Preparation method of a ternary nickel-manganese-aluminum precursor material with internal pores

Abstract

The present invention provides a method for preparing an internal pore type nickel manganese aluminum ternary precursor material. Sodium aluminate solution is prepared by dissolving aluminum salt crystals in an excessive amount of NaOH solution; nickel crystals and manganese crystals are dissolved in pure water to prepare a mixed salt solution; the sodium aluminate solution and the mixed salt solution are added into a reaction kettle, and a complexing agent and a precipitating agent are added for mixed reaction. The internal environment of the reaction kettle is controlled, and the reaction is continuously carried out at 40-75 °C for 40-80 h to obtain a nickel manganese aluminum precursor. In the present invention, the prepared particle structure is designed with a loose internal pore and a dense external core-shell structure. The loose internal structure has high activity, which is beneficial to the diffusion of lithium ions during the sintering of the positive electrode and improves the sintering yield rate; at the battery end, it effectively increases the contact area between the material and the electrolyte, improves the battery output performance, and can also buffer the volume change of the positive electrode active material during charge and discharge, stabilize the material structure, and improve the cycle performance.

Description

Technical Field

[0001] The present invention relates to the field of preparation of cathode materials for lithium-ion batteries, and particularly to a method for preparing an internal pore type nickel-manganese-aluminum ternary precursor material. Background Art

[0002] The ternary precursor is a key raw material for the preparation of ternary cathode materials. The nickel-manganese-aluminum ternary precursor is nickel-manganese-aluminum hydroxide. In the lithium-ion battery cathode industrial chain, the final performance of the cathode material will inherit the morphological and structural characteristics of its precursor. The quality of the precursor (morphology, particle size, particle size distribution, specific surface area, impurity content, tap density, etc.) directly determines the physical and chemical indexes of the cathode sintered product.

[0003] Ternary cathodes generally refer to NCM and NCA. By configuring the three elements in different proportions, different battery performances can be obtained. However, cobalt resources are relatively scarce, the supply chain is fragile, the price is high and volatile, which is not conducive to cost control. Therefore, ternary materials are gradually developing towards cobalt-free. Summary of the Invention

[0004] The purpose of the present invention is to solve the drawbacks existing in the prior art, and to propose a method for preparing an internal pore type nickel-manganese-aluminum ternary precursor material.

[0005] In order to achieve the above purpose, the present invention adopts the following technical scheme: A method for preparing an internal pore type nickel-manganese-aluminum ternary precursor material, comprising the following steps:

[0006] S1. Dissolve aluminum salt crystals with an excessive amount of NaOH solution to prepare a sodium aluminate solution;

[0007] S2. Dissolve nickel crystals and manganese crystals with pure water to prepare a mixed salt solution;

[0008] S3. Add the sodium aluminate solution and the mixed salt solution into a reaction kettle, and add a complexing agent and a precipitating agent for mixed reaction. Control the pH value in the reaction kettle to be 10 - 13, and introduce Gas 1 and Gas 2, and continuously react at 40 - 75 °C for 40 - 80 h to obtain a nickel-manganese-aluminum precursor: Ni 1-x-y Mn x Al y (OH) 2 , where: 0.1 < x < 0.6, 0.01 < y < 0.1;

[0009] The nickel-manganese-aluminum ternary precursor has a structure with loose internal pores and dense external core-shell.

[0010] As a further description of the above technical scheme:

[0011] In step S1, the aluminum crystal is aluminum nitrate, in step S2, the nickel crystal is nickel nitrate, and in step S2, the manganese crystal is manganese nitrate.

[0012] As a further description of the above technical solution:

[0013] In step S1, the concentration of NaOH is 8 - 12N.

[0014] As a further description of the above technical solution:

[0015] In step S3, the concentration of sodium aluminate is AL: 6 - 40 g / L, the concentration of free NaOH in step S3 is 5 - 15N, and the total concentration of the mixed salt solution in step S3 is 80 - 130 g / L.

[0016] As a further description of the above technical solution:

[0017] In step S3, the feeding flow rate of sodium aluminate is controlled at 400 - 2000 mL / h, and the feeding flow rate of the mixed salt solution in step S3 is controlled at 3000 - 8000 mL / h.

