CN112125353B - Preparation method of high-nickel ternary cathode material for lithium ion battery - Google Patents
Preparation method of high-nickel ternary cathode material for lithium ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-nickel ternary cathode material for a lithium ion battery, which comprises the following steps of: (1) uniformly mixing a precursor of the high-nickel ternary cathode material with lithium salt, and then pre-sintering in a rotary kiln, wherein the sintering temperature in the high-temperature region is 450-; (2) performing primary sintering on the material obtained by the pre-sintering in a roller kiln, (3) performing secondary sintering in the roller kiln after crushing, washing and coating the material obtained by the primary sintering to obtain the high-nickel ternary cathode material, wherein the temperature of the secondary sintering is 500-600 ℃, and the sintering time is 6-10 h. According to the invention, the ternary positive material precursor and the lithium salt are uniformly mixed and presintered in the rotary kiln, and then are loaded into the roller kiln for sintering, so that the productivity of the roller kiln is improved by more than 100%; the precursor and the lithium salt are pre-sintered, so that volatile components in the material are greatly reduced, the sintering atmosphere of the roller kiln is improved, and the product quality is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a high-nickel ternary cathode material for a lithium ion battery.
Background
Lithium ion batteries (lithium secondary batteries) are increasingly favored by the battery industry because of their advantages of light weight, long life, cleanliness and environmental protection. The positive electrode material of lithium ion batteries has been the focus of research and development in the industry as a key material. At present, lithium cobaltate, lithium iron phosphate, lithium manganate and nickel cobalt manganese ternary materials are mainstream as positive electrode materials of lithium ion batteries, and new materials such as NCA (nickel cobalt aluminum) system and LOL (lithium manganese rich solid solution) are added into the ternary materials, so that the ternary materials are widely applied in commercialization. Among them, the lithium nickel cobalt manganese oxide ternary material, especially the NCA material, meets the requirements of higher and higher energy density due to its characteristics of high capacity and high energy density, and is more popular. Materials such as NCA \ NCM811 with higher nickel content are generally called high-nickel ternary cathode materials in the industry.
The high-nickel ternary cathode material has higher requirements on production equipment, workshop environment, production raw materials and the like, so that the application and popularization of the high-nickel cathode material are influenced. In the industrial production of the high-nickel ternary cathode material, generally, hydroxide (namely a precursor) and lithium salt with high nickel content are used as raw materials, and are mixed and then produced in a kiln by a high-temperature sintering method, wherein the adopted sintering kiln is a rotary kiln or a roller kiln. The Chinese patent application with the publication number of CN109768273A discloses a high-nickel anode material for a lithium ion battery prepared by a rotary kiln, a preparation method and an application thereof, wherein the anode material is prepared in an independent closed rotary device, the working temperature of the rotary device is 450-860 ℃, the rotating speed is 10-20rpm, and the inner wall of the rotary device is provided with a ceramic lining sheet or coating. The production process of the ternary cathode material is under high-alkali and high-temperature conditions, the ceramic lining sheet is easy to crack under the conditions, especially under long-term high-temperature conditions, the ceramic lining sheet is not suitable for being sintered at high temperature for a long time, and the coating is easy to corrode, so that the production of the high-nickel cathode material for a long time is not facilitated. If a roller kiln is adopted for sintering, the roller kiln is a static sintering device, the precursor and the lithium salt are required to be uniformly mixed and then are loaded into the roller kiln for sintering, and under the condition of certain loading thickness, the productivity of the roller kiln is very limited, so that the high-nickel anode material is high in manufacturing cost and low in productivity. Therefore, it is desirable to find a method for producing a ternary cathode material with low equipment requirement and high productivity.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-nickel ternary cathode material for a lithium ion battery, which has low requirement on equipment and improves the productivity.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the high-nickel ternary cathode material for the lithium ion battery comprises the following steps of:
(1) uniformly mixing a precursor of the high-nickel ternary cathode material with lithium salt, and then pre-sintering by adopting a rotary kiln, wherein the rotary kiln comprises a heating area, a high-temperature area and a cooling area, the sintering temperature of the high-temperature area is 450-600 ℃, and the sintering time is 3-8 h;
(2) performing primary sintering on the material obtained by the pre-sintering by adopting a roller kiln, wherein the primary sintering temperature is 650-900 ℃, and the sintering time is 0-16 h;
(3) and (3) crushing, washing and coating the materials obtained by the primary sintering, and then performing secondary sintering in a roller kiln to obtain the high-nickel ternary cathode material, wherein the secondary sintering temperature is 500-600 ℃, and the sintering time is 6-10 h.
