A spherical structure nickel-cobalt-manganese hydroxide and a preparation method and application thereof

Abstract

The application provides a spherical nickel-cobalt-manganese hydroxide and a preparation method and application thereof, and the preparation method comprises the following steps: (1) preparing a nickel-cobalt-manganese ternary salt solution, an inorganic strong alkali solution, a complexing agent solution and an anionic surfactant solution respectively; (2) taking the inorganic strong alkali solution as a bottom liquid, and injecting the nickel-cobalt-manganese ternary salt solution, the inorganic strong alkali solution, the complexing agent solution and the anionic surfactant solution into the bottom liquid to perform reaction; (3) after a period of reaction, the injection of the anionic surfactant solution is stopped, and the nickel-cobalt-manganese ternary salt solution, the inorganic strong alkali solution and the complexing agent solution continue to be injected into the bottom liquid to perform reaction; and (4) the reaction liquid is sequentially subjected to solid-liquid separation, washing and drying to obtain the nickel-cobalt-manganese hydroxide. The preparation method avoids the agglomeration phenomenon caused by the mutual attraction of particles with different potentials as much as possible, reduces the particle size, maintains a high sphericity, and improves the uniformity of the subsequent calcination.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lithium ion batteries, and relates to a nickel-cobalt-manganese hydroxide, in particular to a nickel-cobalt-manganese hydroxide with a spherical structure and a preparation method and application thereof. BACKGROUND

[0002] At present, with the continuous development of the new energy industry, the sales of lithium ion batteries are increasing. Different types of battery positive materials are continuously applied to the market for different use scenarios, and the market side also puts forward higher requirements for battery materials. The particle size of the nickel-cobalt-manganese hydroxide precursor required by the current market is getting smaller and smaller, but due to the influence of the van der Waals force and the charge attraction between particles during the opening of the reactor, it is difficult for technicians to obtain a hydroxide with a particle size of less than 2 microns and a high sphericity.

[0003] CN 109516510A discloses a nickel-cobalt-manganese hydroxide with a special micro-nano structure and a preparation method thereof. A composite system of a surfactant + a complexing agent is used to make metal ions and hydroxyl ions undergo a coprecipitation reaction in a reaction kettle in a nitrogen protective atmosphere to obtain a nickel-cobalt-manganese hydroxide with a special micro-nano structure. However, the above-mentioned special micro-nano structure is a micron-sized secondary pie-shaped assembly composed of nano-sized primary spherical particles, that is, the particle morphology is ellipsoidal, not spherical, and the flowability of the particles is poor during the calcination of the positive electrode material in the later stage, which easily leads to uneven calcination and even agglomeration, and the positive electrode material prepared from such ellipsoidal particles is difficult to break, thereby unnecessarily increasing the preparation cost.

[0004] Therefore, it is urgent for the technical personnel in the field to provide a nickel-cobalt-manganese hydroxide with a spherical structure and a preparation method thereof, to avoid the agglomeration phenomenon caused by the mutual attraction between the particles due to the different potentials of the particles during the opening of the reactor, to reduce the particle size while maintaining a high sphericity, and to improve the uniformity of the calcination in the later stage. SUMMARY

[0005] The purpose of the present application is to provide a nickel-cobalt-manganese hydroxide with a spherical structure and a preparation method thereof, which can avoid the agglomeration phenomenon caused by the mutual attraction between the particles due to the different potentials of the particles during the opening of the reactor, reduce the particle size while maintaining a high sphericity, and improve the uniformity of the calcination in the later stage, thereby facilitating large-scale popularization and application.