[0018] As a further description of the above technical solution:

[0019] The complexing agent is ammonia water, the concentration of the complexing agent is 6N, and the feeding flow rate of the complexing agent in step S3 is controlled at 100 - 1000 mL / h.

[0020] As a further description of the above technical solution:

[0021] The precipitating agent is sodium hydroxide solution, the concentration of the precipitating agent is 10N, and the feeding flow rate of the precipitating agent in step S3 is controlled at 400 - 2000 mL / min.

[0022] As a further description of the above technical solution:

[0023] The gas 1 is compressed air, the gas 2 is nitrogen, both the gas 1 and the gas 2 are added in a sub - liquid way, the feeding flow rate of the gas 1 in step S3 is 200 - 500 mL / min, and the feeding flow rate of the gas 2 in step S3 is 3000 - 4000 mL / min.

[0024] The present invention has the following beneficial effects:

[0025] 1. Compared with the prior art, for the preparation method of the internal - pore - type nickel - manganese - aluminum ternary precursor material, using aluminum element to replace cobalt element reduces the material cost, the crystal structure changes from loose and porous to dense, while ensuring the capacity, the material stability is improved, and the preparation process is simple, having advantages such as low production cost.

[0026] 2. Compared with the prior art, for the preparation method of the internal pore type nickel-manganese-aluminum ternary precursor material, the prepared particle structure design adopts a structure with loose internal pores and dense external core-shell, with an inner:outer ratio of 1:1. The loose internal structure has high activity, which is beneficial to the diffusion of lithium ions during the sintering of the positive electrode, improving the sintering yield rate; at the battery end, it effectively increases the contact area between the material and the electrolyte, improves the battery output performance, and can also buffer the volume change of the positive electrode active material during charge and discharge, stabilize the material structure, and improve the cycle performance.

[0027] 3. Compared with the prior art, the preparation method of the internal pore type nickel-manganese-aluminum ternary precursor material uses a new material structure to solve problems such as low yield rate of the positive electrode material and poor battery cycle stability. Description of the Drawings

[0028] Figure 1 SEM cross-sectional view of the nickel-manganese-aluminum ternary precursor of the preparation method of the internal pore type nickel-manganese-aluminum ternary precursor material proposed by the present invention;

[0029] Figure 2 Magnified SEM cross-sectional view of the nickel-manganese-aluminum ternary precursor of the preparation method of the internal pore type nickel-manganese-aluminum ternary precursor material proposed by the present invention;

[0030] Figure 3 XRD diagram of the preparation method of the internal pore type nickel-manganese-aluminum ternary precursor material proposed by the present invention;

[0031] Figure 4 Magnified SEM cross-sectional view of the conventional nickel-manganese-aluminum ternary precursor material in the comparative case of the present invention. Detailed Embodiments

[0032] The preparation method of the internal pore type nickel-manganese-aluminum ternary precursor material provided by the present invention includes the following steps:

[0033] S1. Dissolve the aluminum salt crystal with an excessive amount of NaOH solution to prepare a sodium aluminate solution. When the alkalinity of the solution increases, it is more conducive to the stability of the sodium aluminate solution. On the other hand, the remaining free sodium hydroxide solution in the sodium aluminate solution acts as a precipitating agent in the system to participate in the reaction, which is beneficial to improving the stability of the nickel-manganese-aluminum precursor. The NaOH concentration is 8 - 12N, the concentration of the obtained sodium aluminate solution is AL: 6 - 40 g / L, and the free NaOH concentration in the sodium aluminate solution is 5 - 15N;

[0034] S2. Dissolve the nickel crystal and manganese crystal with pure water to prepare a mixed salt solution, and the obtained mixed salt solution is a nickel-manganese metal mixed solution, where the total concentration of nickel and manganese is 80 - 130 g / L;

