PREPARATION METHOD OF TERNARY PRECURSOR

Abstract

The present disclosure discloses a preparation method of a ternary precursor, including: S1: mixing a first metal salt solution with a soluble nickel salt, a soluble cobalt salt, and a soluble manganese salt, ammonia water, and a sodium hydroxide solution, adjusting a pH, and heating and stirring a resulting mixture to allow a reaction; and aging and filtering a resulting slurry to obtain a precursor seed crystal; S2: adding the precursor seed crystal to a dilute acid solution, and stirring and filtering a resulting mixture to obtain an acidified seed crystal; and S3: mixing a second metal salt solution with a soluble nickel salt, a soluble cobalt salt, and a soluble manganese salt, a sodium hydroxide solution, and the acidified seed crystal, adjusting a pH, and heating and stirring a resulting mixture to allow a reaction; and aging, filtering, and drying a resulting slurry to obtain the ternary precursor.

Claims

1. A preparation method of a ternary precursor, comprising the following steps: S1: mixing a first metal salt solution containing a soluble nickel salt, a soluble cobalt salt and a soluble manganese salt with ammonia water and a sodium hydroxide solution, adjusting pH, and performing a reaction under heating and stirring to obtain a slurry; aging and filtering the slurry to obtain a precursor seed crystal; S2: adding the precursor seed crystal to a dilute acid solution, and stirring and filtering a resulting mixture to obtain an acidified seed crystal, the dilute acid solution is one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid; and the dilute acid solution has a concentration of 0.1-1 mol/L; and S3: mixing a second metal salt solution containing a soluble nickel salt, a soluble cobalt salt and a soluble manganese salt with a sodium hydroxide solution and the acidified seed crystal, adjusting pH, and performing a reaction under heating and stirring; aging, filtering, and drying a resulting slurry to obtain the ternary precursor, in S3, the heating is conducted at 40-80 C., the pH is adjusted to 9.0-12.0.

2. The preparation method according to claim 1, wherein in S1, the pH is adjusted to 10-13.

3. The preparation method according to claim 1, wherein in S1, the heating is conducted at 40-80 C.

4. The preparation method according to claim 1, wherein in S1, particles in the slurry have a particle size D50 of 1.5-4 m.

5. The preparation method according to claim 1, wherein in S2, the stirring is conducted for 0.5-2 h.

6. The preparation method according to claim 1, wherein in S3, particles in the slurry have a particle size D50 of 3-12 m.

7. The preparation method according to claim 1, wherein S3 specifically comprises: adding the acidified seed crystal and water to a reactor, and starting stirring and heating; introducing an inert gas, and adding the sodium hydroxide solution to the reactor to adjust the pH; and simultaneously pumping the sodium hydroxide solution and the second metal salt solution to perform the reaction; during the reaction, adjusting the pH constantly to control the nucleation and growth of particles of the ternary precursor, filtering out a supernatant in the reactor to keep a liquid level highly stable; the particles continuously growing until reach a target particle size.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The present disclosure is further described below with reference to accompanying drawings and examples.

[0027] FIG. 1 is a scanning electron microscopy (SEM) image of the precursor product obtained in Example 1 of the present disclosure at a magnification of 50,000;

[0028] FIG. 2 is an SEM image of the precursor product obtained in Example 1 of the present disclosure at a magnification of 1,000;

[0029] FIG. 3 is an SEM image of the precursor product obtained in Comparative Example 1 of the present disclosure at a magnification of 50,000; and

[0030] FIG. 4 is an SEM image of the precursor product obtained in Comparative Example 1 of the present disclosure at a magnification of 1,000.

DETAILED DESCRIPTION

[0031] The concepts and technical effects of the present disclosure are clearly and completely described below in conjunction with examples, so as to allow the objectives, features and effects of the present disclosure to be fully understood. Apparently, the described examples are merely some rather than all of the examples of the present disclosure. All other examples obtained by those skilled in the art based on the examples of the present disclosure without creative efforts should fall within the protection scope of the present disclosure.