Further, the temperature of the pre-sintering heating zone is 300-450 ℃, and the time of the heating zone is 1-3 h.
Further, the time for pre-sintering in the step (1) is 5-10 h.
Further, the presintering atmosphere is an oxygen atmosphere or an air atmosphere.
Further, the primary sintering atmosphere is pure oxygen atmosphere, the oxygen concentration of the hearth is more than or equal to 98%, and the gas pressure in the hearth is 15-20 Pa.
And further, screening and deironing the material obtained by secondary sintering to obtain the high-nickel ternary cathode material.
Furthermore, the chemical formula of the precursor of the high-nickel ternary cathode material is NiaCobMncAldRe(OH)2Wherein R is a doping element, a is more than or equal to 0.6 and less than or equal to 1.0, b is more than or equal to 0.0 and less than or equal to 0.3, c is more than or equal to 0.0 and less than or equal to 0.3, d is more than or equal to 0.0 and less than or equal to 0.3, e is more than or equal to 0.0 and less than or equal to 0.05, and a + b + c + d + e is more than or equal to 0.95 and less than or equal to 1.05.
Further, a precursor of the high-nickel ternary cathode material is acidified and then uniformly mixed with a lithium salt, and then is sintered for the first time by adopting a rotary kiln, wherein the chemical formula of the acidified precursor is NiaCobMncAldReO, wherein a is more than or equal to 0.6 and less than or equal to 1.0, b is more than or equal to 0.0 and less than or equal to 0.4, c is more than or equal to 0.0 and less than or equal to 0.4, d is more than or equal to 0.0 and less than or equal to 0.4, e is more than or equal to 0.0 and less than or equal to 0.05, and a + b + c + d + e is more than or equal to 0.95 and less than or equal to 1.05.
Further, a precursor of the high-nickel ternary cathode material, lithium salt and an additive are uniformly mixed and then sintered for one time by a rotary kiln, wherein the additive can be one or more of oxides, acids and organic matters of non-metallic elements such as boron, fluorine, silicon, phosphorus and sulfur, or one or more of oxides, salts, hydroxides and organic matters of metallic elements such as magnesium, zirconium, iron, zinc, niobium, tin, titanium, tungsten and yttrium.
Further, the lithium salt is one or more of lithium hydroxide, lithium carbonate, lithium acetate and lithium oxalate.
In the production of the conventional ternary cathode material, a rotary kiln or a roller kiln is mostly adopted as sintering equipment, and because the production environment of the ternary cathode material is high temperature and high alkali, the requirement on the equipment is high, a material which is simultaneously high temperature resistant and high alkali resistant is difficult to find as a furnace tube material of the rotary kiln, and the conventional common ceramic is easy to crack under the condition of long-term high temperature, so that the production cost is high; the roller kiln is used as static sintering equipment, the charging amount of the roller kiln is a main factor for limiting the production capacity, the inventor finds that a precursor of the ternary positive electrode material and lithium salt are uniformly mixed and pre-sintered in a rotary kiln in production, and then the precursor and the lithium salt are loaded into the roller kiln for sintering, so that the production capacity of the roller kiln is greatly improved, the manufacturing cost of the high-nickel ternary positive electrode material is reduced, and the obtained ternary positive electrode material has higher specific discharge capacity, better rate performance and cycle performance; the pre-sintering temperature is low, the time is short, and the service life of the rotary kiln is prolonged.