[0035] S3. Add the sodium aluminate solution to the reaction kettle at a flow rate of 400 - 2000 mL / h, add the mixed salt solution to the reaction kettle at a flow rate of 3000 - 8000 mL / h, and add ammonia water with a concentration of 6N and a flow rate of 100 - 1000 mL / h as a complexing agent, and sodium hydroxide solution with a concentration of 10N and a flow rate of 400 - 2000 mL / min as a precipitant into the reaction kettle for internal mixing reaction. Control the pH value in the reaction kettle to be 10 - 13, and introduce gas 1 with a flow rate of 200 - 500 mL / min and gas 2 with a flow rate of 3000 - 4000 mL / min. Among them, gas 1 is one of compressed air and oxygen, and gas 2 is one of nitrogen and helium. Introducing compressed air (the cost of compressed air is lower than that of oxygen) of gas 1 and nitrogen of gas 2 can adjust the ratio of nitrogen to oxygen in the introduced gas, thereby controlling ion oxidation. React continuously at 40 - 75 °C for 40 - 80 h to obtain nickel manganese aluminum hydroxide: Ni 1-x-y Mn x Al y (OH) 2 , where: 0.1 < x < 0.6, 0.01 < y < 0.1.

[0036] The obtained nickel manganese aluminum ternary precursor has a structure with loose internal pores and dense external core - shell. Measure the ratio of the radius of the internal loose structure to the external dense structure from the center of the sphere. Inner: Outer = 1:1. The high - activity internal loose structure is beneficial to the diffusion of lithium ions during the sintering of the positive electrode, improving the sintering yield rate; effectively increasing the contact area between the material and the electrolyte at the battery end, enhancing the battery output performance, and also buffering the volume change of the positive electrode active material during charge and discharge, stabilizing the material structure, and improving the cycle performance.

[0037] In step S1, the aluminum crystal is one or more of aluminum nitrate, aluminum chloride, aluminum sulfate, and aluminum phosphate. Add it to water for dissolution to obtain Al 3+ , in step S2, the nickel crystal is one or more of nickel nitrate, nickel chloride, nickel sulfate, and nickel phosphate. Add it to water for dissolution to obtain Ni 2+ , in step S2, the manganese crystal is one or more of manganese nitrate, manganese chloride, manganese sulfate, and manganese phosphate. Add it to water for dissolution to obtain Mn 2+ .

[0038] Example 1:

[0039] In step S1, the sodium aluminate solution obtained by adding aluminum crystals to a sodium hydroxide solution with a concentration of 12N has a remaining free sodium hydroxide concentration of 6N in the sodium aluminate solution and 20 g / L of Al. In step S2, the total concentration of nickel and manganese in the mixed salt solution after dissolving nickel crystals and manganese crystals is 110 g / L (the nickel-manganese ratio is 1:1). The obtained sodium aluminate solution is added to the inside of the reaction kettle at a flow rate of 500 ml / h, the nickel-manganese metal mixed solution is added to the inside of the reaction kettle at a flow rate of 4000 ml / h, and ammonia water with a concentration of 6N is added to the inside of the reaction kettle as a complexing agent at a flow rate of 100 ml / h, and sodium hydroxide solution with a concentration of 10N is added to the inside of the reaction kettle as a precipitating agent at a flow rate of 1800 ml / h. They are respectively added to the inside of the reaction kettle for reaction, the pH value inside the reaction kettle is controlled at 11.55, and gas 1 and gas 2 are introduced into the reaction kettle by means of submersible injection to control the atmosphere inside the reaction kettle. Among them, gas 1 and gas 2 are introduced in the first 25 h. Gas 1 is one of compressed air and oxygen, gas 2 is one of nitrogen and helium, and the ratio of gas 1 to gas 2 is 1:3. After 25 h, only gas 2 is introduced, and the total gas volume is 5000 ml / h. The gas pressure of the reaction kettle is maintained at 0.45 Mpa, and the temperature inside the reaction kettle is maintained at 50 °C. The solution inside the reaction kettle is heated, and the reaction is carried out continuously for 48 h to obtain a nickel-manganese-aluminum precursor Ni 0.49 Mn 0.49 Al 0.02 (OH) 2 , denoted as NMA-1.

[0040] Sintered into a cathode material, lithium supplementation (the mass ratio of lithium to the precursor nickel, manganese, and aluminum is Li / Me from 1:1 to 1.1:1) is carried out and calcined. Pre-calcination is carried out at 500 - 600 °C for 3 - 6 h, and then the temperature is raised to 800 - 1000 °C and calcined for 12 - 16 h. The heating rate is 3 - 10 degrees Celsius / min to obtain a ternary cathode material with a core-shell structure.