Example 1

[0032] In this example, a ternary precursor was prepared, and a specific preparation process was as follows:

[0033] (1) Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in pure water in a ratio of 83:12:5 to prepare a mixed metal salt solution A, and then the mixed metal salt solution A, ammonia water, and a sodium hydroxide solution were simultaneously added to a reactor for precipitation; a resulting mixture was stirred to allow a reaction at a pH of 12.0 and a temperature of 60 C.; after a particle size D50 reached 4 m, a resulting precipitate was aged, filtered out, and washed to obtain a precursor seed crystal with high sphericity; the precursor seed crystal was filtered out and added to a 1 mol/L dilute hydrochloric acid solution, and a resulting mixture was stirred for 1 h; and an acidified seed crystal was filtered out and washed.

[0034] (2) Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in pure water in a ratio of 83:12:5 to prepare a mixed metal salt solution B; an acidified seed crystal and an appropriate amount of pure water were added to a reactor, a resulting mixture was stirred and heated (keeping at 65 C.), and nitrogen was continuously introduced into the reactor to prevent oxidation; and a small amount of a sodium hydroxide solution was added to the reactor to adjust a pH in the reactor to 10.0, and then the sodium hydroxide solution and the mixed metal salt solution B were simultaneously pumped into the reactor for co-precipitation, where a reaction pH was constantly adjusted to control the nucleation and growth of precursor particles, a supernatant in the reactor was filtered out through a microporous filtration device to keep a liquid level in the reactor stable, a solid content in the material in the reactor continuously increased, and particles continuously grew to a particle size D50 of 10 m.

[0035] (3) Material collection: a material meeting requirements prepared in step (2) was collected into an aging tank, and then filtered, washed, dried, and sieved to obtain a precursor product.

[0036] FIG. 1 and FIG. 2 are SEM images of the precursor product obtained in Example 1 at magnifications of 50,000 and 1,000, respectively. FIG. 1 shows the surface morphology of a single particle. Since there is no ammonia in the late stage of the reaction, primary particles grow into small flakes without amorphous micropowder among flakes, and secondary particles have high sphericity and show no obvious boundaries on the surface, indicating a complete crystal structure. FIG. 2 shows the overall morphology of a large number of particles, almost all of which are well-grown spherical particles. FIG. 1 and FIG. 2 show that the acidified seed crystal plays an excellent growth-guiding role.

Example 2

[0037] In this example, a ternary precursor was prepared, and a specific preparation process was as follows:

[0038] (1) Nickel nitrate, cobalt nitrate, and manganese nitrate were dissolved in pure water in a ratio of 92:04:04 to prepare a mixed metal salt solution A, and then the mixed metal salt solution A, ammonia water, and a sodium hydroxide solution were simultaneously added to a reactor for precipitation; a resulting mixture was stirred to allow a reaction at a pH of 11.5 and a temperature of 60 C.; after a particle size D50 reached 4 m, a resulting precipitate was aged, filtered out, and washed to obtain a precursor seed crystal with high sphericity; the precursor seed crystal was filtered out and added to a 0.8 mol/L dilute sulfuric acid solution, and a resulting mixture was stirred for 1 h; and an acidified seed crystal was filtered out and washed.

[0039] (2) Nickel nitrate, cobalt nitrate, and manganese nitrate were dissolved in pure water in a ratio of 82:12:6 to prepare a mixed metal salt solution B; an acidified seed crystal and an appropriate amount of pure water was added to a reactor, a resulting mixture was stirred and heated (keeping at 65 C.), and nitrogen was continuously introduced into the reactor to prevent oxidation; and a small amount of a sodium hydroxide solution was added to the reactor to adjust a pH in the reactor to 10.2, and then the sodium hydroxide solution and the mixed metal salt solution B were simultaneously pumped into the reactor for co-precipitation, where a reaction pH was constantly adjusted to control the nucleation and growth of precursor particles, a supernatant in the reactor was filtered out through a microporous filtration device to keep a liquid level in the reactor stable, a solid content in the material in the reactor continuously increased, and particles continuously grew to a particle size D50 of 10 m.