[0006] To achieve the purpose of the present application, the following technical solutions are adopted:

[0007] In a first aspect, the present application provides a preparation method of a nickel-cobalt-manganese hydroxide with a spherical structure, which comprises the following steps:

[0008] (1) independently prepare a nickel-cobalt-manganese ternary salt solution, an inorganic strong alkali solution, a complexing agent solution and an anionic surfactant solution respectively;

[0009] (2) take the inorganic strong alkali solution as a base solution, inject the nickel-cobalt-manganese ternary salt solution, the inorganic strong alkali solution, the complexing agent solution and the anionic surfactant solution into the base solution respectively to perform a co-precipitation reaction, and control the Zeta potential of the reaction to be-30 to-60 mV;

[0010] (3) after a period of reaction, stop injecting the anionic surfactant solution, and keep the nickel-cobalt-manganese ternary salt solution, the inorganic strong alkali solution and the complexing agent solution continuing to be injected into the base solution to perform a reaction;

[0011] (4) sequentially perform solid-liquid separation, washing and drying on the reaction solution obtained in step (3) to obtain spherical nickel-cobalt-manganese hydroxide.

[0012] In the present application, the Zeta potential of the reaction in step (2) is controlled to be-60 to-30 mV, for example, it can be-60 mV, -55 mV, -50 mV, -45 mV, -40 mV, -35 mV or-30 mV, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0013] The preparation method provided by the present application neutralizes part of the cations adsorbed on the surface of the particles by adding an anionic surfactant, as much as possible to avoid the agglomeration phenomenon caused by the mutual attraction between the particles due to the different potentials, at the same time, the Zeta potential of the co-precipitation reaction is controlled within a reasonable range, to ensure that the particles are negatively charged and repel each other, further avoiding the agglomeration caused by opening the kettle, thereby reducing the particle size while maintaining a high sphericity, improving the uniformity of the calcination of the positive electrode material in the later stage, and facilitating large-scale popularization and application.

[0014] In addition, the Zeta potential of the co-precipitation reaction should not be too low, otherwise the stability of the product is not enough, the repulsive force between the particles is low, and the early agglomeration is easy to cause; on the contrary, it should not be too high, otherwise the surface charge repulsive force of the particles is large, which is not conducive to the agglomeration and growth between the particles.

[0015] Preferably, the molar ratio of Ni, Co and Mn in the nickel-cobalt-manganese ternary salt solution in step (1) is x:y:z, and x+y+z=1, z≥0.6, for example, it can be z=0.6, 0.65, 0.7, 075, 0.8, 0.85, 0.9 or 0.95, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0016] Preferably, the anions in the nickel-cobalt-manganese ternary salt solution in step (1) comprise sulfate ions, and the concentration of the sulfate ions is 0.5-1.5 mol / L, for example, it can be 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, or 1.5 mol / L, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0017] Preferably, the solute in the inorganic strong alkali solution in step (1) comprises sodium hydroxide and / or potassium hydroxide.

[0018] Preferably, the concentration of the inorganic strong alkali solution in step (1) is 6-9 mol / L, for example, it can be 6 mol / L, 6.5 mol / L, 7 mol / L, 7.5 mol / L, 8 mol / L, 8.5 mol / L, or 9 mol / L, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0019] Preferably, the solute in the complexing agent solution in step (1) comprises any one or a combination of at least two of ammonia, sulfosalicylic acid, oxalic acid, salicylic acid, or acetylacetone, and typical but non-limiting combinations include a combination of ammonia and sulfosalicylic acid, a combination of sulfosalicylic acid and oxalic acid, a combination of oxalic acid and salicylic acid, a combination of salicylic acid and acetylacetone, a combination of ammonia, sulfosalicylic acid, and oxalic acid, a combination of sulfosalicylic acid, oxalic acid, and salicylic acid, or a combination of oxalic acid, salicylic acid, and acetylacetone, and further preferably, ammonia.

[0020] Preferably, the concentration of the complexing agent solution in step (1) is 0.1-0.5 mol / L, for example, it can be 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.35 mol / L, 0.4 mol / L, 0.45 mol / L, or 0.5 mol / L, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0021] Preferably, the solute in the anionic surfactant solution in step (1) comprises any one or a combination of at least two of sodium alkyl sulfonate, sodium alkyl aryl sulfonate, sodium alkyl sulfate, or secondary sodium alkyl sulfate, and typical but non-limiting combinations include a combination of sodium alkyl sulfonate and sodium alkyl aryl sulfonate, a combination of sodium alkyl aryl sulfonate and sodium alkyl sulfate, a combination of sodium alkyl sulfate and secondary sodium alkyl sulfate, a combination of sodium alkyl sulfonate, sodium alkyl aryl sulfonate, and sodium alkyl sulfate, or a combination of sodium alkyl aryl sulfonate, sodium alkyl sulfate, and secondary sodium alkyl sulfate.