[0041] Example 2:

[0042] In step S1, the sodium aluminate solution obtained by adding aluminum crystals to a sodium hydroxide solution with a concentration of 12N has a remaining free sodium hydroxide concentration of 6N in the sodium aluminate solution and an Al concentration of 20 g / L. In step S2, the total concentration of nickel and manganese in the mixed salt solution after dissolving nickel crystals and manganese crystals is 110 g / L (the nickel-manganese ratio is 1:1). The obtained sodium aluminate solution is added to the inside of the reaction kettle at a flow rate of 500 ml / h, the nickel-manganese metal mixed solution is added to the inside of the reaction kettle at a flow rate of 4000 ml / h, and ammonia water with a concentration of 6N is added to the inside of the reaction kettle as a complexing agent at a flow rate of 100 ml / h, and sodium hydroxide solution with a concentration of 10N is added to the inside of the reaction kettle as a precipitating agent at a flow rate of 1800 ml / h. They are respectively added to the inside of the reaction kettle for reaction. The pH value inside the reaction kettle is controlled at 11.80, and gas 1 and gas 2 are introduced into the reaction kettle in a submerged manner. Gas 1 is one of compressed air and oxygen, and gas 2 is one of nitrogen and helium. The atmosphere inside the reaction kettle is controlled. Among them, gas 1 and gas 2 are introduced in the first 29 h, and the ratio of gas 1 to gas 2 is 1:3. After 29 h, only gas 2 is introduced, and the total gas volume is 5000 ml / h. The gas pressure of the reaction kettle is maintained at 0.45 Mpa, and the temperature inside the reaction kettle is maintained at 50 °C. The solution inside the reaction kettle is heated, and the reaction is carried out continuously for 65 h to obtain a nickel-manganese-aluminum precursor, denoted as NMA-2.

[0043] Sintered into a cathode material, lithium supplementation (the mass ratio of lithium to the precursor nickel, manganese, and aluminum is Li / Me from 1:1 to 1.1:1) is carried out and calcined. It is pre-calcined at 500 - 600 °C for 3 - 6 h, and then the temperature is raised to 800 - 1000 °C and calcined for 12 - 16 h. The heating rate is 3 - 10 degrees Celsius / min to obtain a ternary cathode material with a core-shell structure.

[0044] Example 3:

[0045] In step S1, the sodium aluminate solution obtained by adding aluminum crystals to a sodium hydroxide solution with a concentration of 12N has a remaining free sodium hydroxide concentration of 6N and an Al concentration of 20 g / L in the sodium aluminate solution. In step S2, the total concentration of nickel and manganese in the mixed salt solution after dissolving nickel crystals and manganese crystals is 110 g / L (the nickel-manganese ratio is 1:1). The obtained sodium aluminate solution is added to the inside of the reaction kettle at a flow rate of 500 ml / h, the nickel-manganese metal mixed solution is added to the inside of the reaction kettle at a flow rate of 4000 ml / h, and ammonia water with a concentration of 6N is added to the inside of the reaction kettle as a complexing agent at a flow rate of 100 ml / h, and sodium hydroxide solution with a concentration of 10N is added to the inside of the reaction kettle as a precipitating agent at a flow rate of 1800 ml / h. They are respectively added to the inside of the reaction kettle for reaction. The pH value inside the reaction kettle is controlled to be 11.80, and gas 1 and gas 2 are introduced into the reaction kettle in a submerged manner. Among them, gas 1 is one of compressed air and oxygen, and gas 2 is one of nitrogen and helium. The atmosphere inside the reaction kettle is controlled. Among them, gas 1 and gas 2 are introduced in the first 26 h, and the ratio of gas 1 to gas 2 is 1:3. After 26 h, only gas 2 is introduced, and the total gas volume is 5000 ml / h. The gas pressure in the reaction kettle is maintained at 0.45 Mpa, and the temperature inside the reaction kettle is maintained at 55 °C. The solution inside the reaction kettle is heated, and the reaction is carried out continuously for 56 h to obtain a nickel-manganese-aluminum precursor, denoted as NMA-3.