[0040] (3) Material collection: a material meeting requirements prepared in step (2) was collected into an aging tank, and then filtered, washed, dried, and sieved to obtain a precursor product.

Example 3

[0041] In this example, a ternary precursor was prepared, and a specific preparation process was as follows:

[0042] (1) Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in pure water in a ratio of 8:1:1 to prepare a mixed metal salt solution A, and then the mixed metal salt solution A, ammonia water, and a sodium hydroxide solution were simultaneously added to a reactor for precipitation; a resulting mixture was stirred to allow a reaction at a pH of 11.8 and a temperature of 65 C.; after a particle size D50 reached 2 m, a resulting precipitate was aged, filtered out, and washed to obtain a precursor seed crystal with high sphericity; the precursor seed crystal was filtered out and added to a 0.5 mol/L dilute nitric acid solution, and a resulting mixture was stirred for 1 h; and an acidified seed crystal was filtered out and washed.

[0043] (2) Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in pure water in a ratio of 6:2:2 to prepare a mixed metal salt solution B; an acidified seed crystal and an appropriate amount of pure water were added to a reactor, a resulting mixture was stirred and heated (keeping at 65 C.), and nitrogen was continuously introduced into the reactor to prevent oxidation; and a small amount of a sodium hydroxide solution was added to the reactor to adjust a pH in the reactor to 10.0, and then the sodium hydroxide solution and the mixed metal salt solution B were simultaneously pumped into the reactor for co-precipitation, where a reaction pH was constantly adjusted to control the nucleation and growth of precursor particles, a supernatant in the reactor was filtered out through a microporous filtration device to keep a liquid level in the reactor stable, a solid content in the material in the reactor continuously increased, and particles continuously grew to a particle size D50 of 5 m.

[0044] (3) Material collection: a material meeting requirements prepared in step (2) was collected into an aging tank, and then filtered, washed, dried, and sieved to obtain a precursor product.

Example 4

[0045] (1) Nickel acetate, cobalt acetate, and manganese acetate were dissolved in pure water in a ratio of 65:15:20 to prepare a mixed metal salt solution A, and then the mixed metal salt solution A, ammonia water, and a sodium hydroxide solution were simultaneously added to a reactor for precipitation; a resulting mixture was stirred to allow a reaction at a pH of 12.0 and a temperature of 60 C.; after a particle size D50 reached 1.5 m, a resulting precipitate was aged, filtered out, and washed to obtain a precursor seed crystal with high sphericity; the precursor seed crystal was filtered out and added to a 0.4 mol/L dilute hydrochloric acid solution, and a resulting mixture was stirred for 1 h; and an acidified seed crystal was filtered out and washed.

[0046] (2) Nickel acetate, cobalt acetate, and manganese acetate were dissolved in pure water in a ratio of 55:12:33 to prepare a mixed metal salt solution B; an acidified seed crystal and an appropriate amount of pure water were added to a reactor, a resulting mixture was stirred and heated (keeping at 55 C.), and nitrogen was continuously introduced into the reactor to prevent oxidation; and a small amount of a sodium hydroxide solution was added to the reactor to adjust a pH in the reactor to 10.4, and then the sodium hydroxide solution and the mixed metal salt solution B were simultaneously pumped into the reactor for co-precipitation, where a reaction pH was constantly adjusted to control the nucleation and growth of precursor particles, a supernatant in the reactor was filtered out through a microporous filtration device to keep a liquid level in the reactor stable, a solid content in the material in the reactor continuously increased, and particles continuously grew to a particle size D50 of 3 m.

[0047] (3) Material collection: a material meeting requirements prepared in step (2) was collected into an aging tank, and then filtered, washed, dried, and sieved to obtain a precursor product.