[0022] Preferably, the concentration of the anionic surfactant solution in step (1) is 0.1-0.5 mol / L, for example, it can be 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.35 mol / L, 0.4 mol / L, 0.45 mol / L or 0.5 mol / L, but not limited to the listed values, other values not listed in the range are also applicable.

[0023] Preferably, the temperature of the co-precipitation reaction in step (2) is 40-70℃, for example, it can be 40℃, 45℃, 50℃, 55℃, 60℃, 65℃ or 70℃, but not limited to the listed values, other values not listed in the range are also applicable.

[0024] In the present application, the temperature of the co-precipitation reaction needs to be controlled within a reasonable range. When the temperature is lower than 40℃, the co-precipitation reaction is not sufficient, resulting in a decrease in product yield; when the temperature is higher than 70℃, the performance of the product does not improve significantly, resulting in unnecessary increase in energy consumption and cost.

[0025] Preferably, the pH value of the solution in the co-precipitation reaction in step (2) is 9-13, for example, it can be 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5 or 13, but not limited to the listed values, other values not listed in the range are also applicable.

[0026] Preferably, the ammonia concentration in the co-precipitation reaction in step (2) is 3-5 g / L, for example, it can be 3 g / L, 3.2 g / L, 3.4 g / L, 3.6 g / L, 3.8 g / L, 4 g / L, 4.2 g / L, 4.4 g / L, 4.6 g / L, 4.8 g / L or 5 g / L, but not limited to the listed values, other values not listed in the range are also applicable.

[0027] Preferably, the co-precipitation reaction in step (2) is accompanied by stirring, and the stirring rate is 200-560 rpm, for example, it can be 200 rpm, 220 rpm, 240 rpm, 260 rpm, 280 rpm, 300 rpm, 320 rpm, 340 rpm, 360 rpm, 380 rpm, 400 rpm, 420 rpm, 440 rpm, 460 rpm, 480 rpm, 500 rpm, 520 rpm, 540 rpm or 560 rpm, but not limited to the listed values, other values not listed in the range are also applicable.

[0028] Preferably, the time period in step (3) is 1-20h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or 20h, but not limited to the listed values, other values not listed in the range are also applicable.

[0029] Preferably, the solid-liquid separation in step (4) includes any one of centrifugation, filtration or decantation, further preferably centrifugation.

[0030] Preferably, the washing liquid used in the washing in step (4) includes an alkali solution.

[0031] Preferably, the temperature for drying in step (4) is 100-210℃, for example, it can be 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃ or 210℃, but not limited to the listed values, other values not listed in the range are also applicable.

[0032] As a preferred technical solution of the first aspect of the present application, the preparation method comprises the following steps:

[0033] (1) independently prepare a nickel-cobalt-manganese ternary salt solution, an inorganic strong alkali solution, a complexing agent solution and an anionic surfactant solution respectively; the molar ratio of Ni, Co and Mn in the nickel-cobalt-manganese ternary salt solution is x:y:z, and x+y+z=1, z≥0.6; the anion in the nickel-cobalt-manganese ternary salt solution includes sulfate, and the concentration of the sulfate is 0.5-1.5mol / L; the solute in the inorganic strong alkali solution includes sodium hydroxide and / or potassium hydroxide, and the concentration is 6-9mol / L; the solute in the complexing agent solution includes any one or a combination of at least two of ammonia, sulfosalicylic acid, oxalic acid, salicylic acid or acetylacetone, and the concentration is 0.1-0.5mol / L; the solute in the anionic surfactant solution includes any one or a combination of at least two of sodium alkyl sulfonate, sodium alkyl aryl sulfonate, sodium alkyl sulfate or secondary sodium alkyl sulfate, and the concentration is 0.1-0.5mol / L;