[0046] Sintered into a cathode material, lithium supplementation (the mass ratio of lithium to the precursor nickel, manganese, and aluminum is Li / Me from 1:1 to 1.1:1) is carried out for calcination. It is pre-calcined at 500 - 600 °C for 3 - 6 h, and then the temperature is raised to 800 - 1000 °C for calcination for 12 - 16 h. The heating rate is 3 - 10 degrees Celsius / min to obtain a ternary cathode material with a core-shell structure.

[0047] Comparative case 1:

[0048] In step S1, the sodium aluminate solution obtained by adding aluminum crystals to a sodium hydroxide solution with a concentration of 12N has a remaining free sodium hydroxide concentration of 6N in the sodium aluminate solution and an Al concentration of 20 g / L. In step S2, the total concentration of nickel and manganese in the mixed salt solution after dissolving nickel crystals and manganese crystals is 110 g / L (the nickel-manganese ratio is 1:1). The obtained sodium aluminate solution is added to the inside of the reaction kettle at a flow rate of 500 ml / h, the nickel-manganese metal mixed solution is added to the inside of the reaction kettle at a flow rate of 4000 ml / h, and ammonia water with a concentration of 6N is added to the inside of the reaction kettle at a flow rate of 100 ml / h as a complexing agent, and sodium hydroxide solution with a concentration of 10N is added to the inside of the reaction kettle at a flow rate of 2100 ml / h as a precipitating agent, and they are respectively added to the inside of the reaction kettle for reaction. The pH value inside the reaction kettle is controlled at 11.80, and gas 2 is introduced into the reaction kettle in a way of being completely submerged. Gas 2 is one of nitrogen and helium. The atmosphere inside the reaction kettle is controlled, the total gas volume is 5000 ml / h, the gas pressure of the reaction kettle is maintained at 0.45 Mpa, the temperature inside the reaction kettle is maintained at 50 °C, the solution inside the reaction kettle is heated, and the reaction is continuously carried out for 62 h to obtain a nickel-manganese-aluminum precursor, denoted as NMA-4.

[0049] Sintered into a cathode material, lithium supplementation (the mass ratio of lithium to the precursor nickel, manganese, and aluminum is Li / Me from 1:1 to 1.1:1) is carried out and calcined. Pre-calcination is carried out at 500 - 600 °C for 3 - 6 h, and then the temperature is raised to 800 - 1000 °C and calcined for 12 - 16 h, and the heating rate is 3 - 10 degrees Celsius / min to obtain a ternary cathode material with a core-shell structure.

[0050] Comparative case 2:

[0051] In step S1, the sodium aluminate solution obtained by adding aluminum crystals to a sodium hydroxide solution with a concentration of 12N has a remaining free sodium hydroxide concentration of 6N in the sodium aluminate solution and 20 g / L of Al. In step S2, the total concentration of nickel and manganese in the mixed salt solution after dissolving nickel crystals and manganese crystals is 110 g / L (the nickel-manganese ratio is 1:1). The obtained sodium aluminate solution is added to the inside of the reaction kettle at a flow rate of 500 ml / h, the nickel-manganese metal mixed solution is added to the inside of the reaction kettle at a flow rate of 4000 ml / h, and ammonia water with a concentration of 6N is added to the inside of the reaction kettle at a flow rate of 100 ml / h as a complexing agent, and sodium hydroxide solution with a concentration of 10N is added to the inside of the reaction kettle at a flow rate of 2100 ml / h as a precipitating agent, and they are respectively added to the inside of the reaction kettle for reaction. The pH value inside the reaction kettle is controlled at 11.80, and gas 2 is introduced into the reaction kettle by the method of full-submerged gas introduction throughout the process, where gas 2 is one of nitrogen and helium. The atmosphere inside the reaction kettle is controlled, the total gas volume is 5000 ml / h, the gas pressure of the reaction kettle is maintained at 0.45 Mpa, the temperature inside the reaction kettle is maintained at 55 °C, the solution inside the reaction kettle is heated, and the reaction is continuously carried out for 56 h to obtain a nickel-manganese-aluminum precursor, denoted as NMA-5.

