CN111717938A - Narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof - Google Patents
Narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof Download PDFInfo
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Abstract
A narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide is used as a precursor of an active substance of a positive electrode material of a nickel-cobalt-aluminum lithium battery, the inner core of secondary spherical particles of the precursor is aluminum hydroxide, and the crystal grain cation layer framework of the outer shell layer contains nickel-cobalt-aluminum elements, wherein the mole percentage of nickel is 85-98%; the secondary spherical particles of the precursor have the characteristic of narrow distribution, K90= (D90-D10)/D50 is not more than 0.90, D50 is 2.0-6.0 μm, and the secondary spherical particles can be used as the anode material of the lithium battery, so that the energy density and the cycle performance of the battery can be further improved; a preparation method of a narrowly-distributed small-particle-size nickel-cobalt-aluminum hydroxide overcomes the defects that a precursor synthesized by a solid phase method cannot reach the uniformity of an atomic layer level, overcomes the defect that aluminum hydroxide flocculent precipitate generated in the synthesis process of a conventional liquid phase method, and obtains the precursor with a core-shell structure, good sphericity, compact particles, a stable structure and high consistency.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode material precursors, and particularly relates to a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide and a preparation method thereof.
Background
The nickel-cobalt-aluminum ternary positive electrode material (NCA, namely, nickel-cobalt-lithium aluminate) has high energy density and good rate performance, and is widely applied to the fields of electric tools, electric automobiles and the like.
At present, the preparation methods of nickel-cobalt-aluminum materials mainly comprise solid-phase synthesis and liquid-phase synthesis. Solid phase synthesis generally adopts coprecipitation to prepare a nickel-cobalt precursor, and then the nickel-cobalt precursor is mixed with an aluminum compound and a lithium source compound and then sintered, but the solid mixing mode cannot achieve atomic-level uniformity, and the performance is difficult to give full play.
Chinese patent CN108767256A discloses a method for preparing a nickel-cobalt lithium aluminate precursor as a battery anode material, wherein the nickel-cobalt lithium aluminate precursor is prepared by adopting a method of roasting with aluminum nitrate, so that the condition that large-particle precipitates are difficult to form due to high precipitation speed of trivalent aluminum ions is avoided, and the nickel-cobalt lithium aluminate precursor obtained by roasting has higher real density; meanwhile, acid radical residue in the precipitate is reduced through roasting, and the purity of the prepared nickel-cobalt lithium aluminate precursor is further increased. The preparation method is the solid phase method, the mixing mode cannot achieve atom-level uniformity, and the effect is not ideal.
The liquid phase synthesis method is to prepare nickel-cobalt-aluminum precursor by chemical coprecipitation method, and then calcine the precursor and lithium salt to obtain NCA material, because the solubility product constant of aluminum hydroxide is 1.3 × 10-33And nickel hydroxide and cobalt hydroxide (divalent) are each 2 × 10-15And 1.6 × 10-15The solubility product constant of the aluminum hydroxide is far less than that of the nickel hydroxide and the cobalt hydroxide, and the aluminum ions are difficult to perform complex reaction with ammonia water, so when a nickel-cobalt-aluminum precursor is prepared by adopting a conventional chemical coprecipitation method, the precipitation speed of trivalent aluminum ions is extremely high, a flocculent product is easily formed, the trivalent aluminum ions are difficult to form a uniform single layered structure with nickel and cobalt precipitates, and a spherical large-particle precipitate is difficult to form, so that the performance index of an NCA material prepared by calcining the precursor doped with lithium salt is not ideal, the particles are loose, the structural stability is poor, and the discharge capacity is low.
Meanwhile, with the continuous improvement of the requirement of the new energy field on the energy density of the anode material, the mole percentage of Ni in the nickel-cobalt-aluminum anode material is gradually improved from 80% to 88% or more, and with the improvement of the Ni content, the cycle performance of the anode material becomes a short plate restricting the application of the anode material, so that higher requirements are provided for the consistency of the NCA precursor.