[0034] (2) take the inorganic strong alkali solution as the base liquid, and inject the nickel-cobalt-manganese ternary salt solution, the inorganic strong alkali solution, the complexing agent solution and the anionic surfactant solution into the base liquid respectively, carry out a co-precipitation reaction at 40-70℃, and control the pH value of the solution in the reaction to be 9-13, the ammonia concentration to be 3-5g / L, and the Zeta potential to be -30 to -60mV, with stirring during the reaction, and the stirring rate being 200-560rpm;

[0035] (3) after 1-20h of reaction, stop injecting the anionic surfactant solution, and keep injecting the nickel-cobalt-manganese ternary salt solution, the inorganic strong alkali solution and the complexing agent solution into the bottom solution to continue the reaction;

[0036] (4) centrifuge the reaction solution obtained in step (3), wash the obtained solid phase with an alkali solution, and dry at 100-210℃ to obtain the spherical nickel-cobalt-manganese hydroxide.

[0037] In the second aspect, the application provides a spherical nickel-cobalt-manganese hydroxide, which is prepared by the method of the first aspect, and the spherical particles in the nickel-cobalt-manganese hydroxide satisfy D50≤2μm, for example, can be 0.2μm, 0.4μm, 0.6μm, 0.8μm, 1μm, 1.2μm, 1.4μm, 1.6μm, 1.8μm or 2μm, but not limited to the listed values, and other values not listed in the range are also applicable.

[0038] In the third aspect, the application provides an application of the nickel-cobalt-manganese hydroxide of the second aspect, which is used as a precursor of a lithium ion battery cathode material.

[0039] Compared with the prior art, the application has the following beneficial effects:

[0040] The preparation method provided by the application neutralizes part of the cations adsorbed on the surface of the particles by adding an anionic surfactant, avoids the agglomeration of particles caused by the mutual attraction of particles with different potentials as much as possible, controls the Zeta potential of the coprecipitation reaction within a reasonable range, ensures that the particles are negatively charged and repel each other, further avoids the agglomeration caused by opening the kettle, reduces the particle size while maintaining a high sphericity, improves the uniformity of the calcination of the cathode material in the later stage, and is conducive to large-scale popularization and application. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 is a scanning electron microscope photo of the nickel-cobalt-manganese hydroxide provided in Example 1;

[0042] Figure 2 is a scanning electron microscope photo of the nickel-cobalt-manganese hydroxide provided in Comparative Example 1;

[0043] Figure 3 is a scanning electron microscope photo of the nickel-cobalt-manganese hydroxide provided in Comparative Example 3. DETAILED DESCRIPTION

[0044] The technical solutions of the application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the application and should not be regarded as specific limitations on the application.

[0045] Example 1

[0046] This embodiment provides a spherical nickel-cobalt-manganese hydroxide and its preparation method, the preparation method comprising the following steps:

[0047] (1) Prepare nickel-cobalt-manganese ternary salt solution (Ni, Co, Mn molar ratio of 0.2:0.2:0.6), sodium hydroxide solution (8 mol / L), ammonia solution (0.3 mol / L), and sodium alkyl sulfonate solution (0.3 mol / L) independently; the anion in the nickel-cobalt-manganese ternary salt solution is sulfate, and the concentration of sulfate is 1 mol / L;

[0048] (2) Using sodium hydroxide solution as the base solution, nickel cobalt manganese ternary salt solution, sodium hydroxide solution, ammonia solution and sodium alkyl sulfonate solution were injected into the base solution respectively. Co-precipitation reaction was carried out at 55℃. The pH value of the reaction solution was controlled to be 11, the ammonia concentration was 4g / L, the Zeta potential was -45mV, and the reaction was accompanied by stirring at a stirring rate of 400rpm.

[0049] (3) After reacting for 10 hours, stop injecting sodium alkyl sulfonate solution, and continue to inject nickel cobalt manganese ternary salt solution, sodium hydroxide solution and ammonia solution into the bottom solution to carry out the reaction;

[0050] (4) Centrifuge the reaction solution obtained in step (3), wash the obtained solid phase with sodium hydroxide solution, and dry it at 150°C to obtain a spherical nickel cobalt manganese hydroxide.