[0052] Sintered into a cathode material, lithium supplementation (the mass ratio of lithium to the precursor nickel, manganese, and aluminum is Li / Me from 1:1 to 1.1:1) is carried out and calcined. It is pre-calcined at 500 - 600 °C for 3 - 6 h, and then the temperature is raised to 800 - 1000 °C and calcined for 12 - 16 h, and the heating rate is 3 - 10 degrees Celsius / min to obtain a ternary cathode material with a core-shell structure.

[0053] The experiments were repeated multiple times and the obtained nickel-manganese-aluminum precursors were detected to obtain the following data:

[0054]

[0055] It can be seen from the above table that the tap density of the nickel-manganese-aluminum precursor materials prepared by first introducing compressed air and then introducing nitrogen in Example 1, Example 2, and Example 3 is less than that of the nickel-manganese-aluminum precursor materials prepared by continuously introducing nitrogen in Comparative Case 1 and Comparative Case 2, and the initial capacity and 100-cycle retention rate of the cathode materials sintered from the nickel-manganese-aluminum precursors prepared by first introducing compressed air and then introducing nitrogen in Example 1, Example 2, and Example 3 are greater than those of the cathode materials sintered from the nickel-manganese-aluminum precursors prepared by continuously introducing nitrogen in Comparative Case 1 and Comparative Case 2.

[0056] In summary, the highly active loose structure inside the nickel-manganese-aluminum ternary precursor prepared in Example 1, Example 2 and Example 3 is beneficial to the diffusion of lithium ions during the sintering of the positive electrode and improves the sintering yield; at the battery end, it effectively increases the contact area between the material and the electrolyte, improves the battery output performance, and can also buffer the volume change of the positive electrode active material during charge and discharge, stabilize the material structure, and improve the cycle performance.

[0057] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material, characterized in that, it includes the following steps: S1. Dissolve aluminum salt crystals with an excessive amount of NaOH solution to prepare a sodium aluminate solution; S2. Dissolve nickel crystals and manganese crystals with pure water to prepare a mixed salt solution; S3. Add the sodium aluminate solution and the mixed salt solution into the reaction kettle, and add a complexing agent and a precipitating agent for mixing reaction. Control the pH value in the reaction kettle to be 10 - 13, and introduce Gas 1 and Gas 2. Continuously react at 40 - 75 °C for 40 - 80 h to obtain a nickel-manganese-aluminum precursor: Ni 1-x-y Mn x Al y (OH) 2 , where: 0.1 < x < 0.6, 0.01 < y < 0.1; The nickel-manganese-aluminum ternary precursor has a structure with loose internal pores and a dense outer core-shell.

2. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: In step S1, the aluminum crystal is aluminum nitrate, in step S2, the nickel crystal is nickel nitrate, and in step S2, the manganese crystal is manganese nitrate.

3. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: The concentration of NaOH in step S1 is 8 - 12N.

4. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: In step S3, the concentration of sodium aluminate is AL: 6 - 40 g / L, the concentration of free NaOH in step S3 is 5 - 15N, and the total concentration of the mixed salt solution in step S3 is 80 - 130 g / L.

5. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: The feeding flow rate of sodium aluminate in step S3 is controlled at 400 - 2000 mL / h, and the feeding flow rate of the mixed salt solution in step S3 is controlled at 3000 - 8000 mL / h.

6. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: The complexing agent is ammonia water, the concentration of the complexing agent is 6N, and the feeding flow rate of the complexing agent in step S3 is controlled at 100 - 1000 mL / h.

7. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: The precipitating agent is a sodium hydroxide solution, the concentration of the precipitating agent is 10N, and the feeding flow rate of the precipitating agent in step S3 is controlled at 400 - 2000 mL / min.

8. The preparation method of an internal pore type nickel-manganese-aluminum ternary precursor material according to claim 1, characterized in that: Gas 1 is compressed air, gas 2 is nitrogen, both gas 1 and gas 2 are added in a submersible manner, the feeding flow rate of gas 1 in step S3 is 200 - 500 mL / min, and the feeding flow rate of gas 2 in step S3 is 3000 - 4000 mL / min.

Images