Disclosure of Invention
One of the purposes of the invention is to provide a precursor of a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as an active material of a nickel-cobalt-aluminum lithium battery positive electrode material, wherein the inner core of secondary spherical particles of the precursor is aluminum hydroxide, and the crystal grain positive ion layer skeleton of the outer shell layer contains nickel-cobalt-aluminum elements, wherein the mole percentage of nickel is 85-98%; the secondary spherical particles of the precursor have the characteristic of narrow distribution, K90= (D90-D10)/D50 is not more than 0.90, and D50 is 2.0-6.0 μm, and the secondary spherical particles can be used as the anode material of the lithium battery, so that the energy density and the cycle performance of the battery can be further improved.
The second purpose of the invention is to provide a preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, which overcomes the defect that the precursor synthesized by a solid phase method cannot achieve atom level uniformity on one hand, and overcomes the defect that aluminum hydroxide flocculent precipitate generated in the conventional liquid phase method synthesis process on the other hand, so as to obtain the precursor with a core-shell structure, good sphericity, compact particles, stable structure and high consistency.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide which is spherical or spheroidal particles, wherein the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide particles are composed of an inner core and an outer shell layer, the inner core of the particles is aluminum hydroxide, and the outer shell layer is made of Ni with a general formulaxCoyAlz(OH)2x+2y+3zWherein x is more than or equal to 0.85 and less than or equal to 0.98, y is more than 0 and less than or equal to 0.15, z is more than 0 and less than or equal to 0.15, and the crystal grain cation layer framework of the outer shell layer contains nickel, cobalt and aluminum elements; the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide particles have the characteristic of narrow distribution, wherein K90= (D90-D10)/D50 is less than or equal to 0.90, and D50 is 2.0-6.0 μm.
The invention provides a preparation method of a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide, which comprises the following steps:
step 1, according to the mole ratio of nickel, cobalt and aluminum, namely x: y: z, preparing a nickel-cobalt-aluminum mixed salt solution by using nickel, cobalt and aluminum soluble salts as raw materials and pure water;
step 2, preparing a sodium hydroxide solution;
step 3, preparing an aluminum alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution;
step 4, preparing ammonia water as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2, the aluminum-alkali mixed solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a bottom solution for starting up the reaction;
step 7, adding a certain amount of additive into the base solution, and adjusting the pH of the base solution to form aluminum hydroxide seed crystals;
step 8, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature, the pH value and the ammonia concentration in the kettle; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 2.0-6.0 mu m;
and 9, washing and drying the slurry obtained in the step 8, and then sequentially sieving and demagnetizing to obtain the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, in the step 1 and the step 3, the soluble salt of nickel, cobalt and aluminum is one or more of chloride, nitrate and sulfate.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, in the step 1, the total molar concentration of nickel-cobalt-aluminum metal ions in a mixed salt solution is 1.0-2.5 mol/L.
In the preparation method of the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide, in the step 2, the molar concentration of the prepared sodium hydroxide solution is 4.0-11.0 mol/L.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, in the step 3, the molar concentration of Al in the prepared aluminum-alkali mixed solution is 0.1-0.8 mol/L.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, the concentration of the prepared ammonia water in the step 4 is 6.0-12.0 mol/L.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, in the step 6, the pH value in the base solution is 12.0-14.0, and the ammonia concentration is 2.0-5.0 g/L.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, in the step 7, the type of the additive is one or more of organic acid, inorganic acid, strong acid weak base salt and weak acid weak base salt, and the pH value in the base solution is adjusted to be 10.8-11.5.
In the preparation method of the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide, in the step 8, the reaction temperature in a kettle is controlled to be 45-65 ℃, the pH value is 10.8-11.5, and the ammonia concentration is 2.0-5.0 g/L.
The invention has the beneficial effects that:
a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide has a proper particle size, a proper specific surface area and a good layered structure with less impurities, can be used as a precursor of an active substance of a positive electrode material of a nickel-cobalt-lithium aluminate battery, the inner core of secondary spherical particles of the precursor is aluminum hydroxide, the crystal grain cation layer skeleton of an outer shell layer contains nickel-cobalt-aluminum elements, wherein the mole percentage of nickel is 85-98%, the secondary spherical particles of the precursor have the characteristic of narrow distribution, the K90= (D90-D10)/D50 is less than or equal to 0.90, the D50 is 2.0-6.0 mu m, the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide utilizes the characteristic of easy diffusion of aluminum hydroxide, when the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide is sintered with a lithium source to prepare the positive electrode material, the aluminum hydroxide inner core can further diffuse to the outer layer, so as to further improve the coating effect of the outer layer, and the narrow-, the energy density and the cycle performance of the battery can be further improved; a preparation method of a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide overcomes the defects that a precursor synthesized by a solid phase method cannot achieve atom level uniformity, and overcomes aluminum hydroxide flocculent precipitate generated in the synthesis process of a conventional liquid phase method to obtain a precursor with a core-shell structure, good sphericity, compact particles, a stable structure and high consistency. The narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide product can be widely applied to the sintering production of the lithium battery anode material, and is particularly suitable for the sintering production of the nickel-cobalt-aluminum lithium battery anode material; the method of the invention has simple operation, is suitable for industrial production, can be widely applied to the production process of nickel-manganese-aluminum hydroxide, and is particularly suitable for the production process of narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide.