The invention has the beneficial effects that: according to the invention, the ternary positive material precursor and the lithium salt are uniformly mixed and pre-sintered in a rotary kiln, and then are loaded into a roller kiln for sintering, so that the productivity of the roller kiln is improved by more than 100%; the precursor and the lithium salt are pre-sintered to greatly reduce volatile components in the material, improve the sintering atmosphere of the roller kiln, improve the product quality, reduce the corrosivity of the material in the roller kiln, reduce the loss of the roller kiln box body and reduce the use cost of the box body.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
1) 20kg of NCA precursor Ni0.87Co0.1Al0.03(OH)29.7kg of lithium hydroxide, 100g of TiO2Adding into a high-speed stirring mixer, stirring at 300rpm for 15min, and stirring at 600rpm for 30min to obtain a high-mixing material;
2) adding the high mixture into a rotary kiln at a constant speed for presintering at 600 deg.C for 6h in the presence of pure oxygen at a flow rate of 500L/min to obtain presintering material with a bulk density of 1.6-1.8g/cm3；
3) Performing primary sintering on the pre-sintered material in a roller kiln with an atmosphere of 10 meters, wherein the loading amount of a sagger is 7 kg/sagger, the loading height is approximately equal to 4.5cm, the sintering temperature is 735 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, the oxygen ventilation amount is 1000L/min, so as to obtain a primary sintered material, and the discharging loading amount is 6.5-6.6 kg/sagger;
4) pulverizing the primary sinter, controlling D50 at 13.0 + -2.0 μm and D90 at 24.0 + -2.0 μm, washing with water at a ratio of 1:1 for 20min, stirring at 200rpm, water temperature of 25 deg.C, and coating agent H3BO3The coating agent accounts for 1.5% of the mass of the anode material, and then the filter pressing and drying are carried out, and the moisture is controlled below 1%;
5) and (3) carrying out secondary sintering on the dried material in a roller kiln, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 550 ℃, the sintering time is 8h, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Performing a power-off test on the high-nickel ternary cathode material obtained in the embodiment, wherein the first charge-discharge multiplying factor is 0.1C/0.1C, and performing a cycle test according to the charge-discharge multiplying factor of 1.0C/1.0C after continuous charge-discharge for 3 times; under the condition of 0.1C, the specific discharge capacity of the obtained high-nickel ternary cathode material is 208.1mAh/g, the first effect is 89.70%, the gram discharge capacity of the high-nickel ternary cathode material under the condition of 1C is 188.7mAh/g, the high-nickel ternary cathode material has high specific discharge capacity and good rate capability, and under the condition of 1.0C/1.0C charge and discharge, after 50 cycles of circulation, the specific discharge capacity is 175.3mAh/g, and the high-nickel ternary cathode material has good cycle capability.
Example 2:
1) 20kg of NCA precursor Ni0.87Co0.1Al0.03(OH)29.7kg of lithium hydroxide, 100g of TiO2Adding into a high-speed stirring mixer, stirring at 300rpm for 15min, and stirring at 600rpm for 30min to obtain a high-mixing material;
2) adding the high mixture into a rotary kiln at a constant speed for presintering at a sintering temperature of 500 deg.C for 6h in the presence of pure oxygen at a flow rate of 500L/min to obtain presintering material with a bulk density of 1.2-1.3g/cm3；
3) Performing primary sintering on the pre-sintered material in a roller kiln with an atmosphere of 10 meters, wherein the loading amount of a sagger is 5.8-5.9 kg/sagger, the loading height is approximately equal to 4.5cm, the temperature is 735 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, the oxygen ventilation amount is 1000L/min, so as to obtain a primary sintered material, and the discharging loading amount is 4.9-5.0 kg/sagger;
4) pulverizing the primary sinter, controlling D50 at 13.0 + -2.0 μm and D90 at 24.0 + -2.0 μm, washing with water at a ratio of 1:1 for 20min, stirring at 200rpm, water temperature of 25 deg.C, and coating agent H3BO3The coating agent accounts for 1.5% of the mass of the anode material, and then the filter pressing and drying are carried out, and the moisture is controlled below 1%;
5) and (3) carrying out secondary sintering on the dried material in a roller kiln, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 550 ℃, the sintering time is 8h, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Performing a power-off test on the high-nickel ternary cathode material obtained in the embodiment, wherein the first charge-discharge multiplying factor is 0.1C/0.1C, and performing a cycle test according to the charge-discharge multiplying factor of 1.0C/1.0C after continuous charge-discharge for 3 times; under the condition of 0.1C, the specific discharge capacity of the obtained high-nickel ternary cathode material is 207.4mAh/g, the first effect is 89.56%, and the gram discharge capacity of the obtained high-nickel ternary cathode material under the condition of 1C is 187.3mAh/g, so that the high-nickel ternary cathode material has high specific discharge capacity and good rate capability. Under the condition of charging and discharging at 1.0C/1.0C, after 50 cycles, the specific discharge capacity is 174.8mAh/g, and the lithium ion battery has better cycle performance.