[0051] Figure 1 This is a scanning electron microscope image of the nickel-cobalt-manganese hydroxide obtained in this embodiment.

[0052] Depend on Figure 1 It can be seen that the micro-particles of nickel cobalt manganese hydroxide obtained in this embodiment are spherical with high sphericity and no obvious particle agglomeration phenomenon is observed. At the same time, the particles satisfy D50≤2μm.

[0053] Example 2

[0054] This embodiment provides a spherical nickel-cobalt-manganese hydroxide and its preparation method, the preparation method comprising the following steps:

[0055] (1) Prepare nickel-cobalt-manganese ternary salt solution (Ni, Co, Mn molar ratio of 0.1:0.1:0.8), potassium hydroxide solution (6 mol / L), ammonia solution (0.1 mol / L), and alkyl sulfate solution (0.1 mol / L) independently; the anion in the nickel-cobalt-manganese ternary salt solution is sulfate, and the concentration of sulfate is 0.5 mol / L;

[0056] (2) using the potassium hydroxide solution as a base solution, respectively injecting the nickel-cobalt-manganese ternary salt solution, the potassium hydroxide solution, the ammonia solution and the alkyl sulfate sodium solution into the base solution, and performing a co-precipitation reaction at 40°C, and controlling the solution pH value of the reaction to be 9, the ammonia concentration to be 3 g / L and the Zeta potential to be -30 mV, with stirring during the reaction and the stirring rate being 200 rpm;

[0057] (3) after 1 h of reaction, stopping the injection of the alkyl sulfate sodium solution, and keeping the nickel-cobalt-manganese ternary salt solution, the potassium hydroxide solution and the ammonia solution to continue to be injected into the base solution for reaction;

[0058] (4) centrifuging the reaction solution obtained in step (3), washing the obtained solid phase with a sodium hydroxide solution, and drying at 100°C to obtain the spherical nickel-cobalt-manganese hydroxide.

[0059] The micro-morphology of the nickel-cobalt-manganese hydroxide obtained in this example is similar to that of Example 1, and thus is not described herein.

[0060] Example 3

[0061] This example provides a spherical nickel-cobalt-manganese hydroxide and a preparation method thereof, and the preparation method comprises the following steps:

[0062] (1) respectively and independently preparing a nickel-cobalt-manganese ternary salt solution (the molar ratio of Ni, Co and Mn is 0.1:0.2:0.7), a sodium hydroxide solution (9 mol / L), an ammonia solution (0.5 mol / L) and an alkyl aryl sulfonate sodium solution (0.5 mol / L); the anion in the nickel-cobalt-manganese ternary salt solution is sulfate, and the concentration of the sulfate is 1.5 mol / L;

[0063] (2) using the sodium hydroxide solution as a base solution, respectively injecting the nickel-cobalt-manganese ternary salt solution, the sodium hydroxide solution, the ammonia solution and the alkyl aryl sulfonate sodium solution into the base solution, and performing a co-precipitation reaction at 70°C, and controlling the solution pH value of the reaction to be 13, the ammonia concentration to be 5 g / L and the Zeta potential to be -60 mV, with stirring during the reaction and the stirring rate being 560 rpm;

[0064] (3) after 20 h of reaction, stopping the injection of the alkyl aryl sulfonate sodium solution, and keeping the nickel-cobalt-manganese ternary salt solution, the sodium hydroxide solution and the ammonia solution to continue to be injected into the base solution for reaction;

[0065] (4) centrifuging the reaction solution obtained in step (3), washing the obtained solid phase with a sodium hydroxide solution, and drying at 210°C to obtain the spherical nickel-cobalt-manganese hydroxide.

[0066] The micro-morphology of the nickel-cobalt-manganese hydroxide obtained in this example is similar to that of Example 1, and thus is not described herein.

[0067] Example 4

[0068] This example provides a spherical structure of nickel-cobalt-manganese hydroxide and a preparation method thereof. In the preparation method, the temperature of the coprecipitation reaction in step (2) is reduced to 35°C, and the other steps and conditions are the same as those in Example 1, and thus are not described here.