Drawings
Figure 1 is a 1000-fold FESEM image of a narrow distribution nickel cobalt aluminum hydroxide seed prepared in example 1;
FIG. 2 is a 1000-fold FESEM image of a narrowly distributed nickel cobalt aluminum hydroxide endpoint sample prepared in example 1;
FIG. 3 is a 1000-fold FESEM image of a nickel cobalt aluminum hydroxide seed crystal prepared in comparative example 1;
figure 4 is a 1000-fold FESEM image of a nickel cobalt aluminum hydroxide endpoint sample prepared in comparative example 1.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
The narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide is spherical or spheroidal particles, and consists of an inner core and an outer shell, wherein the inner core of the particles is aluminum hydroxide, and the outer shell is made of Ni with a general formula0.9Co0.07Al0.03(OH)2.03The crystal grain cation layer skeleton of the outer shell layer contains nickel, cobalt and aluminum elements. The nickel-cobalt-aluminum hydroxide particles have the characteristic of narrow distribution, K90= (D90-D10)/D50 is not more than 0.90, D50 is 3.6 mu m, and the preparation method is as follows:
step 1, according to the mole ratio of the required nickel, cobalt and aluminum elements, namely 0.9: 0.07: 0.03, preparing a mixed salt solution with the total molar concentration of nickel, cobalt and aluminum metal ions of 2.0mol/L by using nickel sulfate, cobalt sulfate and aluminum sulfate as raw materials and pure water;
step 2, preparing a sodium hydroxide solution with the molar concentration of 10.0 mol/L;
step 3, selecting an aluminum sulfate and sodium hydroxide solution to prepare an aluminum-alkali mixed solution, wherein the molar concentration of Al in the aluminum-alkali mixed solution is 0.3 mol/L;
step 4, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows a bottom layer stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2, the aluminum-alkali mixed solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a bottom solution for starting up the reaction, wherein the pH value of the bottom solution is 12.0, and the ammonia concentration is 4.0 g/L;
step 7, adding sulfuric acid into the base solution, and adjusting the pH value of the base solution to 11.0 to form aluminum hydroxide seed crystals;
step 8, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature in the kettle to be 50 ℃, the pH value to be 11.2 and the ammonia concentration to be 4.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 3.6 mu m, stopping feeding;
and 9, washing and drying the slurry obtained in the step 8, and then sequentially sieving and demagnetizing to obtain the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide.
The FESEM of the prepared seed crystal is shown in figure 1 and has good uniformity and dispersibility, the FESEM of the end point sample is shown in figure 2, the particle size of the end point sample is basically consistent, and the sphericity is good.