Example 3:
1) 20kg of NCA precursor Ni0.87Co0.1Al0.03(OH)29.7kg of lithium hydroxide, 100g of TiO2Adding into a high-speed stirring mixer, stirring at 300rpm for 15min, and stirring at 600rpm for 30min to obtain a high-mixing material;
2) adding the high-temperature mixed material into a rotary kiln at a constant speed for presintering at 450 deg.C for 3h in a pure oxygen atmosphere with a gas flow rate of 500L/min to obtain presintering material with a bulk density of 0.9-1.0g/cm3；
3) Performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 4.4 kg/sagger, the loading height is approximately equal to 4.5cm, the temperature is 735 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, the oxygen ventilation volume is 1000L/min, so as to obtain a primary sintered material, and the discharging loading amount is 3.3-3.4 kg/sagger;
4) pulverizing the primary sintering material, wherein D50 is controlled to be 13.0 +/-2.0 mu m, and D90 is controlled to be 24.0 +/-2.0 mu m. Then washing with water at a ratio of 1:1 for 20min at a rotation speed of 200rpm with water temperature of 25 deg.C, and coating agent H3BO3The coating agent accounts for 1.5% of the mass of the anode material, and then the filter pressing and drying are carried out, and the moisture is controlled below 1%;
5) and (3) carrying out secondary sintering on the dried material in a roller kiln, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 550 ℃, the sintering time is 8h, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Performing a power-off test on the high-nickel ternary cathode material obtained in the embodiment, wherein the first charge-discharge multiplying factor is 0.1C/0.1C, and performing a cycle test according to the charge-discharge multiplying factor of 1.0C/1.0C after continuous charge-discharge for 3 times; under the condition of 0.1C, the specific discharge capacity of the obtained high-nickel ternary cathode material is 208.7mAh/g, the first effect is 89.70%, and the gram discharge capacity of the high-nickel ternary cathode material under the condition of 1C is 188.7mAh/g, so that the high-nickel ternary cathode material has high specific discharge capacity and good rate capability. Under the condition of charging and discharging at 1.0C/1.0C, after circulating for 50 circles, the specific discharge capacity is 175.3mAh/g, and the lithium ion battery has better cycle performance.
Comparative example 1:
1) 20kg of NCA precursor Ni0.87Co0.1Al0.03(OH)29.7kg of lithium hydroxide, 100g of TiO2Adding into a high-speed stirring mixer, stirring at 300rpm for 15min, and stirring at 600rpm for 30min to obtain a high-mixing material;
2) adding the high-mixed material into a rotary kiln at a constant speed for presintering at 250 deg.C for 3h in a pure oxygen atmosphere with a gas flow rate of 500L/min to obtain presintering material with a bulk density of 0.7g/cm3；
3) Performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 3.5 kg/sagger, the loading height is approximately equal to 4.5cm, the temperature is 735 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, the oxygen ventilation amount is 1000L/min, so as to obtain a primary sintered material, and the discharging loading amount is 2.4-2.5 kg/sagger;
4) pulverizing the primary sintering material, wherein D50 is controlled to be 13.0 +/-2.0 mu m, and D90 is controlled to be 24.0 +/-2.0 mu m. Then washing with water at a ratio of 1:1 for 20min at a rotation speed of 200rpm with water temperature of 25 deg.C, and coating agent H3BO3The coating agent accounts for 1.5% of the mass of the anode material, and then the filter pressing and drying are carried out, and the moisture is controlled below 1%;
5) and (3) carrying out secondary sintering on the dried material in a roller kiln, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 550 ℃, the sintering time is 8h, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Performing a power-off test on the high-nickel ternary cathode material obtained in the embodiment, wherein the first charge-discharge multiplying factor is 0.1C/0.1C, and performing a cycle test according to the charge-discharge multiplying factor of 1.0C/1.0C after continuous charge-discharge for 3 times; under the condition of 0.1C, the specific discharge capacity of the obtained high-nickel ternary cathode material is 207.5mAh/g, the first effect is 89.70%, and the gram discharge capacity of the high-nickel ternary cathode material under the condition of 1C is 188.7mAh/g, so that the high-nickel ternary cathode material has high specific discharge capacity and good rate capability. Under the condition of charging and discharging at 1.0C/1.0C, after circulating for 50 circles, the specific discharge capacity is 175.3mAh/g, and the lithium ion battery has better cycle performance.
Comparative example 2:
1) 20kg of NCA precursor Ni0.87Co0.1Al0.03O, 9.7kg of lithium hydroxide, 100g of TiO2Adding into a high-speed stirring mixer, stirring at 300rpm for 15min, and stirring at 600rpm for 30min to obtain a high-mixing material;
2) carrying out primary sintering on the high-mixed material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 3.5 kg/sagger, the loading height is approximately equal to 4.5cm, the temperature is 735 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, the oxygen ventilation amount is 1000L/min, secondary sintering material is obtained, and the discharging loading amount is 2.4-2.5 kg/sagger;
4) pulverizing the primary sinter, controlling D50 at 13.0 + -2.0 μm and D90 at 24.0 + -2.0 μm, washing with water at a ratio of 1:1 for 20min, stirring at 200rpm, water temperature of 25 deg.C, and coating agent H3BO3The coating agent accounts for 1.5% of the mass of the anode material, and then the filter pressing and drying are carried out, and the moisture is controlled below 1%;
5) and (3) carrying out secondary sintering on the dried material in a roller kiln, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 550 ℃, the sintering time is 8h, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
The high-nickel ternary cathode material obtained in the comparative example is assembled into a button cell for testing, the first charge-discharge multiplying power is 0.1C/0.1C, and after 3 times of continuous charge-discharge, a cyclic test is carried out according to the charge-discharge multiplying power of 1.0C/1.0C. Under the condition of 0.1C, the specific discharge capacity of the obtained high-nickel ternary cathode material is 209.0mAh/g, the first effect is 89.63%, and the gram discharge capacity of the high-nickel ternary cathode material under the condition of 1C is 187.5mAh/g, so that the high-nickel ternary cathode material has high specific discharge capacity and good rate capability. Under the charging and discharging conditions of 1.0C/1.0C, after 50 cycles, the specific discharge capacity is 175.9mAh/g, and the material has better cycle performance.