[0069] Compared with Example 1, the coprecipitation reaction is not sufficient in this example due to the excessively low temperature of the coprecipitation reaction, and the product yield is not as good as that in Example 1.

[0070] Example 5

[0071] This example provides a spherical structure of nickel-cobalt-manganese hydroxide and a preparation method thereof. In the preparation method, the temperature of the coprecipitation reaction in step (2) is increased to 85°C, and the other steps and conditions are the same as those in Example 1, and thus are not described here.

[0072] Compared with Example 1, the performance of the product is not significantly improved in this example due to the excessively high temperature of the coprecipitation reaction, thereby causing unnecessary increase in energy consumption and cost.

[0073] Comparative Example 1

[0074] This comparative example provides a nickel-cobalt-manganese hydroxide and a preparation method thereof. In the preparation method, the Zeta potential in step (2) is changed to -20 mV, and the other steps and conditions are the same as those in Example 1, and thus are not described here.

[0075] Figure 2 The scanning electron microscope photograph of the nickel-cobalt-manganese hydroxide obtained in this comparative example.

[0076] From the above, Figure 2 It can be seen that the micro-particles of the nickel-cobalt-manganese hydroxide obtained in this comparative example are seriously agglomerated in the early stage, mainly because the Zeta potential is too low, the stability of the product is not enough, and the repulsive force between the particles is low, thereby easily causing early agglomeration.

[0077] Comparative Example 2

[0078] This comparative example provides a nickel-cobalt-manganese hydroxide and a preparation method thereof. In the preparation method, the Zeta potential in step (2) is changed to -70 mV, and the other steps and conditions are the same as those in Example 1, and thus are not described here.

[0079] Figure 3 The scanning electron microscope photograph of the nickel-cobalt-manganese hydroxide obtained in this comparative example.

[0080] From the above, Figure 3It can be known that the micro-particle of the nickel-cobalt-manganese hydroxide obtained in the present comparative example is too dispersed and the morphology is too poor in the early stage, mainly because the Zeta potential is too high, the repulsive force of the particle surface charge is larger, and it is not conducive to the agglomeration and growth between the particles.

[0081] It can be seen that the preparation method provided by the present application neutralizes part of the cations adsorbed on the surface of the particles by adding an anionic surfactant, as much as possible to avoid the agglomeration phenomenon caused by the mutual attraction between the particles due to the different potentials, at the same time, the Zeta potential of the coprecipitation reaction is controlled within a reasonable range, to ensure that the particles are negatively charged and repel each other, further avoiding the agglomeration caused by opening the kettle, thereby reducing the particle size while maintaining a high sphericity, improving the uniformity of the calcination of the positive electrode material in the later stage, and being conducive to large-scale popularization and application.

[0082] The applicant declares that the above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by any person skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a spherical nickel-cobalt-manganese hydroxide, characterized in that, The preparation method includes the following steps: (1) Prepare nickel-cobalt-manganese ternary salt solution, inorganic strong base solution, complexing agent solution and anionic surfactant solution independently; the molar ratio of Ni, Co and Mn in the nickel-cobalt-manganese ternary salt solution is x:y:z, and x+y+z=1, z≥0.6; the anion in the nickel-cobalt-manganese ternary salt solution includes sulfate, and the concentration of sulfate is 0.5-1.5mol / L; the solute in the complexing agent solution is ammonia; the solute in the anionic surfactant solution includes any one or a combination of at least two of sodium alkyl sulfonate, sodium alkyl aryl sulfonate, sodium alkyl sulfate or sodium secondary alkyl sulfate. (2) Using an inorganic strong base solution as the base solution, nickel-cobalt-manganese ternary salt solution, inorganic strong base solution, complexing agent solution and anionic surfactant solution are injected into the base solution respectively, and co-precipitation reaction is carried out at 40-70℃. The pH value of the reaction solution is controlled to be 9-13, the ammonia concentration is 3-5g / L, and the Zeta potential is -60 to -30mV. (3) After the reaction has been going on for a period of time, stop injecting the anionic surfactant solution, and continue to inject the nickel-cobalt-manganese ternary salt solution, inorganic strong base solution and complexing agent solution into the bottom solution to carry out the reaction. (4) The reaction solution obtained in step (3) is subjected to solid-liquid separation, washing and drying in sequence to obtain nickel cobalt manganese hydroxide with spherical structure, and the spherical particles in the nickel cobalt manganese hydroxide satisfy D50≤2μm.

