3 + NaBr was 0.5 wt% of the total of the lithium source and the co-solvent. Then sintering in an oxygen atmosphere, firstly heating to a first sintering temperature of 200 ℃ at the rate of 0.5 ℃/min, and sintering for 2h, then heating to a second sintering temperature of 400 ℃ at the rate of 0.5 ℃/min, and sintering for 2h, cooling at the rate of 0.5 ℃/min after sintering, and crushing after discharging the product to obtain the single crystal NCM cathode material;
(2) taking a certain amount of primary sintered single crystal NCM cathode material, adding deionized water in a mass ratio of 1:1 for washing, stirring for 5min, performing suction filtration, drying and sieving;
(3) carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 200 ℃, the sintering time is 1h, cooling along with the furnace after sintering is finished, and sieving the product after the product is discharged from the furnace to obtain a single crystal NCM cathode material;
(4) mixing single crystal NCM cathode material with 500ppm Li 3 PO 4 And (3) sintering for three times in an oxygen atmosphere after mixing, wherein the sintering temperature is 100 ℃, the sintering time is 2 hours, cooling along with the furnace after sintering is finished, and sieving the product after the product is discharged to obtain a single crystal NCM product (as shown in figure 5).
Comparative example 1:
the conventional high-temperature sintering method for preparing the single crystal ternary material comprises the following steps:
(1) the precursor Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 Mixing with a lithium source (lithium hydroxide) and zirconium dioxide, wherein the molar ratio of lithium ions in the lithium source to the precursor is 1.3:1, and the mass ratio of the doping agent zirconium dioxide to the precursor is 5000 ppm. Then sintering in an oxygen atmosphere, wherein the sintering temperature is 900 ℃, the sintering time is 24h, cooling along with the furnace after sintering is finished, and crushing after the product is discharged to obtain a single crystal NCM cathode material;
(2) carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 24 hours, cooling along with a furnace after sintering is finished, and sieving a product after the product is discharged from the furnace to obtain a single crystal NCM cathode material;
(3) mixing single crystal NCM anode material with 5000ppm of H 3 BO 3 And (3) sintering for three times in an oxygen atmosphere after mixing, wherein the sintering temperature is 600 ℃, the sintering time is 15h, cooling along with the furnace after sintering is finished, and sieving the product after the product is discharged to obtain a single crystal NCM product (as shown in figure 6).
Comparative example 2:
the method comprises the following steps:
(1) a certain amount of precursor Ni 0.88 Co 0.09 Mn 0.03 (OH) 2 With lithium source (lithium hydroxide), yttrium oxide, Na 2 SO 4 Mixing, wherein the molar ratio of lithium ions in the lithium source to the precursor is 1.3:1, the mass ratio of the doping agent yttrium oxide to the precursor is 5000ppm, and the fluxing agent Na 2 SO 4 The molar ratio of the lithium source to the cosolvent is 60 wt%. Sintering in an oxygen atmosphere at the sintering temperature of 900 ℃ for 24 hours, cooling along with the furnace after sintering is finished, and crushing the product after the product is discharged from the furnace to obtain a single crystal NCM cathode material;
(2) taking a certain amount of primary sintered single crystal NCM cathode material, adding deionized water with the mass ratio of 5:1 for washing, washing and stirring for 60min, performing suction filtration after completion, drying and sieving;
(3) carrying out secondary sintering on the dried material in an oxygen atmosphere, wherein the sintering temperature is 800 ℃, the sintering time is 24 hours, cooling along with a furnace after sintering is finished, and sieving a product after the product is discharged from the furnace to obtain a single crystal NCM cathode material;
(4) mixing single crystal NCM anode material with 5000ppm of H 3 BO 3 And (3) sintering for three times in an oxygen atmosphere after mixing, wherein the sintering temperature is 600 ℃, the sintering time is 15h, cooling along with a furnace after sintering is finished, and sieving after the product is discharged to obtain a single crystal NCM product (as shown in figure 7).