Example 2
The narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide is spherical or spheroidal particles, and consists of an inner core and an outer shell, wherein the inner core of the particles is aluminum hydroxide, and the outer shell is made of Ni with a general formula0.88Co0.09Al0.03(OH)2.03The crystal grain cation layer skeleton of the outer shell layer contains nickel, cobalt and aluminum elements. The nickel-cobalt-aluminum hydroxide particles have the characteristic of narrow distribution, K90= (D90-D10)/D50 is not more than 0.90, D50 is 5.7 mu m, and the preparation method is as follows:
step 1, according to the mole ratio of the required nickel, cobalt and aluminum elements, namely 0.88: 0.09: 0.03, preparing a mixed salt solution with the total molar concentration of nickel, cobalt and aluminum metal ions of 2.1mol/L by using nickel chloride, cobalt chloride and aluminum chloride as raw materials and pure water;
step 2, preparing a sodium hydroxide solution with the molar concentration of 8.0 mol/L;
step 3, selecting an aluminum sulfate and sodium hydroxide solution to prepare an aluminum-alkali mixed solution, wherein the molar concentration of Al in the aluminum-alkali mixed solution is 0.6 mol/L;
step 4, preparing ammonia water with the concentration of 10.0mol/L as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows a bottom layer stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2, the aluminum-alkali mixed solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a bottom solution for starting up the reaction, wherein the pH value of the bottom solution is 13.0, and the ammonia concentration is 2.0 g/L;
step 7, adding hydrochloric acid into the base solution, and adjusting the pH value of the base solution to 10.9 to form aluminum hydroxide seed crystals;
step 8, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature in the kettle to be 55 ℃, the pH value to be 10.9 and the ammonia concentration to be 2.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 5.7 mu m, stopping feeding;
and 9, washing and drying the slurry obtained in the step 8, and then sequentially sieving and demagnetizing to obtain the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide.
The prepared end point sample has good uniformity and sphericity through FESEM detection.
Example 3
The narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide is spherical or spheroidal particles, and consists of an inner core and an outer shell, wherein the inner core of the particles is aluminum hydroxide, and the outer shell is made of Ni with a general formula0.92Co0.06Al0.02(OH)2.02The crystal grain cation layer skeleton of the outer shell layer contains nickel, cobalt and aluminum elements. The nickel-cobalt-aluminum hydroxide particles have the characteristic of narrow distribution, K90= (D90-D10)/D50 is not more than 0.90, D50 is 2.5 mu m, and the preparation method is as follows:
step 1, according to the mole ratio of the required nickel, cobalt and aluminum elements, namely 0.92: 0.06: 0.02, preparing a mixed salt solution with the total molar concentration of nickel, cobalt and aluminum metal ions of 1.5mol/L by using nickel nitrate, cobalt nitrate and aluminum nitrate as raw materials and pure water;
step 2, preparing a sodium hydroxide solution with the molar concentration of 6.0 mol/L;
step 3, selecting an aluminum sulfate and sodium hydroxide solution to prepare an aluminum-alkali mixed solution, wherein the molar concentration of Al in the aluminum-alkali mixed solution is 0.4 mol/L;
step 4, preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows a bottom layer stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2, the aluminum-alkali mixed solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a bottom solution for starting up the reaction, wherein the pH value of the bottom solution is 14.0, and the ammonia concentration is 4.0 g/L;
step 7, adding nitric acid into the base solution, and adjusting the pH value of the base solution to 11.3 to form aluminum hydroxide seed crystals;
step 8, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature in the kettle to be 60 ℃, the pH value to be 11.3 and the ammonia concentration to be 4.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 2.5 mu m, stopping feeding;
and 9, washing and drying the slurry obtained in the step 8, and then sequentially sieving and demagnetizing to obtain the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide.
The prepared end point sample has good uniformity and sphericity through FESEM detection.
Comparative example 1
The preparation method of the nickel-cobalt-aluminum hydroxide comprises the following steps:
step 1, according to the mole ratio of the required nickel, cobalt and aluminum elements, namely 0.9: 0.07: 0.03, preparing a mixed salt solution with the total molar concentration of nickel, cobalt and aluminum metal ions of 2.0mol/L by using nickel sulfate, cobalt sulfate and aluminum sulfate as raw materials and pure water;
step 2, preparing a sodium hydroxide solution with the molar concentration of 10.0 mol/L;
step 3, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 4, opening a jacket of the reaction kettle for water inlet and water return, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 5, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 to form a bottom solution for starting up the reaction, wherein the pH value of the bottom solution is 12.0, and the ammonia concentration is 4.0 g/L;
step 6, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature in the kettle to be 50 ℃, the pH to be 12.0 and the ammonia concentration to be 4.0g/L to generate the required amount of seed crystals;
step 7, feeding when the number of the seed crystals reaches the requirement, and controlling the temperature in the kettle to be 50 ℃, the pH value to be 11.2 and the ammonia concentration to be 4.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 3.6 mu m, stopping feeding;
and 8, washing and drying the slurry obtained in the step 7, and then sequentially sieving and demagnetizing to obtain the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide.