Example 5

[0048] (1) Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in pure water in a ratio of 5:2:3 to prepare a mixed metal salt solution A, and then the mixed metal salt solution A, ammonia water, and a sodium hydroxide solution were simultaneously added to a reactor for precipitation; a resulting mixture was stirred to allow a reaction at a pH of 11.0 and a temperature of 70 C.; after a particle size D50 reached 1.5 m, a resulting precipitate was aged, filtered out, and washed to obtain a precursor seed crystal with high sphericity; the precursor seed crystal was filtered out and added to a 0.3 mol/L dilute sulfuric acid solution, and a resulting mixture was stirred for 1 h; and an acidified seed crystal was filtered out and washed.

[0049] (2) Nickel sulfate, cobalt sulfate, and manganese sulfate were dissolved in pure water in a ratio of 3:3:3 to prepare a mixed metal salt solution B; an acidified seed crystal and an appropriate amount of pure water were added to a reactor, a resulting mixture was stirred and heated (keeping at 65 C.), and nitrogen was continuously introduced into the reactor to prevent oxidation; and a small amount of a sodium hydroxide solution was added to the reactor to adjust a pH in the reactor to 9.8, and then the sodium hydroxide solution and the mixed metal salt solution B were simultaneously pumped into the reactor for co-precipitation, where a reaction pH was constantly adjusted to control the nucleation and growth of precursor particles, a supernatant in the reactor was filtered out through a microporous filtration device to keep a liquid level in the reactor stable, a solid content in the material in the reactor continuously increased, and particles continuously grew to a particle size D50 of 4 m.

[0050] (3) Material collection: a material meeting requirements prepared in step (2) was collected into an aging tank, and then filtered, washed, dried, and sieved to obtain a precursor product.

Comparative Example 1

[0051] In this comparative example, a ternary precursor was prepared. A preparation process was different from Example 1 in that the seed crystal obtained in step (1) was directly filtered out and washed without acidification treatment.

[0052] FIG. 3 and FIG. 4 are SEM images of the precursor product obtained in Comparative Example 1 at magnifications of 50,000 and 1,000, respectively. FIG. 1 shows the surface morphology of a single particle. Since there is no ammonia in the late stage of the reaction, primary particles grow into small flakes with a large amount of amorphous micropowder among flakes, and secondary particles have poor sphericity and show an obvious boundary on the surface, indicating different crystalline orientations and an incomplete crystal structure. FIG. 4 shows the overall morphology of a large number of particles, and it can be seen that most of the particles are deformed agglomerated secondary particles with a large number of boundaries. It shows that the unacidified seed crystal does not play a prominent growth-guiding role, and new crystal nuclei appear in the subsequent ammonia-free reaction process, some of which voluntarily agglomerate into deformed seed crystals and then continue to grow, and some of which adhere to a surface of the original seed crystal, thereby reducing the sphericity and crystallinity of particles and ultimately resulting in low sphericity of final particles.

Test Example

[0053] Table 1 shows the performance data of the precursor products obtained in the examples and comparative example.

TABLE-US-00001 TABLE 1 Initial specific discharge D10 D50 D90 BET TD capacity at 1 Sample (m) (m) (m) (m.sup.2/g) (g/cm.sup.3) C (mAh/g) Example 1 4.90 9.99 16.70 21.2 1.36 189 Example 2 5.74 9.72 15.04 16.3 1.42 202 Example 3 3.20 5.06 8.12 29.7 1.25 177 Example 4 1.79 3.03 5.08 42.3 1.04 164 Example 5 2.46 4.04 6.59 33.5 1.07 158 Comparative 5.36 9.92 15.93 24.1 1.34 183 Example 1

[0054] It can be seen from Table 1 that in Comparative Example 1, as no acidification treatment is conducted, the initial specific discharge capacity at 1 C is 6 mAh/g lower than that of Example 1.

[0055] The examples of present disclosure are described in detail with reference to the accompanying drawings, but the present disclosure is not limited to the above examples. Within the scope of knowledge possessed by those of ordinary skill in the technical field, various changes can also be made without departing from the purpose of the present disclosure. In addition, the examples in the present disclosure or features in the examples may be combined with each other in a non-conflicting situation.