The results of the performance tests on the products obtained in the examples and comparative examples are given in the following table:
as can be seen from the table above, the positive electrode material prepared by the method has good tap density, first charge-discharge efficiency, discharge capacity and capacity retention rate, and is greatly improved compared with comparative examples 1-2.
Claims (9)
1. The preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material is characterized by comprising the following specific operation steps of:
step 1: mixing a high-nickel ternary precursor with a lithium source, a doping agent and a fluxing agent, then sintering for the first time in an oxygen atmosphere, firstly heating to a first sintering temperature of 200-600 ℃, sintering for 2-24 hours, then heating to a second sintering temperature of 400-900 ℃, sintering for 2-24 hours, cooling at a cooling rate of 0.5-10 ℃/min after sintering is finished, and crushing a product after the product is taken out of a furnace to obtain a single crystal NCM substrate;
and 2, step: taking the single crystal NCM substrate obtained in the step 1, adding deionized water for washing, stirring for 5-60 min, performing suction filtration, drying and sieving;
and step 3: performing secondary sintering on the material dried in the step 2 in the air or oxygen atmosphere, wherein the sintering temperature is 200-800 ℃, the sintering time is 1-24 h, cooling along with the furnace after sintering is finished, and sieving the product after discharging to obtain a single crystal NCM (negative control metal) anode material;
and 4, step 4: and (3) mixing the single-crystal NCM positive electrode material obtained in the step (3) with a coating agent, sintering for three times in the air or oxygen atmosphere, wherein the sintering temperature is 100-600 ℃, the sintering time is 2-15 h, cooling along with the furnace after sintering is finished, and sieving after the product is discharged from the furnace to obtain the single-crystal NCM product.
2. The method for preparing the high-nickel single-crystal lithium nickel cobalt manganese oxide ternary positive electrode material according to claim 1, wherein the lithium source in the step 1 is lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxide or lithium acetate.
3. The preparation method of the high-nickel single-crystal nickel cobalt lithium manganate ternary cathode material according to claim 1, wherein the molar ratio of lithium ions in the lithium source to the high-nickel ternary precursor in step 1 is 0.8-1.3.
4. The preparation method of the high-nickel single-crystal nickel cobalt lithium manganate ternary positive electrode material according to claim 1, wherein the mass ratio of the dopant to the precursor in step 1 is 100-5000 ppm; the fluxing agent is LiBr, NaBr, KBr or LiNO 3 One or more of the above; the proportion of the fluxing agent in the total of the lithium source and the fluxing agent is 0.1-80 wt%.
5. The high nickel single crystal lithium nickel cobalt manganese oxide of claim 1The preparation method of the element anode material is characterized in that the high-nickel ternary precursor in the step 1 is Ni x Co y Mn 1-x-y (OH) 2 ，x＞0.6，y＞0，1-x-y＞0。
6. The method for preparing the high-nickel single-crystal nickel cobalt lithium manganate ternary positive electrode material as claimed in claim 4, wherein the heating rate of the temperature rise to the first sintering temperature and the second sintering temperature rise in step 1 is 0.5-10 ℃/min.
7. The method for preparing the high-nickel single-crystal nickel cobalt lithium manganate ternary positive electrode material according to claim 1, wherein the metal element in the dopant in step 1 is one or more of Mg, Zr, W, Ti, Y, Sr, Al, Mo and V.
8. The preparation method of the high-nickel monocrystal nickel cobalt lithium manganate ternary positive electrode material according to claim 1, wherein the mass ratio of the deionized water to the positive electrode material in the step 2 is 1: 1-5: 1.
9. The method for preparing the high-nickel single-crystal nickel cobalt lithium manganate ternary positive electrode material as claimed in claim 1, wherein said coating agent in step 4 is Al 2 O 3 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 One or more of them.
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