The FESEM of the prepared seed crystal is shown in figure 3, obvious agglomeration phenomenon exists, the FESEM of the end point sample is shown in figure 4, the particle size of the end point sample is obviously different, agglomeration exists, and the sphericity is poor.
The end point samples of example 1 and comparative example 1 were tested using a laser particle sizer and the results of D10, D50, and D90 are shown in Table 1.
Table 1 comparison of particle size and distribution of end-point samples of example 1 and comparative example 1
| Numbering | D10/μm | D50/μm | D90/μm | K90=(D90-D10)/D50 |
| Example 1 | 2.37 | 3.57 | 5.27 | 0.812 |
| Comparative example 1 | 2.13 | 3.54 | 5.52 | 0.958 |
Claims (11)
1. The narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide is characterized in that the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide is spherical or spheroidal particles, the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide particles are composed of an inner core and an outer shell, the inner core of the particles is aluminum hydroxide, and the outer shell is made of Ni with a general formulaxCoyAlz(OH)2x+2y+3zWherein x is more than or equal to 0.85 and less than or equal to 0.98, y is more than 0 and less than or equal to 0.15, z is more than 0 and less than or equal to 0.15, and the crystal grain cation layer framework of the outer shell layer contains nickel, cobalt and aluminum elements.
2. The nickel cobalt aluminum hydroxide with narrow distribution and small particle size as claimed in claim 1, wherein the nickel cobalt aluminum hydroxide particles have narrow distribution, K90= (D90-D10)/D50 ≦ 0.90, and D50 is 2.0 μm to 6.0 μm.
3. A preparation method of a narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide is characterized by comprising the following steps:
step 1, according to the mole ratio of nickel, cobalt and aluminum, namely x: y: z, preparing a nickel-cobalt-aluminum mixed salt solution by using nickel, cobalt and aluminum soluble salts as raw materials and pure water;
step 2, preparing a sodium hydroxide solution;
step 3, preparing an aluminum alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution;
step 4, preparing ammonia water as a complexing agent;
step 5, opening a jacket of the reaction kettle for water inlet and water return, starting stirring, introducing nitrogen into the reaction kettle for atmosphere protection, and keeping nitrogen protection in the whole reaction process;
step 6, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding a certain amount of the sodium hydroxide solution prepared in the step 2, the aluminum-alkali mixed solution prepared in the step 3 and the ammonia water prepared in the step 4 to form a bottom solution for starting up the reaction;
step 7, adding a certain amount of additive into the base solution, and adjusting the pH of the base solution to form aluminum hydroxide seed crystals;
step 8, adding the mixed metal salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 4 into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature, the pH value and the ammonia concentration in the kettle; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 2.0-6.0 mu m;
and 9, washing and drying the slurry obtained in the step 8, and then sequentially sieving and demagnetizing to obtain the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide.
4. The method for preparing the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein in the step 1 and the step 3, the soluble salt of nickel-cobalt-aluminum is one or more of chloride, nitrate and sulfate.
5. The method for preparing the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein in the step 1, the total molar concentration of nickel-cobalt-aluminum metal ions in the mixed salt solution is 1.0 mol/L-2.5 mol/L.
6. The method for preparing the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein the molar concentration of the prepared sodium hydroxide solution in the step 2 is 4.0mol/L to 11.0 mol/L.
7. The method for preparing the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein the molar concentration of Al in the prepared aluminum-alkali mixed solution in the step 3 is 0.1mol/L to 0.8 mol/L.
8. The method for preparing the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein the concentration of the prepared ammonia water in the step 4 is 6.0mol/L to 12.0 mol/L.
9. The method for preparing the nickel-cobalt-aluminum hydroxide with the narrow distribution and the small particle size as claimed in claim 3, wherein in the step 6, the pH value of the base solution is 12.0-14.0, and the ammonia concentration is 2.0-5.0 g/L.
10. The method for preparing the narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein in step 7, the type of the additive is one or more of organic acid, inorganic acid, strong acid weak base salt and weak acid weak base salt, and the pH value in the base solution is adjusted to 10.8-11.5.
11. The method for preparing the narrow-distribution small-particle-size nickel-cobalt-aluminum hydroxide as claimed in claim 3, wherein in the step 8, the reaction temperature in the kettle is controlled to be 45-65 ℃, the pH value is 10.8-11.5, and the ammonia concentration is 2.0-5.0 g/L.
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