TABLE 1 EXAMPLES 1-3 AND COMPARATIVE EXAMPLES operating parameters and Experimental results
As can be seen from the above examples and Table 1, the productivity of the roller kiln can be improved by 170% to the maximum extent by using the roller kiln for sintering after the rotary kiln is pre-sintered, and the productivity of the roller kiln is greatly improved.
Claims (8)
1. The preparation method of the high-nickel ternary cathode material for the lithium ion battery is characterized by comprising the following steps of:
(1) uniformly mixing a precursor of the high-nickel ternary cathode material with lithium salt, and then presintering by adopting a rotary kiln, wherein the rotary kiln comprises a heating area, a high-temperature area and a cooling area, the sintering temperature of the high-temperature area is 450-600 ℃, and the sintering time is 3-8 h;
(2) performing primary sintering on the material obtained by the pre-sintering by adopting a roller kiln, wherein the primary sintering temperature is 650-900 ℃, and the sintering time is 0-16 h;
(3) and (3) crushing, washing and coating the materials obtained by the primary sintering, and then performing secondary sintering in a roller kiln to obtain the high-nickel ternary cathode material, wherein the secondary sintering temperature is 500-600 ℃, and the sintering time is 6-10 h.
2. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the temperature of the pre-sintering heating zone is 300-450 ℃, and the time of the heating zone is 1-3 h.
3. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1 or 2, wherein the method comprises the following steps: the pre-sintering time in the step (1) is 5-10 h.
4. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the presintering atmosphere is oxygen atmosphere or air atmosphere.
5. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the primary sintering atmosphere is pure oxygen atmosphere, the oxygen concentration of the hearth is more than or equal to 98 percent, and the gas pressure in the hearth is 15-20 Pa.
6. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: and screening and deironing the material obtained by secondary sintering to obtain the high-nickel ternary cathode material.
7. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the precursor of the high-nickel ternary cathode material, lithium salt and an additive are uniformly mixed and then presintered by adopting a rotary kiln, wherein the additive is one or more of oxides, acids and organic matters of non-metallic elements such as boron, fluorine, silicon, phosphorus and sulfur, or one or more of oxides, salts, hydroxides and organic matters of metallic elements such as magnesium, zirconium, iron, zinc, niobium, tin, titanium, tungsten and yttrium.
8. The method for preparing the high-nickel ternary cathode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: the lithium salt is one or more of lithium carbonate, lithium acetate and lithium oxalate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010455045 | 2020-05-26 | ||
| CN2020104550453 | 2020-05-26 |
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| CN112794371A (en) * | 2020-12-31 | 2021-05-14 | 宜宾锂宝新材料有限公司 | Low-cost high-nickel ternary lithium ion battery cathode material and preparation method thereof |
| CN113823764B (en) * | 2021-09-29 | 2023-06-09 | 北京当升材料科技股份有限公司 | Roller kiln for sintering anode material, multi-element anode material and preparation method thereof |
| CN115043443B (en) * | 2022-07-29 | 2024-03-01 | 宁波容百新能源科技股份有限公司 | Low-cost high-nickel ternary positive electrode material and preparation method and application thereof |
| CN115477333B (en) * | 2022-09-21 | 2024-02-23 | 天津巴莫科技有限责任公司 | Low-cobalt ternary monocrystal positive electrode material, preparation method thereof and lithium ion battery |
| CN115911337B (en) * | 2023-01-06 | 2023-06-23 | 宜宾锂宝新材料有限公司 | High-nickel positive electrode material, preparation method thereof and battery |
| CN116199278B (en) * | 2023-05-05 | 2023-08-04 | 四川新能源汽车创新中心有限公司 | Preparation method of ternary positive electrode material of lithium battery |
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