2. The preparation method according to claim 1, characterized in that, The solute in the inorganic strong base solution in step (1) includes sodium hydroxide and / or potassium hydroxide.

3. The preparation method according to claim 1, characterized in that, The concentration of the inorganic strong alkali solution in step (1) is 6-9 mol / L.

4. The preparation method according to claim 1, characterized in that, The concentration of the complexing agent solution in step (1) is 0.1-0.5 mol / L.

5. The preparation method according to claim 1, characterized in that, The concentration of the anionic surfactant solution in step (1) is 0.1-0.5 mol / L.

6. The preparation method according to claim 1, characterized in that, The coprecipitation reaction in step (2) is accompanied by stirring at a speed of 200-560 rpm.

7. The preparation method according to claim 1, characterized in that, The time period mentioned in step (3) is 1-20 hours.

8. The preparation method according to claim 1, characterized in that, The solid-liquid separation in step (4) includes any one of centrifugation, filtration or decantation.

9. The preparation method according to claim 1, characterized in that, The washing liquid used in step (4) includes an alkaline solution.

10. The preparation method according to claim 1, characterized in that, The drying temperature in step (4) is 100-210℃.

11. The preparation method according to any one of claims 1-10, characterized in that, The preparation method includes the following steps: (1) Prepare nickel-cobalt-manganese ternary salt solution, inorganic strong base solution, complexing agent solution and anionic surfactant solution independently; the molar ratio of Ni, Co and Mn in the nickel-cobalt-manganese ternary salt solution is x:y:z, and x+y+z=1, z≥0.6; the anion in the nickel-cobalt-manganese ternary salt solution includes sulfate, and the concentration of sulfate is 0.5-1.5mol / L; the solute in the inorganic strong base solution includes sodium hydroxide and / or potassium hydroxide, and the concentration is 6-9mol / L; the solute in the complexing agent solution is ammonia, and the concentration is 0.1-0.5mol / L; the solute in the anionic surfactant solution includes any one or a combination of at least two of sodium alkyl sulfonate, sodium alkyl aryl sulfonate, sodium alkyl sulfate or sodium secondary alkyl sulfate, and the concentration is 0.1-0.5mol / L; (2) Using an inorganic strong base solution as the base solution, nickel-cobalt-manganese ternary salt solution, inorganic strong base solution, complexing agent solution and anionic surfactant solution are injected into the base solution respectively. Co-precipitation reaction is carried out at 40-70℃. The pH value of the reaction solution is controlled to be 9-13, the ammonia concentration is 3-5g / L, the Zeta potential is -30 to -60mV, and the reaction is accompanied by stirring at a speed of 200-560rpm. (3) After the reaction has been going on for 1-20 hours, stop injecting the anionic surfactant solution and continue to inject the nickel-cobalt-manganese ternary salt solution, inorganic strong base solution and complexing agent solution into the bottom solution to carry out the reaction. (4) Centrifuge the reaction solution obtained in step (3), wash the obtained solid phase with alkaline solution, and dry it at 100-210℃ to obtain a spherical nickel cobalt manganese hydroxide.

12. A spherical nickel-cobalt-manganese hydroxide, characterized in that, The nickel-cobalt-manganese hydroxide is prepared by the preparation method according to any one of claims 1-11, and the spherical particles in the nickel-cobalt-manganese hydroxide satisfy D50≤2μm.

13. An application of the nickel-cobalt-manganese hydroxide as described in claim 12, characterized in that, The nickel-cobalt-manganese hydroxide is used as a precursor for the cathode material of lithium-ion batteries.

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